JP5730150B2 - Polymerization initiator and production method thereof, and star polymer and production method thereof - Google Patents

Description

  The present invention relates to a polymerization initiator capable of synthesizing a star polymer and a production method thereof, and a star polymer and a production method thereof.

Molecular capsules are expected to be applied to drug delivery systems, catalyst carriers, nanoreactors, and the like.
As a material constituting such a molecular capsule, a dendrimer or a star polymer synthesized using a cyclic compound as a core site is known. For example, porphyrin is used as a template for the core site, and the dendron site is crosslinked. Molecular capsule material made of dendrimer with pores formed in the center (see Non-Patent Document 1), calixarene is used as a template for the core part, and each polymer segment is cross-linked so that pores are formed in the center. A molecular capsule material (see Non-Patent Document 2) composed of the formed star polymer has been proposed.

S.C.Zimmerman et al., Angew.Chem.Int Ed 42,1121-1126 (2003). T. Nishikubo et al., Journal of Polymer Science, Part A: Polymer Chemistry 46, 4879-4888 (2008).

  The present invention has been made based on the circumstances as described above, and the object thereof is a novel polymerization initiator capable of synthesizing a star polymer useful as a molecular capsule material, a production method thereof, and the polymerization. It is to provide a novel star polymer obtained by an initiator and a method for producing the same.

  The polymerization initiator of the present invention is characterized by comprising a compound represented by the following general formula (1).

[In General Formula (1), R ¹ represents a group represented by the following Formula (a), k is 2 or 3, and p is an integer of 2 to 15. ]

[In the formula (a), R ² represents a halogen atom. ]

  The method for producing a polymerization initiator according to the present invention is described in claim 1 by reacting a compound represented by the following general formula (2) with a 2-halogenoisobutyryl halide or 2-halogenoisobutyrate compound. It has the process of obtaining the compound represented by General formula (1).

[In General formula (2), k is 2 or 3, and p is an integer of 2-15. ]

  In the method for producing a polymerization initiator of the present invention, a step of obtaining a compound represented by the general formula (2) by subjecting resorcinol and an alkanedial having an alkylene chain having 4 to 17 carbon atoms to a condensation reaction. It is preferable to have.

  The star polymer of the present invention is represented by the following general formula (3).

[In General Formula (3), R ³ represents a group represented by the following Formula (b), k is 2 or 3, and p is an integer of 2 to 15. ]

[In Formula (b), X shows the polymer segment which consists of a structural unit derived from an ethylenically unsaturated compound. ]

In the star polymer of the present invention, the polymer segment represented by X in the formula (b) is preferably composed of a structural unit derived from an aromatic alkenyl compound.
The aromatic alkenyl compound is preferably styrene and / or 1- (3-butylenyl) -4-vinylbenzene.
In addition, the polymer segment represented by X in the formula (b) is preferably a block copolymer segment of styrene and 1- (3-butylenyl) -4-vinylbenzene.

  The method for producing a star polymer of the present invention is characterized by having a step of polymerizing an ethylenically unsaturated compound in the presence of the above polymerization initiator.

In the method for producing a star polymer of the present invention, the ethylenically unsaturated compound is preferably an aromatic alkenyl compound.
The ethylenically unsaturated compound is preferably styrene and / or 1- (3-butylenyl) -4-vinylbenzene.

  In the method for producing a star polymer of the present invention, 1- (3-butylenyl) -4-vinylbenzene is polymerized in the presence of the polymerization initiator, and styrene is obtained in the presence of the resulting product. It has the process to superpose | polymerize, It is characterized by the above-mentioned.

ADVANTAGE OF THE INVENTION According to this invention, the novel polymerization initiator which can synthesize | combine a star polymer, its manufacturing method, the novel star polymer obtained by this polymerization initiator, and its manufacturing method can be provided.
The star polymer of the present invention is useful as a molecular capsule material and can be applied to drug delivery systems, catalyst carriers, nanoreactors and the like.

