JP2009249500A - Polymerizable highly-branched polymer and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable dendritic polymer easy to handle because the viscosity is low, easy to manufacture and thus manufacturable inexpensively. <P>SOLUTION: A first polymerizable highly-branched polymer has such a structure as the terminal hydroxyl groups of the highly-branched polymer, which has glycidol polymerized in a branched state with the hydroxyl groups of a core molecule as the base points, are added to the epoxy groups of glycidyl ether having a polymerizable carbon-carbon double bond. A second polymerizable highly-branched polymer is the one in which the hydroxyl groups in the first polymerizable highly-branched polymer are etherified. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hyperbranched polymer that is cured by energy irradiation and a method for producing the same.

  Resins that are cured by irradiation with energy such as ultraviolet rays and electron beams are used in various industrial fields. For example, a photocurable resin that is cured by light irradiation is used as a material for lithography in the production of electronic devices. In recent years, the structure of electronic devices has been further miniaturized, and further improvement in processing accuracy has been demanded in lithography technology using a photocurable resin.

  Conventionally, a polymerizable resin composition used in photolithography initiates a photochemical reaction with a polymer resin (prepolymer) that causes a photochemical reaction, and a polyfunctional low molecule (monomer) as a diluent for the prepolymer. (For example, refer patent documents 1-3).

Prepolymers include acrylic acid / 1,6-hexanediol / acrylic acid (formula 1), phthalic anhydride / propylene oxide / acrylic acid (formula 2), trimellitic acid / diethylene glycol / acrylic acid (formula 3 Polyester-based ultraviolet curable resins having a relatively large molecular weight such as

  However, since the prepolymer has a very high viscosity and is difficult to handle such as coating, a polyfunctional monomer copolymerizable with the prepolymer is often added as a diluent. This diluent has a lower molecular weight than the prepolymer, and the viscosity can be lowered by adding it to the prepolymer. Although it is possible to reduce the viscosity by diluting the prepolymer with a solvent, this causes the solvent to volatilize before light irradiation, resulting in irregularities on the surface, which reduces the processing accuracy in photocuring. Problems arise. Further, when the prepolymer is diluted with a solvent, the viscosity changes due to volatilization of the solvent, and handling becomes difficult.

  For this reason, the present inventors have already developed a polymerizable dendritic polymer in which a polymerizable carbon-carbon double bond or an epoxy group is modified at the end of a dendritic polymer having a unique branched structure. (Patent Document 4 and Patent Document 5). These polymerizable dendritic polymers have the property of having a small viscosity for having a large molecular weight. By using this as a prepolymer, a polymerizable resin composition having a low viscosity and easy to handle. It becomes.

As a technique related to the present invention, Patent Document 6 describes a method for producing a highly branched polymer in which glycidol is polymerized in a branched form.
JP 2001-270973 A Japanese Patent Laid-Open No. 9-5997 Japanese Patent Laid-Open No. 10-60655 JP 2007-16154 A JP 2007-246483 A Special table 2002-533495 gazette

  However, the polymerizable dendritic polymers described in Patent Documents 4 and 5 are produced by extending the branched structure step by step, so that the number of production steps is large and time-consuming, and the production cost increases. was there. The present invention has been made in view of such conventional circumstances, and it is intended to provide a polymerizable dendritic polymer that has a low viscosity and is easy to handle, easy to manufacture and inexpensive to manufacture. This is a problem to be solved.

  For dendritic polymers with highly branched structures, a polyfunctional group-containing monomer is chemically reacted step by step to form a branched structure by polycondensing a dendrimer that forms a branched structure with an ABx type monomer. Hyperbranched polymers are known. The polymerizable dendritic polymer described in Patent Documents 4 and 5 is a dendrimer. The inventors have considered that the above-mentioned conventional problems can be solved by modifying a polymerizable functional group in a hyperbranched polymer that is easy to produce instead of a dendrimer, and as a result of conducting extensive research, The invention has been completed.

  That is, the polymerizable hyperbranched polymer of the first invention in the present invention is a glycidyl ether having a carbon-carbon double bond capable of polymerizing a terminal hydroxyl group of a hyperbranched polymer in which glycidol is polymerized in a branched form starting from the hydroxyl group of the core molecule. It is characterized by having a structure added to the epoxy group.

  The branched polymer of the first invention is a highly branched polymer in which glycidol is polymerized in a branched manner starting from the hydroxyl group of the core molecule, and further has a carbon-carbon double bond capable of polymerizing the terminal hydroxyl group of the highly branched polymer. Since it is modified with glycidyl ether, it has the property of having a low viscosity for a large molecular weight. In addition, such a hyperbranched polymer can be subjected to radical polymerization of a modified polymerizable carbon-carbon double bond with a radical initiator or cationic polymerization with an acid.

  As the glycidyl ether having a polymerizable carbon-carbon double bond, any non-target ether having a polymerizable carbon-carbon double bond on the opposite side of the glycidyl group across oxygen can be used. Examples of such glycidyl ether include allyl glycidyl ether and 3,5-bis (3-butenyloxy) benzyl glycidyl ether.

  As the core molecule, any molecule having a hydroxyl group capable of reacting with the epoxy group of glycidol can be used. Examples of such core molecules include glycerol, diglycerin, thioglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, meso-erythritol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol. 1,2-propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, 1,2,4-butanetriol, hexamethylene glycol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) Range amine, N-phenyldiethanolamine, 2-phenyl-1,3-propanediol, 3-methylpentane-1,3,5-triol, 1,2,3-butanetriol, arabitol, ribitol, phloroglucinol, pyrogallol 1,2,4-trihydroxybenzene, hexahydroxybenzene, leucoquinizarin, quinizarin, anthralphine, chrysazine, bisphenol A, 2,6-dihydroxyanthraquinone, purpurine, alizarin, 1,8,9-trihydroxyanthracene, bis ( 3-hydroxyphenyl) disulfide, 4,4′-dihydroxydiphenyl ether-4,4′-biphenol, 1,3,5-cyclohexanetriol, and threitol.

  The polymerizable hyperbranched polymer of the first invention can be produced as follows. That is, the method for producing a polymerizable hyperbranched polymer of the first invention in the present invention comprises a polymerization step in which a glycidol is branched into a highly branched polymer from the hydroxyl group of the core molecule as a base point, and the hydroxyl group of the highly branched polymer is And a modification step of introducing a polymerizable functional group by adding to an epoxy group of a glycidyl ether having a polymerizable carbon-carbon double bond.

  In the polymerization step, the hydroxyl group of the core molecule reacts and bonds with the epoxy group of glycidol, thereby forming a hydroxyl group from the ring-opened epoxy. For this reason, when one molecule of glycidol is bonded to the hydroxyl group of the core molecule, two hydroxyl groups are formed. Furthermore, glycidol is bonded to each of the two hydroxyl groups to form four hydroxyl groups. In this way, glycidol is successively polymerized in a branched manner to form a highly branched polymer. The polymerization of glycidol proceeds by adding a dilute solution of glycidol to a core molecule having a hydroxyl group in the presence of a basic catalyst, and then distilling off the diluting solvent. For this reason, a hyperbranched polymer is automatically obtained in one process, and the number of processes is not large as in the production of dendrimers, and the production is easy and labor-saving, and the production cost can be reduced. The degree of polymerization can be easily adjusted by adjusting the ratio of glycidol added to the core molecule.

  Further, in the modification step, glycidyl ether having a carbon-carbon double bond that can be polymerized to a hydroxyl group formed by ring opening of an epoxy group when a highly branched polymer is produced is modified. Thus, the polymerizable hyperbranched polymer of the first invention can be produced easily and at low cost.

  In the method for producing a polymerizable hyperbranched polymer of the first invention, the polymerization step and the modification step can be simultaneously performed in parallel after the polymerization step is performed halfway. That is, after the glycidol is polymerized in a branched form with the hydroxyl group of the core molecule as a starting point to form a highly branched polymer, the glycidol and the glycidyl ether having a polymerizable carbon-carbon double bond coexist, thereby further increasing the hyperbranching. While extending, a polymerizable carbon-carbon double bond is introduced. In this case, not only the secondary hydroxyl group but also the primary hydroxyl group remains after the introduction of the polymerizable carbon-carbon double bond.

  As described above, the polymerizable hyperbranched polymer of the first invention is a glycidyl ether having a carbon-carbon double bond capable of polymerizing a terminal hydroxyl group of a hyperbranched polymer in which glycidol is polymerized in a branched manner starting from the hydroxyl group of the core molecule. However, by the etherification of the hydroxyl group generated by ring opening in the addition to the epoxy group, it becomes a polymerizable hyperbranched polymer having a new structure.

  That is, the polymerizable hyperbranched polymer of the second invention is an epoxy group of a glycidyl ether having a carbon-carbon double bond capable of polymerizing a terminal hydroxyl group of a highly branched polymer in which glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as a starting point. Further, the structure is characterized in that the hydroxyl group generated by the ring opening of the epoxy group in the addition is an etherified structure.

  The branched polymer of the second invention is a highly branched polymer in which glycidol is polymerized in a branched manner starting from the hydroxyl group of the core molecule, and further has a carbon-carbon double bond capable of polymerizing the terminal hydroxyl group of the highly branched polymer. Since it is modified with glycidyl ether, it has the property of having a low viscosity for a large molecular weight. In addition, such a hyperbranched polymer can be subjected to radical polymerization of a modified polymerizable carbon-carbon double bond with a radical initiator or cationic polymerization with an acid.

  As the glycidyl ether having a polymerizable carbon-carbon double bond, any non-target ether having a polymerizable carbon-carbon double bond on the opposite side of the glycidyl group across oxygen can be used. Examples of such glycidyl ether include allyl glycidyl ether and 3,5-bis (3-butenyloxy) benzyl glycidyl ether.

  The etherification is preferably one that can be easily modified to a hydroxyl group, and examples thereof include allyl etherification, methyl etherification, and 3,5-bis (butenyloxy) benzyl etherification.

  Furthermore, as the core molecule, any molecule having a hydroxyl group capable of reacting with the epoxy group of glycidol can be used. Examples of such core molecules include glycerol, diglycerin, thioglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, meso-erythritol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol. 1,2-propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, 1,2,4-butanetriol, hexamethylene glycol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) Range amine, N-phenyldiethanolamine, 2-phenyl-1,3-propanediol, 3-methylpentane-1,3,5-triol, 1,2,3-butanetriol, arabitol, ribitol, phloroglucinol, pyrogallol 1,2,4-trihydroxybenzene, hexahydroxybenzene, leucoquinizarin, quinizarin, anthralphine, chrysazine, bisphenol A, 2,6-dihydroxyanthraquinone, purpurine, alizarin, 1,8,9-trihydroxyanthracene, bis ( 3-hydroxyphenyl) disulfide, 4,4′-dihydroxydiphenyl ether-4,4′-biphenol, 1,3,5-cyclohexanetriol, and threitol.

  The polymerizable hyperbranched polymer of the second invention can be produced as follows. That is, the method for producing a polymerizable hyperbranched polymer according to the second invention of the present invention comprises a polymerization step in which glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as a base point to form a highly branched polymer, and the hydroxyl group of the hyperbranched polymer is A modification step for introducing a polymerizable functional group by adding to an epoxy group of a glycidyl ether having a polymerizable carbon-carbon double bond, and etherification for etherifying a hydroxyl group generated by ring opening of the epoxy group in the addition And a process.

  In the polymerization step, the hydroxyl group of the core molecule reacts and bonds with the epoxy group of glycidol, thereby forming a hydroxyl group from the ring-opened epoxy. For this reason, when one molecule of glycidol is bonded to the hydroxyl group of the core molecule, two hydroxyl groups are formed. Furthermore, glycidol is bonded to each of the two hydroxyl groups to form four hydroxyl groups. In this way, glycidol is successively polymerized in a branched manner to form a highly branched polymer. The polymerization of glycidol proceeds by adding a dilute solution of glycidol to a core molecule having a hydroxyl group in the presence of a basic catalyst, and then distilling off the diluting solvent. For this reason, a highly branched polymer is automatically obtained in one step, and the number of steps is not large as in the production of dendrimers, and the production is easy and labor-saving, and the production cost can be reduced. The degree of polymerization can be easily adjusted by adjusting the ratio of glycidol added to the core molecule.

  In the modification step, a glycidyl ether having a polymerizable carbon-carbon double bond is modified to a hydroxyl group formed by ring-opening of an epoxy group when a highly branched polymer is formed, and a polymerizable functional group is introduced.

  Further, in the etherification step, the hydroxyl group generated by the ring opening of the epoxy group in the addition of glycidol is substituted with a substituent. Thus, the polymerizable hyperbranched polymer of the present invention can be produced easily and at low cost.

  In the method for producing a polymerizable hyperbranched polymer of the second invention, as in the case of the method for producing a polymerizable hyperbranched polymer of the first invention, after the polymerization step is performed halfway, a polymerization step and a modification step are further performed. It can also be done in parallel. That is, after the glycidol is polymerized in a branched form based on the hydroxyl group of the core molecule to form a highly branched polymer, the glycidol and the glycidyl ether having a polymerizable carbon-carbon double bond coexist, thereby further increasing the hyperbranching. While extending, a polymerizable functional group is introduced. In this case, the introduction of the polymerizable carbon-carbon double bond is introduced not only into the secondary hydroxyl group but also into the primary hydroxyl group.

Hereinafter, embodiments embodying the present invention will be described in detail.
Example 1
In Example 1, trimethylolpropane was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio (molar ratio) of trimethylolpropane: glycidol: allyl glycidyl ether was 1: 3: 12.

Polymerization Step 3.42 g (0.025 mol) of trimethylolpropane was heated to 90 ° C. and melted. To this, 1.98 ml of potassium methoxide (30% methanol solution) was added and stirred for several minutes, and then the pressure was gradually reduced to distill off the methanol. Under argon atmosphere, 7.5 ml of dehydrated diglyme was added and the temperature was raised to 140 ° C. 5.67 g (0.0765 mol) of glycidol was dissolved in 10 ml of dehydrated THF and added dropwise in about 4 hours while distilling off the THF.

Modification Step Subsequently, as a modification step, 34.92 g (0.306 mol) of allyl glycidyl ether was dissolved in 40 ml of dehydrated THF and added dropwise in about 16 hours while distilling off the THF. The mixture was stirred at the same temperature for 1 hour, cooled, diluted with 70 ml of methanol, and neutralized by passing through a column of 50 ml of Amberlite IR 120B H AG. Concentration under reduced pressure and chromatography using a glass column (80 mm ID × 500 mm H) packed with 1100 ml of silica gel (Merck Silicagel 60 70-200 mesh) out of 42.58 g of the brown oil obtained ( Toluene / ethanol = 8/2). Of the obtained yellow liquid (13.06 g), 2.0 g was purified again by chromatography (chloroform / methanol = 10/1) using 400 ml of silica gel. The purified product was filtered through a 0.2 μm membrane filter as a methanol solution and then concentrated under reduced pressure on an 80 ° C. water bath to obtain 1.95 g as a pale yellow liquid. NMR of this product was measured, and the following results were obtained.
¹ H-NMR (600 MHz, methanol-d ₄ ) δ: 0.88 (3H, bs), 1.39 (2H, br), 3.43-3.68 (73H, m), 3.87, (4H, s), 4.01 (24H, s), 4.77 (6H, s), 5.17 (12H, d, J = 9.3 Hz), 5.29 (12H, d, J = 17.0 Hz), 5.90-5.94 (12H, m)
¹³ C-NMR ((600 MHz, methanol-d ₄ ) δ: 7.0, 22.4, 43.4, 69.3, 69.6, 69.7, 70.1, 71.4, 71.8, 72.0, 72.7, 72.9, 78.6, 78.9, 116.1, 134.9, 135.0

(Example 2)
In Example 2, the reaction represented by the following chemical formula was carried out using trimethylolpropane as the core molecule. The ratio (molar ratio) of trimethylolpropane: glycidol: allyl glycidyl ether was 1: 6: 12.

Polymerization process 1.34 g (0.01 mol) of trimethylolpropane was heated to 90 ° C. and melted. To this, 0.78 ml of potassium methoxide (30% methanol solution) was added and stirred for several minutes, and then the pressure was gradually reduced to distill off the methanol. Under an argon atmosphere, 10 ml of dehydrated toluene was added, 4.44 g (0.06 mol) of glycidol was dissolved in 12 ml of dehydrated THF at the same temperature, and dropwise added over 4 hours while distilling off THF.

