JP2782000B2 - Star-shaped hyperbranched polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a star-shaped hyperbranched polymer,
The alkenyl ether polymer is used as a branch, and the crosslinked polymer of a dialkenyl ether is used as a nucleus. It relates to a branched polymer.

[Conventional technology]

The star-shaped multibranched polymer can be generally synthesized by reacting a bifunctional or polyfunctional monomer with a linear living polymer.

On the other hand, alkenyl ethers produce high polymers only by cationic polymerization in homopolymerization. However, in general, migration and termination reactions easily occur, so that living polymerization was difficult.

Therefore, a star-shaped hyperbranched polymer having a branch of an alkenyl ether polymer has not been obtained.

However, the present inventors have recently found that alkenyl ether undergoes living polymerization when an initiator composed of hydrogen iodide and iodine or zinc halide is used (Preprints of the Society of Polymer Science, Vol. 32, 187, 188, 190, 1439). , 1443 (1
983); Macromolecules, 17, 265 (1984), etc.).

[Problems to be solved by the invention]

Due to the difficulty of living cationic polymerization of alkenyl ethers, star-shaped hyperbranched polymers having alkenyl ether polymers as branches have been conventionally used in spite of the fact that many useful applications are expected from an industrial point of view. Had not been synthesized.

The present invention solves the conventional problems as described above, and aims to provide a star-shaped hyperbranched polymer having an alkenyl ether polymer as a branch using living cationic polymerization recently found by the present inventors. I do.

[Means for solving the problem]

The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention.

That is, the present invention provides a compound represented by the general formula [I] CHR ¹ OHOH (OR ² )... [I] (wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group). Polymer of the represented alkenyl ether [II] (Wherein R ¹ and R ² have the same meanings as in the general formula [I], and m represents an integer of 1 or more), and the general formula [III] CHR ³ CHCH—O—R ⁴ —O— CH = CHR ⁵ ... [III] (wherein, R ³ and R ⁵ represents a hydrogen atom or a methyl group, R ⁴
Represents a divalent organic group.) A crosslinked polymer of a dialkenyl ether represented by the formula [IV] (Wherein R ³ , R ⁴ and R ⁵ have the same meaning as in the general formula [III],
n represents an integer of 1 or more), and a star-shaped hyperbranched polymer having a structure in which two or more branches of the alkenyl ether polymer [II] are bonded to the nucleus. Is what you do.

 Hereinafter, the present invention will be described in detail.

The alkenyl ether used in the present invention is represented by the aforementioned general formula [I], wherein R ¹ represents a hydrogen atom or a methyl group. In the formula, R ² represents a monovalent organic group, for example, an alkyl group, an acyloxyalkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, and the like. It may be substituted with a group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group or a phthalimide group, and the carbon chain may have a hetero group. Preferred R ² are an alkyl group, an acyloxyalkyl group and a hydroxyalkyl group, and particularly, these three types of substituents consisting of a lower alkyl group having 1 to 6 carbon atoms are preferred.

Specific examples of the alkenyl ether as described above include the compounds shown in Table 1 to Table 5 below.

The alkenyl ether in which R ² is a hydroxyalkyl group can be easily obtained by alkali hydrolysis of an acyloxyalkyl group, as described below.
It is omitted in the table below.

The alkenyl ether polymer of the present invention is represented by the above general formula [II] and is synthesized by living cationic polymerization.

Details of the polymerization are described in JP-A-60-228509 of the present inventors,
As described in JP-A-62-109373 and Japanese Patent Application No. 63-239400, any polymerization initiator may be used as long as it initiates living cationic polymerization. the proton acids such as (HI and phosphoric acid ester derivative) and initiator combination a Lewis acid (such as I ₂ and zinc halides), and the like below.

HI / I ₂ , HI / ZnI ₂ , HI / ZnCl ₂ , HI / SnCl ₂ , HOP (O) (OC ₆ H ₅ )
₂ / ZnI ₂ , HOPH (OC ₆ H ₅ ) ₂ / ZnCl The above-mentioned protonic acid / Lewis acid has a molar ratio of 500 to 0.01.
, Preferably in the range of 100 to 0.1, more preferably in the range of 50 to 1. These Lewis acids are
It may be used as it is, or may be used after being diluted with an inert solvent.

The polymerization reaction for the synthesis of the polymer [II] may be carried out without a solvent, but is usually an aliphatic hydrocarbon such as n-hexane or cyclohexane; an aromatic hydrocarbon such as benzene or toluene; And halogenated hydrocarbons such as methylene chloride; ethers such as diethyl ether and tetrahydrofuran are used as reaction solvents. These solvents may be used alone or in combination of two or more.