2 is an IR spectrum diagram of the product obtained in Preparation Example 1. FIG. 2 is a ¹ H-NMR spectrum of the product obtained in Preparation Example 1. FIG. 2 is an IR spectrum diagram of the product obtained in Synthesis Example 1. FIG. 1 is a ¹ H-NMR spectrum diagram of a product obtained in Synthesis Example 1. FIG. 4 is an IR spectrum diagram of the product obtained in Synthesis Example 2. FIG. 2 is a ¹ H-NMR spectrum diagram of a product obtained in Synthesis Example 2. FIG. 2 is an IR spectrum diagram of the product obtained in Production Example 1. FIG. 2 is a ¹ H-NMR spectrum of the product obtained in Production Example 1. FIG. 6 is an IR spectrum diagram of the product obtained in Production Example 7. FIG. 6 is a ¹ H-NMR spectrum diagram of a product obtained in Production Example 7. FIG. 6 is an IR spectrum diagram of the product obtained in Production Example 8. FIG. 6 is a ¹ H-NMR spectrum diagram of a product obtained in Production Example 8. FIG. 14 is an IR spectrum diagram of the product obtained in Production Example 14. FIG. ¹ is a ¹ H-NMR spectrum diagram of a product obtained in Production Example 14. FIG. 4 is an IR spectrum diagram of the hydrolyzate obtained in Experimental Example 1. FIG.

Embodiments of the present invention will be described below.
[Polymerization initiator]
The polymerization initiator of the present invention comprises a compound represented by the above general formula (1) (hereinafter referred to as “specific cyclic compound”). In the general formula (1), R ¹ is a group represented by the above formula (a), k is 2 or 3, and p is an integer of 2 to 15, preferably an integer of 2 to 8. .
In the above formula (a), R ² represents a halogen atom, preferably a bromine atom.

  The specific cyclic compound includes a compound represented by the above general formula (2) (hereinafter referred to as “calix resorcinarene cyclic oligomer”) and a 2-halogenoisobutyryl halide or 2-halogenoisobutyrate compound as a base. Can be obtained by reacting in an appropriate solvent.

In the step of synthesizing a specific cyclic compound, 2-bromoisobutyryl bromide or the like can be used as the 2-halogenoisobutyryl halide.
As the base, imidazole, triethylamine, pyridine, N, N-dimethylaminopyridine and the like can be used.
As the solvent, tetrahydrofuran, acetonitrile, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, chloroform, dichloromethane or the like can be used.
Moreover, reaction temperature is 80 degreeC, for example, and reaction time is 48 to 72 hours, for example.

Further, the calix resorcinarene cyclic oligomer comprises resorcinol and an alkane dial having an alkylene chain having 4 to 17 carbon atoms, preferably 4 to 10 carbon atoms (hereinafter referred to as “ specific alkane dial”) as an acid catalyst. In the presence, it can be obtained by an addition condensation reaction in an appropriate solvent.

In the synthesis process of calix resorcin arene cyclic oligomers, specific examples of the specific alkane Earl, 1,6 ares, 1,7-heptane Earl, 1,8-octanediol Earl, 1,9 Nonanjiaru 1,10- decandial , 1,11-undecandial , 1,12-dodecandial .
The ratio of resorcinol to the specific alkane dial is preferably 1: 1 to 4: 1 in molar ratio. When the ratio of specific alkane diar is excessive, there is a problem that reaction between specific alkane dials occurs and the reaction system gels.
As the acid catalyst, hydrochloric acid, sulfuric acid, trifluoroacetic acid, trifluorometasulfonic acid, hydrogen iodide and the like can be used. The amount of the acid catalyst used is appropriately selected depending on the type thereof. For example, when trifluorometasulfonic acid is used as the acid catalyst, 6.7 mmol of resorcinol (functional group equivalent: 13.4 mmol) and a specific alkane dial 1 In the reaction system of 0.7 mmol (functional group equivalent: 3.4 mmol), the amount of the acid catalyst used is 10 to 18 mmol, and the larger the amount of the acid catalyst used, the more the generation of the polymer can be suppressed.
As the solvent, for example, alcohols such as ethanol and ethylene glycol can be used.
The reaction temperature is, for example, 70 to 90 ° C., and the reaction time is, for example, 48 hours.
The synthesis process of calix resorcinarene cyclic oligomer is shown in the following reaction formula (i).

〔上記反応式（ｉ）において、ｎは４〜１７の整数である。〕

[In the said Reaction Formula (i), n is an integer of 4-17. ]

In the above addition condensation reaction, as the specific alkane dial , the alkylene chain having an even number of carbon atoms, specifically, 1,6-hexane dial , 1,8-octane dial , 1,10-decandial , 1,12-dodecandial tends to produce a calixresorcinarene cyclic oligomer in which k in the above general formula (2) is 2, while the alkylene chain has an odd number of carbon atoms, specifically, , 1,7-heptane dial , 1,9-nonane dial , 1,11 -undecandial , a calixresorcinarene cyclic oligomer having k of 3 in the general formula (2) is likely to be produced.

