JP4297353B2 - Multi-branched macromonomer having a plurality of alkyl groups and hydroxyl groups and method for producing the same - Google Patents

Description

  The present invention relates to a multibranched macromonomer (hyperbranched polymer) having one oxetanyl group and a plurality of hydroxyl groups, and a method for producing the same.

  In recent years, polymers with a structure different from linear polymers such as dendrimers, hyperbranched polymers, star polymers, graft polymers, brush polymers, etc. are attracting attention because they have new functions and new performance different from linear polymers. Collecting. Among these, graft polymers and brush polymers are synthesized by a reaction between a polymer and a polymer or a reaction between a polymer and a monomer. That is, a method in which a polymerization initiating species is generated on a polymer and a monomer is polymerized therefrom, or a growth polymer and a polymer chain having a stopping function are coupled. However, these methods may have some drawbacks, such as by-product of trunk and branch homopolymers and / or uneven branch lengths.

  In addition to these, a macromonomer that can be said to be a third method has recently been actively studied. In addition, a macromonomer has a functional group which has high molecular weight to some extent (usually about several hundred to 10,000) and can be polymerized. By synthesizing such a macromonomer with a primary structure controlled and copolymerizing with other monomers, it is possible to easily synthesize a graft polymer having a uniform branch length (for example, non-patented). Reference 1). The macromonomer used for synthesizing the graft polymer or the brush polymer is linear.

On the other hand, recently, dendrons (dendrimer subunits) having a multi-branched structure have been introduced into macromonomers, and studies have been conducted on the synthesis of polydendrons having a dendritic site in the side chain. For example, it has been reported that a polydendron can be obtained by synthesizing a dendritic macromonomer by the reaction of a polyethyldendron having a hydroxyl group in the core with chloromethylstyrene, and then radically copolymerizing with the styrene monomer ( For example, refer nonpatent literature 2). In addition, it has been reported that a polydendron having a degree of polymerization (DP) = 6.7 can be obtained by synthesizing a second generation polyether dendron having a methacryloyl group and carrying out radical polymerization alone. For example, refer nonpatent literature 3).
Similar to dendrons, those using hyperbranched polymers having a multi-branched structure as macromonomers have also been reported (see, for example, Non-Patent Document 4).

  In addition, it has been reported that heterotelechelic hyperbranched polyethers having one oxetanyl group and many hydroxyl groups in the molecule can be obtained by anion ring-opening polymerization of (3-alkyl-3-hydroxymethyl) oxetanes. (For example, refer nonpatent literature 5).

  As a method for producing a hyperbranched polymer using an oxetane compound, a method based on a polyaddition reaction between an oxetane compound and a polyfunctional carboxylic acid compound is known (for example, see Patent Document 1). Moreover, about the reaction of an oxetanyl group and phenols, the method of manufacturing a polyaddition copolymer from a bisoxetane compound and bisphenol is known (for example, refer patent document 2).

JP 2002-3585 A JP-A-11-279277 Yusuke Kawakami, Chemical Review, 71-82 (1993) C. J. Hawker, M. J. Frechet, Polymer, 33, 1507-1512, (1992) Y. M. Chen, C.F. Chen, W.H. Liu, Y. E. Li, F. Xi, Macromol. Rapid Commun, 17, 401-407, (1996) C. Lach, R. Hanselmann, H. Frey, R. Mulhaupt, Macromol.Rapid Commun, 19,461-465, (1998) H. Kudo, A. Morita, T. Nishikubo, Polymer J. 35, 88-91, (2003)

  To provide a multi-branched macromonomer having a plurality of primary hydroxyl groups that can be bonded to a compound having a polymerizable group such as a vinyl group or an epoxy group or a compound having a functional group such as a carboxyl group. And it is providing the manufacturing method.

In order to solve the above problems, the present inventors have conducted various studies. As a result, the oxetane group and a plurality of hydroxyl groups in a molecule obtained by anionic ring-opening polymerization of an oxetane compound having a hydroxyl group are obtained. The above-mentioned problem is caused by a multibranched macromonomer having a plurality of hydroxyl groups (referred to as a multibranched macromonomer) obtained by polyaddition reaction of a multibranched polyether compound (referred to as a multibranched polyether compound) with a polyvalent carboxylic acid. I found that it can be solved. Moreover, the manufacturing method for obtaining this multibranched macromonomer is provided.
Hereinafter, the present invention will be described in detail.

The multibranched macromonomer of the present invention and the production method thereof will be described.
Oxetane compound having a hydroxyl group Examples of the oxetane compound having a hydroxyl group used for the synthesis of a multi-branched polyether compound include the following formula (1).

R ₁ in the formula (1) represents an alkyl group having 1 to 4 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms having a hydroxyl group.

The R ₁ in the formula (1), an alkyl group which may have a branch having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, more preferably an ethyl group. R ₂ is a C 1-4 alkyl group having a hydroxyl group, and is preferably a hydroxymethyl group. Specific examples include 3-ethyl-3-hydroxymethyloxetane and 3-methyl-3-hydroxymethyloxetane.

○ Multi-branched polyether compound having one oxetanyl group and a plurality of hydroxyl groups Having one oxetanyl group and a plurality of hydroxyl groups in the molecule by anionic ring-opening polymerization of the compound represented by formula (1) Multi-branched polyether compounds can be synthesized. As an initiator for this anion ring-opening polymerization, alkali zinc, alkali metal hydroxide, alkali metal alkoxide, organozinc such as diethyl zinc, aluminum porphyrin complex, combined use system of alkali metal alkoxide and crown ether, etc. can be used. A combined system of an alkali metal alkoxide and a crown ether is preferred.

  Examples of the alkali metal alkoxide used for anion ring-opening polymerization include sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, t-butoxy sodium, t-butoxy potassium and the like.

  Examples of the crown ether include 12-crown-4, 15-crown-5, 18-crown-6, cis-dicyclohexano-18-crown-6, 21-crown-7, and 24-crown-8. Is mentioned.

A multibranched macromonomer having a plurality of hydroxyl groups The multibranched macromonomer of the present invention can be obtained by polyaddition reaction of a multibranched polyether compound and a polyvalent carboxylic acid.
As the polyaddition reaction, it is preferable to use a quaternary onium salt, a crown ether complex, a tertiary amine, or the like as a catalyst and carry out the polyaddition reaction in the presence of these. Among these catalysts, the use of a quaternary onium salt or a crown ether complex is more preferable from the viewpoint of the reactivity between the oxetane ring and the polyvalent carboxylic acid.

○ Polyvalent carboxylic acid The polyvalent carboxylic acid for obtaining the multibranched macromonomer of the present invention is a compound having 2 or more, preferably 2 to 200 carboxyl groups in the molecule, more preferably 2 to 2 It is a compound having 150 carboxyl groups.