The charging ratio of the solvent and the monomer is usually preferably 1: 1 to 100: 1 (weight ratio), and particularly preferably 5: 1 to 30: 1. The charge ratio (weight ratio) of the monomer and the initiator is usually in the range of 2: 1 to 1000: 1, and particularly preferably 5: 1 to 100: 1. The polymerization temperature is
The temperature may be 60 ° C. or lower, but polymerization is preferably performed at 40 ° C. or lower. Of course, a low temperature of 0 ° C. or lower can be used.

In the polymerization, the alkenyl ether [I] may be homopolymerized, or two or more alkenyl ethers may be copolymerized, using the initiator as described above. Furthermore, after one or two or more alkenyl ethers are polymerized, another one or two or more alkenyl ethers may be added and further polymerized to form a block copolymer.

The side chain substituent of the polymer [II] thus obtained may be converted to another substituent by a polymer reaction after synthesizing the star-shaped multibranched polymer of the present invention. As a conversion side of such a side chain substituent, there is conversion of an acyloxy group to a hydroxyl group by alkali hydrolysis.

The dialkenyl ether serving as a raw material of the core of the star-shaped multibranched polymer of the present invention is represented by the aforementioned general formula (III),
³ and R ⁵ represent a hydrogen atom or a methyl group. In the formula, R
⁴ represents a divalent organic group, and a preferable organic group is, for example,
A methylene group, a phenylene group and the like, which may be substituted with a hetero group. Specific examples of such dialkenyl ethers include, but are not limited to, the following compounds.

CH ₂ = CH-OCH _{2 l} O-CH = CH ₂ (l: an integer of 1 or more) CH ₂ = CH-OCH ₂ CH ₂ -R ⁶ -CH ₂ CH ₂ O-CH = CH ₂ The star-shaped hyperbranched polymer of the present invention comprises a monomer (I)
The living polymer [I
I] is synthesized, and then to the solution is immediately added without stopping the reaction, a dialkenyl ether [III], which is a raw material of a nucleus. [III] /
The charged molar ratio of [II] may be in the range of 1: 1 to 100: 1, and particularly preferably 3: 1 to 10: 1. The reaction solvent and temperature may be the same as those for the synthesis of the polymer [II], but are not limited thereto.

In general, when a dialkenyl ether [III] is added to the living polymer [II], it is considered that one of the two vinyl groups of [III] is added to the active terminal of [II]. This addition reaction was repeated several times, and [II] was replaced by [II
A] forms a kind of AB block polymer in which several [I] are bonded. In this block polymer, unreacted vinyl groups derived from (III) are present as side-chain substituents, and these vinyl groups and the active terminals of the AB block polymer react one after another between molecules to cause a crosslinking reaction. It is thought that the nucleation of the star-shaped hyperbranched polymer occurs. In fact, (II)
When I) is added, both of the two vinyl groups of [III] are completely consumed, and although the product is completely soluble in the organic solvent used in the reaction, its weight average molecular weight is [I
As compared with the molecular weight of [I], the molecular weight is increased about several times to about 100 times.
These facts indicate that through the above crosslinking reaction, several polymers [II] are chemically bonded to the crosslinked polymer [IV] of [III],
This indicates that a star-shaped hyperbranched polymer was formed.

FIG. 1 is a schematic structural view of the star-shaped multibranched polymer of the present invention obtained as described above, wherein (1) is a nucleus of cross-linked copolymer [IV], and (2) Is a branch of the conjugate [II] bonded to the nucleus [IV] and is present in two or more branches.

〔Example〕

 Next, the present invention will be described more specifically with reference to examples.

In addition, in the following Examples, each measurement was performed by the following method.

(1) The number average molecular weight n of the branching polymer is determined by GPC
("TRIROTAR" chromatograph, manufactured by JASCO Corporation, column: polystyrene gel A802, A803, A804, manufactured by Showa Denko (3 series in total); each column was determined by an inner diameter of 8 mm and a length of 500 mm).

(2) The weight-average molecular weight (w) of the star polymer was measured by small-angle laser light scattering (KMX-6 manufactured by Chromatix, light source: He).
-Ne laser (λ = 633 nm), solvent: THF.

(3) The H-NMR spectrum of the star-shaped polymer was measured at room temperature by using a JSX G270 spectroscopic nuclear magnetic resonance apparatus.
Measured in ₂ .