  According to the polymerization initiator of the present invention, since it has a cyclic structure and a group represented by the above formula (a) serving as an atom transfer radical polymerization initiating species, it is ethylenically unsaturated in the presence of the polymerization initiator. A star polymer can be easily synthesized by subjecting the compound to atom transfer radical polymerization.

[Star polymer]
The star polymer of the present invention is represented by the above general formula (3). In the general formula (3), R ³ represents a group represented by the above formula (b), k is 2 or 3, and p is an integer of 2 to 8.
In the above formula (b), X represents a polymer segment composed of a structural unit derived from an ethylenically unsaturated compound.

The ethylenically unsaturated compound that is a monomer for forming the polymer segment is not particularly limited as long as it has an ethylenically unsaturated bond, but it is preferable to use an aromatic alkenyl compound. , Styrene, 1- (3-butylenyl) -4-vinylbenzene, and the like. These ethylenically unsaturated compounds can be used alone or in combination of two or more.
Further, the polymer segment may be a block copolymer segment, for example, a block copolymer segment of styrene and 1- (3-butylenyl) -4-vinylbenzene.
Moreover, the star polymer in which the polymer segment has a structural unit derived from 1- (3-butylenyl) -4-vinylbenzene can easily crosslink the polymer segments.

The star polymer of the present invention can be obtained by atom transfer radical polymerization of an ethylenically unsaturated compound using a catalyst system in an appropriate solvent in the presence of the above polymerization initiator.
Any catalyst system may be used as long as it is used in the atom transfer radical polymerization method. Specific examples thereof include those composed of a complex of a transition metal compound such as cuprous bromide / 2,2′-bipyridyl and an amine. Is mentioned.
As the solvent, N, N′-dimethylformamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, anisole and the like can be used.
Moreover, reaction temperature is 100 degreeC, for example, and reaction time is 3 to 24 hours, for example.

  In the case of synthesizing a star polymer having a block copolymer segment, an ethylenically unsaturated compound such as 1- (3) is used in a suitable solvent in the presence of the above polymerization initiator in the presence of the above polymerization initiator. -Butylenyl) -4-vinylbenzene may be subjected to atom transfer radical polymerization, and other ethylenically unsaturated compounds such as styrene may be subjected to atom transfer radical polymerization in the presence of the obtained product.

In the star polymer of the present invention, the calixresorcinarene cyclic oligomer skeleton can be separated by hydrolysis in an appropriate solvent in the presence of alkali and water.
Examples of the alkali used for the hydrolysis reaction include potassium hydroxide and sodium hydroxide.
Examples of the solvent used for the hydrolysis reaction include tetrahydrofuran, ethanol, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, trichloromethane, and dichloromethane.
Moreover, the reaction temperature of a hydrolysis reaction is 70 degreeC, for example, and reaction time is 24 hours, for example.

  The star polymer of the present invention is useful as a molecular capsule material and can be applied to uses such as drug delivery systems, catalyst carriers, and nanoreactors.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

[Preparation of calixresorcinarene cyclic oligomer]
<Preparation Example 1>
In a 10 mL eggplant flask, 0.74 g (6.7 mmol, functional group equivalent 13.4 mmol) of resorcinol was dissolved in 3 mL of ethylene glycol. To the obtained solution, 0.19 g (1.7 mmol, functional group equivalent: 3.4 mmol) of 1,6-hexane dial was added dropwise under ice cooling, and 18 mmol of trifluoroacetic acid was further added dropwise as a catalyst, with stirring. And reacted at 80 ° C. for 48 hours. Then, the obtained reaction solution was poured into water, the product was precipitated and filtered, and then the precipitate was washed with methanol and dried under reduced pressure at room temperature for 24 hours to obtain a product consisting of a red solid. . The product yield was 0.1434 g, and the yield was 28%.
As a result of performing IR analysis and NMR analysis about the obtained product, it was confirmed that the product is a calix resorcinarene cyclic oligomer represented by the following formula (2-1). Moreover, when the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of polystyrene conversion by gel permeation chromatography were measured, the number average molecular weight (Mn) was 1882 and the molecular weight distribution was 1.04. Hereinafter, this product is referred to as “cyclic oligomer (1)”.

