JPH082923B2 - Method for producing star compound - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to three-branched polyalkenyl ethers, four-branched star polyalkenyl ethers, three-branched star polyalkyloxystyrenes, four-branched star polyalkyloxystyrenes, and the like. The present invention relates to a method for producing a branched or four-branched star compound.

Such polyfunctional polyolefins are expected as useful polymeric materials such as prepolymers for elastomers, cross-linking agents, ionomers, surfactants and compatibilizers.

[0003]

2. Description of the Related Art Alkenyl ethers and alkyloxystyrenes are polymerized only by cationic polymerization, but the growing carbon cations that grow in ordinary cationic polymerization are unstable.
It became difficult to suppress migration and termination reaction, and it was difficult to produce a polymer or block copolymer having a narrow molecular weight distribution, that is, a monodisperse polymer.

However, the present inventors have found that cation-providing compounds HI and I ₂ , ZnI ₂ or metal halides (Z
nI ₂ , ZnBr ₂ , ZnCl ₂ , SnI ₂ , SnCl
It has been found that when a binary initiator composed of ₂ , ₂ , MgCl ₂ , BF ₃ OEt ₂ , SnCl ₄ ) is used, isobutyl vinyl ether undergoes living polymerization to form a polymer or block copolymer having a narrow molecular weight distribution (HI.
/ I ₂ -based initiators, Macromolecules, 1984,
17 , 3,265-272 and HI / ZnI ₂
Macromolecules, 1987, 20 , 11, 2693-2
696, Macromolecules, 19 for metal halides
89, 22, 4, 1552-1557).

With regard to alkyloxystyrenes, the present inventors have also found that cation supplying compounds HI and Z.
It was found that p-methoxystyrene and Pt-butoxystyrene can undergo living polymerization to produce a polymer having a narrow molecular weight distribution by using a binary initiator composed of nI ₂ (Polymer Bulletin, 1988, 1).
9 , 7-11 and Makromol, Chem., Suppl. 1989, 1 .
5 , 127,136).

[0006] A three- or four-branched star polymer is a polymer having three or four branched chains radially extending from one common center, and has three or four active ends. It has physical properties not found in linear polymers, for example,
Prepolymer for elastomer, cross-linking agent, ionomer,
It is expected to be a useful polymer material because it can be applied and developed as a surfactant and compatibilizer.

[0007]

However, in the living cationic polymerization of the alkenyl ether, the initiator is an adduct of a monofunctional alkenyl ether and a cation-providing compound, which is one per molecule. It was impossible to synthesize the above star polymer, because only the active sites of the above were produced.

In view of the above points, an object of the present invention is to provide a method for producing a three- or four-armed star compound.

[0009]

SUMMARY OF THE INVENTION To achieve the above object, the present invention provides:

[0010]

[Chemical 9]

(Wherein R ¹ is a hydrogen atom or a methyl group, n
Is an integer 3 or 4, R ² is a trivalent organic group when n is 3, n
Represents a tetravalent organic group when 4 is 4, and a polyfunctional alkenyl ether represented by the general formula RCOOH
(R is a hydrogen atom, a methyl group or a halogen-substituted
Chill group) and HX (X represents a halogen atom).
Li Cheng cationic feed compound selected from the group (hereinafter, mosquito
A compound represented by the general formula CHR ³ ═CH | ... [II] A-OR ⁴ (in the formula, A is a single bond or a phenylene group, and A is a single bond). R ³ is a hydrogen atom or a methyl group, R ⁴ is a monovalent organic group,
A is the R ³ when a phenylene group is polymerized olefin compound represented by R ⁴ means respectively an alkyl group) with a hydrogen atom, Ani dissociated by a solvent or heating
There are few polymerization terminators that generate on
Add at least equimolar amount to stop the reaction,

[0012]

[Chemical 10]

(In the formula, x is 1 to 10000, Z is a terminator residue, R ¹ , R ² , R ³ , R ⁴ , A and n have the same meanings as described above) Alternatively, the present invention provides a method for producing a four-branched star compound. Among the methods of the present invention, first, a method for producing a triple-branched star compound will be described.

According to the method of the present invention, the general formula (Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a trivalent organic group, respectively) using an adduct of a trifunctional alkenyl ether and a cation-providing compound as an initiator. (In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group).

[0015]

[Chemical 11]

(Wherein x is 1 to 10000, Z is a terminating residue, and R ¹ , R ² and R ⁴ have the same meanings as above)
A three-branched star alkenyl ether represented by

In addition, an adduct of the trifunctional alkenyl ether represented by the above general formula [1a] and a cation supplying compound is used as an initiator, and a divalent metal halide is used as an activator. (Wherein A represents a phenylene group and R ⁴ represents an alkyl group), and an alkyloxystyrene represented by the following formula is polymerized:

[0018]

[Chemical 12]

A corresponding three-star alkyloxy group represented by the formula: wherein x is 1 to 10000, Z is a terminating agent residue, and R ¹ , R ² , R ⁴ and A have the same meanings as described above. Produces styrene.

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

According to the method of the present invention,

[0022]

[Chemical 13]

(Wherein R ¹ is a hydrogen atom or a methyl group, R 1
² means a tetravalent organic group respectively) and an adduct of a tetrafunctional alkenyl ether represented by (In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group).

[0024]

Embedded image

(Wherein x is 1 to 10000, Z is a terminating residue, R ¹ , R ² , R ^{3 and} R ⁴ have the same meanings as described above) To manufacture.

Further, an adduct of a tetrafunctional alkenyl ether represented by the above general formula [Ib] and a cation supplying compound is used as an initiator, and a divalent metal halide is used as an activator. (Wherein A represents a phenylene group and R4 represents an alkyl group, respectively), and an alkyloxystyrene represented by the following formula is polymerized:

[0027]

[Chemical 15]

The corresponding four-star alkyloxy group represented by the formula (wherein x is 1 to 10000, Z is a stopper residue, R ¹ , R ² , R ⁴ and A have the same meanings as described above). Produces styrene.

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

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

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

Also, a trifunctional alkenyl ether [Ia]
Among the compounds R ² radicals having an ester bond, for example, 2-hydroxyethyl vinyl ether or 2-hydroxyethyl propenyl ether was used as a sodium salt with sodium hydrogen reduction in toluene corresponding trifunctional carboxylic acid chloride This It is obtained by reacting with.

In the preparation of the four-branched polymer, the tetrafunctional alkenyl ether [Ib ' ] [Ib " ] has the following structure:

[0039]

Embedded image

Specific examples of the tetrafunctional alkenyl ether [I b ′ ] (wherein R ¹ represents a hydrogen atom or a methyl group) are as follows: 1,1,4,4-tetrakis [ 4- (2-vinyloxy)
Ethoxyphenyl] cyclohexane 1,1,4,4-tetrakis [4- (2-propenyloxy) ethoxyphenyl] cyclohexane.

Specific examples of the tetrafunctional alkenyl ether [Ib " ] are as follows: 1,1,3,3-tetrakis [4- (2-vinyloxy)]
Ethoxyphenyl] cyclohexane 1,1,3,3-tetrakis [4- (2-propenyloxy) ethoxyphenyl] cyclohexane.