Example 1 0.75 ml (0.475 mol /) of isobutyl vinyl ether was dissolved in 10.5 ml of sufficiently purified toluene under a nitrogen atmosphere, and 0.75 ml of carbon tetrachloride as an internal standard for gas chromatography was added. And cooled.

Next, 1.0 ml of a toluene solution of hydrogen iodide (150 mM) and 2.0 ml of a diethyl ether solution of zinc iodide (1.5 mM) were added in this order to start polymerization, and polymerization was continued for 40 minutes.

When the conversion of isobutyl vinyl ether was almost 100%, the polymerization temperature was lowered to -78 ° C, and 3.0 ml of a toluene solution of divinyl ether (250 mM) represented by the following formula (5 equivalents to the living chain) was added.

Immediately thereafter, the temperature was raised to −40 ° C., and stirring was sufficiently continued with a magnetic stirrer. The divinyl ether was completely consumed in one hour.

Thereafter, the reaction was further continued for 16 hours. When the polymerization system was colored yellow-brown, the polymerization was stopped with methanol containing a small amount of aqueous ammonia.

Next, the mixture obtained by terminating the polymerization was washed with an aqueous solution of sodium thiosulfate (about 10 wt / vol%) and then with water, and then the solvent was evaporated from the mixture to collect a product.

As a result, it is soluble in organic solvents such as hexane, toluene, methylene chloride and chloroform, and the degree of branch polymerization is 38.
0.85 g of a star-shaped polyvinyl ether having w = 7.8 × 10 ⁴ and 14 branches per molecule was obtained. The yield is Ca.100%
Met. As a result of NMR analysis, no vinyl group was detected in the resulting polymer.

Example 2 0.75 ml (0.713 mol /) of isobutyl vinyl ether was added to and dissolved in 6.5 ml of sufficiently purified toluene under a nitrogen atmosphere, and 0.75 ml of carbon tetrachloride as an internal standard for gas chromatography was added. Cooled to 40 ° C.

Next, 1.0 ml of a toluene solution of hydrogen iodide (150 mM) and 1.0 ml of a diethyl ether solution of zinc iodide (2.0 mM) were added in this order to initiate polymerization. Here, the concentration [P ^* ] of the living growing terminal was set to be 1.5 times that of Example 1.

Hereinafter, the procedure was performed in the same manner as in Example 1 except that the amount of divinyl ether used in Example 1 was changed to 7 equivalents to the living chain and the reaction time after the addition of divinyl ether was changed to 25 hours.

As a result, the degree of polymerization of the branches was 38, w = 3.8 × 10 ⁵ , and the number of branches
59 star polymers were obtained (0.85 g, yield: Ca.100
%).

The solubility of the obtained polymer was the same as in Example 1.

Example 3 The procedure of Example 1 was repeated, except that the polymerization degree of the branch (ie, polyisobutyl vinyl ether) in Example 1 was changed to 76, and the reaction time after the addition of divinyl ether was changed to 30 hours.

As a result, a star polymer having w = 5.6 × 10 ⁴ and six branches was obtained (0.95 g, yield: 100% Ca).

 The solubility of the polymer was the same as in Example 1.

Example 4 The procedure was performed in the same manner as in Example 1 except that the reaction time after the addition of divinyl ether to the branched polyethyl vinyl ether in Example 1 was changed to 35 hours.

As a result, a star-shaped polymer having w = 5.41 × 10 ⁴ and 11 branches was obtained (0.70 g, yield: 100% Ca).

Example 5 Example 5 was carried out in the same manner as in Example 1 except that divinyl ether forming a nucleus in Example 1 was changed to a compound of the following formula, and a polymerization solvent was changed to methylene chloride.

Divinyl ether was completely dissolved at room temperature, but when added to the polymerization system at -40 ° C, it precipitated out despite its low concentration.

The divinyl ether was completely consumed in about 12 hours after the addition, and the polymerization system became homogeneous. Thereafter, the reaction was further performed for 12 hours. When the reaction was colored light yellow, the polymerization was stopped in the same manner as in Example 1, and the polymerization was performed in the same manner as in the case of the decrease.

As a result, a star-shaped polymer having w = 2.61 × 10 ⁴ and five branches was obtained.

 The solubility of the polymer was the same as in Example 1.

Example 6 Example 6 was carried out in the same manner as in Example 1 except that divinyl ether was changed to a compound having the following formula having a more flexible spacer.