The results of IR analysis and NMR analysis are shown below, the IR spectrum diagram is shown in FIG. 1, and the ¹ H-NMR spectrum diagram is shown in FIG.
IR (KRS, cm ^-1 )
3332 (νO-H hydroxyl), 2931, 2858 (νCH methylen), 1620, 1501, 1443 (νC = C aromatic)
¹ H-NMR (600 MHz, CDCl ₃ -d ₆ , TMS)
δppm: 1.25-2.39 (m, 32.0H, H ^a and H ^b ), 4.18 (s, 7.9 H, H ^c ), 6.19 (s, 8.0 H, H ^c ), ^{7.17 (s, 8.0H, H d} ), 9.08 (16.0H, H f)

<Preparation Example 2>
In a 25 mL eggplant flask, 0.74 g (6.67 mmol, functional group equivalent 13.4 mmol) of resorcinol was dissolved in 3 mL of ethylene glycol. To the resulting solution, 0.261 g (1.7 mmol, functional group equivalent: 3.4 mmol) of 1,9-nonanedial was added dropwise under ice cooling, and 11.25 mmol of trifluoroacetic acid was added dropwise as a catalyst, and the mixture was stirred. And reacted at 90 ° C. for 48 hours. Subsequently, the obtained reaction solution was poured into water to precipitate the product, and after filtration, the precipitate was washed with methanol and dried under reduced pressure at room temperature for 24 hours to obtain a product consisting of a red solid. . The yield was 46%.
As a result of conducting IR analysis and NMR analysis about the obtained product, it was confirmed that the product is a calix resorcinarene cyclic oligomer represented by the following formula (2-2). Hereinafter, this product is referred to as “cyclic oligomer (2)”.

[Synthesis of specific cyclic compounds]
<Synthesis Example 1>
In a 50 mL three-necked eggplant flask, 1.2 g (1 mmol, hydroxyl equivalent 16 mmol) of cyclic oligomer (1) and 3.3 g of imidazole (48 mmol, 3 equivalents relative to 1 equivalent of hydroxyl group of cyclic oligomer (1)) were added. After replacing the inside of the flask with argon gas, 45 mL of distilled and purified tetrahydrofuran was added to dissolve the cyclic oligomer. To the obtained solution, 6 mL of 2-bromoisobutyryl bromide (48 mmol, 3 equivalents relative to 1 equivalent of the hydroxyl group of the cyclic oligomer (1)) was added under ice cooling, and the mixture was reacted at 80 ° C. for 48 hours. Next, the reaction solution was diluted with chloroform, and the obtained diluted solution was subjected to a liquid separation operation twice with sodium bicarbonate water, twice with oxalic acid, and twice with saturated saline. The organic phase of the resulting solution was recovered and dried with a desiccant composed of anhydrous magnesium sulfate. The desiccant was filtered off, concentrated and poured into n-hexane to precipitate a white solid, and the pressure was reduced for 24 hours. Dried. The yield of the obtained product was 2.314 g, and the yield was 51%.
When IR analysis and NMR analysis were performed about the obtained product, it was confirmed that it was a specific cyclic compound represented by the following formula (1-1).
Further, from the results of IR analysis, it was confirmed that the peak due to the hydroxyl group disappeared, and from this, 99% or more of the hydrogen atoms related to the hydroxyl group were substituted with the group represented by the above formula (a). It was confirmed.
Moreover, when the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of polystyrene conversion by gel permeation chromatography were measured, the number average molecular weight (Mn) was 2111 and the molecular weight distribution was 1.03.
Hereinafter, this specific cyclic compound is referred to as “specific cyclic compound (1)”.

Moreover, the result of IR analysis and NMR analysis is shown below, IR spectrum figure is shown in FIG. 3, and < ¹ > H-NMR spectrum figure is shown in FIG.
IR (KRS, cm ^-1 )
2981, 2933, 2876 (νCH methylene), 1757 (νC = O carbonyl), 1137, 1102 (νC—O—C ether)
¹ H-NMR (600 MHz, CDCl ₃ -d ₆ , TMS)
δppm: 0.87-2.09 (m, 112.0H, H a, H b, H f andH g), 3.46-4.49 (bs, 7.40H, H c), 6.09- ^{7.50 (m, 16.54H, H e} andH d)