Tetrafunctional alkenyl ether [I b ' ] [I
b ″ ] is obtained, for example, by reacting tetrakis (4-hydroxyphenyl) cyclohexane with chloroethyl vinyl ether or chloroethyl propenyl ether in dimethylsulfoxide in the presence of sodium hydroxide.

In the method of the present invention, examples of the cation supplying compound include CF ₃ COOH, CCl ₃ COOH and C
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 supplying compound, that is, an adduct of a trifunctional alkenyl ether [Ia] and a cation supplying compound, or a tetrafunctional alkenyl ether [ Ib ' ].
An adduct of [Ib " ] and a cation-providing compound is used as an initiator. When the cation-providing compound is represented by HB,
This adduct is

[0045]

[Chemical 17]

(In the formula, R ¹ , R ² and n have the same meanings as described above, and B means the cation-feeding balance of the cation-feeding compound).

As a general method for synthesizing the adduct [IV], an inert solvent such as carbon tetrachloride, n-hexane, or toluene (preferably the same kind as the polymerization reaction solvent) 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 a cation-providing compound HB is added thereto and reacted. Trifunctional alkenyl ether [Ia] used and cation-providing compound H
The molar ratio with B is substantially 1: 3, and the molar ratio between the tetrafunctional alkenyl ether [Ib ' ] [Ib " ] and the cation-providing compound is substantially 1: 4. −
The temperature is appropriately set in the range of 90 ° C to 100 ° C. The reaction pressure is usually normal pressure, but it can be increased. The reaction time is 10 seconds to 24 hours, preferably 5 minutes to 1 hour. According to this synthetic method, the reaction proceeds rapidly to quantitatively obtain a solution of the adduct [IV]. Further, the adduct [IV] may be isolated from this solution, but it may be subjected to polymerization in the state of the above solution without isolation.

Since the degree of polymerization of the polymer is determined by the molar ratio (100% polymerization rate) of the olefin compound [II] and the adduct [IV], the amount of the adduct [IV] used is important. The molecular weight can be set by determining the molar ratio of the olefin compound [II] and the adduct [IV] according to the desired degree of polymerization. This molar ratio is 3 or more to obtain a three-branch star compound, and 4 or more to obtain a four-branch star compound.
It is appropriately determined according to the desired degree of polymerization.

In the alkenyl ether represented by the general formula [IIa] of the olefin compound [II] which is a monomer for polymerization in the method of the present invention, the following are exemplified as R ⁴ which represents a monovalent organic group. To be done.

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, 4
-Ethyl-1-methyloctyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n
-Alkyl group such as eicosyl and n-docosyl: Cycloalkyl group such as cyclohexyl: cyclohexylmethyl,
Terpene two Le, menthyl, bornyl, cycloalkylalkyl group isobornyl like: benzyl, p- methylbenzyl, p- chlorobenzyl, p- phenylbenzyl, 1-
Aralkyl groups such as phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 1,1-dimethylbenzyl, benzhydryl, 3-phenylpropan-2-yl: cinnamyl, 1-methylcinnamyl, 3- Methylcinnamyl, 3-phenylcinnamyl,
Arylalkenyl groups such as 2-phenylallyl and 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-
Aryl groups such as bromophenyl, p-bromophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl, 2,4-dinitrophenyl: 1 -Chloroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,
Haloalkyl groups such as 2,2-trifluoroethyl and 3-chloropropyl: methoxyethyl, ethoxyethyl, 2
- alkoxy shear alkyl groups such as ethoxyethoxy ethyl,
Phenoxyethyl, p-chlorophenoxyethyl, p-
Aryloxyalkyl groups such as bromophenoxyethyl, p-fluorophenoxyethyl, p-methoxyphenoxyethyl and the like: 2-acetoxyethyl, 2-benzoxyethyl, 2- (p-methoxybenzoxy) ethyl, 2-
Acyloxyalkyl groups such as (p-chlorobenzoxy) ethyl: 2-phthaliminoethyl, 2- (di-tert)
- Buchirukaruboki Castanopsis amino) iminoalkyl groups ethyl and the like: 2-diethyl malonyl ethyl, 2-diphenyl malonyl ethyl and the like malonyl alkyl group: 2-acryloxyethyl, 2-methacryloxyethyl, 2-cinnamyl b carboxyethyl, 2 - allyl oxyalkyl groups such as Sol vinyl Rokishiechiru like.

The olefin [IIa] may be used alone or in combination of two or more kinds.

In the method using olefin [IIa], it is preferable to adopt a method for promoting polymerization (living polymerization), and there are the following two methods.

The first method is a method in which side reactions are 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. The nucleophilicity of is adjusted by a Lewis acid to prevent side reactions and living polymerization is carried out.

These methods will be described in more detail.

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

R ⁵ r AlXs ... [V] (wherein R ⁵ represents a monovalent organic group, X represents a halogen atom, r and s are integers, r + s = 3, and 0 ≦ r <
In the 3,0 ≦ s <3 of the relationship. ) Examples of the organoaluminum compound [V] include, for example, trichloroaluminum, tribromoaluminum, ethylaluminum dichloride, ethylaluminum dibromide, diethylaluminum chloride, diethylaluminum bromide, ethylaluminum diiodo, ethylaluminum difluoride, methyl. Aluminum dichloride, methyl aluminum dibromide, dimethyl aluminum chloride,
Dimethyl aluminum bromide and the like can be mentioned. These organoaluminum compounds may be used alone or in a combination of two or more kinds, and the amount used is generally in a molar ratio of olefin [II] / organoaluminum compound [V] =
It is in the range of 2 to 10,000, 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, p-.
Ethyl methylbenzoate, ethyl p-methoxybenzoate,
Ester compounds such as methyl acetate, isopropyl acetate, t-butyl acetate: 1,4-dioxane, diethyl ether, tetrahydrofuran, di-n-hexyl ether,
Ether compounds such as diisopropyl ether, di-n-butyl ether, methoxytoluene, propylene oxide, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, acetal: pyridine, 2,6
-Dimethylpyridine, 2-methylpyridine, 2,4,6
-Trimethylpyridine, 2,4-dimethylpyridine,
Examples thereof include pyridine derivatives such as 2,6-di-t-butylpyridine.

These Lewis bases can be used alone or in combination of two or more. Also, they can be used in bulk or in solution in an inert solvent. Further, these Lewis bases are added to the reaction system in an amount according to the basicity of the Lewis base within the range of the following relationship between the amount of the Lewis base and the amount of the alkenyl ether [I] used.

0.001 ≦ amount of Lewis base used / amount of polyfunctional alkenyl ether [I] ≦ 100 In the above relationship, the amount of Lewis base used and a polyfunctional alkenyl ether [ When the ratio of the amount of [I] used is less than 0.001 and exceeds 100, it is difficult to form a complete living system, which is not preferable.