In the modification step, 13.7 g (0.12 mol) of allyl glycidyl ether was dissolved in 38 ml of dehydrated THF and added dropwise while distilling off THF. After stirring at the same temperature for about 2 hours, the pressure was gently reduced and the remaining THF was distilled off. The reaction solution was diluted with 70 ml of methanol, passed through a column of Amberlite IR 120B H AG 25 ml, neutralized, and then concentrated under reduced pressure. The resulting light brown oil was purified by silica gel column chromatography (chloroform / methanol = 10/1). The purified product was filtered as a methanol solution through a 0.2 μm membrane filter and then concentrated under reduced pressure on a water bath at 80 ° C. to obtain 14.09 g of the title compound as a pale yellow liquid. NMR of this product was measured, and the following results were obtained.
¹ H-NMR (600 MHz, methanol-d ₄ ) δ: 0.88 (3H, bs), 1.38 (2H, br), 3.44-3.67 (87H, m), 3.87 (9H, s), 4.01 (24H, s ), 4.79 (9H, s), 5.17 (12H, d, J = 9.9 Hz), 5.28 (12H, d, J = 17.6 Hz), 5.90-5.94 (12H, m)
¹³ C-NMR ((600 MHz, methanol-d ₄ ) δ: 6.9, 22.3, 43.5, 69.3, 69.6, 69.7, 70.0, 71.4, 71.8, 72.0, 72.7, 72.9, 78.6, 78.9, 116.0, 134.8, 135.0

(Example 3)
In Example 3, using trimethylolpropane as the core molecule, the reaction represented by the following chemical formula was performed. The ratio (molar ratio) of trimethylolpropane: glycidol: allyl glycidyl ether was 1: 9: 12.

Polymerization process 1.34 g (0.01 mol) of trimethylolpropane was heated to 90 ° C. and melted. To this, 0.78 ml of potassium methoxide (30% methanol solution) was added and stirred for several minutes, and then the pressure was gradually reduced to distill off the methanol. Under argon atmosphere, 7.5 ml of dehydrated diglyme was added and the temperature was raised to 140 ° C. 6.67 g (0.09 mol) of glycidol was dissolved in 17 ml of dehydrated THF, and added dropwise over about 5.5 hours while distilling off the THF.

Modification Step Subsequently, 13.7 g (0.12 mol) of allyl glycidyl ether was dissolved in 33 ml of dehydrated THF, and dropwise added in about 11 hours while distilling off the THF. The mixture was stirred at the same temperature for 4 hours, cooled, diluted with 70 ml of methanol, and passed through a column of Amberlite IR 120B H AG 25 ml for neutralization. Concentration under reduced pressure gave 19.09 g of a brown oil. Of this, 11.97 g was purified by chromatography (chloroform / methanol = 10/1) using a glass column (80 mm ID × 500 mm H) packed with 1200 ml of silica gel (Merck Silicagel 60 70-200 mesh). The resulting yellow-brown solution (8.3 g) was purified again by chromatography using 800 ml of silica gel (toluene / methanol = 8/2). The purified product was filtered through a 0.2 μm membrane filter as a methanol solution and then concentrated under reduced pressure on an 80 ° C. water bath to obtain 5.96 g of the title compound as a pale yellow liquid. The NMR measurement results of this product are shown below.
¹ H-NMR (600 MHz, methanol-d ₄ ) δ: 0.87 (3H, bs), 1.38 (2H, br), 3.46-3.67 (94H, m), 3.87 (12H, s), 4.02 (12H, s ), 4.72 (12H, s), 5.16 (12H, d, J = 9.9 Hz), 5.29 (12H, d, J = 17.6 Hz), 5.91-5.93 (12H, m)
¹³ C-NMR ((600 MHz, methanol-d ₄ ) δ: 8.0, 23.5, 43.5, 69.4, 69.7, 70.0, 71.4, 71.8, 72.0, 72.7, 72.9, 78.6, 78.9, 116.1, 134.8, 135.0

すなわち、水1.4 mlに水酸化ナトリウム1.4 g (35.0 mmol)および臭化テトラブチルアンモニウム 0.22 g (0.68 mmol)を溶解し、これに上記修飾工程で得た化合物0.98 gをトルエン1 mlに溶解した加えた。40℃に加温、攪拌下臭化アリル 0.94 g (7.77 mmol)を50分で滴下した。同温度で24時間攪拌した後水10 ml、トルエン20 mlを加えて抽出した。水層を再度15 mlのトルエンで抽出し、抽出液を飽和食塩水で洗浄後無水硫酸マグネシウムで脱水して濃縮した。残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝40/1）で精製し、精製物をメタノール溶液として0.2μmメンブランフィルターにより濾過した。80℃水浴上減圧下濃縮し、微黄色液として0.8 g得た。このもののＮＭＲの測定結果を以下に示す。
¹H -NMR (600 MHz, methanol-d₄) δ: 0.88 (3H, bs), 1.42 (2H, br), 3.48-3.67 (111H, m), 4.01(24H, s), 4.15(24H, s), 5.14 (12H, d, J = 12.6 Hz), 5.16 (12H d, J = 11.0 Hz), 5.29 (24H, d, J = 17.0 Hz), 5.91-5.93 (24H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 8.0, 24.0, 44.3, 71.3, 72.2, 72.6, 73.2, 78.5, 78.8, 80.0 80.2, 117.0, 117.1, 136.2, 136.7 Example 4
Etherification Step In Example 4, the compound obtained in Example 3 was further etherified with allyl bromide as the etherification step, as shown in the following chemical formula.

That is, 1.4 g (35.0 mmol) of sodium hydroxide and 0.22 g (0.68 mmol) of tetrabutylammonium bromide were dissolved in 1.4 ml of water, and 0.98 g of the compound obtained in the modification step was dissolved in 1 ml of toluene. It was. Warming to 40 ° C., 0.94 g (7.77 mmol) of allyl bromide was added dropwise over 50 minutes with stirring. After stirring at the same temperature for 24 hours, 10 ml of water and 20 ml of toluene were added for extraction. The aqueous layer was extracted again with 15 ml of toluene, and the extract was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residual liquid was purified by silica gel column chromatography (chloroform / ethanol = 40/1), and the purified product was filtered through a 0.2 μm membrane filter as a methanol solution. Concentration in a water bath at 80 ° C. under reduced pressure gave 0.8 g as a slightly yellow liquid. The NMR measurement results of this product are shown below.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.88 (3H, bs), 1.42 (2H, br), 3.48-3.67 (111H, m), 4.01 (24H, s), 4.15 (24H, s ), 5.14 (12H, d, J = 12.6 Hz), 5.16 (12H d, J = 11.0 Hz), 5.29 (24H, d, J = 17.0 Hz), 5.91-5.93 (24H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 8.0, 24.0, 44.3, 71.3, 72.2, 72.6, 73.2, 78.5, 78.8, 80.0 80.2, 117.0, 117.1, 136.2, 136.7

すなわち、水2.4 mlに水酸化ナトリウム2.4 g (60.0 mmol)および臭化テトラブチルアンモニウム 0.35 g (1.09 mmol)を溶解し、これに実施例１における修飾工程で得られた化合物1.5 gを加えた。35-38℃に加温、攪拌下ヨウ化メチル 1.77 g (12.4 mmol)を約１時間で滴下した。同温度で19時間攪拌した後ヨウ化メチル 1.77 g (12.4 mmol)を追加滴下し、さらに3.5時間攪拌した。水10 mlを加えてトルエン20 mlで２回抽出した。抽出液を飽和食塩水で洗浄し、無水硫酸マグネシウムで脱水後濃縮した。残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝40/1）で精製し、精製物をメタノール溶液として0.2μmメンブランフィルターにより濾過した。80℃水浴上減圧下濃縮し、表題のメチルエーテル体を微黄色油状物を1.01 g得た。このもののＮＭＲの測定結果を以下に示す。
¹H -NMR (600 MHz, methanol-d₄) δ: 0.85 (3H, bs), 1.38 (2H, br), 3.27-3.67(111H, m), 3.41 (36H, s), 3.98, (24H, s), 5.14 (12H, d, J = 9.9 Hz), 5.26 (12H, d, J = 17.0 Hz), 5.86-5.91 (12H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 7.0, 22.9, 43.2, 57.1, 58.4, 69.6, 70.1, 71.0, 71.3, 72.0, 78.7, 79.0, 79.5, 79.7, 116.0, 135.0 (Example 5)
In Example 5, the hydroxyl group of the compound obtained in the modification step in Example 3 was a methoxy group (see the following chemical formula).

That is, 2.4 g (60.0 mmol) of sodium hydroxide and 0.35 g (1.09 mmol) of tetrabutylammonium bromide were dissolved in 2.4 ml of water, and 1.5 g of the compound obtained in the modification step in Example 1 was added thereto. While heating to 35-38 ° C., 1.77 g (12.4 mmol) of methyl iodide was added dropwise over about 1 hour with stirring. After stirring at the same temperature for 19 hours, 1.77 g (12.4 mmol) of methyl iodide was further added dropwise, and the mixture was further stirred for 3.5 hours. 10 ml of water was added and extracted twice with 20 ml of toluene. The extract was washed with saturated brine, dehydrated over anhydrous magnesium sulfate and concentrated. The residual liquid was purified by silica gel column chromatography (chloroform / methanol = 40/1), and the purified product was filtered through a 0.2 μm membrane filter as a methanol solution. Concentration in an 80 ° C. water bath under reduced pressure gave 1.01 g of the title methyl ether compound as a pale yellow oil. The NMR measurement results of this product are shown below.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.85 (3H, bs), 1.38 (2H, br), 3.27-3.67 (111H, m), 3.41 (36H, s), 3.98, (24H, s), 5.14 (12H, d, J = 9.9 Hz), 5.26 (12H, d, J = 17.0 Hz), 5.86-5.91 (12H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 7.0, 22.9, 43.2, 57.1, 58.4, 69.6, 70.1, 71.0, 71.3, 72.0, 78.7, 79.0, 79.5, 79.7, 116.0, 135.0

(Example 6)
In Example 6, pentaerythritol was used as a core molecule, and a reaction represented by the following chemical formula was performed as a polymerization step and a modification step. The ratio of pentaerythritol: glycidol: allyl glycidyl ether was 1: 8: 12 (molar ratio). Moreover, diglyme was used as a reaction solvent.

Polymerization Step 0.68 g (0.005 mol) of pentaerythritol was suspended in 5 ml of diglyme and 5 ml of methanol. The mixture was heated to 90 ° C., 0.52 ml of potassium methoxide (30% methanol solution) was added thereto and stirred for several minutes, and then the pressure was gradually reduced to distill off the methanol. Add 3 ml of diglyme under argon atmosphere, raise the temperature to 125 ° C, dissolve 2.96 g (0.04 mol) of glycidol in 7.5 ml of dehydrated THF, and add dropwise over about 1 hour while distilling off THF. .

Modification process
After stirring for 1 hour, 6.85 g (0.06 mol) of allyl glycidyl ether was dissolved in 17.5 ml of dehydrated THF and added dropwise over about 2 hours while distilling off the THF. The light brown liquid obtained after stirring at the same temperature for about 1 hour was diluted with 25 ml of methanol and neutralized by passing through a column of Amberlite IR 120B H AG 10 ml. The column was washed with 20 ml of methanol, and both washing solutions were concentrated under reduced pressure. 10.18 g of a light brown oil was obtained. Of this, 2.2 g was purified by silica gel column chromatography (toluene / methanol = 3/1). The purified product was filtered through a 0.2 μm membrane filter as a methanol solution and concentrated (bath temperature 80 ° C.) to obtain 1.44 g of the title polymer as a pale yellow liquid. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.45-3.67 (96H, m), 3.87 (12H, s), 4.01 (24H, s), 4.77 (12H, s), 5.17 (12H, d , J = 10.5 Hz), 5.29 (12H, d, J = 17.0 Hz), 5.89-5.95 (12H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 45.9, 69.3, 69.6, 69.7, 70.0, 70.3, 71.4, 71.5, 71.8, 72.0, 72.9, 78.6, 78.8, 116.1, 134.8, 134.9

すなわち、修飾工程で得た化合物 5.05 gをトルエン10 mlに溶解し、これに臭化テトラブチルアンモニウム 1.22 g (3.78 mmol) および水10 mlに溶解した水酸化ナトリウム7.7 g (192.5 mmol) を加えた。40℃に加温、攪拌下臭化アリル 5.24 g (43.3 mmol)を約１時間で滴下した。同温度で17時間攪拌した後水20 ml、トルエン20 mlを加えて抽出、分液した。水層を再度20 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で３回洗浄した。無水硫酸マグネシウムで脱水後濃縮し、残留液6.03 gをシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝25/1）で精製した。表題化合物を無色油状物を3.82 g得た。このもののＮＭＲの測定結果を以下に示す。
¹H -NMR (600 MHz, methanol-d₄) δ: 3.44-3.68 (108H, m), 4.00, 4.01 (各12H, S), 4.15 (24H, s), 5.14 (12H, d, J = 12.1 Hz), 5.16 (12H, d, J = 11.0 Hz), 5.29 (24H, d, J = 17.0 Hz), 5.91-5.93 (24H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 46.8, 71.3, 72.1, 72.5, 73.2, 78.5, 78.7, 79.9, 80.1, 116.9, 117.1, 136.1, 136.64 (Example 7)
Etherification Step In Example 7, the hydroxyl group of the compound obtained in the above modification step was modified with allyl bromide as the etherification step for the compound obtained in Example 6 (see the following chemical formula).

That is, 5.05 g of the compound obtained in the modification step was dissolved in 10 ml of toluene, and 1.22 g (3.78 mmol) of tetrabutylammonium bromide and 7.7 g (192.5 mmol) of sodium hydroxide dissolved in 10 ml of water were added thereto. . The mixture was heated to 40 ° C. and 5.24 g (43.3 mmol) of allyl bromide was added dropwise with stirring for about 1 hour. After stirring at the same temperature for 17 hours, 20 ml of water and 20 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 20 ml of toluene, and the extracts were combined and washed three times with saturated brine. After dehydration with anhydrous magnesium sulfate and concentration, 6.03 g of the residual liquid was purified by silica gel column chromatography (chloroform / ethanol = 25/1). 3.82 g of the title compound was obtained as a colorless oil. The NMR measurement results of this product are shown below.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.44-3.68 (108H, m), 4.00, 4.01 (12H, S each), 4.15 (24H, s), 5.14 (12H, d, J = 12.1 Hz), 5.16 (12H, d, J = 11.0 Hz), 5.29 (24H, d, J = 17.0 Hz), 5.91-5.93 (24H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 46.8, 71.3, 72.1, 72.5, 73.2, 78.5, 78.7, 79.9, 80.1, 116.9, 117.1, 136.1, 136.64

(Example 8)
In Example 8, the reaction represented by the following chemical formula was performed using triethanolamine as the core molecule. The ratio (molar ratio) of triethanolamine: glycidol: allyl glycidyl ether was 1: 6: 9. Moreover, diglyme was used as a reaction solvent.

Polymerization step 1.86 g (12.47 mmol) of triethanolamine was heated to 90 ° C under an argon atmosphere, 0.87 g (3.72 mmol) of potassium methoxide (30% methanol solution) was added thereto, and the mixture was stirred for several minutes and then gradually reduced in pressure. The methanol was distilled off. 10 ml of diglyme was added, 5.54 g (74.78 mmol) of glycidol was dissolved in 18 ml of dehydrated THF, and dropwise added over about 5.5 hours while distilling off the THF.

Modification process
After stirring for 30 minutes, 12.82 g (112.32 mmol) of allyl glycidyl ether was dissolved in 35 ml of dehydrated THF and added dropwise over about 11.5 hours while distilling off the THF. The mixture was stirred for about 4 hours at the same temperature, cooled, diluted with 30 ml of methanol, and passed through a 30 ml column of Amberlite IR 120B HAG to neutralize. The column was washed with 30 ml of methanol, and both washing solutions were concentrated under reduced pressure. The residual liquid 15.1 g was purified by silica gel column chromatography (chloroform / methanol = 6/1). The title compound was obtained as a colorless oil (3.13 g). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.82 (6H, m), 3.44-3.67 (72H, br), 3.87 (9H, s), 4.01 and 4.02 (18H, each s), 4.83 ( 9H, s), 5.16 (9H, d, J = 9.9 Hz), 5.30 (9H, d, J = 17.0 Hz), 5.90-5.94 (9H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 54.2, 63.1, 69.2, 69.6, 70.9, 71.1, 71.3, 71.6, 72.0, 72.6, 78.6, 78.9, 80.1, 80.3, 116.0, 134.9

すなわち、上記修飾工程で化合物 3.13 gをトルエン6 mlに溶解しこれに臭化テトラブチルアンモニウム 0.75 g (2.33 mmol) および水5.5 mlに溶解した水酸化ナトリウム4.7 g (117.5 mmol) を加えた。40℃に加温、攪拌下臭化アリル 3.15 g (26.0 mmol)を2 mlのトルエンに溶解して約１時間で滴下した。同温度で18時間攪拌した後水20 ml、トルエン20 mlを加えて抽出、分液した。水層を再度20 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。微黄色残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝15/1）で精製し、表題化合物を微黄色油状物を2.52 g得た。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 2.79 (6H, s), 3.50-3.71 (81H, br), 3.99 and 4.00 (18H, each s), 4.13 (18H, s), 5.12-5.16 (18H, m), 5.27 (18H, d, J = 17.0 Hz), 5.87-5.95 (18H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 55.6, 71.3, 72.1, 72.6, 73.2, 78.5, 78.8, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6 Example 9
Etherification Step In Example 9, the hydroxyl group of the compound obtained in the above modification step was allyl etherified with allyl bromide for the compound obtained in Example 8 (see the following chemical formula).