<Synthesis Example 2>
In a 50 mL three-necked eggplant flask, 2.07 g (1 mmol, hydroxyl equivalent 16 mmol) of cyclic oligomer (2) and 4.97 g of imidazole (72.9 mmol, 3 equivalents per hydroxyl equivalent of cyclic oligomer (2)) were placed. After replacing the inside of the eggplant flask with nitrogen gas, 10 mL of distilled and purified tetrahydrofuran was added to dissolve the cyclic oligomer. To the obtained solution, 8.9 mL of 2-bromoisobutyryl bromide (72.9 mmol, 3 equivalents relative to 1 equivalent of the hydroxyl group of the cyclic oligomer (2)) was added, and the mixture was reacted by heating under reflux for 72 hours. Next, the precipitated imidazole salt in the obtained reaction solution was removed, and the reaction solution was subjected to a liquid separation operation twice with a sodium bicarbonate solution and once with a saturated saline solution. The organic phase of the obtained solution is recovered and dried with a desiccant composed of anhydrous magnesium sulfate. The desiccant is filtered off, concentrated, reprecipitated with methanol, and further subjected to preparative HPLC. Isolated. The yield of the obtained product was 250 mg, and the yield was 4.4%.
When the obtained product was subjected to IR analysis and NMR analysis, it was confirmed to be a specific cyclic compound represented by the following formula (1-2).
Further, from the results of IR analysis, it was confirmed that the peak due to the hydroxyl group disappeared, and from this, 99% or more of the hydrogen atoms related to the hydroxyl group were substituted with the group represented by the above formula (a). It was confirmed.
Hereinafter, this specific cyclic compound is referred to as “specific cyclic compound (2)”.

Moreover, the result of IR analysis and NMR analysis is shown below, IR spectrum figure is shown in FIG. 5, and < ¹ > H-NMR spectrum figure is shown in FIG.
IR (KRS, cm ^-1 )
3005, 2978, 2931, 2856 (νC-H aromatic), 2931, 2872 (νCH), 1757 (νC = O carbonyl), 1611, 1505 (νC = C aromatic)
¹ H-NMR (600 MHz, CDCl ₃ -d ₆ , TMS)
δppm: 0.97-2.17 (m, 239H, H b andH f), 4.27-4.54 (m, 12H, H c), 5.98-7.44 (m, 27H, H e andH ^d )

[Production of star polymer]
<Production Example 1>
In a polymerization tube containing a rotor, 0.019 g (functional group equivalent 0.08 mmol) of a specific cyclic compound (1), 0.011 g (0.08 mmol) of purified cuprous bromide, 2,2-bipyridyl 0 0.025 g (0.16 mmol), 1- (3-butylenyl) -4-vinylbenzene 0.63 g (4 mmol) and anisole 1.3 mL were added, and after deaeration and sealed tube, the reaction was performed at 100 ° C. for 6 hours. I let you. After the reaction was completed, the reaction solution was diluted with chloroform and passed through an alumina column to remove copper in the reaction solution. Next, chloroform in the reaction solution was distilled under reduced pressure, the reaction solution was poured into n-hexane to precipitate the product, and the product was filtered to obtain a white powder.
When the obtained product was subjected to IR analysis and NMR analysis, it was confirmed to be a star polymer represented by the following formula (3-1).
Further, when the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and average degree of polymerization were measured by gel permeation chromatography and a multi-angle laser light scattering detector (GPS-MALS), the weight average molecular weight (Mw) ) Was 15110, the molecular weight distribution (Mw / Mn) was 1.19, and the average degree of polymerization was 4.

The results of IR analysis and NMR analysis are shown below, the IR spectrum diagram is shown in FIG. 7, and the ¹ H-NMR spectrum diagram is shown in FIG.
IR (KRS, cm ^-1 )
3076, 3011, 2978, 2925, 2853 (νC-H methylene), 1751 (νC = O ester), 1640 (νC = C vinyl), 1511, 1474 (νC = C aromatic)
¹ H-NMR (600 MHz, CDCl ₃ -d ₆ , TMS)
δppm: 0.17-2.09 (brm, 310H, H f, H a, H b, H n andH g), 2.32 (brs, 214H, H k), 2.64 (brm, 167H H d ), 4.49 (brs, 8H, H c), 4.98 (brs, 165H, H m), 5.84 (brs, 84H, H i), 6.56-7.42 (brs, 271H, H ^e , H ^d , H ^h and H ⁱ )

<Production Examples 2-6>
In a polymerization tube containing a rotor, 0.019 g (functional group equivalent 0.08 mmol) of a specific cyclic compound (1), 0.011 g (0.08 mmol) of purified cuprous bromide, 2,2-bipyridyl 0 0.025 g (0.16 mmol), 0.417 g (4 mmol) of styrene, and 1.3 mL of anisole were added, and after deaeration and sealing, 3 hours, 6 hours, 12 hours, 18 hours, The reaction was performed for 24 hours. After the reaction was completed, the reaction solution was diluted with chloroform and passed through an alumina column to remove copper in the reaction solution. Next, chloroform in the reaction solution was distilled under reduced pressure, the reaction solution was poured into n-hexane to precipitate the product, and the product was filtered to obtain a white powder.
When the obtained product was subjected to IR analysis and NMR analysis, it was confirmed to be a star polymer represented by the following formula (3-2).