The divinyl ether was completely consumed two and a half hours after the addition, but the reaction continued for another 25 hours.

As a result, a star polymer soluble in general organic solvents was produced (50 wt%), but a large amount of low molecular weight products were by-produced (50 wt%). This low molecular weight product is believed to be an AB-type block polymer of isobutyl vinyl ether and divinyl ether.

Example 7 7.2 ml of sufficiently purified methylene chloride under a nitrogen atmosphere
Was added and dissolved in 0.39 ml (0.375 mol /) of 2-vinyloxyethyl acetate having an ester group in the side chain, and bromobenzene as an internal standard for gas chromatography was dissolved.
0.41 ml was added and cooled to -15 ° C.

Next, 1.0 ml of a hexane solution (100 mM) of hydrogen iodide and 1.0 ml of a diethyl ether solution of zinc iodide (20 mM) were added in this order to start polymerization, and polymerization was continued for 4 hours.

Hereinafter, it carried out similarly to Example 1 except having changed the reaction time after addition of divinyl ether into 3 hours.

As a result, a star-shaped polymer soluble in an organic solvent such as toluene or methylene chloride having a degree of branching of 30, w = 8.9 × 10 ⁴ and 15 branches was obtained (0.58 g, yield: Ca). .100%).

The above polymer (0.3g) was mixed with acetone / water mixed solvent (1: 1v
ol / vol) of 20 ml, and 5 equivalents of sodium hydroxide (2NNaOHaq) 3.84 ml per ester group was added thereto.
Stirred for days.

As a result, a side chain ester group was quantitatively converted into a hydroxyl group, and a hydrophilic raw star polymer was obtained, which was soluble in water and methanol and unnecessary in organic solvents such as toluene and methylene chloride.

 The polymer was purified by dialysis.

Example 8 It carried out similarly to Example 1 except having changed the branch in Example 1 to the block polymer (polymerization degree ratio: 10/30) of 2-vinyloxyethyl acetate and isobutyl vinyl ether.

As a result, a star-shaped block polymer having w = 5.02 × 10 ⁴ and eight branches was obtained (0.60 g, yield: 100% Ca).

The above polymer (0.6 g) was dissolved in dioxane (20 ml) and reacted in the same manner as in Example 7 for 4 days.

As a result, an amphiphilic star-shaped block polymer having a branch composed of a hydrophilic segment and a hydrophobic segment was obtained. The obtained polymer was soluble in toluene, methylene chloride, chloroform, methanol and ethanol.

Example 9 Example 9 was carried out in the same manner as in Example 1 except that the initiator in Example 1 was changed to a hydrogen iodide adduct of 2-vinyloxyethyl acetate.

As a result, a star polymer was obtained with w = 7.35 × 10 ⁴ , 13 branches, and only the surface was covered with a functional group (ester group).

In addition, by performing hydrolysis in the same manner as in Example 8, a star polymer having a hydroxyl group on the surface was also synthesized.

〔The invention's effect〕

As is apparent from the above results, the present invention has a remarkable industrial value effect of providing a star-shaped multibranched polymer of alkenyl ether which has not been obtained conventionally. These polymers have an unprecedented structure and spatial form, and are expected to be sufficiently used as a reinforcing agent for multiphase polymers, adsorbents and carriers for low-molecular and ionic polymers, reaction catalysts, etc. .

[Brief description of the drawings]

FIG. 1 is a schematic structural view of a star-shaped multibranched polymer of the present invention, wherein (1) represents a nucleus of a crosslinked copolymer [IV];
(2) represents a branch of the polymer [II] bonded to the core [IV].

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 293/00-297/08 C08F 299/00-299/08 C08F 290/00-290/14 CA (STN ) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound represented by the general formula [I] CHR ¹ CHCH (OR ² ) [I] (wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group). Alkenyl ether polymer [II] (Wherein R ¹ and R ² have the same meanings as in the general formula [I], and m represents an integer of 1 or more), and the general formula [III] CHR ³ CHCH—O—R ⁴ —O— CH = CHR ⁵ ... [III] (wherein, R ³ and R ⁵ represents a hydrogen atom or a methyl group, R ⁴
Represents a divalent organic group.) A crosslinked polymer of a dialkenyl ether represented by the formula [IV] (Wherein R ³ , R ⁴ and R ⁵ have the same meaning as in the general formula [III],
n is an integer of 1 or more), wherein the nucleus has a structure in which two or more branches of the alkenyl ether polymer [II] are bonded to each other.