That is, in the modification step, 3.13 g of the compound was dissolved in 6 ml of toluene, and 0.75 g (2.33 mmol) of tetrabutylammonium bromide and 4.7 g (117.5 mmol) of sodium hydroxide dissolved in 5.5 ml of water were added thereto. The mixture was heated to 40 ° C., and 3.15 g (26.0 mmol) of allyl bromide was dissolved in 2 ml of toluene with stirring and added dropwise in about 1 hour. After stirring at the same temperature for 18 hours, 20 ml of water and 20 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 20 ml of toluene, and the extracts were combined, washed with saturated brine three times, dried over anhydrous sodium sulfate, and concentrated. The slightly yellow residual liquid was purified by silica gel column chromatography (chloroform / methanol = 15/1) to obtain 2.52 g of the title compound as a slightly yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.79 (6H, s), 3.50-3.71 (81H, br), 3.99 and 4.00 (18H, each s), 4.13 (18H, s), 5.12- 5.16 (18H, m), 5.27 (18H, d, J = 17.0 Hz), 5.87-5.95 (18H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 55.6, 71.3, 72.1, 72.6, 73.2, 78.5, 78.8, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6

(Example 10)
In Example 10, the reaction represented by the following chemical formula was performed using triethanolamine as the core molecule. The ratio (molar ratio) of triethanolamine: glycidol: allyl glycidyl ether was 1: 9: 12. Moreover, diglyme was used as a reaction solvent.

Polymerization step 1.49 g (0.01 mol) of triethanolamine was heated to 90 ° C under an argon atmosphere, 0.78 ml of potassium methoxide (30% methanol solution) was added thereto, and the mixture was stirred for several minutes. Left. 7.5 ml of diglyme was added, and 6.67 g (0.09 mol) of glycidol was dissolved in 17 ml of dehydrated THF, and dropwise added over about 5.5 hours while distilling off the THF.

Modification Step Then, after stirring for 30 minutes, 13.7 g (0.12 mol) of allyl glycidyl ether was dissolved in 33 ml of dehydrated THF, and dropwise added over about 11.5 hours while distilling off THF. The mixture was stirred at the same temperature for about 5.5 hours, cooled, diluted with 50 ml of methanol, and neutralized by passing through a column of Amberlite IR 120B H AG 30 ml. The column was washed with 40 ml of methanol, and both washing solutions were concentrated under reduced pressure. 14.4 g of the title compound was obtained as a brown oil. NMR of this product was measured, and the following results were obtained. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.83 (6H, b), 3.43-3.67 (99H, m), 3.88 (12H, s), 4.01, 4.02 (each 12H, s), 4.84 ( 12H, s), 5.17 (12H, d, J = 9.9 Hz), 5.29 (12H, d, J = 17.0 Hz), 5.90-5.94 (12H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 54.1, 69.3, 69.7, 70.0, 70.9, 71.2, 71.3, 71.7, 72.0, 72.8, 78.6, 78.8, 80.2, 80.4, 116.0, 134.8, 134.9

Example 11
Etherification Step In Example 11, the hydroxyl group of the compound obtained in Example 10 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 6.5 g of the compound obtained in the above modification step was dissolved in 13 ml of toluene, and 1.55 g (4.8 mmol) of tetrabutylammonium bromide and 9.59 g (239.8 mmol) of sodium hydroxide dissolved in 12 ml of water were added thereto. . With heating and stirring at 40 ° C. under an argon atmosphere, 6.48 g (53.5 mmol) of allyl bromide was dissolved in 4 ml of toluene and added dropwise in about 1 hour. After stirring at the same temperature for 17 hours, 20 ml of water was added to separate the layers. The aqueous layer was extracted with 20 ml of toluene, and the organic layers were combined, washed twice with water, dried over anhydrous sodium sulfate, and concentrated. The slightly yellow residue was purified by silica gel column chromatography (chloroform / methanol = 15/1). 4.13 g of the title compound was obtained as a pale yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.79 (6H, bs), 3.51-3.71 (111H, m), 4.00 and 4.01 (24H, each s) 4.15 (24H, s), 5.15 (12H , d, J = 12.1 Hz), 5.17 (12H, d, J = 11.5 Hz), 5.29 (24H, d, J = 17.1 Hz), 5.91-5.96 (24H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 55.6, 71.2, 72.1, 72.5, 73.2, 78.5, 78.8, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6

Example 12
In Example 12, N, N-bis (2,3-dihydroxypropyl) octylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of N, N-bis (2,3-dihydroxypropyl) octylamine: glycidol: allyl glycidyl ether was 1: 4: 8 (molar ratio).

Polymerization Step N, N-bis (2,3-dihydroxypropyl) octylamine 1.88 g (6.77 mol) in an argon stream was stirred in an oil bath at 80 ° C. and potassium methoxide (30% methanol solution) 0.63 g (2.69 mmol) Was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. While adding 5 ml of dehydrated diglyme and heating to 90 ° C., 2.01 g (27.1 mmol) of glycidol was dissolved in 11 ml of dehydrated THF and added dropwise over about 2.5 hours while distilling off THF.

Modification Step Subsequently, 6.19 g (54.2 mmol) of allyl glycidyl ether was dissolved in 22 ml of dehydrated THF, and dropwise added over about 5.5 hours while distilling off the THF. After stirring at the same temperature for 2.5 hours, the mixture was cooled, 30 ml of methanol was added, and neutralized through a column of 25 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 2/1), further treated with activated carbon, and filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 3.57 g of a pale yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.49 (2H, bs), 2.59, 3.44-3.77 (58H, m,), 3.88 ( 8H, s), 4.02 (16H, s), 4.85 (8H, s), 5.16 (8H, d, J = 9.3 Hz), 5.28 8H, d, J = 17.6 Hz), 5.88-5.94 (8H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.3, 23.7, 28.5, 30.4, 30.6, 33.0, 57.0, 62.8, 64.6, 70.6, 70.9, 71.2, 72.6, 73.0, 73.3, 74.1, 79.8, 80.1, 81.2, 117.3,136.0, 136.1

すなわち、水3 mlに水酸化ナトリウム2.9 g (72.5 mmol) を溶解し、これに臭化テトラブチルアンモニウム 0.46 g (1.43 mmol) および上記修飾工程で得た化合物2.0 gをトルエン3.5 mlに溶解して加えた。40℃に加温、攪拌下臭化アリル 1.95 g (16.1 mmol)を0.5 mlのトルエンに溶解して滴下した。同温度で24時間攪拌した後水10 ml、トルエン15 mlを加えて抽出、分液した。水層を再度15 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で３回洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝20/1）で精製し、次いで0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、無色油状物を1.84 g得た。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 0.90 (3H, bs), 1.32 (10H, bs), 1.46 (2H, bs), 2.50-2.59 (6H, m), 3.48-3.72 (66H, m), 4.00 and 4.01(32H, each s), 4.15 (16H, s), 5.14 (8H, d, J = 11.5 Hz), 5.16 (8H, d, J = 11.6 Hz,), 5.29 (16H, d, J = 17.0 Hz), 5.88-5.95 (16H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 14.3, 23.7, 28.6, 30.6, 30.8, 33.1, 57.0, 57.8, 71.3, 72.2, 72.6, 73.3, 78.5, 78.8, 80.0, 80.2, 117.0, 117.1, 136.2, 136.6 (Example 13)
Etherification Step In Example 13, the hydroxyl group of the compound obtained in Example 12 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 2.9 g (72.5 mmol) of sodium hydroxide was dissolved in 3 ml of water, and 0.46 g (1.43 mmol) of tetrabutylammonium bromide and 2.0 g of the compound obtained in the modification step were dissolved in 3.5 ml of toluene. added. The mixture was heated to 40 ° C., and 1.95 g (16.1 mmol) of allyl bromide was dissolved in 0.5 ml of toluene with stirring. The mixture was stirred at the same temperature for 24 hours, extracted with 10 ml of water and 15 ml of toluene, and separated. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed three times with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / ethanol = 20/1), and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 1.84 g of a colorless oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.90 (3H, bs), 1.32 (10H, bs), 1.46 (2H, bs), 2.50-2.59 (6H, m), 3.48-3.72 (66H , m), 4.00 and 4.01 (32H, each s), 4.15 (16H, s), 5.14 (8H, d, J = 11.5 Hz), 5.16 (8H, d, J = 11.6 Hz,), 5.29 (16H, d, J = 17.0 Hz), 5.88-5.95 (16H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.3, 23.7, 28.6, 30.6, 30.8, 33.1, 57.0, 57.8, 71.3, 72.2, 72.6, 73.3, 78.5, 78.8, 80.0, 80.2, 117.0, 117.1, 136.2, 136.6

(Example 14)
In Example 14, N, N-bis (2,3-dihydroxypropyl) octylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. N, N-bis (2,3-dihydroxypropyl) octylamine: glycidol: allyl glycidyl ether was in a ratio (molar ratio) of 1:12:16.

Polymerization step While stirring 1.90 g (3.91 mmol) of N, N-bis (2,3-dihydroxypropyl) octylamine in an 80 ° C. oil bath under an argon stream, 0.364 g (1.56 mmol) of potassium methoxide (30% methanol solution) Was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. While adding 5 ml of dehydrated diglyme and heating to 90 ° C., 3.47 g (46.9 mmol) of glycidol was dissolved in 11 ml of dehydrated THF and added dropwise over about 3.5 hours while distilling off THF.

Modification Step Subsequently, 7.14 g (62.6 mmol) of allyl glycidyl ether was dissolved in 22 ml of dehydrated THF, and dropwise added over about 7 hours while distilling off the THF. The mixture was stirred at the same temperature for 3 hours, cooled, neutralized through a column of 25 ml of Amberlite IR 120B H AG by adding 30 ml of methanol. The solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 3/1), further treated with activated carbon, and filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 3.61 g of a pale yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.50 (2H, bs), 2.59 (6H, b), 3.42-3.77 (180H, m ), 3.88 (16H, s), 4.01 (32H, s), 4.84 (16H, s), 5.17 (16H, d, J = 9.3 Hz), 5.30 (16H, d, J = 17.6 Hz), 5.90-5.94 (16H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.5, 23.7, 28.5, 30.6, 30.8, 33.0, 57.0, 62.8, 64.3, 70.6, 70.9, 71.2, 72.2, 72.4, 72.6, 73.0, 73.3, 74.1, 79.8, 80.1, 81.4, 136.0, 136.1

すなわち、水3 mlに水酸化ナトリウム2.8 g (70.6 mmol) を溶解し、これに臭化テトラブチルアンモニウム 0.45 g (1.40 mmol) および上記修飾工程で得た化合物1.95 gをトルエン3.5 mlに溶解して加えた。40℃に加温、攪拌下臭化アリル 1.90 g (15.7 mmol)を0.5 mlのトルエンに溶解して滴下した。同温度で21時間攪拌した後水10 ml、トルエン20 mlを加えて抽出、分液した。水層を再度15 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で３回洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝25/1）で精製し、次いでメタノール溶液として0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、無色油状物を1.2 g得た。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.46 (2H, bs), 2.51-2.59 (6H, m), 3.49-3.70 (146H, m), 4.01 (32H, s), 4.15 (32H, s), 5.14 (16H, d, J = 11.0 Hz), 5.16 (16H, d, J = 11.5 Hz), 5.29 (32H, d, J = 17.0 Hz,), 5.85-5.91 (32H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 14.6, 23.8, 28.6, 30.6, 33.1, 57.0, 71.3, 72.2, 72.6, 73.3, 78.6, 78.8, 80.0, 80.2, 117.0, 117.2, 136.2, 136.6 (Example 15)
Etherification Step In Example 15, the hydroxyl group of the compound obtained in Example 14 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 2.8 g (70.6 mmol) of sodium hydroxide was dissolved in 3 ml of water, and 0.45 g (1.40 mmol) of tetrabutylammonium bromide and 1.95 g of the compound obtained in the modification step were dissolved in 3.5 ml of toluene. added. The mixture was heated to 40 ° C., and 1.90 g (15.7 mmol) of allyl bromide was dissolved in 0.5 ml of toluene with stirring. After stirring at the same temperature for 21 hours, 10 ml of water and 20 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed three times with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / ethanol = 25/1), and then filtered through a 0.2 μm filter as a methanol solution. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 1.2 g of a colorless oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.46 (2H, bs), 2.51-2.59 (6H, m), 3.49-3.70 (146H , m), 4.01 (32H, s), 4.15 (32H, s), 5.14 (16H, d, J = 11.0 Hz), 5.16 (16H, d, J = 11.5 Hz), 5.29 (32H, d, J = 17.0 Hz,), 5.85-5.91 (32H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.6, 23.8, 28.6, 30.6, 33.1, 57.0, 71.3, 72.2, 72.6, 73.3, 78.6, 78.8, 80.0, 80.2, 117.0, 117.2, 136.2, 136.6

(Example 16)
In Example 16, N, N-bis (2,3-dihydroxypropyl) octylamine was used as the core molecule, and the reaction represented by the following chemical formula was performed. N, N-bis (2,3-dihydroxypropyl) octylamine: glycidol: allyl glycidyl ether: allyl bromide was in a ratio (molar ratio) of 1: 28: 32: 32.

Polymerization Step N, N-Bis (2,3-dihydroxypropyl) octylamine 0.4 g (1.44 mmol) was stirred in an 80 ° C. oil bath under an argon stream, and potassium methoxide (30% methanol solution) 0.134 g (0.576 mmol) ) Was added. After stirring for several minutes, methanol was distilled off under reduced pressure. While adding 5 ml of dehydrated diglyme and heating to 100 ° C., 2.99 g (40.37 mmol) of glycidol was dissolved in 10 ml of dehydrated THF and added dropwise over about 3 hours while distilling off THF.

Modification Step After stirring for 1 hour, 5.27 g (46.14 mmol) of allyl glycidyl ether was dissolved in 20 ml of dehydrated THF and added dropwise over about 6 hours while distilling off the THF. The mixture was stirred at the same temperature for 3 hours, cooled, added with 25 ml of methanol, and neutralized through a column of 20 ml of Amberlite IR 120B H AG. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 6.53 g of an orange oil.

Etherification step Further, as an etherification step, 3.0 g of the oily substance obtained in the modification step was dissolved in 7 ml of toluene, and 0.69 g (2.14 mmol) of tetrabutylammonium bromide and 4.32 g of sodium hydroxide ( 108.0 mmol) was dissolved in 5 ml of water and added. The mixture was heated to 40 ° C., and 2.90 g (24.0 mmol) of allyl bromide was dissolved in 1 ml of toluene with stirring and added dropwise over 1.5 hours. After stirring at the same temperature for 18 hours, 10 ml each of water and toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 10 ml of toluene, and the organic layers were combined and washed twice with water. After dehydrating with anhydrous sodium sulfate and concentrating, the residual liquid was purified by silica gel column chromatography (chloroform / methanol = 30/1) to obtain 1.4 g of a main fraction. This was purified again by silica gel column chromatography (chloroform / methanol = 20/1), and then filtered through a 0.2 μm filter as a methanol solution. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 0.59 g of a colorless oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.46 (2H, bs), 2.52-2.60 (6H, m), 3.33 and 3.52-. 3.66 (306H, m), 4.01 (64H, s), 4.15 (64H, s), 5.14 (32H, d, J = 11.0 Hz), 5.16 (32H, d, J = 11.5 Hz), 5.29 (64H, d , J = 15.9.0 Hz), 5.91-5.92 (64H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.6, 23.8, 28.6, 30.6, 33.1, 57.0, 71.3, 72.2, 72.6, 73.3, 78.6, 78.8, 80.0, 80.2, 117.0, 117.2, 136.2, 136.7

(Example 17)
In Example 17, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine: glycidol: allyl glycidyl ether was in a ratio (molar ratio) of 1: 8: 16.

Polymerization Step N, N, N ′, N′-Tetrakis (2,3-dihydroxypropyl) ethylenediamine 1.67 g (4.7 mmol) in an argon gas stream with stirring in a 90 ° C. oil bath, potassium methoxide (30% methanol solution) 0.88 g (3.76 mmol) was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. While adding 10 ml of dehydrated diglyme and 5 ml of DMF and heating to 110 ° C., 2.78 g (37.5 mmol) of glycidol was dissolved in 9 ml of dehydrated THF and added dropwise over about 3 hours while distilling off THF.