  Dicarboxylic acids, which are compounds having two carboxyl groups in the molecule, include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecane Linear aliphatic saturated dicarboxylic acid having 2 to 20 carbon atoms, such as diacid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonadecanedioic acid and eicosanedioic acid, methyl Branches having 3 to 20 carbon atoms such as malonic acid, ethylmalonic acid, n-propylmalonic acid, n-butylmalonic acid, methylsuccinic acid, ethylsuccinic acid and 1,1,3,5-tetramethyloctylsuccinic acid Chain aliphatic saturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, γ-methylcitraconic acid, mesacone , Γ-methyl mesaconic acid, itaconic acid and glutaconic acid, etc., linear or branched aliphatic unsaturated dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, methylhexahydroisophthalic acid Acid and tetrahydrophthalic acid such as methylhexahydroterephthalic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-1,6-dicarboxylic acid, cyclohexene-3,4-dicarboxylic acid and cyclohexene-4,5-dicarboxylic acid, cyclohexene Such as tetrahydroisophthalic acid such as 1,3-dicarboxylic acid, cyclohexene-1,5-dicarboxylic acid and cyclohexene-3,5-dicarboxylic acid, cyclohexene-1,4-dicarboxylic acid and cyclohexene-3,6-dicarboxylic acid Te Lahydroterephthalic acid, 1,3-cyclohexadiene-1,2-dicarboxylic acid, 1,3-cyclohexadiene-1,6-dicarboxylic acid, 1,3-cyclohexadiene-2,3-dicarboxylic acid, 1,3 -Dihydrophthalic acid such as cyclohexadiene-5,6-dicarboxylic acid, 1,4-cyclohexadiene-1,2-dicarboxylic acid and 1,4-cyclohexadiene-1,6-dicarboxylic acid, 1,3-cyclohexadiene Dihydroisophthalic acid such as 1,3-dicarboxylic acid and 1,3-cyclohexadiene-3,5-dicarboxylic acid, 1,3-cyclohexadiene-1,4-dicarboxylic acid, 1,3-cyclohexadiene-2, 5-dicarboxylic acid, 1,4-cyclohexadiene-1,4-dicarboxylic acid and 1,4-cyclohexadiene-3,6-dicar Dihydroterephthalic acid such as acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (trade name: nadic acid) and methyl -Saturated or unsaturated alicyclic dicarboxylic acids such as endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (trade name: methylnadic acid), chlorendic acid, phthalic acid Terephthalic acid, isophthalic acid, 3-methylphthalic acid, 3-ethylphthalic acid, 3-n-propylphthalic acid, 3-isopropylphthalic acid, 3-n-butylphthalic acid, 3-isobutylphthalic acid, 3-sec-butylphthalic acid And 3-alkylphthalic acid such as 3-tert-butylphthalic acid, 4-methylphthalic acid, 4-ethylphthalic acid, 4-n 4-alkylphthalic acid such as -propylphthalic acid, 4-isopropylphthalic acid, 4-n-butylphthalic acid, 4-isobutylphthalic acid, 4-sec-butylphthalic acid and 4-tert-butylphthalic acid, 2-methylisophthalic acid 2-ethylisophthalic acid, 2-n-propylisophthalic acid, 2-isopropylisophthalic acid, 2-n-butylisophthalic acid, 2-isobutylisophthalic acid, 2-sec-butylisophthalic acid and 2-tert-butylisophthalic acid 2-alkylisophthalic acid, 4-methylisophthalic acid, 4-ethylisophthalic acid, 4-n-propylisophthalic acid, 4-isopropylisophthalic acid, 4-n-butylisophthalic acid, 4-isobutylisophthalic acid, 4- sec-butylisophthalic acid and 4-tert-butylisophthalic acid 4-alkylisophthalic acid, 5-methylisophthalic acid, 5-ethylisophthalic acid, 5-n-propylisophthalic acid, 5-isopropylisophthalic acid, 5-n-butylisophthalic acid, 5-isobutylisophthalic acid, 5- 5-alkylisophthalic acid such as sec-butylisophthalic acid and 5-tert-butylisophthalic acid, methylterephthalic acid, ethylterephthalic acid, n-propylterephthalic acid, isopropylterephthalic acid, n-butylterephthalic acid, isobutylterephthalic acid, sec -Alkyl terephthalic acid such as butyl terephthalic acid and tert-butyl terephthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-1,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid Acid, naphthalene-1 6-dicarboxylic acid, naphthalene-1,7-dicarboxylic acid, naphthalene-1,8-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, Anthracene-1,3-dicarboxylic acid, anthracene-1,4-dicarboxylic acid, anthracene-1,5-dicarboxylic acid, anthracene-1,9-dicarboxylic acid, anthracene-2,3-dicarboxylic acid and anthracene-9,10 Specific examples include aromatic dicarboxylic acids such as -dicarboxylic acid, 2,2'-bis (carboxyphenyl) hexafluoropropane, and the like.

  Examples of polycarboxylic acids having three carboxyl groups in the molecule include aliphatic tricarboxylic acids such as tricarballylic acid, citric acid, isocitric acid and aconitic acid, and aromatic tricarboxylic acids such as hemimellitic acid, trimellitic acid and trimesic acid Is mentioned.

As polycarboxylic acid having 4 or more carboxyl groups in the molecule,
Aliphatic tetracarboxylic acids having 4 to 13 carbon atoms, such as 1,2,3,4-butanetetracarboxylic acid, alicyclic tetracarboxylic acids such as maleated methylcyclohexene tetracarboxylic acid, merophanic acid, planitic acid And aromatic tetracarboxylic acids such as pyromellitic acid and benzophenonetetracarboxylic acid, hexahydromellitic acid, benzenepentacarboxylic acid, and mellitic acid.

○ Quaternary onium salt Tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium iodide, n-dodecyltrimethylammonium bromide, octadecyltrimethyl Ammonium bromide, trimethylbenzylammonium bromide, cetyldimethylbenzylammonium chloride, cetyldimethylbenzylammonium bromide, cetylpyridium sulfate, tetraethylammonium acetate, trimethylbenzylammonium benzoate, trimethylbenzylammonium borate, 5-benzyl-1,5-diazabi Quaternary ammonium salts such as cyclo [4,3,0] -5-nonenium chloride and 5-benzyl-1,5-diazabicyclo [4,3,0] -5-nonenium tetrafluoroborate, and tetrabutyl Phosphonium bromide, tetrabutylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, triphenylmethoxymethylphosphonium chloride, triphenylmethylcarbonylmethylphosphonium chloride , Triphenylethoxycarbonylmethylphosphonium chloride, trioctylbenzyl borophonium chloride, trioct Methyl phosphonium chloride, trioctyl ethyl phosphonium acetate, tetra-octyl phosphonium chloride, and trioctyl ethyl phosphonium dimethylphosphate quaternary phosphonium salts phosphate and the like.
Among these, quaternary phosphonium salts are preferably used, and tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, or tetrabutylphosphonium chloride is particularly preferable.