In the second method, a Lewis acid is used to moderately activate the counter anion for the growing carbon cation, and examples of the Lewis acid include iodine, zinc (II) halide and halogen. Examples thereof include tin (II) chloride, and particularly I ₂ , ZnI ₂ , ZnBr ₂ , ZnCl ₂ ,
SnI ₂ and SnCl ₂ are preferably used. This Lewis acid is used alone or in combination of two or more. The amount of the polyfunctional alkenyl ether [I] / Lewis acid used is generally in the range of 2 to 100,000, preferably 10 to 10,000 in terms of molar ratio.

Among the olefin compounds [II] of the method of the present invention, alkyloxystyrenes represented by the general formula [IIb] include o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m
-Ethoxystyrene, p-ethoxystyrene, o-normalpropyloxystyrene, m-normalpropyloxystyrene, p-normalpropyloxystyrene,
o-isopropyloxystyrene, m-isopropyloxystyrene, p-isopropyloxystyrene, o-
Examples thereof include normal butoxy styrene, m-normal butoxy styrene, p-normal butoxy styrene, o-t-butoxy styrene, m-t-butoxy styrene, and pt-butoxy styrene. These may be used alone or in combination.

In the method using alkyloxystyrene [IIb], a divalent metal halide is used as an activator to promote polymerization (living polymerization).

This metal halide is for activating the counter anion with respect to the growing carbon cation at the time of polymerization. For example, ZnI ₂ , ZnBr ₂ , ZnCl ₂ ,
Examples include SnI ₂ and SnCl ₂ .

These metal halides may be used alone or in combination with 2.
It is used in combination of one or more kinds, and the amount thereof is such that the molar ratio of polyfunctional alkenyl ether [I] / metal halide is 0.01 to 1000, preferably 0.1 to 100.

In the present invention, the polymerization reaction form is as follows:
Usually, a solution polymerization method is adopted, but a bulk polymerization method or the like can also be adopted. 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 usually appropriately set in the range of -40 ° C to 100 ° C. The reaction pressure is usually normal pressure, but it 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, in order to terminate the polymerization reaction, the reaction solution should be in a solvent.
Alternatively, a polymerization termination that dissociates by heating to produce anions
Add at least an equimolar amount of inhibitor to the growing cations
Stop the reaction. Examples of such a polymerization terminator include alcohols such as methanol, ethanol, propanol, isopropanol and butanol: amines such as dimethylamine and diethylamine, HZ.
A compound represented by (Z is a terminator residue) is preferably used. When methanol is used, it is preferable to use it together with aqueous ammonia. Ammonia has a function of deactivating the activity of the organoaluminum [V] Lewis acid and the metal halide. The molar ratio of the polymerization terminator to the cation supplying compound HB is 1-10000, preferably 1-1.
000.

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

The degree of polymerization x in the star compound which is the reaction product of the present invention is 1 to 10000, preferably 4 to 500.
0, more preferably 10 to 1000, most preferably 1
It is in the range of 0 to 600.

[0069]

According to the production method of the present invention, a star compound having three or four branches of uniform length and having a narrow molecular weight distribution can be obtained. Moreover, since the polymer terminal of the star compound obtained by the method of the present invention is living, it is possible to obtain a block copolymer with another polymer and to introduce a functional group into the terminal. Further, depending on the kind of the monomer, the polymer can be made hydrophilic by the reaction of the polymer, and the block copolymer can be made into a copolymer of a hydrophilic block and a hydrophobic block. Thus, this star polymer can be developed as a functional polymer, and is expected to be used as a prepolymer, a crosslinking agent, an ionomer, a surfactant, a compatibilizing agent, etc. in a novel elastomer.

[0070]

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

The adduct of the polyfunctional alkenyl ether [I] and the cation-providing compound used in each example was
Under a nitrogen stream, dissolve the polyfunctional alkenyl ether [I] in a sufficiently purified and dried inert solvent (the same kind as the polymerization reaction solvent), add an equivalent amount of the cation supplying compound HB, and stir for 15 minutes. It was prepared by. The obtained adduct was subjected to a polymerization reaction in a solution state 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 dissolved in 50 ml of toluene under a nitrogen atmosphere. is the solution to hydrogen sodium powder 2.71 g (1
(13 mmol) was added and the solution was stirred at room temperature for 1 hour.
Then, 10.0 g (3 parts) of trimesic acid chloride was added to this solution.
(3.7 mmol) and 0.5 g of tetra-n-butylammonium chloride were added, and the reaction was carried out 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 1). Yield: 62%, melting point: 92-93
℃ (pale yellow crystal), infrared absorption spectrum (Nujol): νC =
C = 1620 cm-1, vPh = 830 cm-1.

Reference Example 2 (Preparation of trifunctional alkenyl ether) In a glass three-neck flask equipped with a condenser and a stirrer, 1,1,1-tris (4-hydroxy) was added to 75 ml of dimethyl sulfoxide under a nitrogen atmosphere. 10.0 g (32.6 mmol) of phenyl) ethane were dissolved, 23.5 g (587 mmol) of sodium hydroxide powder was added to the solution, and the solution was stirred at 75 ° C. for 3 hours. Then, 59.7 ml (587 mmol) of 2-chloroethyl vinyl ether was added to this liquid, and the reaction was carried out at 80 ° C. for 5 hours. The reaction mixture was purified in the same manner as in Reference Example 1 to obtain 1,1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (second compound in Table 2).

Reference Example 3 (Preparation of tetrafunctional alkenyl ether) In a glass three-necked flask equipped with a condenser and a stirrer, 75 ml of dimethyl sulfoxide was added with 1,1,4,4-tetrakis (4) under a nitrogen atmosphere. -Hydroxyphenyl) cyclohexane 10.0 g (22.1 mmol) was dissolved and 21.2 g (5
(30 mmol) was added and the solution was stirred at 75 ° C. for 3 hours. Then, 53.9 ml (530 mmol) of 2-chloroethyl vinyl ether was added to this liquid, and the reaction was carried out 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. Yield: 48%, melting point: 137.5 to 139 ° C. (pale yellow crystal), infrared absorption spectrum (Nujol): ν _{C = C} = 1620
^{_{cm -1, ν Ph = 830cm -1}} .

Reference Example 4 (Preparation of Tetrafunctional Alkenyl Ether) In Reference Example 3, 2-chloroethylpropenyl ether 63.9 was used instead of 2-chloroethyl vinyl ether.
ml (530 mmol) was used, and otherwise 1,1, 4,4-tetrakis [4- (2-
Propenyloxy) ethoxyphenyl] cyclohexane was obtained.

Reference Example 5 (Preparation of tetrafunctional alkenyl ether) In Reference Example 3, 1,1,4,4-tetrakis (4-
1, instead of (hydroxyphenyl) cyclohexane
Using 10.0 g (22.1 mmol) of 1,3,3-tetrakis (4-hydroxyphenyl) cyclohexane,
Other points are the same as in Reference Example 1, 1, 1, 3, 3-
Tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane was obtained.