Modification Step Subsequently, 8.58 g (75.2 mmol) of allyl glycidyl ether was dissolved in 26 ml of dehydrated THF, and dropwise added over about 6 hours while distilling off the THF. After stirring at the same temperature for 3 hours, the mixture was cooled, 30 ml of methanol was added and neutralized through a column of 30 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 3/1), further treated with activated carbon, and filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 3.67 g of the title compound as a yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.66 (12H, br), 3.47-3.67 (116H, m), 3.86 (16H, s), 4.01 (32H, s), 4.85 (16H, s ), 5.15-5.17 (16H, m), 5.28 (16H, d, J = 17.6 Hz), 5.88-5.94 (16H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 54.5, 59.3, 70.6, 70.9, 71.2, 72.6, 73.0, 73.3, 74.0, 79.9, 80.2, 117.2, 136.2

すなわち、上記修飾工程で得た化合物4.8 g (1.73 mmol)をトルエン10 mlに溶解し、これに水9 mlに溶解した水酸化ナトリウム7.43 g (185.8 mmol) および臭化テトラブチルアンモニウム 1.2 g (3.72mmol)を加えた。40℃に加温、攪拌下臭化アリル 5.02 g (41.5 mmol)を3 mlのトルエンに溶解して1.5時間で滴下した。同温度で15時間攪拌した後水20 ml、トルエン20 mlを加えて抽出、分液した。水層を再度20 mlのトルエンで抽出し、抽出液を併せて水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝15/1）で精製し、次いで0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、黄色油状物を5.19 g得た(収率88.0%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 2.60-2.66 (12H, br), 3.49-3.66 (132H, m), 4.00 (32H, s), 4.14 (32H, s), 5.13 (16H, d, J = 12.1 Hz), 5.15 (16H, d, J = 11.5 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.87-5.92 (32H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 54.0, 56.8, 70.1, 70.9, 71.4, 72.0, 77.3, 77.6, 78.7, 79.0, 115.8, 115.9, 135.0, 135.5
（実施例１９）
実施例１９では、コア分子としてN,N-ビス（2,3-ジヒドロキシプロピル）ベンジルアミンを用い、下記化学式に示す反応を行なった。N,N-ビス（2,3-ジヒドロキシプロピル）ベンジルアミン：グリシドール：アリルグリシジルエーテルは１：１２：１６の割合（モル数比）とした。また、

(Example 18)
Etherification Step In Example 18, the hydroxyl group of the compound obtained in Example 17 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 4.8 g (1.73 mmol) of the compound obtained in the above modification step was dissolved in 10 ml of toluene, and 7.43 g (185.8 mmol) of sodium hydroxide and 1.2 g (3.72) of tetrabutylammonium bromide dissolved in 9 ml of water. mmol) was added. While warming to 40 ° C., 5.02 g (41.5 mmol) of allyl bromide was dissolved in 3 ml of toluene with stirring and added dropwise over 1.5 hours. After stirring at the same temperature for 15 hours, 20 ml of water and 20 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 20 ml of toluene, and the extracts were combined and washed with water. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / methanol = 15/1), and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 5.19 g of a yellow oil (yield: 88.0%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.60-2.66 (12H, br), 3.49-3.66 (132H, m), 4.00 (32H, s), 4.14 (32H, s), 5.13 (16H , d, J = 12.1 Hz), 5.15 (16H, d, J = 11.5 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.87-5.92 (32H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 54.0, 56.8, 70.1, 70.9, 71.4, 72.0, 77.3, 77.6, 78.7, 79.0, 115.8, 115.9, 135.0, 135.5
Example 19
In Example 19, N, N-bis (2,3-dihydroxypropyl) benzylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of N, N-bis (2,3-dihydroxypropyl) benzylamine: glycidol: allyl glycidyl ether was 1:12:16 (molar ratio). Also,

Polymerization process N, N-bis (2,3-dihydroxypropyl) benzylamine (2.05 g, 8.0 mmol) was heated to 100 ° C under argon flow, and potassium methoxide (30% methanol solution) 0.75 g (3.2 mmol) with stirring. Was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. 7 ml of dehydrated diglyme and 5 ml of DMF were added, 7.12 g (96.2 mmol) of glycidol was dissolved in 13 ml of dehydrated THF, and the mixture was added dropwise over about 3.6 hours while distilling off THF.

Modification Step Subsequently, 14.6 g (128.2 mmol) of allyl glycidyl ether was dissolved in 26 ml of dehydrated THF, and dropwise added over about 7.4 hours while distilling off THF. The mixture was stirred at the same temperature for 2 hours and then cooled, and 40 ml of methanol was added and neutralized through a column of 30 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure (80 ° C.), and 10 g of 21.65 g of the residual oil was purified by silica gel column chromatography (chloroform / methanol = 7/3). Filtered. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 7.5 g of a yellow oily substance. (Yield 68.2%) NMR of this product was measured and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.63-2.66 (4H, br), 3.45-3.67 (132H, m), 3.87 (16H, s), 4.01 (32H, s,), 4.77 ( 16H, s), 5.17 (16H, d, J = 9.9 Hz), 5.30 (16H, d, J = 17.0 Hz), 5.90-5.93 (16H, m), 7.25-7.34 (5H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 61.4, 62.8, 64.5, 70.5, 70.9, 71.2, 72.6, 73.0, 73.2, 74.0, 79.8, 80.1, 117.2, 128.1, 129.4, 130.3, 130.4, 136.0 , 136.2,

すなわち、上記修飾工程で得られた化合物4.39 gをトルエン8 mlに溶解し、これに水7.5 mlに溶解した水酸化ナトリウム6.35 g (158.7 mmol) および臭化テトラブチルアンモニウム 1.02 g (3.16mmol)を加えた。アルゴン気流下40℃に加温、攪拌しながら臭化アリル 4.29 g (35.47 mmol)を2 mlのトルエンに溶解して50分で滴下した。同温度で16時間攪拌した後水30 ml、トルエン30 mlを加えて抽出、分液した。水層を再度30 mlのトルエンで抽出し、抽出液を併せて水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝25/1）で精製し、次いで0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、表題化合物を微黄色油状物を4.78 g得た(収率89.6%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 2.62 (4H, br), 3.50-3.65 (148H, m), 3.99 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 12.1 Hz), 5.15 (16H, d, J = 11.0 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90-5.91 (32H, m), 7.24-7.33 (5H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 57.6, 61.5, 71.2, 72.5, 73.2, 72.1, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6, 128.0, 129.3, 130.2, 141.0 (Example 20)
Etherification Step In Example 20, the hydroxyl group of the compound obtained in Example 19 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 4.39 g of the compound obtained in the above modification step was dissolved in 8 ml of toluene, and 6.35 g (158.7 mmol) of sodium hydroxide and 1.02 g (3.16 mmol) of tetrabutylammonium bromide dissolved in 7.5 ml of water were added thereto. added. While being heated to 40 ° C. under an argon stream and stirring, 4.29 g (35.47 mmol) of allyl bromide was dissolved in 2 ml of toluene and added dropwise over 50 minutes. After stirring at the same temperature for 16 hours, 30 ml of water and 30 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 30 ml of toluene, and the extracts were combined and washed with water. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / methanol = 25/1), and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 4.78 g of the title compound as a pale yellow oil (yield 89.6%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.62 (4H, br), 3.50-3.65 (148H, m), 3.99 (32H, s), 4.13 (32H, s), 5.13 (16H, d , J = 12.1 Hz), 5.15 (16H, d, J = 11.0 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90-5.91 (32H, m), 7.24-7.33 (5H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 57.6, 61.5, 71.2, 72.5, 73.2, 72.1, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6, 128.0, 129.3, 130.2, 141.0

(Example 21)
In Example 21, N-phenyldiethanolamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio (molar ratio) of N-phenyldiethanolamine: glycidol: allyl glycidyl ether was 1: 6: 8.

Polymerization step Under an argon stream, N-phenyldiethanolamine 1.0 g (5.52 mmol) was heated to 90 ° C and melted, and potassium methoxide (30% methanol solution) 0.26 g (1.11 mmol) was added thereto. After stirring for several minutes, the pressure was gradually reduced to distill off methanol, and 5 ml of dehydrated diglyme was added. While being heated to 90 ° C., 2.45 g (33.1 mmol) of glycidol was dissolved in 10 ml of dehydrated THF, and added dropwise over about 3 hours while distilling off THF.

Modification Step Subsequently, 5.04 g (44.2 mmol) of allyl glycidyl ether was dissolved in 20 ml of dehydrated THF, and dropwise added over about 6 hours while distilling off the THF. The mixture was stirred at the same temperature for 5 hours, cooled, added with 25 ml of methanol, and neutralized through a column of 20 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure (80 ° C.), dissolved in 30 ml of methanol again, treated with activated carbon, and filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 5.06 g of a yellow oil (yield 60.2%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.40-3.66 (68H, m), 3.86 (8H, s), 4.00 (16H, s), 4.75 (8H, s), 5.16 (8H, d , J = 9.4 Hz), 5.28 (8H, d, J = 17.0 Hz), 5.89-5.92 (8H, m), 6.60-6.61 (1H, m), 6.72-6.73 (2H, m), 7.13-7.16 ( 2H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 50.7, 61.5, 63.2, 69.0, 69.3, 69.6, 70.0, 71.2, 71.4, 71.8, 72.0, 72.9, 78.6, 78.8, 80.1, 80.3, 117.2, 113.1 , 117.2, 130.1, 149.1, 135.9, 136.1

(Example 22)
Etherification Step In Example 22, the hydroxyl group of the compound obtained in Example 21 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 2.0 g of the compound obtained in the modification step was dissolved in 5 ml of toluene, and 0.45 g (1.40 mmol) of tetrabutylammonium bromide and 2.83 g (70.8 mmol) of sodium hydroxide dissolved in 3 ml of water were added thereto. It was. The mixture was heated to 40 ° C., and 1.90 g (15.7 mmol) of allyl bromide was dissolved in 0.5 ml of toluene with stirring and added dropwise over 50 minutes. After stirring at the same temperature for 16.5 hours, 10 ml of water and 15 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / methanol = 20/1), and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 1.48 g of the title compound as a colorless oil. (Yield 61.5%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.50-3.64 (68H, m), 3.99 (16H, s), 4.13 (16H, s), 5.13 (8H, d, J = 11.0 Hz,) , 5.15 (8H, d, J = 11.5 Hz), 5.27 (16H, d, J = 17.1 Hz), 5.89-5.90 (16H, m), 6.58-6.61 (1H, m,), 6.71-6.72 (2H, m,), 7.13-7.15 (2H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 52.0, 70.2, 71.2, 72.1, 72.5, 73.1, 78.4, 78.7, 79.8, 80.1, 116.9, 113.0, 117.1, 130.2, 149.1, 136.2, 136.6

(Example 23)
In Example 23, 2-phenyl-1,3-propanediol was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio (molar ratio) of 2-phenyl-1,3-propanediol: glycidol: allyl glycidyl ether was 1: 6: 8.

Polymerization process
1.52 g (10.0 mmol) of 2-phenyl-1,3-propanediol was heated to 90 ° C. and melted, and 0.47 g (2.0 mmol) of potassium methoxide (30% methanol solution) was added thereto. After stirring for several minutes, the pressure was gradually reduced to distill off methanol, and 5 ml of dehydrated diglyme was added. While heating at 90 ° C., 4.44 g (60.0 mmol) of glycidol was dissolved in 13 ml of dehydrated THF, and added dropwise over about 4 hours while distilling off THF.

Modification Step Subsequently, 9.13 g (80.0 mmol) of allyl glycidyl ether was dissolved in 27 ml of dehydrated THF and added dropwise over about 8 hours while distilling off the THF. The mixture was stirred at the same temperature for 2.5 hours, then cooled, neutralized through a column of 20 ml of Amberlite IR 120B H AG by adding 40 ml of methanol. The solvent was distilled off under reduced pressure (80 ° C.), and the residual yellow liquid was purified by silica gel column chromatography (chloroform / methanol = 8/1). Next, the solution was treated with activated carbon as a methanol solution, filtered through a 0.2 μm filter, and the solvent was distilled off at 80 ° C. under reduced pressure to obtain 5.78 g of a slightly yellow oily substance (yield 38.3%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ3.15 (1H, s), 3.42-3.68 (62H, m), 3.76 (2H, bs), 3.88 (8H, s), 3.95 (2H, m ,), 4.01 (16H, s), 4.79 (8H, s), 5.14 (8H, d, J = 16.9 Hz), 5.26 (8H, d, J = 15.4 Hz), 5.89-5.94 (8H, m), 7.20-7.29 (5H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 46.1 (CH), 61.6, 63.3, 63.6, 69.3, 69.9, 70.0, 71.2, 71.4, 71.8, 72.0, 72.8, 78.6, 78.8, 80.2, 116.1, 134.8, 135.0, 126.4, 128.1, 141.0

すなわち、アルゴン気流下、上記修飾工程で得られた化合物2.54 g (1.68 mmol)をトルエン6 mlに溶解し、これに臭化テトラブチルアンモニウム 0.58 g (1.80mmol) および水4 mlに溶解した水酸化ナトリウム3.63 g (90.8 mmol)を加えた。40℃に加温、攪拌下臭化アリル 2.44 g (20.17 mmol)を0.5 mlのトルエンに溶解して40分で滴下した。同温度で15時間攪拌した後水15 ml、トルエン15 mlを加えて抽出、分液した。水層を再度15 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝30/1）で精製し、次いで0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、無色油状物を2.03 g得た(収率65.9%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 3.13 (1H, br), 3.46-3.65 (70H, m), 3.74 and 3.94 (each 2H, m), 3.99 (16H, s), 4.13 (16H, s), 5.13 (8H, d, J = 11.0 Hz), 5.15 (8H, d, J = 11.0 Hz), 5.27 (16H, d, J = 17.6 Hz), 5.89-5.91 (16H, m), 7.19-7.27 (5H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 47.4, 71.2, 72.1, 72.5, 73.8, 73.2, 78.4, 78.7, 79.8, 80.12, 116.9, 117.1, 136.1, 136.6, 127.6, 129.2, 129.3, 142.3 (Example 24)
Etherification Step In Example 24, the hydroxyl group of the compound obtained in Example 23 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 2.54 g (1.68 mmol) of the compound obtained in the above modification step was dissolved in 6 ml of toluene under an argon stream, and then hydroxylated dissolved in 0.58 g (1.80 mmol) of tetrabutylammonium bromide and 4 ml of water. Sodium 3.63 g (90.8 mmol) was added. While heating to 40 ° C., 2.44 g (20.17 mmol) of allyl bromide was dissolved in 0.5 ml of toluene with stirring and added dropwise over 40 minutes. The mixture was stirred at the same temperature for 15 hours, extracted with 15 ml of water and 15 ml of toluene, and separated. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / methanol = 30/1), and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 2.03 g of colorless oil (yield 65.9%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.13 (1H, br), 3.46-3.65 (70H, m), 3.74 and 3.94 (each 2H, m), 3.99 (16H, s), 4.13 ( 16H, s), 5.13 (8H, d, J = 11.0 Hz), 5.15 (8H, d, J = 11.0 Hz), 5.27 (16H, d, J = 17.6 Hz), 5.89-5.91 (16H, m), 7.19-7.27 (5H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 47.4, 71.2, 72.1, 72.5, 73.8, 73.2, 78.4, 78.7, 79.8, 80.12, 116.9, 117.1, 136.1, 136.6, 127.6, 129.2, 129.3, 142.3

(Example 25)
In Example 25, glycerol was used as the core molecule, and a reaction represented by the following chemical formula was performed. The ratio (molar ratio) of glycerol: glycidol: allyl glycidyl ether was 1: 9: 12.

Polymerization step 0.59 g (2.25 mmol) of potassium methoxide (30% methanol solution) was added while stirring 0.69 g (7.5 mmol) of glycerol in a 90 ° C. oil bath under an argon stream. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. While adding 9 ml of dehydrated diglyme and heating to 130 ° C., 5.0 g (67.5 mmol) of glycidol was dissolved in 20 ml of dehydrated THF and added dropwise over about 5.5 hours while distilling off THF.

Following the modification step, 10.3 g (90.0 mmol) of allyl glycidyl ether was dissolved in 30 ml of dehydrated THF and added dropwise over about 10.5 hours while distilling off THF. After stirring at the same temperature for 4 hours, the mixture was cooled, 20 ml of methanol was added and neutralized through a column of 20 ml of Amberlite IR 120B H AG. After activated carbon treatment, the solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 5/1) to obtain 10.56 g of a light brown oil (yield 66.2). %). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, Methanol-d ₄ ) δ: 3.44-3.66 (98H, m), 3.86 (12H, s), 4.01 (24H, s), 4.77 (12H, s), 5.16 (12H, d , J = 9.9 Hz), 5.28 (12H, d, J = 17.6 Hz), 5.89-5.93 (12H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 61.5, 69.3, 69.6, 69.7, 70.0, 71.2, 71.4 and 71.8, 72.0, 72.9, 78.6, 78., 116.0, 134.8, 135.0

すなわち、上記修飾工程で得た化合物2.0 gをトルエン6 mlに溶解し、これに水3.5 mlに溶解した水酸化ナトリウム3.4 g (85.0 mmol) および臭化テトラブチルアンモニウム 0.49 g (1.5 mmol)を加えた。40℃に加温、攪拌下臭化アリル 2.05 g (16.9 mmol)を0.5 mlのトルエンに溶解して45分で滴下した。同温度で16時間攪拌した後水10 ml、トルエン15 mlを加えて抽出、分液した。水層を再度15 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝50/1）で精製し、次いで0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、表題化合物を無色油状物を1.98 g得た(収率80.8%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, Methanol-d₄) δ: 3.51-3.71 (110H, m), 4.01 (24H, s), 4.15 (24H, s), 5.15 (12H, d, J = 12.1 Hz), 5.16 (12H, d, J = 11.0 Hz), 5.28 (24H, d, J = 17.0 Hz), 5.91-5.93 (24H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 71.2, 72.1, 72.5, 73.2, 78.5, 78.8, 79.9, 80.2, 116.9, 117.1, 136.2, 136.6 (Example 26)
Etherification Step In Example 26, the hydroxyl group of the compound obtained in Example 25 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 2.0 g of the compound obtained in the above modification step was dissolved in 6 ml of toluene, and 3.4 g (85.0 mmol) of sodium hydroxide and 0.49 g (1.5 mmol) of tetrabutylammonium bromide dissolved in 3.5 ml of water were added thereto. It was. While heating to 40 ° C. and stirring, 2.05 g (16.9 mmol) of allyl bromide was dissolved in 0.5 ml of toluene and added dropwise over 45 minutes. After stirring at the same temperature for 16 hours, 10 ml of water and 15 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed with saturated brine. After dehydrating with anhydrous sodium sulfate and concentrating, the residue was purified by silica gel column chromatography (chloroform / ethanol = 50/1) and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 1.98 g of the title compound as a colorless oil (yield 80.8%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, Methanol-d ₄ ) δ: 3.51-3.71 (110H, m), 4.01 (24H, s), 4.15 (24H, s), 5.15 (12H, d, J = 12.1 Hz), 5.16 (12H, d, J = 11.0 Hz), 5.28 (24H, d, J = 17.0 Hz), 5.91-5.93 (24H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 71.2, 72.1, 72.5, 73.2, 78.5, 78.8, 79.9, 80.2, 116.9, 117.1, 136.2, 136.6

(Example 27)
In Example 27, N, N-bis (2,3-dihydroxypropyl) benzylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. N, N-bis (2,3-dihydroxypropyl) benzylamine: glycidol: allyl glycidyl ether: 3-glycidyloxypropyl (dimethoxy) methylsilane was in a ratio (molar ratio) of 1: 4: 4: 4.