-Quaternary onium salt concentration The addition reaction of the multi-branched polyether compound and the polyvalent carboxylic acid is preferably performed in the presence of a catalyst. The amount of the catalyst used is preferably 1 to 40 mol%, more preferably 2 to 20 mol%, based on the multi-branched polyether compound. If the amount of catalyst is less than 1 mol%, the reaction may hardly proceed. On the other hand, even if it is used in a proportion exceeding 40 mol%, no particular effect is observed.

Reaction temperature and reaction time The reaction temperature of the multi-branched polyether compound and the polyvalent carboxylic acid is preferably in the range of 100 to 200 ° C, more preferably in the temperature range of 120 to 180 ° C. When the reaction temperature is 100 ° C. or lower, a long reaction time may be required to obtain a sufficient polymer yield. When the reaction temperature exceeds 200 ° C. or higher, a polymer having a sufficient molecular weight may not be obtained. is there. On the other hand, the reaction time is not particularly limited, but a reaction time of 10 to 50 hours is appropriate in consideration of the reaction temperature.

○ Solvent at the time of reaction In the above reaction, a solvent can be used, and examples thereof include toluene, anisole, N, N-dimethylacetamide, N-methylpyrrolidone, chlorobenzene, ortho-chlorobenzene, and dimethyl sulfoxide. It is not limited to these. The reaction can also be carried out without a solvent.

  The multibranched macromonomer of the present invention has a multibranched structure and can be expected to have superior characteristics as compared with general linear polymers. In particular, the multibranched macromonomer of the present invention is characterized by excellent solubility in various solvents. In addition, since the multibranched macromonomer obtained in the present invention has a primary hydroxyl group in the side chain, a functional group having various functions can be introduced, so that a molecular design considering the expression of the function is possible. . For example, by introducing a methacryloyl group as a radical photopolymerizable group and a carboxyl group as an alkali developable group, it can be used as a negative photosensitive resin capable of alkali development.

<Example>
EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In this example, the number average molecular weight is Mn, the mass average molecular weight is Mw, the molecular weight distribution is Mw / Mn, and the degree of polymerization is D.P. P. , The esterification rate E. , The reaction rate R. , The degree of branching B. IR spectrum is abbreviated as IR, nuclear magnetic resonance as NMR, and gel permeation chromatography as GPC.

<Synthesis Example 1>
Synthesis of Poly (EHO) 100 mmol eggplant type flask with 3-ethyl-3-hydroxymethyloxetane (EHO) 100 mmol, potassium tert-butoxide (t-BuOK) 10 mol%, 18-Crown-6 (18-C -6) was added at 10 mol% and N-methyl-2-pyrrolidone (NMP) (20 mL) and stirred at 180 ° C. for 2 hours. After completion of the reaction, the reaction solution was placed in distilled water, acidified using diluted hydrochloric acid, and the precipitated solid was collected by filtration. The acid precipitate was purified by reprecipitation using tetrahydrofuran (THF) as a good solvent and n-hexane as a poor solvent, and then dried under reduced pressure to obtain a white powder.
Yield: 8.0 g (69%)
Mn: 700, Mw / Mn: 1.24
D. B. : 0.18
IR (film, cm ⁻¹ ): 3365 (O—H), 1109, 1051 (C—O—C ether), 990 (C—O—C oxetane ring)
¹ H-NMR (500 MHz, DMSO-d ₆ TMS) δ ppm: 0.78 (m, —CH ₃ ), 1.25 (m, —CH ₂ CH ₃ ), 1.60 (m, —CH ₂ CH _{3 end group), 2.70-3.30 (m} , -OCH 2, -CH 2 OH), 3.42 (s, -CH 2 O- end group), 4.16 (s, -CH 2 OH ), 4, 42 (AB quartet, 0.66H, —CH ₂ O-oxetane ring)
* ¹³ C-NMR (125 MHz, DMSO-d ₆ , TMS) δ ppm: 7.60, 8.04, 22.0-23.2, 26.5, 40.0, 43.3, 62.0, 71 .6,73.4,77.1
This white powder was determined to be a multi-branched macromonomer (Poly (EHO)) having one oxetane ring in the molecule from analysis of various analysis data.

<Synthesis Example 2>
Synthesis of 3,3-bis (hydroxymethyl) oxetane (BHO) In a 300 mL eggplant-shaped flask, 0.37 mol of pentaerythritol, 0.5 mol of diethyl carbonate, and 3 mmol of potassium carbonate were added and stirred at 110 ° C. for 12 hours. Then, the mixture was further stirred at room temperature for 12 hours. Thereafter, ethanol as a by-product and unreacted diethyl carbonate were removed from the reaction solution by atmospheric distillation. Thereafter, the crude product was purified by distillation under reduced pressure to obtain a colorless and transparent solid.
Yield 18g (42%)
Boiling point 147 ° C. (107 Pa, literature value: 148-160 ° C. (1 mmHg))
IR (film, cm ⁻¹ ): 3314 (OH), 1109, 1053 (C—O—C ether), 983 (C—O—C oxetane ring)
¹ H-NMR (500 MHz, DMSO-d ₆ , TMS) δ ppm: 3.55 (d, 4.0 H, J = 5.4 Hz), 4.27 (S, 4.0 H), 4.75 (t , 2.0H, J = 5.4Hz)
* ¹³ C-NMR (125 MHz, DMSO-d ₆ , TMS) δ ppm: 44.9 (C), 62.0 (CH ₂ ), 74.0 (CH ₂ )

<Synthesis Example 3>
○ Poly (EHO) homopolymerization Add 50 mmol of Poly (EHO) synthesized above, 5 mol% of tetraphenylphosphonium bromide (TPPB), and 1.5 mL of NMP into a 50 mL two-necked eggplant-shaped flask and replace with nitrogen. Then, the reaction was carried out at 160 ° C. for 12 hours or 24 hours. After completion of the reaction, the reaction solution was diluted with chloroform, transferred to a separatory funnel, and washed 5 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and reprecipitation purification was performed twice using n-hexane to obtain a brown solid.
The yields, molecular weights and molecular weight distributions of those subjected to the reaction for 12 hours and 24 hours are shown below.
Reaction time Yield Molecular weight Mn Mw / Mn
・ 12 hours 95% 800 1.23
・ 24 hours 93% 1100 1.52

When the reaction was carried out for 12 hours, there was almost no change in the value of Poly (EHO), but when the reaction was carried out for 24 hours, both the molecular weight and the molecular weight distribution increased compared to Poly (EHO).
Moreover, as a result of measuring GPC of the brown solid, what was reacted for 12 hours was almost the same as the pattern of Poly (EHO). However, when the reaction time was 24 hours, a new shoulder appeared on the high molecular weight side. This indicates that in the case of reaction for 24 hours, the homopolymerization of Poly (EHO) proceeds slightly.