Example 1 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 and 0.5 ml (1.2 mol / l) there
1,4-dioxane was added and the temperature of the solution was kept at 0 ° C. There, 1,1,1-diluted with n-hexane
Tris [4- (2-vinyloxy) ethoxyphenyl] ethane (second compound in Table 2) and trifluoroacetic acid (C
F ₃ COOH) adduct 0.5 ml (1.7 mmol /
1) and 0.5 ml (5.0 mmol / l) of a hexane solution of ethylaluminum dichloride were added in this order to start the polymerization, and the polymerization was continued at 0 ° C. for 3 hours. afterwards,
The polymerization was stopped by adding methanol (170 mmol / l) containing a small amount of aqueous ammonia. The reaction mixture was washed with an aqueous hydrochloric acid solution (8 vol%) and then with water to remove the catalyst residue, and then the solvent and the like were evaporated to recover the polymer.

As a result, Mn = 1.6 × 10 ⁵ , Mw /
A three-branched star polyisobutyl vinyl ether with Mn = 1.04 was obtained. The value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁵ that three branch molecules were generated from one molecule of the adduct.

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured value: <Trifunctional vinyl ether>

[0080]

Embedded image

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) <Trifunctional initiator>

[0082]

[Chemical 19]

Δ (ppm): peak g 1.50 (s, 9
_{H, CH 3) a 2.05 (} s, 3H, CH 3) d + e 4.00 (m, 12H, -CH 2 -) f 6.15 (q, 3H, CH) b 6.70 (d, 6H, aromatic) c 6.90 (d , 6H, aromatic) <Tri-chain polyvinyl ether>

[0084]

Embedded image

Δ (ppm): peak k 0.90 (18x
_{H, CH 3) f 1.20 (} 9H, CH 3) g + j 1.40~2.00 (9xH, -CH 2 -) a 2.10 (3H, CH 3) d, e, h, i, n 3.00~4.00 c 4.10 (6H, _{-CH 2 -) m 4.65 (3H} , CH) b 6.75~7.00 (12H, aromatic) was thoroughly purified dried under example 2 nitrogen n- hexane 2.5
1.0 ml of isobutyl vinyl ether (1.5 ml)
Mol / l) dissolved and 0.5 ml (1.2 mol / l) there
1,4-dioxane was added and the temperature of the solution was kept at 0 ° C. There, 1,3,5-diluted with n-hexane
0.5 ml (3.5 mmol / l) of an adduct of tri (2-vinyloxy) ethyl benzenetricarboxylate (first compound in Table 1) with trifluoroacetic acid, and 0.5 ml of a hexane solution of ethylaluminum dichloride ( 10 mmol / l) was added in this order to initiate the polymerization. The subsequent operations were performed in the same manner as in Example 1 to recover the polymer.

As a result, Mn = 3.8 × 10 ⁴ , Mw /
A tri-branched star polyisobutyl vinyl ether with Mn = 1.12 was obtained. The value of Mn was in good agreement with the calculated value of 3.9 × 10 ⁴ , which was assumed that three branch molecules were generated from one molecule of the adduct.

Furthermore, in order to prove that the three-branched star-shaped polyisobutyl vinyl ether is composed of a branched polymer having a uniform length, three tri-branched star-shaped polyisobutyl vinyl ethers have three groups in the central organic group R ^2. Hydrolysis of the ester bond was performed. This hydrolysis reaction was carried out by immersing the above polymer in an aqueous sodium hydroxide solution at room temperature for 2 days with stirring. The branch polymer obtained has Mn =
1.3 × 10 ⁴ , Mw / Mn = 1.06, demonstrating that the tri-branched star polyisobutyl vinyl ether consisted of tri-branched polymers of uniform length.

Example 3 2.50 ml of toluene sufficiently purified and dried under a nitrogen atmosphere
To this, 1.0 ml (0.38 mol / l) of a solution of methyl vinyl ether in toluene was added, and 0.5 ml (1.2 mol / l) was added.
1) 1,4-dioxane was added, and 0.5 ml (3.5 mmol / l) of the same adduct as used in Example 1 and 0.5 ml (1 ml) of a solution of ethylaluminum dichloride in hexane were added.
0 milmol / l) was added, the polymerization was started at -15 ° C, and the polymerization was continued for 3 hours. Thereafter, the same operation as in Example 1 was carried out to obtain a polymer.

As a result, Mn = 6.7 × 10 ³ , Mw /
A hydrophilic tri-branched star polymethyl vinyl ether with Mn = 1.05 was obtained. The value of Mn was in good agreement with the calculated value of 6.9 × 10 ³ which was determined that three branch molecules were generated from one molecule of the adduct.

Example 4 In Example 1, the polymerization temperature was set to 60 ° C. and the polymerization was continued for 10 minutes. Otherwise in the same manner as in Example 1, a polymer was obtained.

As a result, Mn = 1.5 × 10 ⁵ , Mw /
A tri-branched star polyisobutyl vinyl ether with Mn = 1.10 was obtained. The value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁵ that three branch molecules were generated from one molecule of the adduct.

Example 5 N-hexane 3.2 sufficiently purified and dried under a nitrogen atmosphere
0.25 ml of isobutyl vinyl ether in 5 ml
(0.35 mol / l) was dissolved, 0.5 ml (1.2 mol / l) of 1,4-dioxane was added thereto, and 0.5 ml (3.5 mmol / l) of the same adduct as in Example 1 was added. ) And 0.5 ml (10 mmol / l) of a hexane solution of ethyl aluminum dichloride were added to initiate polymerization at 0 ° C. 3 minutes after the start of the reaction, 0.25 ml of 2-vinyloxyethyl acetate
(0.38 mol / l) was added to bring the polymerization temperature to 40 ° C.,
Polymerization was continued for 3 hours. Thereafter, the same operation as in Example 1 was carried out to obtain a polymer.

As a result, Mn = 2.8 × 10 ⁴ , Mw /
A three-branched star block copolymer with Mn = 1.04 was obtained. The value of Mn was in good agreement with the calculated value of 2.6 × 10 ⁴ that three branch molecules were generated from one molecule of the adduct.

Further, by alcal-hydrolyzing this polymer, the outer poly-2-acetoxyethyl vinyl ether is converted into poly-2-hydroxyethyl vinyl ether, and the amphiphilic three-chain having a hydrophobic group on the inner side and a hydrophilic group on the outer side. A branch star polymer was obtained.

Example 6 In Example 5, first, 0.25 ml of 2-vinyloxyethyl acetate was used instead of isobutyl vinyl ether.
(0.38 mol / l) was added and the mixture was polymerized at 40 ° C. for 2 hours, and then 0.25 ml of isobutyl vinyl ether (0.
38 mol / l) was added, and the polymerization was further continued at 40 ° C. for 1 hour.

As a result, Mn = 2.3 × 10 ⁴ , Mw /
A three-branch star block polymer with Mn = 1.11 was obtained. The value of Mn was in good agreement with the calculated value of 2.6 × 10 ⁴ that three branch molecules were generated from one molecule of the adduct.

Further, by subjecting this polymer to alkali hydrolysis, poly 2-acetoxyethyl vinyl ether on the inside is converted into poly 2-hydroxyethyl vinyl ether, and three amphipathic groups having a hydrophilic group on the inside and a hydrophobic group on the outside are obtained. A branch star polymer was obtained.