Polymerization step N, N-bis (2,3-dihydroxypropyl) benzylamine 1.02 g (4.0 mmol) was heated to 95 ° C under argon flow, and potassium methoxide (30% methanol solution) 0.37 g (1.58 mmol) with stirring. Was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. 7 ml of dehydrated diglyme was added, the temperature was raised to 110 ° C., 1.19 g (16.1 mmol) of glycidol was dissolved in 10 ml of dehydrated THF, and about 2.5 hours were added dropwise while removing THF.

Modification step Subsequently, 1.83 g (16.0 mmol) of allyl glycidyl ether was dissolved in 10 ml of dehydrated THF and added dropwise over about 3 hours while distilling off the THF.
Further, 3.53 g (16.0 mmol) of 3-glycidyloxypropyl (dimethoxy) methylsilane was dissolved in 15 ml of dehydrated THF and added dropwise over about 4.3 hours. The mixture was stirred at the same temperature for 2 hours and then cooled. The gel product was dissolved by adding 30 ml of methanol. This was neutralized through a column of Amberlite IR 120B H AG 10 ml, the solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 6/1). 1.17 g of a slightly yellow oily substance was obtained (yield 15.5%). NMR of this product was measured, and the following results were obtained.
¹ H-NMR (600 MHz, methanol-d ₄ ) δ: 0.11 (12H, s), 0.64 (8H, t, J = 8.2 Hz), 1.62-1.66 (8H, m), 2.55-2.66 (4H, br ), 3.42-3.67 (68H, m), 3.50 (24H, s), 3.85 (8H, s), 4.01 (8H, s), 4.80 (8H, s), 5.17 (4H, d, J = 8.3 Hz) , 5.29 (4H, d, J = 17.0 Hz), 5.91 (4H, br), 7.25-7.35 (5H, m)
¹³ C-NMR (600 MHz, methanol-d ₄ ) δ: 10.0, 23.9, 44.4, 50.4, 51.9, 59.4, 61.5, 64.5, 70.4-75.3 (m), 79.8, 80.0, 117.2, 136.0, 136.2, 128.1, 129.3, 130.3, 130.4

(Example 28)
In Example 28, ethylene glycol was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of ethylene glycol: glycidol: allyl glycidyl ether was 1:14:16 (molar ratio).

Polymerization step Under an argon stream, 0.35 g (1.5 mmol) of potassium methoxide (30% methanol solution) was added while stirring and stirring ethylene glycol 0.31 g (5.0 mmol) at 80 ° C. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. 5 ml of dehydrated diglyme was added, the temperature was raised to 100 ° C., 5.19 g (70.1 mmol) of glycidol was dissolved in 15 ml of dehydrated THF, and about 5 hours were added dropwise while removing THF.

Modification Step Subsequently, 9.13 g (80.0 mmol) of allyl glycidyl ether was dissolved in 25 ml of dehydrated THF and added dropwise over about 3 hours while distilling off the THF. The mixture was stirred at the same temperature for 3 hours, cooled, added with 25 ml of methanol, and neutralized through a column of 20 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure, and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 7/1). Filtration through a 0.2 μm filter as a methanol solution and concentration under reduced pressure (80 ° C.) gave 8.84 g of a pale yellow oil (yield 60.4%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.43-3.67 (154H, m), 3.87 (16H, s), 4.01 (16H, s), 4.73 (16H, s), 5.16 (16H, d , J = 8.8 Hz), 5.28 (16H, d, J = 17.0 Hz), 5.88-5.93 (16H, br)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 59.3, 64.5, 70.4, 70.8, 71.1, 72.5, 72.9, 73.2, 74.0, 79.8, 80.0, 117.2, 136.0, 136.1

すなわち、上記修飾工程で得られた化合物3.0 g (1.025 mmol) をトルエン5 mlに溶解し、これに臭化テトラブチルアンモニウム 0.69 g (2.1 mmol)、 次いで水5.5 mlに溶解した水酸化ナトリウム4.47 g (111.8 mmol)を加えた。40℃に加温、攪拌下臭化アリル 2.98 g (24.6 mmol)を2 mlのトルエンに溶解して約１時間で滴下した。同温度で18時間攪拌した後水10 ml、トルエン10 mlを加えて抽出、分液した。水層を再度10 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝35/1）で精製し、次いでメタノール溶液として0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、無色油状物を2.59 g得た(収率70.9%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 3.50-3.70 (154H, m), 4.00 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 12.1 Hz), 5.15 (16H, d, J = 11.0 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90-5.91 (32H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 59.5, 71.2, 71.9, 72.1, 72.5, 73.2, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.1, 136.6 (Example 29)
Etherification Step In Example 29, the hydroxyl group of the compound obtained in Example 28 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 3.0 g (1.025 mmol) of the compound obtained in the above modification step was dissolved in 5 ml of toluene, 0.69 g (2.1 mmol) of tetrabutylammonium bromide, and then 4.47 g of sodium hydroxide dissolved in 5.5 ml of water. (111.8 mmol) was added. The mixture was heated to 40 ° C., and 2.98 g (24.6 mmol) of allyl bromide was dissolved in 2 ml of toluene with stirring and added dropwise in about 1 hour. After stirring at the same temperature for 18 hours, 10 ml of water and 10 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 10 ml of toluene, and the extracts were combined and washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / ethanol = 35/1), and then filtered through a 0.2 μm filter as a methanol solution. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 2.59 g of colorless oil (yield 70.9%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.50-3.70 (154H, m), 4.00 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 12.1 Hz), 5.15 (16H, d, J = 11.0 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90-5.91 (32H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 59.5, 71.2, 71.9, 72.1, 72.5, 73.2, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.1, 136.6

(Example 30)
In Example 30, a reaction represented by the following chemical formula was performed using polyethylene glycol 200 as the core molecule. The ratio (molar ratio) of polyethylene glycol 200: glycidol: allyl glycidyl ether was 1:14:16.

Polymerization step Under a stream of argon, polyethylene glycol 200 0.8 g (ca. 4 mmol) was heated to 80 ° C., and potassium methoxide (30% methanol solution) 0.19 g (0.8 mmol) was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. 5 ml of dehydrated diglyme was added, the temperature was raised to 100 ° C., 4.15 g (56.0 mmol) of glycidol was dissolved in 12 ml of dehydrated THF, and about 4 hours were added dropwise while removing THF.

Modification Step Subsequently, 7.3 g (64.0 mmol) of allyl glycidyl ether was dissolved in 20 ml of dehydrated THF, and dropwise added over about 6.5 hours while distilling off the THF. The mixture was stirred at the same temperature for 3.5 hours, cooled, neutralized through a column of 20 ml of Amberlite IR 120B H AG by adding 20 ml of methanol. The solvent was distilled off under reduced pressure to obtain 10.56 g of a light brown oil. Of this, 5.0 g was purified by silica gel column chromatography (chloroform / methanol = 6/1 to 2/1). Subsequently, the solution was filtered through a 0.2 μm filter as a methanol solution and concentrated under reduced pressure (80 ° C.) to obtain 0.66 g of the title compound as a pale yellow oil (yield 11.4%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.45-3.67 (166H, m), 3.87 (16H, s), 4.01 (16H, s), 4.76 (16H, s), 5.16 (16H, d , J = 9.9 Hz), 5.28 (16H, d, J = 17.0 Hz), 5.89-5.94 (16H, b)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 62.1, 62.8, 64.4, 70.5, 70.9, 71.1, 71.5, 71.7, 71.8, 72.1, 72.4, 72.6, 72.9, 73.2, 74.0, 79.8, 80.0, 81.3 , 117.2, 136.0, 136.2

すなわち、アルゴン気流下、上記修飾工程で得られた化合物3.0 g (0.98 mmol)をトルエン5 mlに溶解し、これに臭化テトラブチルアンモニウム 0.66 g (2.0 mmol) 次いで水5.5 mlに溶解した水酸化ナトリウム4.27 g (106.8 mmol)を加えた。40℃に加温、攪拌下臭化アリル 2.85 g (23.6 mmol)を2 mlのトルエンに溶解して約45分で滴下した。同温度で17時間攪拌した後水10 ml、トルエン10 mlを加えて抽出、分液した。水層を再度15 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝25/1）で精製し、次いでメタノール溶液として0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、無色油状物を2.8 g得た(収率78.9%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 3.53-3.65 (166H, m), 3.99 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 10.0 Hz), 5.15 (16H, d, J = 10.5 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90 (32H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 59.5, 70.5, 70.8, 71.2, 71.5, 71.8, 72.5, 72.1, 73.2, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.1, 136.6 (Example 31)
Etherification Step In Example 31, the hydroxyl group of the compound obtained in Example 30 was allyl etherified with allyl bromide (see the following chemical formula).

That is, under argon flow, 3.0 g (0.98 mmol) of the compound obtained in the above modification step was dissolved in 5 ml of toluene, and then this was dissolved in 0.66 g (2.0 mmol) of tetrabutylammonium bromide and then dissolved in 5.5 ml of water. Sodium 4.27 g (106.8 mmol) was added. The mixture was heated to 40 ° C., and 2.85 g (23.6 mmol) of allyl bromide was dissolved in 2 ml of toluene with stirring and added dropwise in about 45 minutes. After stirring for 17 hours at the same temperature, 10 ml of water and 10 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / ethanol = 25/1), and then filtered through a 0.2 μm filter as a methanol solution. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 2.8 g of a colorless oil (yield 78.9%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.53-3.65 (166H, m), 3.99 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 10.0 Hz), 5.15 (16H, d, J = 10.5 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90 (32H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 59.5, 70.5, 70.8, 71.2, 71.5, 71.8, 72.5, 72.1, 73.2, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.1, 136.6

(Example 32)
In Example 32, 1,4-butanediol was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of 1,4-butanediol: glycidol: allyl glycidyl ether was 1:14:16 (molar ratio).

Polymerization process Under argon atmosphere, 1,4-butanediol 0.27 g (3 mmol) was heated to 90 ° C, potassium methoxide (30% methanol solution) 0.21 g (0.9 mmol) was added thereto, and the mixture was stirred for several minutes and then gradually. The methanol was distilled off. After 4 ml of diglyme was added and the temperature was raised to 110 ° C., 3.11 g (42 mmol) of glycidol was dissolved in 9 ml of dehydrated THF and added dropwise over about 3 hours while distilling off the THF.

Modification process
After stirring for 20 minutes, 5.48 g (48 mmol) of allyl glycidyl ether was dissolved in 15 ml of dehydrated THF and added dropwise over about 5 hours while distilling off the THF. After stirring for about 3.5 hours at the same temperature, the reaction solution was diluted with 25 ml of methanol and passed through a column of Amberlite IR 120B HAG 25 ml to neutralize. The column was washed with 30 ml of methanol, and both washing solutions were concentrated under reduced pressure. The residual liquid 8.67 g was purified by silica gel column chromatography (chloroform / methanol = 7/1) to obtain 2.96 g of a pale yellow oil (yield 33.4%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 1.63 (4H, s), 3.43-3.67 (138H, br), 3.87 (16H, s), 4.01 (32H, s), 4.74 (16H, s ), 5.17 (16H, d, J = 3.8 Hz), 5.28 (16H, d, J = 17.1 Hz), 5.89-5.93 (16H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 27.5, 70.5, 70.9, 71.2, 71.3, 72.6, 73.0, 73.2, 74.0, 79.8, 80.1, 117.2, 136.2

すなわち、修飾工程で得た化合物2.95 g (1.0 mmol)をトルエン6 mlに溶解しこれに臭化テトラブチルアンモニウム 0.69 g (2.14 mmol) および水5 mlに溶解した水酸化ナトリウム4.34 g (108.5 mmol) を加えた。40℃に加温、攪拌下臭化アリル 2.91 g (24.1 mmol)を約１時間で滴下した。同温度で18時間攪拌した後水、トルエン各15 mlを加えて抽出、分液した。水層を再度15 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝30/1）で精製し、次いでメタノール溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、淡黄色油状物を2.5 g得た(収率69.4%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 1.62 (4H, s), 3.50-3.66 (154H, m), 4.00 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 12.6 Hz), 5.15 (16H, d, J = 11.5 Hz), 5.28 (32H, d, J = 17.1 Hz), 5.87-5.92 (32H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 27.5, 71.3, 71.7, 72.1, 72.6, 73.2, 78.5, 78.8, 79.9, 80.2, 116.9, 117.1, 136.2, 136.7 (Example 33)
Etherification Step In Example 33, the hydroxyl group of the compound obtained in Example 32 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 2.95 g (1.0 mmol) of the compound obtained in the modification step was dissolved in 6 ml of toluene, and 0.64 g (2.14 mmol) of tetrabutylammonium bromide and 4.34 g (108.5 mmol) of sodium hydroxide dissolved in 5 ml of water. Was added. The mixture was heated to 40 ° C. and 2.91 g (24.1 mmol) of allyl bromide was added dropwise with stirring for about 1 hour. The mixture was stirred at the same temperature for 18 hours, extracted with 15 ml of water and toluene, and separated. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined, washed with saturated brine three times, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography (chloroform / methanol = 30/1), and then filtered through a 0.2 μm filter as a methanol solution. Concentration under reduced pressure at 80 ° C. gave 2.5 g of a pale yellow oil (yield 69.4%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 1.62 (4H, s), 3.50-3.66 (154H, m), 4.00 (32H, s), 4.13 (32H, s), 5.13 (16H, d , J = 12.6 Hz), 5.15 (16H, d, J = 11.5 Hz), 5.28 (32H, d, J = 17.1 Hz), 5.87-5.92 (32H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 27.5, 71.3, 71.7, 72.1, 72.6, 73.2, 78.5, 78.8, 79.9, 80.2, 116.9, 117.1, 136.2, 136.7

(Example 34)
In Example 34, 1,2,4-butanetriol was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of 1,2,4-butanetriol: glycidol: allyl glycidyl ether was 1: 9: 12 (molar ratio).

Polymerization step Under argon atmosphere, 1,2,4-butanetriol 0.4 g (3.77 mmol) was heated to 90 ° C, potassium methoxide (30% methanol solution) 0.26 g (1.13 mmol) was added thereto, and the mixture was stirred for several minutes. Thereafter, the pressure was gradually reduced, and methanol was distilled off. 5 ml of diglyme was added, 2.52 g (33.9 mmol) of glycidol was dissolved in 10 ml of dehydrated THF, and about 3 hours were added dropwise while removing THF.