<Synthesis Example 4>
○ Anionic ring-opening polymerization of BHO (Poly (BHO))
In a sliding test tube, 3 mmol of BHO, 10 mol% of t-BuOK, 10 mol% of 18-C-6, and 0.6 mL of NMP were added, and the reaction was performed at 180 ° C. for 24 hours. After completion of the reaction, the reaction solution was placed in a large amount of methanol, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 60 ° C. to obtain a brown powder (Poly (BHO)). In addition, since the obtained brown powder was insoluble in various organic solvents, acetylation was performed.
A 20 mL eggplant-shaped flask was charged with 0.2 g of the Poly (BHO) obtained above, 3.2 mL of acetic anhydride, and 1.0 mL of pyridine, and refluxed for 3 hours. After the reaction, the reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering off the desiccant, the solvent was distilled off under reduced pressure to obtain a brown viscous liquid (Poly (BHO) -Ac).
Yield: 96%
Mn: 3700, Mw / Mn: 1.64
D. B. : 0.51 (calculated from the signal value of ¹³ C-NMR of quaternary carbon. Y. Chen, M. Bednarek, P. Kubisa, S. Penczek, J. Polym. Chem. Part A: Polym. Chem., 40 , 1991 (2002))

<Synthesis Example 5>
○ Cationic ring-opening polymerization of Poly (BHO) 0.3 mmol of Poly (BHO) -Ac (D.B. = 0.30) in a test tube with sliding, and 3-ethyl-3- 3 in the charge ratio shown in Table 1 (Phenoxymethyl) oxetane (EPO) and chloroform were added and cooled to 0 ° C. Thereafter, 10 mol% of boron trifluoride ethyl ether complex compound was added as an initiator, and the reaction was carried out at 0 ° C. for 24 hours. Then, after a small amount of pyridine was added to stop the reaction, the reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering the desiccant, reprecipitation purification was performed using n-hexane for Run 1 and methanol for Run 2 and Run 3 as a poor solvent, and dried under reduced pressure at room temperature to obtain a white polymer. The results are shown in Table 1.

  In the multibranched macromonomer obtained by polymerizing Poly (BHO) and EPO described above, the same multibranched macromonomer can be obtained even if Poly (EHO) is used instead of Poly (BHO). In addition, a multibranched macromonomer can be obtained in the same manner using another oxetane compound instead of EPO.

Synthesis of TMA-poly (EHO) by addition reaction of trifunctional carboxylic acid and Poly (EHO) 0.1 mmol of 1,3,5-benzenetricarboxylic acid (TMA) in a 50 mL two-necked eggplant type flask After 0.3 mmol of (EHO), 5 mol% of TPPB and 1.5 mL of NMP were substituted with nitrogen, the reaction was performed at 160 ° C. for 12 hours. After completion of the reaction, the reaction solution was diluted with chloroform, transferred to a separatory funnel, and washed 5 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and reprecipitation purification was performed twice using n-hexane to obtain a brown solid (TMA-poly (EHO)).
Yield: 0.17 g (83%)
・ D. E. = 94%
IR (film, cm ⁻¹ ): 3460 (O—H), 1740 (C = O ester), 1486 (C = C aromatic), 1240 (C—O—C ester), l109, 1038 (C—O) -C ether)
¹ H-NMR (500 MHz, CDCl ₃ , TMS) δ ppm: 0.73-0.76 (m, 35.0), 0.84-0.87 (m, 8.6), 1.26-1 .27 (m, 22.7), 1.30-1.32 (m, 5.4), 1.70-1.80 (m, 0.60), 3.07-3.38 (m, 54.1), 3.79-4.19 (28.8), 4.19 (s, 0.9), 4.42 (AB quartet, 0.66), 8.63-8.66 (m , 3.0)

As a result of GPC measurement of the obtained brown solid, the peak was shifted to the polymer side, and the peak of Poly (EHO) almost disappeared. Moreover, the peak shifted to the polymer side showed unimodality.
TMA-poly (EHO), which is the multibranched macromonomer obtained here, can be used as one that can easily give various functional groups.

Synthesis of TPA-poly (EHO) by addition reaction of bifunctional carboxylic acid and Poly (EHO) 1 mmol of terephthalic acid (TPA), 2 mmol of Poly (EHO), 5 mol of TPPB in a 100 mL two-necked eggplant type flask %, NMP (5 mL) was added, and the atmosphere was replaced with nitrogen, followed by reaction at 160 ° C. for 12 hours. After completion of the reaction, the reaction solution was poured into distilled water, acidified using diluted hydrochloric acid, and the precipitated solid was collected by filtration. Thereafter, reprecipitation purification was performed using THF as a good solvent and n-hexane as a poor solvent, followed by drying under reduced pressure to obtain a brown solid (TPA-poly (EHO)).
Yield: 1.26 g (81%)
・ D. E. = 93%
IR (film, cm ⁻¹ ): 3460 (O—H), 1740 (C = O ester), 1486 (C = C aromatic), 1240 (C—O—C ester), 1109, 1038 (C—O) -C ether)
¹ H-NMR (500 MHz, DMSO-d ₆ , TMS) δ ppm: 0.73-0.76 (m, 35.0), 0.84-0.87 (m, 8.6), 1.26 -1.27 (m, 22.7), 1.30-1.32 (m, 5.4), 1.70-1.80 (m, 0.78), 3.10-3.42 ( m, 80.1), 4.19 (s, 0.9), 4.42 (AB quotet, 0.66, oxane ring), 8.10-8.20 (m, 4.0)

As a result of measuring GPC for the obtained brown solid, the peak of Poly (EHO) disappeared and the peak was shifted to the high molecular weight side.
The multi-branched macromonomer obtained here, TPA-poly (EHO), can be used as one that can easily give various functional groups.