  Moreover, the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and average degree of polymerization were measured by gel permeation chromatography and a multi-angle laser light scattering detector (GPS-MALS). The results are shown in Table 1 below.

<Production Example 7>
In a polymerization tube containing a rotor, 0.027 g of the star polymer obtained in Production Example 1, 0.011 g (0.08 mmol) of purified cuprous bromide, 0.025 g (0.16 mmol) of 2,2-bipyridyl ), 0.417 g (4 mmol) of styrene and 1.3 mL of anisole were added, and after deaeration and sealing, the reaction was carried out at 100 ° C. for 12 hours. After the reaction was completed, the reaction solution was diluted with chloroform and passed through an alumina column to remove copper in the reaction solution. Next, chloroform in the reaction solution was distilled under reduced pressure, the reaction solution was poured into n-hexane to precipitate the product, and the product was filtered to obtain a white powder.
When the obtained product was subjected to IR analysis and NMR analysis, it was confirmed to be a star polymer represented by the following formula (3-3).
Further, when the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and average degree of polymerization were measured by gel permeation chromatography and a multi-angle laser light scattering detector (GPS-MALS), the weight average molecular weight (Mw) ) Was 24500, the molecular weight distribution (Mw / Mn) was 1.03, and the average degree of polymerization was 6.

Moreover, the result of IR analysis and NMR analysis is shown below, IR spectrum figure is shown in FIG. 9, and < ¹ > H-NMR spectrum figure is shown in FIG.
IR (KRS, cm ^-1 )
3060, 3025, 2924, 2925, 2852 (νC-H methylene), 1731 (νC = O ester), 1640, 1601 (νC = C vinyl), 1511, 1493, 1453 (νC = C aromatic)
¹ H-NMR (600 MHz, CDCl ₃ -d ₆ , TMS)
δ ppm: 0.82 to 2.02 (brm, 1633H, H ^f , H ^g , H ^a , H ^b , H ⁿ and H ^o ), 2.38 (brs, 228H, H ^k ), 2.61 (brm, 159H H ^j ), 4.50 (brs, 8H, H ^c ), 5.00 (brs, 165H, H ^m ), 5.84 (brs, 74H, H ⁱ ), 6.14-7.73 (brs ^{, 1832H, H e, H d} , H h, H i, H p, H q andH r)

<Production Example 8>
In a polymerization tube containing a rotor, 0.030 g (0.005 mmol, functional group equivalent 0.12 mmol) of a specific cyclic compound (2), 0.017 g (0.12 mmol) of purified cuprous bromide, 2, 0.037 g (0.12 mmol) of 2-bipyridyl, 0.95 g (6 mmol) of 1- (3-butylenyl) -4-vinylbenzene and 2 mL of anisole were added, and after deaeration and sealing, 4 ° C. was added at 100 ° C. Reacted for hours. After the reaction was completed, the reaction solution was diluted with chloroform and passed through an alumina column to remove copper in the reaction solution. Next, the solution in the reaction solution was distilled under reduced pressure and isolated by preparative HPLC (high performance liquid chromatography) to obtain a viscous solid.
When the obtained product was subjected to IR analysis and NMR analysis, it was confirmed to be a star polymer represented by the following formula (3-4).
Further, when the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and average degree of polymerization were measured by gel permeation chromatography and a multi-angle laser light scattering detector (GPS-MALS), the weight average molecular weight (Mw) ) Was 11900, the molecular weight distribution (Mw / Mn) was 1.01, and the average degree of polymerization was 1.66.

The results of IR analysis and NMR analysis are shown below, the IR spectrum diagram is shown in FIG. 11, and the ¹ H-NMR spectrum diagram is shown in FIG.
IR (KRS, cm ^-1 )
3076, 3011, 2976, 2927, 2854 (νC-H methylene), 1751 (νC = O ester), 1639 (νC = C vinyl), 1511, 1471 (νC = C aromatic)
¹ H-NMR (600 MHz, CDCl ₃ -d ₆ , TMS)
δppm: 0.17-2.09 (brm, 310H, H f, H a, H b, H n andH g), 2.32 (brs, 214H, H k), 2.64 (brm, 167H H d ), 4.49 (brs, 8H, H c), 4.98 (brs, 165H, H m), 5.84 (brs, 84H, H i), 6.56-7.42 (brs, 271H, H ^e , H ^d , H ^h and H ⁱ )