Modification process
After stirring for 15 minutes, 5.16 g (45.2 mmol) of allyl glycidyl ether was dissolved in 15 ml of dehydrated THF and added dropwise over about 4.5 hours while distilling off the THF. After stirring at the same temperature for about 3.5 hours, the reaction solution was diluted with 20 ml of methanol and passed through a 20 ml column of Amberlite IR 120B HAG to neutralize. The column was washed with 30 ml of methanol, and both washing solutions were concentrated under reduced pressure. The residue was taken from 7.56 g to 4.0 and purified by silica gel column chromatography (chloroform / methanol = 5/1). The solution was further treated with activated carbon as a methanol solution, filtered through a 0.2 μm filter, and concentrated at 80 ° C. under reduced pressure to obtain 2.35 g of a slightly yellow oil (yield 55.0%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, Methanol-d ₄ ) δ: 1.62, 1.71 and 1.78 (2H, each br), 3.43-3.66 (98H, b), 3.86 (12H, s), 4.01 (24H, s), 4.73 (12H, s), 5.16 (12H, d, J = 9.9 Hz), 5.28 (12H, d, J = 17.0 Hz), 5.89-5.93 (12H, m)
¹³ C -NMR ((600 MHz, Methanol-d ₄ ) δ: 33.0, 70.5, 70.8, 71.1, 72.5, 72.9, 74.0, 79.8, 80.0, 73.2, 116.9, 117.2, 136.0, 136.1

すなわち、上記修飾工程で得た化合物1.64 g (0.765 mmol)をトルエン6 mlに溶解しこれに臭化テトラブチルアンモニウム 0.77 g (2.39 mmol) および水6.5 mlに溶解した水酸化ナトリウム4.99 g (124.8 mmol) を加えた。40℃に加温、攪拌下臭化アリル 3.34 g (27.6 mmol)を約１時間で滴下した。同温度で21時間攪拌した後水、トルエン各10 mlを加えて抽出、分液した。水層を再度10 mlのトルエンで抽出し、抽出液を併せて水で2回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留物をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝30/1）で精製し、次いでメタノール溶液として0.2μmフィルターでろ過して減圧下80℃で濃縮した。表題化合物を微黄色油状物を1.2 g得た(収率60.0%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 1.62, 1.70 and 1.78 (2H, each br), 3.50-3.70 (110H, br), 3.99 and 4.00 (24H, each s), 4.13 (24H, s), 5.13 (12H, d, J = 12.1 Hz), 5.15 (12H, d, J = 11.5 Hz), 5.27 (24H, d, J = 17.0 Hz), 5.90-5.92 (24H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 33.2, 71.3, 72.1, 72.5, 73.2, 78.5, 78.7, 79.8, 80.1, 116.9, 117.1, 136.2, 136.6 (Example 35)
Etherification Step In Example 35, the hydroxyl group of the compound obtained in Example 34 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 1.64 g (0.765 mmol) of the compound obtained in the above modification step was dissolved in 6 ml of toluene and dissolved in 0.77 g (2.39 mmol) of tetrabutylammonium bromide and 4.99 g (124.8 mmol) of sodium hydroxide dissolved in 6.5 ml of water. ) Was added. The mixture was heated to 40 ° C. and 3.34 g (27.6 mmol) of allyl bromide was added dropwise with stirring for about 1 hour. After stirring for 21 hours at the same temperature, 10 ml each of water and toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 10 ml of toluene, and the extracts were combined, washed twice with water, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (chloroform / methanol = 30/1), then filtered through a 0.2 μm filter as a methanol solution and concentrated at 80 ° C. under reduced pressure. 1.2 g of the title compound was obtained as a pale yellow oil (yield 60.0%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 1.62, 1.70 and 1.78 (2H, each br), 3.50-3.70 (110H, br), 3.99 and 4.00 (24H, each s), 4.13 (24H, s), 5.13 (12H, d, J = 12.1 Hz), 5.15 (12H, d, J = 11.5 Hz), 5.27 (24H, d, J = 17.0 Hz), 5.90-5.92 (24H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 33.2, 71.3, 72.1, 72.5, 73.2, 78.5, 78.7, 79.8, 80.1, 116.9, 117.1, 136.2, 136.6

(Example 36)
In Example 36, N, N-bis (2,3-dihydroxypropyl) diphenylmethylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. N, N-bis (2,3-dihydroxypropyl) diphenylmethylamine: glycidol: allyl glycidyl ether was in a ratio (molar ratio) of 1:12:24.

Polymerization Step Under argon atmosphere, N, N-bis (2,3-dihydroxypropyl) diphenylmethylamine 0.83 g (2.5 mmol) was heated to 135 ° C., and potassium methoxide (30% methanol solution)) 0.234 g (1.0 mmol) was added and stirred for several minutes, then the pressure was gradually reduced and methanol was distilled off. 7 ml of diglyme was added, and 2.23 g (30.05 mmol) of glycidol was dissolved in 10 ml of dehydrated THF, and added dropwise over about 3 hours while distilling off the THF.

Modification Step Next, 4.57 g (40.07 mmol) of allyl glycidyl ether was dissolved in 15 ml of dehydrated THF, and dropwise added over about 5 hours while distilling off the THF. The mixture was stirred at the same temperature for 2 hours, cooled, diluted with 25 ml of methanol, and neutralized through a column of Amberlite IR-120 HAG 20 ml. After concentration under reduced pressure, the brown residual liquid was purified by silica gel column chromatography (chloroform / methanol = 7/1) to obtain 2.85 g of a light brown oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.63-2.78 (4H, br), 3.45-3.67 (170H, m), 3.87 (16H, s), 4.01 (48H, s), 4.84 (16H , s), 5.17 (25H, m), 5.27-5.30 (24H, m), 5.89-5.95 (24H, m), 7.26-7.39 (10H, br)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 70.6, 70.9, 71.3, 72.6, 73.0, 73.3, 74.0, 74.1, 79.9, 80.1, 117.2, 117.3, 136.2, 128.1, 129.4, 130.5

すなわち、上記修飾工程で得た化合物2.29 g (0.578 mmol)をトルエン5 mlに溶解し、これに臭化テトラブチルアンモニウム 0.5 g (1.55 mmol) および水4 mlに溶解した水酸化ナトリウム3.28 g (82.0 mmol) を加えた。40℃に加温、攪拌下臭化アリル 2.19 g (18.1 mmol)を1 mlのトルエンに溶解して30分で滴下した。同温度で18時間攪拌した後水、トルエン各10 mlを加えて抽出、分液した。水層をさらに10 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で３回洗浄した。無水硫酸ナトリウムで脱水後濃縮して残留液2.64 gをシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、微黄色油状物を2.15 g得た(収率80.8%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 2.63-2.83 (4H, br), 3.51-3.66 (202H, m), 4.01 (48H, s), 4.14 (32H, s), 5.3-5.17 (41H, m), 5.27-5.30 (40H, m), 5.91 (40H, m), 7.25-7.39 (10H, br)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 70.6, 70.9, 71.3, 72.6, 73.0, 73.3, 74.0, 74.1, 79.9, 80.1, 117.2, 117.3, 136.2, 128.1, 129.4, 130.5 (Example 37)
Etherification Step In Example 37, the hydroxyl group of the compound obtained in Example 36 was allyl etherified with allyl bromide (see the following chemical formula).

That is, 2.29 g (0.578 mmol) of the compound obtained in the above modification step was dissolved in 5 ml of toluene, and 3.28 g (82.0) of sodium hydroxide dissolved in 0.5 g (1.55 mmol) of tetrabutylammonium bromide and 4 ml of water. mmol) was added. The mixture was heated to 40 ° C. and 2.19 g (18.1 mmol) of allyl bromide was dissolved in 1 ml of toluene with stirring and added dropwise over 30 minutes. After stirring at the same temperature for 18 hours, 10 ml each of water and toluene were added for extraction and liquid separation. The aqueous layer was further extracted with 10 ml of toluene, and the extracts were combined and washed three times with saturated brine. After dehydrating with anhydrous sodium sulfate and concentrating, 2.64 g of the residual liquid was purified by silica gel column chromatography (chloroform / methanol = 20/1), and then filtered through a 0.2 μm filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. yielded 2.15 g of a slightly yellow oil (yield 80.8%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.63-2.83 (4H, br), 3.51-3.66 (202H, m), 4.01 (48H, s), 4.14 (32H, s), 5.3-5.17 (41H, m), 5.27-5.30 (40H, m), 5.91 (40H, m), 7.25-7.39 (10H, br)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 70.6, 70.9, 71.3, 72.6, 73.0, 73.3, 74.0, 74.1, 79.9, 80.1, 117.2, 117.3, 136.2, 128.1, 129.4, 130.5

(Example 38)
In Example 38, 1,3,5-benzenetrimethanol was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of 1,3,5-benzenetrimethanol: glycidol: allyl glycidyl ether was 1: 9: 12 (molar ratio).

Polymerization process Under argon atmosphere, 1,3,5-benzenetrimethanol 0.5 g (2.97 mmol) is heated and melted to 120 ° C, and potassium methoxide (30% methanol solution) 0.417 g (1.78 mmol) is added thereto for several minutes. After stirring, the pressure was gradually reduced and methanol was distilled off. 7 ml of diglyme was added, the temperature was raised to 140 ° C., 1.98 g (26.76 mmol) of glycidol was dissolved in 10 ml of dehydrated THF, and dropwise added in about 2.5 hours while distilling off THF.

Modification Step Next, 4.07 g (35.67 mmol) of allyl glycidyl ether was dissolved in 15 ml of dehydrated THF, and dropwise added over about 5 hours while distilling off the THF. The mixture was stirred at the same temperature for 2.5 hours, cooled, diluted with 20 ml of methanol and neutralized through a column of 20 ml of Amberlite IR-120 HAG. After concentration under reduced pressure, the brown residual liquid was purified by silica gel column chromatography (chloroform / methanol = 5/1) to obtain 1.43 g of a light brown oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.44-3.67 (94H, m), 3.86 (12H, s), 4.00 (24H, s), 4.56 (6H, s), 4.85 (12H, s ), 5.16 (12H, d, J = 7.2 Hz), 5.28 (12H, d, J = 17.6 Hz), 5.89-5.91 (12H, m), 7.28 (3H, s)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 62.9, 70.6, 70.9, 71.2, 72.4, 72.6, 73.0, 73.3, 74.2, 79.9, 80.1, 117.2, 136.2, 127.4, 140.0

すなわち、上記修飾工程で得た化合物1.38 g (0.626 mmol)をトルエン3 mlに溶解し、これに臭化テトラブチルアンモニウム 0.3 g (0.93 mmol) および水3 mlに溶解した水酸化ナトリウム2.04 g (51.0 mmol) を加えた。アルゴン気流下40℃に加温、攪拌しながら臭化アリル 1.36 g (11.2 mmol)を1 mlのトルエンに溶解して20分で滴下した。同温度で19時間攪拌した後水、トルエン各10 mlを加えて抽出、分液した。水層をさらに10 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で2回洗浄した。無水硫酸ナトリウムで脱水後濃縮して残留液1.6 gをシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、微黄色油状物を1.0 g得た(収率59.5%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 3.49-3.64 (94H, m), 3.98 and 4.12 (each 24H, s), 4.54 (6H, s), 5.14-5.15 (24H, m), 5.25-5.28 (24H, m), 5.89-5.90 (12H, m), 7.26 (3H, s)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 71.2, 72.1, 72.5, 73.3, 74.1, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 127.1, 136.1, 136.6, 140.0 (Example 39)
Etherification Step In Example 39, the hydroxyl group of the compound obtained in Example 38 was allyl etherified with allyl bromide (see the chemical formula below).

That is, 1.38 g (0.626 mmol) of the compound obtained in the above modification step was dissolved in 3 ml of toluene, and 2.04 g (51.0) of sodium hydroxide dissolved in 0.3 g (0.93 mmol) of tetrabutylammonium bromide and 3 ml of water. mmol) was added. While heating at 40 ° C. under an argon stream and stirring, 1.36 g (11.2 mmol) of allyl bromide was dissolved in 1 ml of toluene and added dropwise over 20 minutes. After stirring for 19 hours at the same temperature, 10 ml each of water and toluene were added for extraction and liquid separation. The aqueous layer was further extracted with 10 ml of toluene, and the extracts were combined and washed twice with saturated brine. After dehydrating with anhydrous sodium sulfate and concentrating, 1.6 g of the residual liquid was purified by silica gel column chromatography (chloroform / methanol = 20/1), and then filtered through a 0.2 μm filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. yielded 1.0 g of a slightly yellow oil (yield 59.5%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.49-3.64 (94H, m), 3.98 and 4.12 (each 24H, s), 4.54 (6H, s), 5.14-5.15 (24H, m), 5.25-5.28 (24H, m), 5.89-5.90 (12H, m), 7.26 (3H, s)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 71.2, 72.1, 72.5, 73.3, 74.1, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 127.1, 136.1, 136.6, 140.0

すなわち、実施例２５の修飾工程で得た化合物1.17 g (0.55 mmol)をトルエン2 mlに溶解し、これに臭化テトラブチルアンモニウム 0.24 g (0.74 mmol) および水1.8 mlに溶解した水酸化ナトリウム1.52 g (38.0 mmol)を加えた。アルゴン気流下40℃に加温攪拌しながら 3,5-ビス(ブテニルオキシ)ベンジルブロミド 3.07 g (9.86 mmol)を1.5 mlのトルエンに溶解して滴下した。同温度で20時間攪拌した後冷後し、トルエン、水各10 mlを加えて抽出、分液した。水層を再度10 mlのトルエンで抽出し、抽出液を併せて水で2回洗浄した。無水硫酸ナトリウムで脱水後濃縮して残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝100/1〜20/1）で精製した。次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、淡黄色油状物を1.7 g得た(63.4%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.49 (48H, s), 3.51-3.69 (110H, m), 3.96 (72H, s), 4.59 (24H, s), 5.08-5.16 and 5.23-5.25 (72H, m), 5.86-5.89 (36H, bs), 6.34 (12H, s), 6.50 (24H, s)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 67.3, 70.3, 70.5, 72.1, 72.4, 73.0, 78.8, 79.1, 100.7, 106.2, 141.3, 160.1, 117.1, 134.6 (Example 40)
In Example 40, 3,5-bis (butenyloxy) benzyl bromide was used as the etherification step for the compound obtained in the modification step of Example 25, and the reaction represented by the following chemical formula was performed.

That is, 1.17 g (0.55 mmol) of the compound obtained in the modification step of Example 25 was dissolved in 2 ml of toluene, and 1.52 sodium hydroxide dissolved in 0.24 g (0.74 mmol) of tetrabutylammonium bromide and 1.8 ml of water. g (38.0 mmol) was added. While heating and stirring at 40 ° C. under an argon stream, 3.07 g (9.86 mmol) of 3,5-bis (butenyloxy) benzyl bromide was dissolved in 1.5 ml of toluene and added dropwise. The mixture was stirred at the same temperature for 20 hours, cooled, extracted with 10 ml of toluene and water, and separated. The aqueous layer was extracted again with 10 ml of toluene, and the extracts were combined and washed twice with water. After dehydrating with anhydrous sodium sulfate and concentrating, the residue was purified by silica gel column chromatography (chloroform / methanol = 100/1 to 20/1). Subsequently, it filtered with the 0.2 micrometer filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. yielded 1.7 g of a pale yellow oil (63.4%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.49 (48H, s), 3.51-3.69 (110H, m), 3.96 (72H, s), 4.59 (24H, s), 5.08-5.16 and 5.23-5.25 (72H, m), 5.86-5.89 (36H, bs), 6.34 (12H, s), 6.50 (24H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 67.3, 70.3, 70.5, 72.1, 72.4, 73.0, 78.8, 79.1, 100.7, 106.2, 141.3, 160.1, 117.1, 134.6

すなわち、実施例１０の修飾工程で得た化合物0.8 g (0.37 mmol)をトルエン1 mlに溶解し、これに臭化テトラブチルアンモニウム 0.13 g (0.4 mmol)、および水1 mlに溶解した水酸化ナトリウム0.84 g (21.0 mmol)を加えた。アルゴン気流下40℃に加温攪拌しながら 3,5-ビス(ブテニルオキシ)ベンジルブロミド 1.87 g (5.5 mmol)を1 mlのトルエンに溶解して滴下した。同温度で19時間攪拌した後冷後し、トルエン10 ml、水5 mlを加えて抽出、分液した。水層を再度10 mlのトルエンで抽出し、抽出液を併せて水で2回洗浄した。無水硫酸ナトリウムで脱水後濃縮して残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝30/1）で精製した。次いでトルエン溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、黄色油状物1.18 gを得た(65.2%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.50 (48H, s), 2.72 (6H, br), 3.47-3.69 (111H, m), 3.95 (72H, s), 4.42 and 4.59 (24H, s), 5.08-5.15 and 5.23-5.26 (72H, m), 5.86-5.92 (36H, br), 6.35 (12H, s), 6.50 (24H, s)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 54.8, 67.3, 70.6, 72.2, 72.3, 73.5, 78.8, 79.1, 100.7, 106.2, 141.3, 160.1, 117.0, 134.6 (Example 41)
In Example 41, the compound obtained in the modification step of Example 10 was subjected to a reaction represented by the following chemical formula using 3,5-bis (butenyloxy) benzyl bromide as an etherification step.

That is, 0.8 g (0.37 mmol) of the compound obtained in the modification step of Example 10 was dissolved in 1 ml of toluene, and 0.13 g (0.4 mmol) of tetrabutylammonium bromide and sodium hydroxide dissolved in 1 ml of water. 0.84 g (21.0 mmol) was added. While stirring under heating at 40 ° C. under an argon stream, 1.87 g (5.5 mmol) of 3,5-bis (butenyloxy) benzyl bromide was dissolved in 1 ml of toluene and added dropwise. The mixture was stirred at the same temperature for 19 hours, cooled, extracted with 10 ml of toluene and 5 ml of water, and separated. The aqueous layer was extracted again with 10 ml of toluene, and the extracts were combined and washed twice with water. After dehydrating with anhydrous sodium sulfate and concentrating, the residue was purified by silica gel column chromatography (chloroform / methanol = 30/1). Subsequently, it filtered with the 0.2 micrometer filter as a toluene solution. Concentration under reduced pressure at 80 ° C. gave 1.18 g of a yellow oil (65.2%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.50 (48H, s), 2.72 (6H, br), 3.47-3.69 (111H, m), 3.95 (72H, s), 4.42 and 4.59 (24H, s ), 5.08-5.15 and 5.23-5.26 (72H, m), 5.86-5.92 (36H, br), 6.35 (12H, s), 6.50 (24H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 54.8, 67.3, 70.6, 72.2, 72.3, 73.5, 78.8, 79.1, 100.7, 106.2, 141.3, 160.1, 117.0, 134.6

(Example 42)
In Example 42, glycerol was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of glycerol: glycidol: 3,5-bis (3-butenyloxy) benzylglycidyl ether was 1: 9: 12 (molar ratio).