<Synthesis Example 6>
Synthesis of CRA derivative having ethyl ester residue (CRA-COOEt) In a 100 mL eggplant type flask, 2 mmol of calixarene (CRA), 24 mmol of anhydrous potassium carbonate, 0.05 mmol of tetrabutylammonium bromide (TBAB), NMP 7 mL was added and stirred at room temperature for 12 hours. Thereafter, bromobutyric acid ethyl ester (BBE) was added to the reaction solution, and the mixture was stirred at 75 ° C. for 48 hours in a nitrogen atmosphere. After the reaction, the salt was removed by filtration, diluted with acetic acid ethyl ester, and washed 5 times with distilled water. The ethyl acetate layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the ethyl acetate was distilled off under reduced pressure. This residue was purified by reprecipitation twice using n-hexane (CRA-COOEt).
Yield: 0.51 g (18%)
・ D. E. : 100%
IR (film, cm ^-1 ): 1733 (C-O ester), 1584, 1503, (C = C aromatic), 1177 (C-O-C ether)
^{· 1 H-NMR (500MHz,} CDC1 3, TMS) δ (ppm): 1.20~1.30 (m, 6.0), 1.40~1.50 (m, 3.0), 4. 00 to 4.20 (m, 16.0) 4.65 to 4.74 (m, 1.0), 5.90 to 7.25 (m, 2.0)
・ Mass spectrometry (MALDI-TOF MS)
matrix: 2,5-dihydroxybenzoic acid
Calculated value (m / s) 1457.76 [M + Na] ⁺
Actual value (m / s) 1460.76 [M + Na] ⁺

<Synthesis Example 7>
○ Synthesis of CRA derivative having carboxyl group (octafunctional carboxylic acid, CRA-COOH) 0.2 mmol of CRA-COOEt previously synthesized in a 100 mL eggplant type flask, 3.2 mmol of potassium hydroxide, 5 mol% of TBAB And 10 mL of distilled water were added and stirred at 90 ° C. for 72 hours. After completion of the reaction, the solution was dropped into an aqueous citric acid solution to precipitate a solid. The solid was collected by filtration and dried at room temperature for 24 hours to obtain a white solid (CRA-COOH).
Yield: 0.21 g (82%)
・ D. R. = 100%
IR (film, cm ⁻¹ ): 3408 (O—H), 1731 (C═O), 1499 (C═C aromatic), 1188 (C—O—C ether)
^{· 1 H-NMR (500MHz,} CDC1 3, TMS) δ (ppm): 1.40~1.50 (m, 3.0), 4.00~4.19 (m, 12.0), 4. 65 to 4.74 (m, 1.0), 5.90 to 7.25 (m, 2.0)
・ Mass spectrometry (MALDI-TOF MS)
matrix: 2,5-dihydroxybenzoic acid
Calculated value (m / s) 1319.76 [M + Na] ⁺
Actual value (m / s) 1320.76 [M + Na] ⁺

O Synthesis of CRA-poly (EHO) by addition reaction of CRA-COOH and Poly (EHO). 1 mmol, 0.8 mmol of Poly (EHO), 5 mol% of TPPB, and 2 mL of NMP were added, and the atmosphere was purged with nitrogen, followed by reaction at 160 ° C. for 12 hours. After completion of the reaction, the reaction solution was poured into distilled water, acidified using diluted hydrochloric acid, and the precipitated solid was collected by filtration. Thereafter, reprecipitation purification was performed using THF as a good solvent and n-hexane as a poor solvent, followed by drying under reduced pressure to obtain a brown solid.
・ Recovery amount: 0.59 g (85%)
・ D. E. = 62%
IR (film, cm ⁻¹ ): 3460 (O—H), 1740 (C = O ester), 1486 (C = C aromatic), 1240 (C—O—C ester), 1109, 1038 (C—O) -C ether)
¹ H-NMR (500 MHz, DMSO-d ₆ , TMS) δ ppm: 0.73-0.76 (m, 350.0), 1.12-1.20 (m, 216.0), 1.36 -1.40 (m, 14, 7), 1.70-1.80 (m, 0.44), 3.07-3.38 (m, 656.0), 4.42 (AB quartet, 0 .95), 7.60-8.20 (m, 8.0)

As a result of GPC measurement of the obtained brown solid, the peak of Poly (EHO) disappeared and the peak was shifted to the high molecular weight side (Note that unreacted Poly (EHO) and CRA were shifted to the low molecular weight side. Some derivative peaks remained).
The multi-branched macromonomer obtained here, CRA-poly (EHO), can be used as one that can easily give various functional groups.

<Synthesis Example 8>
Synthesis of 4-vinylbenzoic acid (VBA) A 300 mL three-necked flask was charged with 80 mmol of magnesium chip and 50 mL of dehydrated THF, and purged with nitrogen. Thereafter, a THF solution of p-chlorostyrene containing 70 mmol was added dropwise and stirred at 80 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled with dry ice. Thereafter, acid precipitation was carried out using dilute hydrochloric acid, and ethyl acetate was added, followed by washing 5 times with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. The desiccant was filtered off and then distilled off under reduced pressure. The precipitated solid was recrystallized using ethyl acetate: n-hexane (10: 1). The obtained solid was dried under reduced pressure to obtain a white solid (VBA).
Yield: 8.2 g (82%)
Melting point: 144.3 to 145.1 ° C, literature value (143.0 to 144.0 ° C)
IR (film, cm ⁻¹ ): 1682 (C = O ester), 1710 (C = C vinyl), 1581, 1486 (C = C aromatic)
¹ H-NMR (500 MHz, CDC 1 ₃ , TMS) δ ppm: 5.30-5.40 (dd J = 11.4 Hz, J = 11.4 Hz, 1.0), 5.80-5.90 (dd , J = 11.4 Hz, J = 17.4 Hz, 1.0), 6.70-6.80 (dd, J = 13.4 Hz, J = 17.4 Hz, 1.0), 7.51 (d , J = 1.8 Hz, 2.0), 8.12 (d, J = 1.8 Hz, 2.0)

<Synthesis Example 9>
○ VBA homopolymerization (PolyVBA)
A 50 mL eggplant-shaped flask was charged with 2.5 mmol of VBA, 10 mol% of azobisisobutyronitrile (AIBN), and 1 mL of NMP, and stirred at 60 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into a mixed solvent of n-hexane: isopropanol (1: 2) to precipitate a solid. The solid was collected by filtration and dried under reduced pressure to obtain a white solid (Poly-VBA).
Yield: 0.23 g (60%)
Mn: 20000 Mw / Mn: 1.50
IR (film, cm ⁻¹ ): 1682 (C═O), 1581, 1486 (C═C aromatic)
¹ H-NMR (500 MHz, DMSO-d ₆ , TMS) δPPm: 1.20 to 1.70 (m), 6.40-6.85 (m, aromatic), 7.40-7.90 (m , Aromatic)

O Synthesis of PolyVBA-PolyEHO Poly-VBA was added to a 100 mL eggplant-shaped flask. 1 mmol, 0.8 mmol of Poly (EHO), 5 mol% of TPPB, and 2 mL of NMP were added, and the atmosphere was purged with nitrogen, followed by reaction at 160 ° C. for 12 hours. After completion of the reaction, the reaction solution was poured into distilled water, acidified using diluted hydrochloric acid, and the precipitated solid was collected by filtration. Thereafter, reprecipitation purification was performed using THF as a good solvent and n-hexane as a poor solvent, followed by drying under reduced pressure to obtain a brown solid (PolyVBA-PolyEHO).
PolyVBA-Poly (EHO), which is the multi-branched macromonomer obtained here, can be used as one that can easily impart various functional groups.