Example 7 0.5 ml (0.76 mol / l) of isobutyl vinyl ether was dissolved in 3.5 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere, and the solution temperature was kept at -15 ° C. 0.5 ml (3.0 mmol) of an adduct of 1,1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (the second compound in Table 2) diluted with toluene and hydrogen iodide. / L) and an ether solution of zinc iodide (Znl ₂ ) (0.2 mmol / l) were added in this order to start the polymerization, and the polymerization was continued at -15 ° C for 1 hour. Then, methanol containing a small amount of ammonia (300 mmol / l)
The polymerization was stopped by the addition of. The reaction mixture was washed first with aqueous sodium thiosulfate (8 vol%) and then with water,
After removing the catalyst residue, the solvent and the like were evaporated to recover the product.

As a result, Mn = 2.8 × 10 ⁴ , Mw /
A three-branched star polyisobutyl vinyl ether with Mn = 1.04 was obtained. The value of Mn was in good agreement with the calculated value of 2.6 × 10 ⁴ that three branch molecules were generated from one molecule of the adduct.

Example 8 In Example 7, addition of tri (2-vinyloxy) ethyl 1,3,5-benzenetricarboxylate (the first compound in Table 1) diluted with toluene and hydrogen iodide as an adduct. The same procedure as in Example 7 was carried out except that the body (3.0 mmol / l) was used. As a result, Mn = 3.3 × 10 ⁴ , Mw / Mn =
A 1.04 triple-branched star polyisobutyl vinyl ether was obtained.

Example 9 0.25 ml of 2-vinyloxyethyl acetate was added to 3.0 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere.
(0.38 mol / l) was dissolved and the temperature of the solution was kept at -15 ° C. 0.5 ml of the adduct used in Example 5
(3.0 milmol / l) and a toluene solution of iodine (I ₂ ) (9.0 milmol / l) were added in this order to start the polymerization, and the polymerization was continued at -15 ° C for 1 hour. Thereafter, the same operation as in Example 5 was carried out to obtain a polymer.

As a result, Mn = 1.9 × 10 ⁴ , Mw /
A three-branched star poly-2-acetoxyethyl vinyl ether with Mn = 1.08 was obtained. The value of this Mn is
Calculated value that three branch molecules are generated from the molecule (1.7
It was in good agreement with × 10 ⁴ ). Example 10 3.75 ml of toluene sufficiently purified and dried under a nitrogen atmosphere
0.25 ml (0.38 mol / l) of p-methoxystyrene was dissolved therein, and the temperature of the solution was kept at -78 ° C. There, 1,1,1-tris [4-
0.5 ml of an adduct of (2-vinyloxy) ethoxyphenyl] ethane (the second compound in Table 2) with hydrogen iodide.
(3.3 mmol / l) and 0.5 ml of an ether solution of zinc iodide (3.3 mmol / l) were added in this order,
The solution was allowed to stand at −78 ° C. for 20 hours, then heated to −15 ° C. to start polymerization, and continued at −15 ° C. for 2 hours. After that, methanol containing a small amount of ammonia water (3
The polymerization was stopped by the addition of 30 mmol / l) to obtain a mixture containing the polymer. This mixture was washed with an aqueous hydrochloric acid solution (8 vol%) and then with water, and the solvent and the like were evaporated to obtain a polymer.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained had Mn = 1.4 × 10 ⁴ , Mw / Mn
= 1.05 triple-stranded star poly (p-methoxystyrene)
Met. The value of Mn was in good agreement with the calculated value of 1.5 × 10 ⁴ that three branch molecules were produced from one molecule of the adduct.

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured value: <triple-chain poly (P-methoxystyrene)>

[0105]

[Chemical 21]

Δ (ppm): peak f 0.90 (9H,
_{CH 3) g + h 1.20~2.20 (} 9xH, -CH 2 -CH-) a 2.10 (3H, CH 3) k 3.00 (9H, OCH 3) c 3.10~3.40 (6H, -CH 2 -) d 3.00~4.00 ( 6H, -CH ₂ -) j 3.70 in _{(9xH, OCH 3) e 3.00~4.00} (3H, -CH-) b + i 6.25~7.05 (12 (x + 1) H, aromatic) example 11 example 10, A polymer was obtained in the same manner as in Example 10 except that tri (2-vinyloxy) ethyl 1,3,5-benzenetricarboxylate (the first compound in Table 1) was used as the trifunctional alkenyl ether.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained had Mn = 1.6 × 10 ⁴ , Mw / Mn
= 1.06 triple chain star poly (p-methoxystyrene)
Met. The value of Mn was in good agreement with the calculated value of 1.5 × 10 ⁴ that three branch molecules were produced from one molecule of the adduct.

Further, the above-mentioned three-chain star-shaped poly (p-methoxystyrene) was immersed in a sodium hydroxide aqueous solution at room temperature for 2 days to hydrolyze the three ester bonds at the center of the three chains to form a branched polymer. Obtained. As a result of GPC analysis, the obtained branch polymer had Mn = 5.0 × 10 ³ , Mw / Mn =
It was 1.07.

Example 12 Example 10 was repeated except that hydrogen chloride was used in place of hydrogen iodide, zinc chloride was used in place of zinc iodide, the polymerization temperature was 0 ° C., and the reaction time was 20 minutes. 10
A polymer was obtained in the same manner as in.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained had Mn = 1.4 × 10 ⁴ , Mw / Mn
= 1.06 triple chain star poly (p-methoxystyrene)
Met. The value of Mn was in good agreement with the calculated value of 1.5 × 10 ⁴ that three branch molecules were produced from one molecule of the adduct.

Example 13 In Example 10, p-methoxystyrene (0.38
Mol / l) instead of pt-butoxystyrene (0.
26 mol / l) was used and a polymer was obtained in the same manner as in Example 10 except that the polymerization temperature was 25 ° C.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained had Mn = 1.3 × 10 ⁴ , Mw / Mn
It was a triple-stranded star poly (pt-butoxystyrene) of = 1.07. The value of Mn was in good agreement with the calculated value of 1.4 × 10 ⁴ that three branch molecules were generated from one molecule of the adduct.

Example 14 After polymerizing p-methoxystyrene in the same manner as in Example 10, 25 ml of pt-butoxystyrene (0.
26 mol / l) was added, the temperature was raised to 25 ° C., and the polymerization was continued for 2 hours. Then, the polymerization was stopped by adding methanol (330 mmol / l) containing a small amount of aqueous ammonia to obtain a mixture containing the polymer. This mixture was washed with an aqueous hydrochloric acid solution (8 vol%) and then with water, and the solvent and the like were evaporated to obtain a polymer.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained had Mn = 3.Mn consisting of poly (p-methoxystyrene) and poly (pt-butoxystyrene).
It was a triple chain star block copolymer with 0 × 10 ⁴ and Mw / Mn = 1.05.