Polymerization step Glycerol 0.4 g (3.77 mmol) was heated to 90 ° C under an argon atmosphere, potassium methoxide (30% methanol solution) 0.26 g (1.13 mmol) was added and stirred for several minutes. Left. 5 ml of diglyme was added, 2.52 g (33.9 mmol) of glycidol was dissolved in 10 ml of dehydrated THF, and about 3 hours were added dropwise while removing THF.

Modification process
After stirring for 15 minutes, 5.16 g (45.2 mmol) of 3,5-bis (3-butenyloxy) benzylglycidyl ether was dissolved in 15 ml of dehydrated THF, and added dropwise over about 4.5 hours while distilling off THF. After stirring at the same temperature for about 3.5 hours, the reaction solution was diluted with 20 ml of methanol and passed through a 20 ml column of Amberlite IR 120B H AG to neutralize. The column was washed with 30 ml of methanol, and both washing solutions were concentrated under reduced pressure. The residue was taken from 7.56 g to 4.0 and purified by silica gel column chromatography (chloroform / methanol = 5/1). The solution was further treated with activated carbon as a methanol solution, filtered through a 0.2 μm filter, and concentrated at 80 ° C. under reduced pressure to obtain 2.35 g of a slightly yellow oil (yield 55.0%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.50 (48H, s), 3.46-3.70 (110H, m), 3.96 and 3.97 (48H, s), 3.98 (12H, s), 4.43 (24H, s ), 5.08-5.16 (48H, m), 5.87-5.89 (24H, m), 6.37 (12H, s), 6.46 (24H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 67.3, 69.5, 71.3, 71.9, 78.5, 78.8, 79.8, 73.5, 100.7, 106.2, 140.7, 160.2, 117.1, 134.5

すなわち、上記修飾工程で得られた化合物0.6 g (0.136 mmol)をトルエン2 mlに溶解し、これに臭化テトラブチルアンモニウム 0.06 g (0.186 mmol)、水0.6 mlに溶解した水酸化ナトリウム0.39 g (9.75 mmol)およびヨウ化メチル 0.7 g (4.93 mmol)を加えてアルゴン気流下35-37℃で18時間攪拌した。冷却後水、トルエン各5 mlを加えて抽出、分液した。水層を再度5 mlのトルエンで抽出し、抽出液を併せて水で2回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧80℃で濃縮し、無色油状物を0.56 g得た(90.3%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.50 (48H, s), 3.31-3.65 (166H, m), 3.96 (48H, s), 4.44 (24H, s), 5.09 (24H, d, J = 7.7 Hz), 5.15 (24H, d, J = 17.0 Hz), 5.87 (24H, bs), 6.36 (12H, s), 6.47 (24H, s)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 58.1, 58.2, 59.3, 67.2, 70.1, 70.4, 71.5, 71.6, 78.8, 79.1, 79.5, 79.7, 79.8, 73.4, 100.7,106.1, 140.8, 160.2, 117.1, 134.5 (Example 43)
Etherification Step In Example 43, the hydroxyl group of the compound obtained in Example 42 was methoxylated with methyl iodide (see the following chemical formula).

That is, 0.6 g (0.136 mmol) of the compound obtained in the modification step was dissolved in 2 ml of toluene, and 0.09 g (0.186 mmol) of tetrabutylammonium bromide and 0.39 g of sodium hydroxide dissolved in 0.6 ml of water ( 9.75 mmol) and 0.7 g (4.93 mmol) of methyl iodide were added, and the mixture was stirred at 35-37 ° C. for 18 hours under an argon stream. After cooling, 5 ml each of water and toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 5 ml of toluene, and the extracts were combined, washed twice with water, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography (chloroform / methanol = 20/1), and then filtered through a 0.2 μm filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. gave 0.56 g of colorless oil (90.3%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.50 (48H, s), 3.31-3.65 (166H, m), 3.96 (48H, s), 4.44 (24H, s), 5.09 (24H, d, J = 7.7 Hz), 5.15 (24H, d, J = 17.0 Hz), 5.87 (24H, bs), 6.36 (12H, s), 6.47 (24H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 58.1, 58.2, 59.3, 67.2, 70.1, 70.4, 71.5, 71.6, 78.8, 79.1, 79.5, 79.7, 79.8, 73.4, 100.7,106.1, 140.8, 160.2, 117.1, 134.5

(Example 44)
In Example 44, triethanolamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. Triethanolamine: glycidol: 3,5-bis (3-butenyloxy) benzylglycidyl ether was in a ratio (molar ratio) of 1: 9: 12.

Polymerization step Under argon atmosphere, triethanolamine 0.2 g (1.34 mmol) was heated to 90 ° C, potassium methoxide (30% methanol solution) 0.09 g (0.385 mmol) was added thereto, and the mixture was stirred for several minutes and then gradually reduced in pressure. The methanol was distilled off. After 4 ml of diglyme was added and the temperature was raised to 130 ° C., 0.91 g (12.2 mmol) of glycidol was dissolved in 4.5 ml of dehydrated THF, and dropwise added in about 1.5 hours while distilling off THF.

Modification process
After stirring for 30 minutes, 5.0 g (1.4 mmol) of 3,5-bis (3-butenyloxy) benzylglycidyl ether was dissolved in 7 ml of dehydrated THF, and dropwise added over about 3.5 hours while distilling off THF. The mixture was stirred at the same temperature for about 2.5 hours, cooled, diluted with 25 ml of toluene and washed with 20 ml of 0.5% oxalic acid. The mixture was further washed twice with saturated brine and concentrated under reduced pressure. 6.28 g of the residual liquid was purified by silica gel column chromatography (chloroform / methanol = 10/1) to obtain 4.65 g of a yellow oil (yield 77.6%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.50 (48H, s), 2.72 (6H, s), 3.30-3.70 (123H, m), 3.95 (48H, s), 4.43 (24H, s), 5.08 (24H, d, J = 8.2 Hz), 5.15 (24H, d, J = 16.5 Hz), 5.86 (24H, bs), 6.36 (12H, s), 6.45 (24H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 58.1, 58.2, 67.3, 69.5, 69.8, 70.4, 71.9, 72.2, 72.8, 78.7, 73.4, 100.7, 106.2, 140.7, 160.2, 117.1, 134.6)

すなわち、上記修飾工程で得た化合物0.936 g (0.209 mmol)をトルエン3 mlに溶解し、これに臭化テトラブチルアンモニウム 0.09 g (0.28 mmol) および水3 mlに溶解した水酸化ナトリウム0.6 g (15.0 mmol) およびヨウ化メチル 1.07 g (7.54 mmolを加えた。35-37℃で8時間攪拌した後ヨウ化メチル 0.5 g (3.52 mmol)を追加してさらに16時間攪拌した。水、トルエン各10 mlを加えて抽出、分液し、水層を再度10 mlのトルエンで抽出した。抽出液を併せて水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、表題化合物を淡黄色油状物を0.48 g得た(収率54.7%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.49 (48H, s), 3.31-3.70 (153H, m), 3.95 (48H, s), 4.43 (24H, s), 5.08 (24H, d, J = 9.4 Hz), 5.14 (24H, d, J = 16.5 Hz), 5.87 (24H, bs), 6.35 (12H, s), 6.46 (24H, s)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 58.1, 58.2, 67.3, 70.1, 71.6, 78.8, 79.1, 79.5, 79.6, 79.8, 73.4, 100.7, 106.2, 140.8, 160.2, 117.1, 134.5 (Example 45)
Etherification Step In Example 45, the hydroxyl group of the compound obtained in Example 44 was methoxylated with methyl iodide (see the following chemical formula).

That is, 0.936 g (0.209 mmol) of the compound obtained in the above modification step was dissolved in 3 ml of toluene, and 0.6 g (15.0 mg) of sodium hydroxide dissolved in 0.09 g (0.28 mmol) of tetrabutylammonium bromide and 3 ml of water. mmol) and 1.07 g (7.54 mmol) of methyl iodide. After stirring at 35-37 ° C. for 8 hours, 0.5 g (3.52 mmol) of methyl iodide was added and the mixture was further stirred for 16 hours. The aqueous layer was extracted again with 10 ml of toluene, and the combined extracts were washed three times with water, dehydrated with anhydrous sodium sulfate, and concentrated. Chloroform / methanol = 20/1) and then filtered through a 0.2 μm filter as a chloroform solution and concentrated under reduced pressure at 80 ° C. to obtain 0.48 g of the title compound as a pale yellow oil (yield 54.7%). The NMR of this product was measured and the following results were obtained. .
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.49 (48H, s), 3.31-3.70 (153H, m), 3.95 (48H, s), 4.43 (24H, s), 5.08 (24H, d, J = 9.4 Hz), 5.14 (24H, d, J = 16.5 Hz), 5.87 (24H, bs), 6.35 (12H, s), 6.46 (24H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 58.1, 58.2, 67.3, 70.1, 71.6, 78.8, 79.1, 79.5, 79.6, 79.8, 73.4, 100.7, 106.2, 140.8, 160.2, 117.1, 134.5

すなわち、実施例２３の修飾工程で得た化合物0.84 g (0.188 mmol)をトルエン2 mlに溶解し、これに臭化テトラブチルアンモニウム 0.082 g (0.25 mmol)、3,5-ビス(ブテニルオキシ)ベンジルブロミド 0.88 g (2.83 mmol) および水0.7 mlに溶解した水酸化ナトリウム0.51 g (12.75 mmol) を加えた。40℃に加温して20時間攪拌した後水、トルエン各10 mlを加えて抽出、分液した。水層を再度10 mlのトルエンで抽出し、抽出液を併せて水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝100/0〜20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、黄色油状物を0.7 g得た(収率51.5%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.45 (96H, s), 2.69 (6H, bs), 3.38-3.70 (101H, m), 3.89 (96H, s), 4.38 and 4.56 (each 24H, s), 5.05 and 5.10 (each 48H, bs), 5.83 (48H, bs), 6.31 (24H, s), 6.43 and 6.46 (48H, each s)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 67.2, 70.6, 71.0, 72.1, 77.8, 78.7, 79.1, 73.3, 100.6, 106.0, 141.0, 141.4, 160.2, 117.0, 134.6 (Example 46)
In Example 46, 3,5-bis (butenyloxy) benzyl bromide was used as the etherification step for the compound obtained in the modification step of Example 44, and the reaction represented by the following chemical formula was performed.

That is, 0.84 g (0.188 mmol) of the compound obtained in the modification step of Example 23 was dissolved in 2 ml of toluene, and 0.082 g (0.25 mmol) of tetrabutylammonium bromide and 3,5-bis (butenyloxy) benzyl bromide were dissolved therein. 0.88 g (2.83 mmol) and 0.51 g (12.75 mmol) sodium hydroxide dissolved in 0.7 ml water were added. The mixture was heated to 40 ° C. and stirred for 20 hours, followed by extraction with 10 ml of water and toluene, followed by liquid separation. The aqueous layer was extracted again with 10 ml of toluene, and the extracts were combined, washed three times with water, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography (chloroform / methanol = 100/0 to 20/1), and then filtered through a 0.2 μm filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. gave 0.7 g of a yellow oil (yield 51.5%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.45 (96H, s), 2.69 (6H, bs), 3.38-3.70 (101H, m), 3.89 (96H, s), 4.38 and 4.56 (each 24H, s), 5.05 and 5.10 (each 48H, bs), 5.83 (48H, bs), 6.31 (24H, s), 6.43 and 6.46 (48H, each s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 67.2, 70.6, 71.0, 72.1, 77.8, 78.7, 79.1, 73.3, 100.6, 106.0, 141.0, 141.4, 160.2, 117.0, 134.6

(Example 47)
In Example 47, N, N-bis (2,3-dihydroxypropyl) octylamine is used as a core molecule, and 3,5-bis (3-butenyloxy) is used as a glycidyl ether having a polymerizable carbon-carbon double bond. Using benzyl glycidyl ether, a reaction represented by the following chemical formula was carried out. N, N-bis (2,3-dihydroxypropyl) octylamine: glycidol: 3,5-bis (3-butenyloxy) benzylglycidyl ether was in a ratio (molar ratio) of 1:12:16.

Polymerization process Under argon atmosphere, N, N-bis (2,3-dihydroxypropyl) octylamine 0.29 g (1.04 mmol) was heated to 90 ° C and potassium methoxide (30% methanol solution) 0.096 g (0.41 mmol) was added. And stirred for several minutes. The pressure was gradually reduced, methanol was distilled off, 5 ml of diglyme was added, and the temperature was raised to 140 ° C. 0.91 g (12.3 mmol) of glycidol was dissolved in 5 ml of dehydrated THF and added dropwise over about 2 hours while distilling off the THF.

Modification Step Next, 5.0 g (16.4 mmol) of 3,5-bis (3-butenyloxy) benzylglycidyl ether was dissolved in 15 ml of dehydrated THF, and added dropwise over about 6 hours while distilling off THF. After stirring for 2.5 hours at the same temperature, the reaction solution was diluted with 20 ml of chloroform and washed twice with 20 ml of 0.5% oxalic acid and then with water. The mixture was dehydrated with anhydrous sodium sulfate, concentrated, and purified twice by silica gel column chromatography (chloroform / methanol = 10/1). Furthermore, it filtered with a 0.2 micrometer filter as a chloroform solution, and concentrated under reduced pressure at 80 degreeC. 1.35 g of the title compound was obtained as a light brown oil (yield 21.8%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 0.87 (3H, bs), 1.25 (10H, bs), 1.42 (2H, bs), 2.49 (64H, s), 2.61 (6H, b), 3.45- 3.66 (146H, m), 3.95 (64H, s), 3.98 (16H, s), 4.42 (32H, s), 5.08-5.14 (64H, m), 5.86 (32H, bs), 6.35 (16H, s) , 6.45 (32H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 22.8, 27.7, 29.5, 32.0, 33.7, 67.3, 69.5, 71.3, 71.4, 78.8, 73.5, 100.7, 106.2, 140.6, 160.2, 117.1, 134.6

すなわち、上記修飾工程で得た化合物0.85 g (0.14 mmol)をトルエン2.2 mlに溶解し、これに臭化テトラブチルアンモニウム 85 mg (0.26 mmol)、水0.7 mlに溶解した水酸化ナトリウム0.53 g (13.25 mmol)および3,5-ビス(ブテニルオキシ)ベンジルブロミド 0.91 g (2.92 mmol)を加えてアルゴン気流下43-45℃で18時間攪拌した。冷却後水5 ml、トルエン10 mlを加えて抽出、分液した。水層を再度5 mlのトルエンで抽出し、抽出液を併せて水で2回洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（トルエン/エタノール＝100/1〜10/1）で2回精製した。次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、淡褐色油状物を0.35 g得た(25.7%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 0.84 (3H, bs), 1.26 (10H, bs), 1.36 (2H, bs), 2.44 (128H, bs), 3.40-3.70 (146H, m), 3.88 (128H, s), 4.38 (32H, s), 4.56 (32H, s), (5.06-5.11 (128H, m), 5.82 (64H, bs), 6.31 (32H, s), 6.42 - 6.45 (64H, m)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7 (CH2), 67.2 (OCH2), 70.9, 72.2, 78.8, 73.2, 100.7, 106.0, 140.6, 160.2, 117.0, 134.6 (Example 48)
Etherification Step In Example 48, the hydroxyl group of the compound obtained in Example 47 was etherified with 3,5-bis (butenyloxy) benzyl bromide (see the following chemical formula).

That is, 0.85 g (0.14 mmol) of the compound obtained in the above modification step was dissolved in 2.2 ml of toluene, and 85 mg (0.26 mmol) of tetrabutylammonium bromide and 0.53 g (13.25) of sodium hydroxide dissolved in 0.7 ml of water. mmol) and 3,5-bis (butenyloxy) benzyl bromide (0.91 g, 2.92 mmol) were added, and the mixture was stirred at 43-45 ° C. for 18 hours under an argon stream. After cooling, 5 ml of water and 10 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 5 ml of toluene, and the extracts were combined and washed twice with water. The mixture was dehydrated with anhydrous sodium sulfate and concentrated, and the residue was purified twice by silica gel column chromatography (toluene / ethanol = 100/1 to 10/1). Subsequently, it filtered with the 0.2 micrometer filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. gave 0.35 g of a light brown oil (25.7%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 0.84 (3H, bs), 1.26 (10H, bs), 1.36 (2H, bs), 2.44 (128H, bs), 3.40-3.70 (146H, m), 3.88 (128H, s), 4.38 (32H, s), 4.56 (32H, s), (5.06-5.11 (128H, m), 5.82 (64H, bs), 6.31 (32H, s), 6.42-6.45 (64H , m)
¹³ C -NMR ((600 MHz, CDCl ₃ ) δ: 33.7 (CH2), 67.2 (OCH2), 70.9, 72.2, 78.8, 73.2, 100.7, 106.0, 140.6, 160.2, 117.0, 134.6

(Example 49)
In Example 49, N, N-bis (2,3-dihydroxypropyl) benzylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. N, N-bis (2,3-dihydroxypropyl) benzylamine: glycidol: 3,5-bis (3-butenyloxy) benzylglycidyl ether was in a ratio (molar ratio) of 1:12:16.