<Synthesis Example 10>
○ Copolymerization of styrene and VBA (1: 1) (Styrene-co-VBA)
A 50 mL eggplant-shaped flask was charged with 2.5 mmol of styrene, 2.5 mmol of VBA, 10 mol% of AIBN, and 1 mL of NMP, and stirred at 60 ° C. for 3 hours. After completion of the reaction, reprecipitation purification was carried out using Koichi Teru and dried under reduced pressure to obtain a white powder solid (Styrene-co-VBA).
Yield: 0.38 g (62%)
Mn: 9000 Mw / Mn: 1.36
Polymer composition ratio; styrene: VBA = 1: 1
IR (film, cm ⁻¹ ): 1682 (C═O), 1581, 1486 (C═C aromatic)
¹ H-NMR (500 MHz, DMSO-d ₆ , TMS): δPPm: 1.20 to 1.62 (m), 6.20-6.80 (m, aromatic), 6.90-7.25 ( m, aromatic), 7.40-7.90 (m, aromatic)

Synthesis of Styrene-co-VBA-polyEHO Styrene-co-VBA was added to a 100 mL eggplant-shaped flask. 1 mmol, 0.8 mmol of Poly (EHO), 5 mol% of TPPB, and 2 mL of NMP were added, and the atmosphere was purged with nitrogen, followed by reaction at 160 ° C. for 12 hours. After completion of the reaction, the reaction solution was poured into distilled water, acidified using diluted hydrochloric acid, and the precipitated solid was collected by filtration. Thereafter, reprecipitation purification was performed using THF as a good solvent and n-hexane as a poor solvent, followed by drying under reduced pressure to obtain a brown solid (Styrene-co-VBA-polyEHO).
The resulting multi-branched macromonomer, Styrene-co-VBA-poly (EHO), can be used as one that can easily add various functional groups.
A similar multi-branched macromonomer can be obtained by using Poly (BHO) instead of Poly (EHO) described above.

<Synthesis Example 11>
○ Introduction of methacryloyl group into Poly (BHO) 1.6 mmol of Poly (BHO), 16 mmol of methacrylic anhydride, 1.0 mL of pyridine, and a small amount of hydroquinone as a polymerization inhibitor in an eggplant type flask at 90 ° C. Stir for 3 hours. After completion of the reaction, the reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering the desiccant, a brown viscous polymer was obtained by reprecipitation purification using chloroform as a good solvent and n-hexane as a poor solvent.
Esterification rate (DE) = 83%
Yield: 0.14 g (34%)
IR (film, cm ⁻¹ ): 1742 (C═O), 1232 (C—O—C ester), 1109, 1053 (C—O—C ether), 983 (C—O—C oxetane ring)
¹ H-NMR (500 MHz, DMSO-d ⁶ , TMS) δ ppm: 1.9 (S, 4.9H), 3.16-3.64 (m, 4.0H), 4.00-4.41 (M, 4.0H), 5.55 (s, 1.6H), 6.05 (s, 1.6H)
Poly (BHO) was able to react with methacrylic anhydride to form a methacrylic ester.

○ Synthesis of Poly (EHO-MA) -TPA having a radically polymerizable group in the side chain by addition reaction of TPA-poly (EHO) and methacrylic anhydride. TPA-poly (EHO) is 0 in a 100 mL eggplant-shaped flask. 0.1 mmol (hydroxyl equivalent 1.8 mmol) was weighed and dissolved in 0.5 mL of pyridine. Next, 3.6 mmol of methacrylic anhydride and a small amount of hydroquinone were added, and the mixture was stirred at room temperature for 48 hours. After completion of the reaction, the reaction mixture was diluted with chloroform, washed twice with 1N hydrochloric acid and five times with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, the solvent was distilled off from the filtrate under reduced pressure, and the resulting liquid was precipitated in n-hexane. The solid was collected by filtration and dried under reduced pressure to obtain a brown adduct compound.
With respect to this brown adduct compound, absorption due to νC═C of the methacryloyl group was confirmed at 1638 cm ⁻¹ in the IR spectrum. In ¹ H NMR, a peak attributed to the methyl proton of the methacryloyl group at 1.8 ppm and a peak attributed to the vinyl proton of the methacryloyl group at 5.6 ppm and 6.0 ppm were confirmed. Furthermore, when the esterification rate was calculated from the integral value of the methyl proton of the methacryloyl group based on the integral value of the methylene proton of Poly (EHO), it was 80%. From the above, it was determined as Poly (EHO-MA) -TPA having 80% methacryloyl group.
Esterification rate (DE) = 80%
Yield: 0.16 g (45%)
IR (film, cm ⁻¹ ): 3220, 1721, 1638, 1460, 1108, 1050.
¹ H NMR (500 MHz, DMSO-d ₆ , TMS) δ ppm: 0.50 to 1.02 (m, 10H), 1.20 to 1.50 (m, 6.7H), 1.80 (s, 8.9H), 3.68-4.00 (m, 110.0H), 5.61 (s, 3H), 6.00 (s, 2.8H), 8.20-8.88 (m, 4H).

○ Synthesis of Poly (EHO-MA) -TMA having a radically polymerizable group in the side chain by addition reaction of TMA-poly (EHO) and methacrylic anhydride. 0% of TMA-poly (EHO) was added to a 100 mL eggplant-shaped flask. .3 mmol (hydroxyl equivalent: 3.6 mmol) was weighed and dissolved in 2 mL of pyridine. Next, 11.0 mmol of methacrylic anhydride and a small amount of hydroquinone were added, and the mixture was stirred at room temperature for 48 hours. After completion of the reaction, the reaction mixture was diluted with chloroform, washed twice with 1N hydrochloric acid and five times with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the solvent was distilled off from the filtrate under reduced pressure. The liquid obtained here was put in n-hexane to obtain a precipitate. A brown adduct compound was obtained by obtaining a precipitate by filtration and drying under reduced pressure.
The brown adduct compound confirmed the absorption due to νC═C of the methacryloyl group at 1638 cm ⁻¹ in the IR spectrum. In ¹ H NMR, a peak attributed to the methyl proton of the methacryloyl group appeared at 1.8 ppm, and a peak attributed to the vinyl proton of the methacryloyl group appeared at 5.6 ppm and 6.0 ppm. Furthermore, when the esterification rate was calculated from the integral value of the methyl proton of the methacryloyl group based on the integral value of the methylene proton of Poly (EHO), it was 78%. From the above, it was determined as Poly (EHO-MA) -TMA having 78% of methacryloyl group.
Esterification rate (DE): 78%
Yield: 0.16 g (45%)
IR (film, cm ⁻¹ ) 3285, 1721, 1638, 1523, 1103, 1050.
^{· 1 H NMR (500MHz, DMSO} -d 6, TMS) δppm: 0.60-0.72 (m, 9.0H), 1.20-1.39 (m, 5.9H), 1.80 ( s, 5.0H), 3.68-4.00 (m, 110.0H), 5.61 (s, 2.5H), 6.00 (s, 2.4H), 8.50-8. 68 (m, 3.0H).