<Production Examples 9 to 13>
In a polymerization tube containing a rotor, 0.030 g (0.005 mmol, functional group equivalent 0.12 mmol) of a specific cyclic compound (2), 0.017 g (0.12 mmol) of purified cuprous bromide, 2, 2-bipyridyl 0.037 g (0.12 mmol), styrene 0.625 g (6 mmol), and anisole 2 mL were added, and after deaeration and sealing, 3 hours, 6 hours, 12 hours, 18 hours at 100 ° C., respectively. The reaction was allowed for 24 hours. After the reaction was completed, the reaction solution was diluted with chloroform and passed through an alumina column to remove copper in the reaction solution. Next, the solution in the reaction solution was distilled under reduced pressure and isolated by preparative HPLC (high performance liquid chromatography) to obtain a viscous solid.
When the obtained product was subjected to IR analysis and NMR analysis, it was confirmed to be a star polymer represented by the following formula (3-5).

  Moreover, the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and average degree of polymerization were measured by gel permeation chromatography and a multi-angle laser light scattering detector (GPS-MALS). The results are shown in Table 2 below.

<Production Example 14>
In a polymerization tube containing a rotor, 0.021 g of the star polymer obtained in Production Example 8, 0.017 g (0.12 mmol) of purified cuprous bromide, 0.037 g (0.12 mmol) of 2,2-bipyridyl ), 0.695 g (6 mmol) of styrene and 2 mL of anisole were added, and after deaeration and sealing, the reaction was carried out at 100 ° C. for 12 hours. After the reaction was completed, the reaction solution was diluted with chloroform and passed through an alumina column to remove copper in the reaction solution. Subsequently, the solution in the reaction solution was distilled under reduced pressure, and reprecipitation treatment was performed using methanol to obtain a white powder.
When the obtained product was subjected to IR analysis and NMR analysis, it was confirmed to be a star polymer represented by the following formula (3-6).
Further, when the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and average degree of polymerization were measured by gel permeation chromatography and a multi-angle laser light scattering detector (GPS-MALS), the weight average molecular weight (Mw) ) Was 35700, the molecular weight distribution (Mw / Mn) was 1.05, and the average degree of polymerization was 9.5.

The results of IR analysis and NMR analysis are shown below, the IR spectrum diagram is shown in FIG. 13, and the ¹ H-NMR spectrum diagram is shown in FIG.
IR (KRS, cm ^-1 )
3059, 3025, 2924, 2925, 2851 (νC-H methylene), 1750 (νC = O ester), 1640, 1600 (νC = C vinyl), 1511, 1493, 1453 (νC = C aromatic)
¹ H-NMR (600 MHz, CDCl ₃ -d ₆ , TMS)
δ ppm: 0.82 to 2.02 (brm, 1633H, H ^f , H ^g , H ^a , H ^b , H ⁿ and H ^o ), 2.38 (brs, 228H, H ^k ), 2.61 (brm, 159H H ^j ), 4.50 (brs, 8H, H ^c ), 5.00 (brs, 165H, H ^m ), 5.84 (brs, 74H, H ⁱ ), 6.14-7.73 (brs ^{, 1832H, H e, H d} , H h, H i, H p, H q andH r)

[Hydrolysis of star polymer]
<Experimental example 1>
In a 50 mL eggplant flask, 0.05 g of the star polymer obtained in Production Example 6, 0.46 g (8.3 mmol) of potassium hydroxide, 10 mL of tetrahydrofuran, 2 mL of water, 2 mL of ethanol, and 0.0013 g (0.003 g) of tetrabutylammonium. 0042 mmol) was added and reacted at 70 ° C. for 24 hours. After the reaction is complete, dilute the reaction solution with chloroform, repeat the separation operation with 1N hydrochloric acid until the organic phase shows weak acidity, and then perform the separation operation once with saturated saline. It was. The organic phase was dried with a desiccant composed of anhydrous magnesium sulfate, the desiccant was filtered off, concentrated, and reprecipitated with methanol.
The obtained product was subjected to IR analysis. The results of IR analysis are shown below, and the IR spectrum is shown in FIG.
Moreover, when the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured with the gel permeation chromatography and the multi-angle laser light scattering detector (GPS-MALS) about the obtained product, the weight average The molecular weight (Mw) was 4273, and the molecular weight distribution (Mw / Mn) was 1.07.
From the above results, it was confirmed that the star polymer obtained in Production Example 6 can separate the calix resorcinarene cyclic oligomer skeleton by hydrolysis.