Polymerization process Under argon atmosphere, N, N-bis (2,3-dihydroxypropyl) benzylamine 0.37 g (1.44 mmol) was heated to 90 ° C., and potassium methoxide (30% methanol solution) 0.13 g (0.56 mmol) And stirred for several minutes. The pressure was gradually reduced, methanol was distilled off, 5 ml of diglyme was added, and the temperature was raised to 130 ° C. 1.28 g (17.3 mmol) of glycidol was dissolved in 5 ml of dehydrated THF and added dropwise over about 2 hours while distilling off the THF.

Modification Step Next, 7.0 g (23.0 mmol) of 3,5-bis (3-butenyloxy) benzylglycidyl ether was dissolved in 15 ml of dehydrated THF, and added dropwise over about 7 hours while distilling off THF. After stirring at the same temperature for 3 hours, the reaction solution was diluted with 50 ml of toluene and washed twice with 30 ml of 0.5% oxalic acid and then with saturated saline. The mixture was dehydrated with anhydrous sodium sulfate, concentrated, and purified twice by silica gel column chromatography (chloroform / methanol = 15/1). Furthermore, it filtered with a 0.2 micrometer filter as a chloroform solution, and concentrated under reduced pressure at 80 degreeC. 4.6 g of the title compound was obtained as a light brown oil (yield 53.5%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.49 (64H, s), 2.58 (4H, br), 3.45-3.65 (148H, m), 3.94 (80H, bs), 4.41 (32H, s), 5.07-5.15 (64H, m), 5.85 (32H, bs), 6.35 (16H, s), 6.41 (32H, s), 7.20 (1H, b), 7.26 (4H, br)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 67.3, 69.3, 71.3, 78.8, 73.4, 100.7, 106.2, 140.7, 160.2, 117.1, 134.6

すなわち、上記修飾工程で得た化合物2.0 g (0.33 mmol)をトルエン5 mlに溶解し、これに臭化テトラブチルアンモニウム 0.2 g (0.62 mmol)、3,5-ビス(ブテニルオキシ)ベンジルブロミド2.15 g (6.91 mmol) および水1.6 mlに溶解した水酸化ナトリウム1.25 g (31.25 mmol) を加えた。40℃に加温して17時間攪拌した後水10 ml、トルエン20 mlを加えて抽出、分液した。抽出液を飽和食塩水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留液をシリカゲルカラムクロマトグラフィー（トルエン/エタノール＝20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、淡褐色油状物を1.6 g得た(収率49.7%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.41 (132H, s), 3.40-3.67 (148H, m), 3.85 (128H, bs), 4.35 (32H, s), 4.53 (32H, bs), 5.04 (128H, bs), 5.80 (64H, bs), 6.28 (32H, bs), 6.40 (64H, bs), 7.20 (1H, b), 7.26 (4H, br)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 67.2, 71.0, 72.1, 79.0, 73.2, 100.6, 105.8, 106.0, 141.0, 141.4, 160.1, 117.0, 134.6 (Example 50)
Etherification Step In Example 50, the hydroxyl group of the compound obtained in Example 49 was etherified with 3,5-bis (butenyloxy) benzyl bromide (see the following chemical formula).

That is, 2.0 g (0.33 mmol) of the compound obtained in the above modification step was dissolved in 5 ml of toluene, and 0.2 g (0.62 mmol) of tetrabutylammonium bromide and 2.15 g of 3,5-bis (butenyloxy) benzyl bromide ( 6.91 mmol) and 1.25 g (31.25 mmol) of sodium hydroxide dissolved in 1.6 ml of water were added. After heating to 40 ° C. and stirring for 17 hours, 10 ml of water and 20 ml of toluene were added for extraction and liquid separation. The extract was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography (toluene / ethanol = 20/1), and then filtered through a 0.2 μm filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. yielded 1.6 g of a light brown oil (yield 49.7%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.41 (132H, s), 3.40-3.67 (148H, m), 3.85 (128H, bs), 4.35 (32H, s), 4.53 (32H, bs), 5.04 (128H, bs), 5.80 (64H, bs), 6.28 (32H, bs), 6.40 (64H, bs), 7.20 (1H, b), 7.26 (4H, br)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 67.2, 71.0, 72.1, 79.0, 73.2, 100.6, 105.8, 106.0, 141.0, 141.4, 160.1, 117.0, 134.6

(Example 51)
In Example 51, tris (hydroxymethyl) aminomethane was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of tris (hydroxymethyl) aminomethane: glycidol: allyl glycidyl ether was 1: 9: 12 (molar ratio).

Polymerization process
The mixture was heated to 90 ° C., and 0.3 g (2.48 mmol) of tris (hydroxymethyl) aminomethane was dissolved in 5 ml of DMSO under an argon atmosphere with vigorous stirring. The mixture was heated to 90 ° C., 0.174 g (0.74 mmol) of potassium methoxide (30% methanol solution) was added and stirred for several minutes, and then the pressure was gradually reduced to distill off methanol. Next, 1.65 g (22.27 mmol) of glycidol was dissolved in 8 ml of dehydrated THF and added dropwise over about 3 hours while distilling off the THF.

Modification Step Next, 3.39 g (29.7 mmol) of allyl glycidyl ether was dissolved in 15 ml of dehydrated THF, and added dropwise over about 4.5 hours while distilling off the THF. The mixture was stirred at the same temperature for 1.5 hours, cooled, diluted with 20 ml of methanol, and neutralized through a column of Amberlite IR-120B H AG 10 ml. After concentration under reduced pressure, the brown residual liquid was purified by silica gel column chromatography (chloroform / methanol = 3/1) to obtain 2.92 g of a light brown oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.43-3.67 (99H, m), 3.87 (12H, s), 4.01 (24H, s), 4.84 (12H, s), 5.16 (12H, d , J = 10.4 Hz), 5.28 (12H, d, J = 17.0 Hz), 5.88-5.94 (12H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 69.3, 69.7, 69.9, 70.9, 71.3, 71.7, 72.9, 78.6, 78.9, 72.0, 116.0, 134.9, 135.0

すなわち、上記修飾工程で得た化合物 1.06 g (0.49 mmol)をトルエン3 mlに溶解し、これに臭化テトラブチルアンモニウム 0.32 g (0.995 mmol) 、水3 mlに溶解した水酸化ナトリウム2.12 g (53.0 mmol) およびヨウ化メチル 1.67 g (11.77 mmol)を加えた。40℃に加温下6時間攪拌した後ヨウ化メチル0.8 g (5.64 mmol)を追加し、さらに1時間拡販した。冷後、水、トルエン各15 mlを加えて抽出、分液した。抽出液を飽和食塩水で2回洗浄した後無水硫酸ナトリウムで脱水、濃縮して残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝7/1）で精製し、微黄色油状物を0.72 g得た(収率63.0%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 3.44 (36H, s), 3.50-3.70 (111H, m), 4.01 (24H, s), 5.17 (12H, d, J = 10.4 Hz), 5.28 (12H, d, J = 17.0 Hz), 5.90-5.92 (12H, m),
¹³C -NMR ((600 MHz, methanol-d₄) δ: 58.1, 59.7, 70.8, 71.3, 72.1, 72.5, 73.3, 80.0, 80.4, 80.8, 81.0, 117.2, 136.2 (Example 52)
Etherification Step In Example 52, the hydroxyl group of the compound obtained in Example 51 was methoxylated with methyl iodide (see the following chemical formula).

That is, 1.06 g (0.49 mmol) of the compound obtained in the above modification step was dissolved in 3 ml of toluene, and 0.32 g (0.995 mmol) of tetrabutylammonium bromide and 2.12 g (53.0 g) of sodium hydroxide dissolved in 3 ml of water. mmol) and 1.67 g (11.77 mmol) of methyl iodide were added. After stirring at 40 ° C. for 6 hours under heating, 0.8 g (5.64 mmol) of methyl iodide was added, and sales were further expanded for 1 hour. After cooling, 15 ml each of water and toluene were added for extraction and liquid separation. The extract was washed twice with saturated brine, dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography (chloroform / methanol = 7/1) to obtain 0.72 g of a pale yellow oil. (Yield 63.0%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.44 (36H, s), 3.50-3.70 (111H, m), 4.01 (24H, s), 5.17 (12H, d, J = 10.4 Hz), 5.28 (12H, d, J = 17.0 Hz), 5.90-5.92 (12H, m),
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 58.1, 59.7, 70.8, 71.3, 72.1, 72.5, 73.3, 80.0, 80.4, 80.8, 81.0, 117.2, 136.2

(Example 53)
In Example 53, di [3,5-bis (hydroxymethyl) phenyl] disulfide was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of di [3,5-bis (hydroxymethyl) phenyl] disulfide: glycidol: allyl glycidyl ether was 1:12:16 (molar ratio).

Polymerization process Dissolve 0.51 g (1.5 mmol) of di [3,5-bis (hydroxymethyl) phenyl] disulfide in 5 ml of DMSO under an argon atmosphere, and heat to 90 ° C while stirring with potassium methoxide (30% methanol solution). 0.14 g (0.60 mmol) was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. Next, 1.34 g (18.1 mmol) of glycidol was dissolved in 7 ml of dehydrated THF and added dropwise over about 2 hours while distilling off the THF.

Modification Step Subsequently, 2.75 g (24.17 mmol) of allyl glycidyl ether was dissolved in 12 ml of dehydrated THF, and dropwise added over about 3.5 hours while distilling off the THF. The mixture was stirred at the same temperature for 1.5 hours, cooled, diluted with 30 ml of methanol, and neutralized through a column of 10 ml of Amberlite IR-120B HAG. After concentration under reduced pressure, the brown residue was purified by silica gel column chromatography (chloroform / methanol = 5/1) to obtain 1.21 g of a light brown oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.42-3.70 (132H, m), 3.87 (16H, s), 4.00 (32H, s), 4.53 (8H, s), 4.81 (16H, s ), 5.16 (16H, m), 5.27 (16H, m), 5.87-5.92 (16H, m), 7.16, 7.30 (6H, br)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 69.4, 69.6, 71.1, 71.3, 71.7, 72.0, 72.8, 78.6, 78.8, 74.7, 117.2, 136.0, 136.2, 125.6, 128.0, 138.2, 140.1

すなわち、上記修飾工程で得た化合物1.21 g (0.40 mmol)をトルエン3 mlに溶解し、これに臭化テトラブチルアンモニウム 0.34 g (1.05 mmol) 、水3 mlに溶解した水酸化ナトリウム2.3 g (57.5 mmol) およびヨウ化メチル 1.8 g (12.7 mmol)を加えた。38℃に加温下19時間攪拌した後、水10 mlおよびトルエン15 mlを加えて抽出、分液した。抽出液を水で4回洗浄した後無水硫酸ナトリウムで脱水、濃縮して残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝10/1）で精製し、微黄色油状物を1.13 g得た(収率86.9%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 3.42 (48H, s), 3.49-3.65 (140H, m), 3.99 (32H, s), 4.52 (8H, s), 5.16 (16H, m), 5.27 (16H, m), 5.88-5.90 (16H, m), 7.14, 7.29 (6H, br)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 57.0, 69.5, 69.9, 70.8, 71.3, 72.0, 72.6, 74.6, 78.5, 78.7, 115.9, 134.9, 124.1, 126.8, 137.2, 139.6 (Example 54)
Etherification Step In Example 54, the hydroxyl group of the compound obtained in Example 53 was methoxylated with methyl iodide (see the following chemical formula).

That is, 1.21 g (0.40 mmol) of the compound obtained in the above modification step was dissolved in 3 ml of toluene, and 0.34 g (1.05 mmol) of tetrabutylammonium bromide and 2.3 g (57.5 mg) of sodium hydroxide dissolved in 3 ml of water. mmol) and 1.8 g (12.7 mmol) of methyl iodide were added. After stirring at 38 ° C. for 19 hours while heating, 10 ml of water and 15 ml of toluene were added for extraction and liquid separation. The extract was washed four times with water, dehydrated with anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography (chloroform / methanol = 10/1) to obtain 1.13 g of a slightly yellow oil (yield). (Rate 86.9%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.42 (48H, s), 3.49-3.65 (140H, m), 3.99 (32H, s), 4.52 (8H, s), 5.16 (16H, m ), 5.27 (16H, m), 5.88-5.90 (16H, m), 7.14, 7.29 (6H, br)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 57.0, 69.5, 69.9, 70.8, 71.3, 72.0, 72.6, 74.6, 78.5, 78.7, 115.9, 134.9, 124.1, 126.8, 137.2, 139.6

<Evaluation>
The polymerizable hyperbranched polymers of Examples 1 to 54 had a lower viscosity than conventional prepolymers and were easy to handle in and out of containers. Further, when stored in a cool and dark place, the polymer was not solidified without adding a polymerization inhibitor and could be stored stably. Moreover, by adding a small amount of an initiator to these polymerizable hyperbranched polymers and irradiating with light, photocuring could be carried out by either radical photopolymerization or cationic photopolymerization.

<Viscosity measurement>
For the polymerizable hyperbranched polymers of Examples 7, 9, 11, 18, 20, 26, 29, 31 and 35, the viscosity was measured using a vibration viscometer. As a result, as shown in Table 1, it was in the range of 170 to 378 mPa · s, and the viscosity was much lower than that of the conventional prepolymer.

  The present invention can be used as a material for photolithography in the production of electronic devices.

Claims (14)

  It is characterized in that the terminal hydroxyl group of a highly branched polymer in which glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as a starting point is added to the epoxy group of a glycidyl ether having a polymerizable carbon-carbon double bond. Polymerizable hyperbranched polymer.   The polymerization according to claim 1, wherein the polymerizable glycidyl ether having a carbon-carbon double bond is any of allyl glycidyl ether and 3,5-bis (3-butenyloxy) benzyl glycidyl ether. Highly branched polymer.   Core molecules are glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, polyethylene glycol, 1,4-butanediol, 1,2,4-butanetriol, triethanolamine, N, N-bis (2,3-dihydroxypropyl) ) Benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine, N-phenyldiethanolamine and 2-phenyl- The polymerizable hyperbranched polymer according to claim 1, which is any one of 1,3-propanediol. A polymerization process in which a glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as a base point to form a highly branched polymer;
And a modification step of introducing a polymerizable functional group by adding a hydroxyl group of the hyperbranched polymer to an epoxy group of a glycidyl ether having a polymerizable carbon-carbon double bond. Production method.   The polymerizable hyperbranched structure according to claim 4, wherein the glycidyl ether having a polymerizable carbon-carbon double bond is allyl glycidyl ether or 3,5-bis (3-butenyloxy) benzyl glycidyl ether. A method for producing a polymer.   The core molecule is glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, polyethylene glycol, 1,4-butanediol, 1,2,4-butanetriol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine, N-phenyldiethanolamine and 2-phenyl The method for producing a polymerizable hyperbranched polymer according to claim 3, which is any one of -1,3-propanediol.   The terminal hydroxyl group of the hyperbranched polymer in which the glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as the starting point has a structure in which it is added to the epoxy group of the glycidyl ether having a polymerizable carbon-carbon double bond. A polymerizable hyperbranched polymer having a structure in which a hydroxyl group produced by ring-opening of the epoxy group is etherified.   The polymerizable hyperbranched structure according to claim 7, wherein the polymerizable glycidyl ether having a carbon-carbon double bond is allyl glycidyl ether or 3,5-bis (3-butenyloxy) benzyl glycidyl ether. polymer.   The core molecule is glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, polyethylene glycol, 1,4-butanediol, 1,2,4-butanetriol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine, N-phenyldiethanolamine and 2-phenyl The polymerizable hyperbranched polymer according to claim 7 or 8, which is any one of -1,3-propanediol.   10. The etherification of a hydroxyl group produced by ring opening of an epoxy group is allyl etherification, methyl etherification, or 3,5-bis (butenyloxy) benzyl etherification. The polymerizable hyperbranched polymer according to Item. A polymerization process in which a glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as a base point to form a highly branched polymer;
A modification step of introducing a polymerizable functional group by adding a hydroxyl group of the hyperbranched polymer to an epoxy group of a glycidyl ether having a polymerizable carbon-carbon double bond;
An etherification step of etherifying a hydroxyl group generated by ring opening of the epoxy group in the addition;
A process for producing a polymerizable hyperbranched polymer, comprising:   The polymerizable hyperbranched structure according to claim 11, wherein the polymerizable glycidyl ether having a carbon-carbon double bond is allyl glycidyl ether or 3,5-bis (3-butenyloxy) benzyl glycidyl ether. A method for producing a polymer.   The core molecule is glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, polyethylene glycol, 1,4-butanediol, 1,2,4-butanetriol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine, N-phenyldiethanolamine and 2-phenyl The method for producing a polymerizable hyperbranched polymer according to claim 11 or 12, which is any one of -1,3-propanediol.   14. The etherification of a hydroxyl group generated by ring opening of an epoxy group is allyl etherification, methyl etherification, or 3,5-bis (butenyloxy) benzyl etherification. A method for producing the polymerizable hyperbranched polymer according to Item.