The value of Mn is 3 from one molecule of the adduct.
Calculated value to generate 2.9 × 10 ^FourWell matched.

Further, by treating the above copolymer with hydrogen bromide, the outer poly (pt-butoxystyrene) is converted into poly (p-vinylphenol), and the inner hydrophobic group and the outer hydrophilic group are added. We obtained an amphipathic three-chain star copolymer.

Example 15 In Example 10, p-methoxystyrene (0.38
Mol / l) instead of pt-butoxystyrene (0.
26 mol / l) was used, and pt-butoxystyrene was polymerized in the same manner as in Example 10 except that the temperature was 25 ° C., and then 25 ml of p-methoxystyrene (0.38 mol / l)
1) was added, and the polymerization was continued at 25 ° C. for 20 minutes. Then, the polymerization was stopped by adding methanol (330 mmol / l) containing a small amount of aqueous ammonia to obtain a mixture containing the polymer. This mixture was first treated with an aqueous hydrochloric acid solution (8 vol.
%), And then water, and the solvent and the like were evaporated to obtain a polymer.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained is poly (pt-butoxystyrene).
And Mn = 2.
It was a triple chain star block copolymer with 8 × 10 ⁴ and Mw / Mn = 1.06.

The value of Mn is three from one molecule of the adduct.
Calculated value to generate 2.9 × 10 ^FourWell matched.

Further, by treating the above copolymer with hydrogen bromide, the inner poly (pt-butoxystyrene) is converted into poly (p-vinylphenol), and the hydrophilic group is inside and the hydrophobic group is outside. We obtained an amphipathic three-chain star copolymer.

Example 16 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 and 0.5 ml (1.2 mol / l) there
1,4-dioxane was added and the temperature of the solution was kept at 0 ° C. There, 1,1,4 diluted with n-hexane
4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane and trifluoroacetic acid (CF ₃ CO
0.5 ml (1.7 mmol / l) of an adduct with OH) and 0.5 of a solution of ethylaluminum dichloride in hexane.
The polymerization was initiated by adding ml (5.0 mmol / l) in this order, and the polymerization was continued at 0 ° C. for 3 hours. Then, the polymerization was stopped by adding methanol (330 mmol / l) containing a small amount of aqueous ammonia. The reaction mixture was washed with an aqueous hydrochloric acid solution (8 vol%) and then with water to remove the catalyst residue, and then the solvent and the like were evaporated to recover the polymer.

As a result, Mn = 1.6 × 10 ⁵ , Mw /
A four-branched star polyisobutyl vinyl ether with Mn = 1.06 was obtained. The value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁵ that four branch molecules were generated from one molecule of the adduct.

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured value: <tetrafunctional vinyl ether>

[0124]

[Chemical formula 22]

Δ (ppm): peak a 2.25 (m, 8
H, 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) <Tetrafunctional initiator>

[0126]

[Chemical formula 23]

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 polyvinyl ether>

[0128]

[Chemical formula 24]

Δ (ppm): peak k 0.90 (24x
_{H, CH 3) f 1.20 (} 12H, CH 3) g + j 1.40~2.00 (12xH, -CH 2 -) a 2.10-2.40 (8H, cyclohexane ring) d, e, h, i , n 3.00~4.00 c 4.10 ( _{8H, -CH 2 -) m 4.65} (4H, CH) b 6.75~7.00 (16H, aromatic) was thoroughly purified and dried under example 17 a nitrogen atmosphere n- hexane 2.5
1.0 ml of isobutyl vinyl ether (1.5 ml)
Mol / l) dissolved and 0.5 ml (1.2 mol / l) there
1,4-dioxane was added and the temperature of the solution was kept at 0 ° C. There, 1,1,4 diluted with n-hexane
0.5 ml (3.5 mmol / l) of an adduct of 4-tetrakis [4- (2-propenyloxy) ethoxyphenyl] cyclohexane and trifluoroacetic acid, and 0.5 ml (10 mmol / l) of a solution of ethylaluminum dichloride in hexane. ) Was added in this order to start the polymerization. Subsequent operations were carried out in the same manner as in Example 16 to recover the polymer.

As a result, Mn = 3.7 × 10 ⁴ , Mw /
A four-branched star polyisobutyl vinyl ether with Mn = 1.08 was obtained. The value of Mn was in good agreement with the calculated value of 3.9 × 10 ⁴ which was assumed that four branch molecules were generated from one molecule of the adduct.

Example 18 2.50 ml of sufficiently purified and dried toluene under a nitrogen atmosphere
To this, 1.0 ml (0.38 mol / l) of a solution of methyl vinyl ether in toluene was added, and 0.5 ml (1.2 mol / l) was added.
1) 1,4-dioxane was added, and 0.5 ml (3.5 mmol / l) of the same adduct as used in Example 16 and 0.5 ml of a solution of ethylaluminum dichloride in hexane were added.
(10 milmol / l) was added, the polymerization was started at -15 ° C, and the polymerization was continued for 3 hours. Thereafter, the same operation as in Example 16 was carried out to obtain a polymer.

As a result, Mn = 6.6 × 10 ³ , Mw /
A hydrophilic four-branched star polymethyl vinyl ether having Mn = 1.06 was obtained. The value of Mn was in good agreement with the calculated value of 6.9 × 10 ³ that four branch molecules were generated from one molecule of the adduct.

Example 19 In Example 16, the polymerization temperature was set to 60 ° C. and the polymerization was continued for 10 minutes. Otherwise in the same manner as in Example 16, a polymer was obtained.

As a result, Mn = 1.6 × 10 ⁵ , Mw /
A four-branched star polyisobutyl vinyl ether with Mn = 1.10 was obtained. The value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁵ that four branch molecules were generated from one molecule of the adduct.

Example 20 n-Hexane 3.2 thoroughly purified and dried under a nitrogen atmosphere
0.25 ml of isobutyl vinyl ether in 5 ml
(0.35 mol / l) was dissolved, to which 0.5 ml (1.2 mol / l) of 1,4-dioxane was added, and 0.5 ml (3.5 mmol / l) of the same adduct as in Example 16 was added. ) And 0.5 ml (10 mmol / l) of a hexane solution of ethyl aluminum dichloride were added to initiate polymerization at 0 ° C. 3 minutes after the start of the reaction, 0.25 ml of 2-vinyloxyethyl acetate
(0.38 mol / l) was added to bring the polymerization temperature to 40 ° C.,
Polymerization was continued for 3 hours. Thereafter, the same operation as in Example 16 was carried out to obtain a polymer.

As a result, Mn = 2.6 × 10 ⁴ , Mw /
A four-branched star block copolymer with Mn = 1.06 was obtained. The value of Mn was in good agreement with the calculated value of 2.6 × 10 ⁴ that four branch molecules were generated from one molecule of the adduct.

Further, by alcal-hydrolyzing this polymer, the poly (2-acetoxyethyl vinyl ether) on the outside is converted to poly (2-hydroxyethyl vinyl ether), and four amphipathic groups having a hydrophobic group on the inside and a hydrophilic group on the outside are obtained. A branch star polymer was obtained.