<Experimental example 2>
In a 50 mL eggplant flask, 0.05 g of the star polymer obtained in Production Example 11, 0.75 g (11.8 mmol) of potassium hydroxide, 10 mL of tetrahydrofuran, 2 mL of water, 2 mL of ethanol, and 0.002 g (0.002 g) of tetrabutylammonium. 006 mmol) and reacted at 70 ° C. for 24 hours. After the reaction is complete, dilute the reaction solution with chloroform, repeat the separation operation with 1N hydrochloric acid until the organic phase shows weak acidity, and then perform the separation operation once with saturated saline. It was. The organic phase was dried with a desiccant composed of anhydrous magnesium sulfate, the desiccant was filtered off, concentrated, and reprecipitated with methanol.
About the obtained product, when the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography and a multi-angle laser light scattering detector (GPS-MALS), the weight average molecular weight ( Mw) was 3000, and the molecular weight distribution (Mw / Mn) was 1.05.
Moreover, when IR analysis was performed about the obtained product, it was confirmed that the peak of C = O resulting from ester has disappeared.
From the above results, it was confirmed that the star polymer obtained in Production Example 11 can separate the calix resorcinarene cyclic oligomer skeleton by hydrolysis.

<Experimental example 3>
In a 50 mL eggplant flask, 0.05 g of the star polymer obtained in Production Example 13, 0.75 g (11.8 mmol) of potassium hydroxide, 10 mL of tetrahydrofuran, 2 mL of water, 2 mL of ethanol, and 0.002 g (0.002 g) of tetrabutylammonium. 006 mmol) and reacted at 70 ° C. for 24 hours. After the reaction is complete, dilute the reaction solution with chloroform, repeat the separation operation with 1N hydrochloric acid until the organic phase shows weak acidity, and then perform the separation operation once with saturated saline. It was. The organic phase was dried with a desiccant composed of anhydrous magnesium sulfate, the desiccant was filtered off, concentrated, and reprecipitated with methanol.
About the obtained product, when the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography and a multi-angle laser light scattering detector (GPS-MALS), the weight average molecular weight ( Mw) was 3900, and the molecular weight distribution (Mw / Mn) was 1.01.
Moreover, when IR analysis was performed about the obtained product, it was confirmed that the peak of C = O resulting from ester has disappeared.
From the above results, it was confirmed that the star polymer obtained in Production Example 13 can separate the calix resorcinarene cyclic oligomer skeleton by hydrolysis.

Claims (11)

A polymerization initiator comprising a compound represented by the following general formula (1).

[In General Formula (1), R ¹ represents a group represented by the following Formula (a), k is 2 or 3, and p is an integer of 2 to 15. ]

[In the formula (a), R ² represents a halogen atom. ] The compound represented by the general formula (1) according to claim 1 by reacting the compound represented by the following general formula (2) with a 2-halogenoisobutyryl halide or a 2-halogenoisobutyrate compound. A process for producing a polymerization initiator comprising the step of:

  3. The method according to claim 2, further comprising a step of obtaining a compound represented by the general formula (2) by subjecting resorcinol and an alkanedial having an alkylene chain having 4 to 17 carbon atoms to a condensation reaction. A method for producing a polymerization initiator. A star polymer represented by the following general formula (3).

[In General Formula (3), R ³ represents a group represented by the following Formula (b), k is 2 or 3, and p is an integer of 2 to 15. ]

[In Formula (b), X shows the polymer segment which consists of a structural unit derived from an ethylenically unsaturated compound. ]   The star polymer according to claim 4, wherein the polymer segment represented by X in the formula (b) comprises a structural unit derived from an aromatic alkenyl compound.   The star polymer according to claim 5, wherein the aromatic alkenyl compound is styrene and / or 1- (3-butenyl) -4-vinylbenzene.   The star polymer according to claim 4, wherein the polymer segment represented by X in the formula (b) is a block copolymer segment of styrene and 1- (3-butylenyl) -4-vinylbenzene. .   A method for producing a star polymer, comprising a step of polymerizing an ethylenically unsaturated compound in the presence of the polymerization initiator according to claim 1.   The method for producing a star polymer according to claim 8, wherein the ethylenically unsaturated compound is an aromatic alkenyl compound.   The method for producing a star polymer according to claim 8, wherein the ethylenically unsaturated compound is styrene and / or 1- (3-butylenyl) -4-vinylbenzene.   A method comprising polymerizing 1- (3-butylenyl) -4-vinylbenzene in the presence of the polymerization initiator according to claim 1 and polymerizing styrene in the presence of the obtained product. A method for producing a star polymer.

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