○ Synthesis of Poly (EHO-MA) -CRA having a radically polymerizable group in the side chain by addition reaction of CRA-poly (EHO) and methacrylic anhydride 0% CRA-poly (EHO) in a 100 mL eggplant-shaped flask .05 mmol (hydroxyl equivalent: 3.0 mmol) was weighed and dissolved in 3.0 mL of pyridine. Next, 9.0 mmol of methacrylic anhydride and a small amount of hydroquinone were added and stirred at room temperature for 48 hours. After completion of the reaction, the reaction mixture was diluted with chloroform, washed twice with 1N hydrochloric acid and five times with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, the solvent was distilled off from the filtrate under reduced pressure, and the resulting liquid was put into n-hexane to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure to obtain a brown adduct compound.
This brown adduct compound confirmed absorption due to νC═C of the methacryloyl group at 1638 cm ⁻¹ in the IR spectrum. In ¹ H NMR, a peak attributed to the methyl proton of the methacryloyl group was observed at 1.8 ppm, and a peak attributed to the vinyl proton of the methacryloyl group was observed at 5.6 ppm and 6.8 ppm. Furthermore, when the esterification rate was calculated from the integral value of the methyl proton of the methacryloyl group based on the integral value of the methylene proton of Poly (EHO), it was 65%. From the above, it was determined as Poly (EHO-MA) -CRA having 65% of methacryloyl group.
Esterification rate: 65%
Yield: 0.25 g (52%)
IR (film, cm ⁻¹ ) 3220, 1735, 1638, 1523, 1103, 1050.
^{· 1 H NMR (500MHz, DMSO} -d 6, TMS) δppm: 0.50-0.75 (m, 66.0H), 1.20-1.39 (m, 47.9H), 1.80 ( s, 46.0H), 3.68-4.00 (m, 80.0H), 5.61 (s, 15.5H), 5.80 (s, 15.4H), 8.50-8. 68 (m, 3.0H).

○ Photopolymerization reaction of Poly (EHO-MA) -TPA, Poly (EHO-MA) -TMA, Poly (EHO-MA) -CRA Adduct compound having a radical polymerizable group [Poly (EHO-MA) -TPA, Poly (EHO-MA) -TMA, Poly (EHO-MA) -CRA] each 0.2 g (60 wt%), Irgracure 907 as a photo radical initiator, 0.01 g (3 wt%), and a sensitizer 2- 0.003 g (1 wt%) of ethyl anthraquinone (2E-AQ) was weighed and mixed until uniform to prepare a sample. This mixture was applied onto a KBr plate to produce a film having an absorbance of about 1 near 2850 cm ⁻¹ . The light source in the photopolymerization reaction was a 250 W high-pressure mercury lamp, and the illuminance was 254 nm (810 mJ / cm ² ). The conversion rate in the photopolymerization reaction was calculated from the attenuation of absorption due to the methacryloyl group at 1638 cm ⁻¹ .
As a result, the cured coating film after UV irradiation of Poly (EHO-MA) -TPA, Poly (EHO-MA) -TMA, and Poly (EHO-MA) -CRA film became insoluble in THF. Poly (EHO-MA) -TPA has a conversion rate of about 45%, Poly (EHO-MA) -TMA has a conversion rate of about 36%, and Poly (EHO-MA) -CRA has a conversion rate of about 27%. there were.

○ Synthesis of Poly (EHO-MA-THPA) -TPA having a radical polymerizable group and an alkali-developable group in the side chain by addition reaction of Poly (EHO-MA) -TPA and tetrahydrophthalic anhydride (THPA) 100 mL Of poly (EHO-MA) -TPA, 0.6 mmol of THPA, 5 mol% of triphenylphosphine (TPP), and 2 mL of 1,4-dioxane were stirred in an eggplant-shaped flask of 24 hours at room temperature. . After completion of the reaction, chloroform was added, washed twice with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the solvent was distilled off from the filtrate under reduced pressure. The liquid obtained here was put in n-hexane to produce a precipitate. The precipitate was collected by filtration and dried under reduced pressure to obtain a brown adduct compound.
This brown adduct compound confirmed a peak due to O—H of carboxylic acid in the vicinity of 3300 cm ⁻¹ by IR spectrum. Furthermore, a new peak attributable to the vinyl proton of THPA was confirmed at 5.63 ppm by ¹ H NMR spectrum. Further, the THPA addition rate (DE) was calculated from the integral value of 5.63 ppm THPA with the vinyl proton based on the peak due to the methyl proton of the methacryloyl group in the vicinity of 1.92 ppm according to the ¹ H NMR spectrum. Calculated. As a result, it was 20%. From the above, it was determined as Poly (EHO-MA-THPA) -TPA having 80% methacryloyl group and 20% carboxyl group.
D. E. = 65%
Yield: 0.17 g (80%)
IR (film, cm ⁻¹ ) 3300, 1718, 1637, 1163.
^{· 1 H NMR (500MHz, DMSO} -d 6, TMS) δppm: 0.50-0.75 (m, 20.0H), 1.20-1.39 (m, 15.9H), 1.80 ( s, 12.0H), 2.20-2.40 (m, 4.0H), 3.68-4.00 (s, 58.0H), 5.61 (s, 3.5H), 5. 70 (s, 2.0H), 5.80 (s, 3.4H), 8.00-8.28 (m, 4.0H).