Example 21 In Example 20, first 0.25 ml of 2-vinyloxyethyl acetate was used instead of isobutyl vinyl ether.
(0.38 mol / l) was added and the mixture was polymerized at 40 ° C. for 2 hours, and then 0.25 ml of isobutyl vinyl ether (0.
38 mol / l) was added, and the polymerization was further continued at 40 ° C. for 1 hour.

As a result, Mn = 2.4 × 10 ⁴ , Mw /
A four-branched star block polymer with Mn = 1.10 was obtained. The value of Mn was in good agreement with the calculated value of 2.6 × 10 ⁴ that four branch molecules were generated from one molecule of the adduct.

Further, by subjecting this polymer to alkali hydrolysis, poly 2-acetoxyethyl vinyl ether on the inside is converted into poly 2-hydroxyethyl vinyl ether, and four amphipathic groups having a hydrophilic group on the inside and a hydrophobic group on the outside are converted. A branch star polymer was obtained.

Example 22 0.5 ml (0.76 mol / l) of isobutyl vinyl ether was dissolved in 3.5 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere, and the solution temperature was kept at -15 ° C. 1,1,4,4-tetrakis [4-diluted with toluene there
0.5 ml of an adduct of (2-vinyloxy) ethoxyphenyl] cyclohexane with hydrogen iodide (3.0 mmol /
1) and an ether solution of zinc iodide (Znl ₂ ) (0.2 mmol / l) were added in this order to start the polymerization, and the polymerization was continued at −15 ° C. for 1 hour. Then, the polymerization was stopped by adding methanol (300 mmol / l) containing a small amount of ammonia. The reaction mixture was washed with an aqueous sodium thiosulfate solution (8 vol%) and then with water to remove the catalyst residue, and then the solvent and the like were evaporated to recover the product.

As a result, Mn = 2.4 × 10 ⁴ , Mw /
A four-branched star polyisobutyl vinyl ether with Mn = 1.06 was obtained. The value of Mn was in good agreement with the calculated value of 2.6 × 10 ⁴ that four branch molecules were generated from one molecule of the adduct.

Example 23 In Example 22, as an adduct, an adduct of 1,1,4,4-tetrakis [4- (2-propenyloxy) ethoxyphenyl] cyclohexane diluted with toluene and hydrogen iodide (3. Example 2 except that 0 mmol / l) was used.
As a result of making it similar to 2, Mn = 2.8 × 10 ⁴ , Mw / M
A four-branched star polyisobutyl vinyl ether with n = 1.07 was obtained.

Example 24 0.25 ml of 2-vinyloxyethyl acetate was added to 3.0 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere.
(0.38 mol / l) was dissolved and the temperature of the solution was kept at -15 ° C. 0.5 ml of the adduct used in Example 22
(3.0 milmol / l) and a toluene solution of iodine (I ₂ ) (9.0 milmol / l) were added in this order to start the polymerization, and the polymerization was continued at -15 ° C for 1 hour. Thereafter, the same operation as in Example 22 was carried out to obtain a polymer.

As a result, Mn = 1.6 × 10 ⁴ , Mw /
A four-branched star poly-2-acetoxyethyl vinyl ether with Mn = 1.06 was obtained. The value of this Mn is
Calculated value that four branch molecules are generated from the molecule (1.7
It was in good agreement with × 10 ⁴ ). Example 25 3.75 ml of toluene sufficiently purified and dried under a nitrogen atmosphere
0.25 ml (0.38 mol / l) of p-methoxystyrene was dissolved therein, and the temperature of the solution was kept at -78 ° C. 0.5 ml (3.3 mmol / l) of an adduct of 1,1,4,4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane diluted with toluene and hydrogen iodide, and iodine were added thereto. 0.5 ml of zinc chloride in ether
(3.3 mmol / l) was added in this order, and the solution was added to -7.
After standing at 8 ° C for 20 hours, the temperature was raised to -15 ° C to start the polymerization, and the polymerization was continued at -15 ° C for 2 hours. afterwards,
The polymerization was stopped by adding methanol (330 mmol / l) containing a small amount of aqueous ammonia to obtain a mixture containing a polymer. The mixture was washed first with an aqueous solution of sodium thiosulfate (8 vol%) and then with water, and the solvent and the like were evaporated to obtain a polymer.

As a result of analysis by GPC and ¹ H-NMR,
The obtained polymer has Mn = 1.5 × 10 ⁴ , Mw / Mn
= 1.05 four-chain star poly (p-methoxystyrene)
Met. The value of Mn was in good agreement with the calculated value of 1.5 × 10 ⁴ that four branch molecules were generated from one molecule of the adduct.

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured value: <quadruple-chain poly (P-methoxystyrene)>

[0148]

[Chemical 25]

Δ (ppm): peak f 0.90 (12
_{H, CH 3) g + h} 1.20~2.20 (12xH, -CH 2 -CH-) a 2.10~2.40 (8H, cyclohexane _{ring) k 3.00 (12H, OCH 3} ) c 3.10~3.40 (8H, -CH 2 -) d _{3.00~4.00 (8H, -CH 2 -)} j 3.70 (12xH, OCH 3) e 3.00~4.00 (4H, -CH-) b + i 6.25~7.05 (16 (x + 1) H, aromatic) eXAMPLE 26 In Example 25, 1,1,3,3-tetrakis [4- (2-vinyloxy) was used as the trifunctional alkenyl ether.
A polymer was obtained in the same manner as in Example 25 except that 0.5 ml (3.3 mmol / l) of the adduct of ethoxyphenyl] cyclohexane and hydrogen iodide was used.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained had Mn = 1.4 × 10 ⁴ , Mw / Mn
= 1.09 four-chain star poly (p-methoxystyrene)
Met. The value of Mn was in good agreement with the calculated value of 1.5 × 10 ⁴ that four branch molecules were generated from one molecule of the adduct.

Example 27 Example 27 was repeated except that hydrogen chloride was used instead of hydrogen iodide, zinc chloride was used instead of zinc iodide, the polymerization temperature was 0 ° C., and the reaction time was 20 minutes. 25
A polymer was obtained in the same manner as in.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained had Mn = 1.4 × 10 ⁴ , Mw / Mn
= 1.05 four-chain star poly (p-methoxystyrene)
Met. The value of Mn was in good agreement with the calculated value of 1.5 × 10 ⁴ that four branch molecules were generated from one molecule of the adduct.

Example 28 In Example 25, p-methoxystyrene (0.38
Mol / l) instead of pt-butoxystyrene (0.
26 mol / l) was used, and a polymer was obtained in the same manner as in Example 25 except that the polymerization temperature was 25 ° C.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained had Mn = 1.4 × 10 ⁴ , Mw / Mn
It was a four-chain star poly (pt-butoxystyrene) of = 1.06. The value of Mn was in good agreement with the calculated value of 1.4 × 10 ^4, which was assumed to generate four branch molecules from one molecule of the adduct.

Example 29 After polymerizing p-methoxystyrene in the same manner as in Example 25, 25 ml of pt-butoxystyrene (0.
26 mol / l) was added, the temperature was raised to 25 ° C., and the polymerization was continued for 2 hours. Then, the polymerization was stopped by adding methanol (330 mmol / l) containing a small amount of aqueous ammonia to obtain a mixture containing the polymer. This mixture was washed with an aqueous hydrochloric acid solution (8 vol%) and then with water, and the solvent and the like were evaporated to obtain a polymer.

As a result of analysis by GPC and ¹ H-NMR,
The obtained polymer was Mn = 2. Consisting of poly (p-methoxystyrene) and poly (pt-butoxystyrene).
It was a four-chain star block copolymer with 8 × 10 ⁴ and Mw / Mn = 1.05.

The value of Mn is 4 from one molecule of the adduct.
Calculated value to generate 2.9 × 10 ^FourWell matched.

Further, by treating the above-mentioned copolymer with hydrogen bromide, the outer poly (pt-butoxystyrene) is converted into poly (p-vinylphenol), and the inner hydrophobic group and the outer hydrophilic group are added. We obtained an amphipathic four-chain star copolymer.

Example 30 In Example 25, p-methoxystyrene (0.38
Mol / l) instead of pt-butoxystyrene (0.
26 mol / l) was used and pt-butoxystyrene was polymerized in the same manner as in Example 25 except that the temperature was 25 ° C., and then 25 ml of p-methoxystyrene (0.38 mol / l)
1) was added, and the polymerization was continued at 25 ° C. for 20 minutes. Then, the polymerization was stopped by adding methanol (330 mmol / l) containing a small amount of aqueous ammonia to obtain a mixture containing the polymer. This mixture was first treated with an aqueous hydrochloric acid solution (8 vol.
%), And then water, and the solvent and the like were evaporated to obtain a polymer.

As a result of analysis by GPC and ¹ H-NMR,
The polymer obtained is poly (pt-butoxystyrene).
Mn = 3.
It was a four-chain star block copolymer with 0 × 10 ⁴ and Mw / Mn = 1.08.

The value of Mn is 4 from one molecule of the adduct.
Calculated value to generate 2.9 × 10 ^FourWell matched.

Further, by treating the above copolymer with hydrogen bromide, the inside poly (pt-butoxystyrene) is converted into poly (p-vinylphenol), and the inside has a hydrophilic group and the outside has a hydrophobic group. We obtained an amphipathic four-chain star copolymer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 61-255914 (JP, A) JP 61-255915 (JP, A) JP 61-278513 (JP, A)

Claims (5)

[Claims] Claims: (In the formula, R ¹ represents a hydrogen atom or a methyl group, n represents an integer 3 or 4, R ² represents a trivalent organic group when n is 3, and a tetravalent organic group when n is 4.) A polyfunctional alkenyl ether represented by the general formula RC
OOH (R is substituted with hydrogen atom, methyl group or halogen
Represents a methyl group) and HX (X represents a halogen atom)
As initiator adduct of cationic feed compound selected from the group consisting of to), the general formula ^{CHR 3 = CH | ...... [II} ] A-OR 4 ( wherein, A represents a single bond or a phenylene group, A When is a single bond, R ³ is a hydrogen atom or a methyl group and R ⁴ is a monovalent organic group,
A is the R ³ when a phenylene group is polymerized olefin compound represented by R ⁴ means respectively an alkyl group) with a hydrogen atom, if in a solvent
A polymerization terminator that dissociates by heating to produce anions
The stops the reaction by at least an equimolar addition to the growth cation, embedded image (In the formula, x is 1 to 10000, Z is a terminator residue, R ¹ ,
Method of manufacturing ^{R 2, R 3, R 4} , A and n are star-type compound, characterized by producing three branches or four Edaboshi type compound represented by have the same meaning as above). 2. The general formula CHR ¹ ═CH—O—R ² —O—CH═CHR ¹ | ... [Ia] O—CH═CHR ¹ (wherein R ¹ is a hydrogen atom or a methyl group, R ² Means a trivalent organic group) and a trifunctional alkenyl ether represented by the general formula RC
OOH (R is substituted with hydrogen atom, methyl group or halogen
Represents a methyl group) and HX (X represents a halogen atom)
As initiator adduct of cationic feed compound selected from the group consisting of to), the general formula ^{CHR 3 = CH | ...... [IIa} ] OR 4 ( wherein, R ³ is a hydrogen atom or a methyl group, R ⁴ Means a monovalent organic group) and polymerizes an alkenyl ether represented by (In the formula, x is 1 to 10000, Z is a stopper residue, R ¹ ,
The method according to claim 1, wherein the three-branched star alkenyl ether represented by the formula: R ² , R ³ and R ⁴ has the same meaning as above. 3. The general formula CHR ¹ ═CH—O—R ² —O—CH═CHR ¹ | ... [Ia] O—CH═CHR ¹ (wherein R ¹ is a hydrogen atom or a methyl group, R ² Means a trivalent organic group) and a trifunctional alkenyl ether represented by the general formula RC
OOH (R is substituted with hydrogen atom, methyl group or halogen
Represents a methyl group) and HX (X represents a halogen atom)
The adducts of cationic feed compound selected from the group consisting of be) as initiator, a divalent metal halide of the active agent of the general formula _{CH 2 = CH | ......... [IIb} ] A-OR 4 (Wherein A represents a phenylene group and R ⁴ represents an alkyl group), and an alkyloxystyrene represented by the formula: (In the formula, x is 1 to 10000, Z is a stopper residue, R ¹ ,
The method according to claim 1, wherein the three-branched alkyloxystyrene represented by the formula: R ² , R ⁴ and A has the same meaning as above. 4. A compound represented by the formula: (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a tetravalent organic group) and a general formula RC
OOH (R is substituted with hydrogen atom, methyl group or halogen
Represents a methyl group) and HX (X represents a halogen atom)
As initiator adduct of cationic feed compound selected from the group consisting of to), the general formula ^{CHR 3 = CH | ...... [IIa} ] OR 4 ( wherein, R ³ is a hydrogen atom or a methyl group, R ⁴ Means a monovalent organic group) and polymerizes an alkenyl ether represented by (In the formula, x is 1 to 10000, Z is a stopper residue, R ¹ ,
The method according to claim 1, wherein a four-branched star alkenyl ether represented by the formula: R ² , R ³ and R ⁴ has the same meaning as above. 5. A chemical formula: (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a tetravalent organic group) and a general formula RC
OOH (R is substituted with hydrogen atom, methyl group or halogen
Represents a methyl group) and HX (X represents a halogen atom)
The adducts of cationic feed compound selected from the group consisting of be) as initiator, a divalent metal halide of the active agent of the general formula _{CH 2 = CH | ......... [IIb} ] A-OR 4 (Wherein A represents a phenylene group and R ⁴ represents an alkyl group), and an alkyloxystyrene represented by the formula: (In the formula, x is 1 to 10000, Z is a stopper residue, R ¹ ,
The method according to claim 1, wherein a four-branched star alkyloxystyrene represented by the formula: R ² , R ⁴ and A has the same meaning as above.