-Synthesis of Poly (EHO-MA-THPA) -TMA having a radically polymerizable group and an alkali-developable group in the side chain by addition reaction of Poly (EHO-MA) -TMA and THPA. Poly was added to a 100 mL eggplant-shaped flask. (EHO-MA) -TMA (0.1 mmol), THPA (1.2 mmol), triphenylphosphine (5 mol%), and 3 mL of 1,4-dioxane were added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, chloroform was added, washed twice with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the solvent was distilled off from the filtrate under reduced pressure. The obtained liquid was put in n-hexane to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure to obtain a brown adduct compound.
The brown adduct compound showed a peak due to OH of carboxylic acid in the vicinity of 3352 cm ⁻¹ by IR spectrum. Furthermore, a new peak attributable to the vinyl proton of THPA was observed at 5.63 ppm by ¹ H NMR spectrum. Further, the THPA addition rate (DE) is based on an integral value of 5.56 ppm of THPA with a vinyl proton on the basis of a peak due to methyl proton of a methacryloyl group near 1.72 ppm according to ¹ H NMR spectrum. Calculated. As a result, it was 20%. From the above, the brown adduct compound was determined to be Poly (EHO-MA-THPA) -TMA having 80% methacryloyl group and 20% carboxyl group.
D. E. = 20%
Yield: 0.4g (80%)
IR (film, cm ⁻¹ ): 3300, 1718, 1637, 1163.
¹ H NMR (500 MHz, DMSO-d ₆ , TMS) δ ppm: 0.50-0.75 (m, 20.0H), 1.10-1.39 (m, 18.9H), 1.70 ( s, 20.4H), 2.10-2.30 (m, 2.7H), 3.68-4.00 (s, 30.0H), 5.61 (s, 3.5H), 5. 80 (s, 3.4H), 5.90 (s, 2.7H), 8.10-8.23 (m, 3.0H).

○ Synthesis of Poly (EHO-MA-THPA) -CRA having a radically polymerizable group and an alkali-developable group in the side chain by addition reaction of Poly (EHO-MA) -CRA and THPA. Poly was added to a 100 mL eggplant-shaped flask. (EHO-MA) -CRA (0.1 mmol), THPA (24 mmol), and triphenylphosphine (5 mol%) were weighed and stirred in 3 mL of 1,4-dioxane at room temperature for 24 hours. After completion of the reaction, chloroform was added, washed twice with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off and the solvent was distilled off under reduced pressure. The remaining liquid was put in n-hexane to obtain a precipitate.
In this precipitate, a peak attributed to OH of the carboxylic acid was observed in the vicinity of 3250 cm ⁻¹ by IR spectrum. Furthermore, a new peak attributable to the vinyl proton of THPA was observed at 5.65 ppm by ¹ H NMR spectrum. The THPA addition rate (DE) was calculated from the integral value of 5.65 ppm THPA with the vinyl proton based on the peak due to the methyl proton of the methacryloyl group near 1.80 ppm according to ¹ H NMR spectrum. And 25%. From the above, this precipitation was determined to be Poly (EHO-MA-THPA) -CRA having 65% methacryloyl group and 25% carboxyl group.
D. E. = 25%
Yield: 0.95 g (85%)
IR (film, cm ⁻¹ ): 3300, 1718, 1637, 1163.
^{· 1 H NMR (500MHz, DMSO} -d 6, TMS) δppm: 0.50-0.75 (m, 66.0H), 1.20-1.39 (m, 47.9H), 1.80 ( s, 46.0H), 2.20-2.40 (m, 31.0H), 3.68-4.00 (s, 80.0H), 5.61 (s, 15.5H), 5. 72 (s, 14.0H), 5.80 (s, 15.4H), 7.50-8.28 (m, 8.0H).

○ Solubility test 2 mL of the solvent described in Tables 2 to 4 was added to 2 mg of the sample described in Tables 2 to 4, and allowed to stand at room temperature for 10 minutes.
The sample dissolved at room temperature for 10 minutes was evaluated as “++”, the sample dissolved by heating as “+”, the sample partially undissolved as “±”, and the sample undissolved as “−”.
The solubility in the alkaline aqueous solution described in Table 5 (tetramethylammonium hydroxide is referred to as TMAH) in 2 mg of the sample described in Table 5 was also examined. These results are shown in Tables 2 to 5 below. Note that Poly (EHO) -TPA is “I”, Poly (EHO-MA) -TPA is “Ro”, Poly (EHO-MA-THPA) -TPA is “Ha”, and Poly (EHO) -TMA. To “D”, Poly (EHO-MA) -TMA to “Ho”, Poly (EHO-MA-THPA) -TMA to “He”, Poly (EHO) -CRA to “To”, Poly ( EHO-MA) -CRA was indicated as “Chi” and Poly (EHO-MA-THPA) -CRA was indicated as “Li”.

○ Thermal Analysis of Adduct Compound 4 mg of the adduct compound shown in Table 6 (using the abbreviations described in Example 13) was weighed in an aluminum pan, and 20 to 600 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. The temperature was raised to TG / DTA measurement.
The DSC measurement was performed by weighing 4 mg of the one shown in Table 6 in an aluminum pan, sealing it, and raising the temperature to 20 to 200 ° C. at a temperature raising rate of 10 ° C./min in a nitrogen atmosphere.
These results are shown in Table 6 below. Td 5% indicates a 5% mass loss temperature (° C.), and Td 10% indicates a 10% mass loss temperature (° C.).

As a result, each adduct compound could not recognize a clear glass transition temperature (Tg) between 20 and 200 ° C.
The 5% mass reduction temperature was 333 to 351 ° C. when the terminal of the polymer was a hydroxyl group, 355 to 357 ° C. when the terminal was a methacryloyl group, and 333 to 351 ° C. after photocrosslinking. Further, the 10% mass reduction temperature is 354 to 368 ° C. when the terminal of the polymer is a hydroxyl group, 389 to 392 ° C. when the terminal methacryloyl group is used, and 390 to 395 ° C. after photocrosslinking. As a result, it was found that both the 5% and 10% mass reduction temperatures were slightly improved.

  In the multibranched macromonomer of the present invention, it is easy to add a compound having a functional group such as a vinyl group, a (meth) acrylate group, an epoxy group or a carboxyl group to the hydroxyl group present in the molecule. From this, the multibranched macromonomer of the present invention can be derived into a multibranched macromonomer having many functions. In addition, the multibranched macromonomer of the present invention can be expected to have functions such as improved solubility. From this, it can utilize as a raw material of resin used for various uses.

Claims (3)

A multibranched macromonomer obtained by polyaddition reaction of a multibranched polyether compound having one oxetanyl group and a plurality of hydroxyl groups and a polyvalent carboxylic acid. A polybranched polyether compound having one oxetanyl group and a plurality of hydroxyl groups in a molecule obtained by anion ring-opening polymerization of an oxetane compound having a hydroxyl group is subjected to a polyaddition reaction with a polyvalent carboxylic acid. The method for producing a multibranched macromonomer according to claim 1. The method for producing a multibranched macromonomer according to claim 2, wherein the oxetane compound having a hydroxyl group is represented by the following formula (1).

(R ₁ in Formula (1) represents an alkyl group having 1 to 4 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms having a hydroxyl group.)