Polymer, oxetane compound, and curable resin composition

Abstract

To provide a new compound, polymer and composition which can be derived from a biomass-derived compound.SOLUTION: A polymer includes a plurality of constitutional units represented by the following formula (1) or (2), wherein R1 represents a methylene group or an ethane-1,2-diyl group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a polymer, an oxetane compound, and a curable resin composition. The present disclosure also relates to a compound that can be derived from an epoxy compound or an oxetane compound.

Background Art

[0002] Levoglucosenone (LGO) can be obtained from biomass-derived raw materials such as cellulose (Non-Patent Document 1). Dihydrolevoglucosenone, which is a hydrogenated product of levoglucosenone, is commercially available as Cyrene (registered trademark), and its use as an organic solvent has been studied (Non-Patent Document 2). The synthesis of a polymer from an acrylic monomer derived from Cyrene (registered trademark) has also been proposed (Non-Patent Document 3).

Chemical Formula

[0003] On the other hand, Non-Patent Document 4 discloses the synthesis of a spiroepoxide from Cyrene (registered trademark) as a compound for verifying the theoretical calculation of the relative configuration of a spiroepoxide containing a quaternary carbon atom. Non-Patent Document 5 discloses a compound in which the carbonyl group of levoglucosenone is converted to an epoxy group as an intermediate for the synthesis of saccharides.

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Non-Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present disclosure relates to novel compounds, polymers, and compositions that can be derived from biomass-derived compounds.

Means for Solving the Problems

[0006] The present disclosure includes the following. [1] The following formula (1) or (2):

Chemical Formula

Chemical Formula

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Chemical Formula

Chemical formula

Chemical formula

Chemical formula

[10] The following formula (12) or (22):

Chemical formula

Chemical formula

[11] The following formula (10) or (20):

Chemical formula

Chemical formula

[12] The following formula (15) or (25):

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0007] Novel compounds, polymers and compositions that can be derived from biomass-derived compounds can be provided.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

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Figure 5

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Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15

Figure 16

Figure 17

Figure 18

Figure 19

Mode for Carrying Out the Invention

[0009] The present invention is not limited to the following examples.

[0010] An example of the polymer according to the present disclosure includes a plurality of structural units represented by the following formula (1) or (2). In formula (1) and (2), R 1represents a methylene group (-CH2-) or an ethane-1,2-diyl group (-CH2CH2-). This polymer can have a molecular chain containing, as part or all of the repeating units, a structural unit represented by formula (1), a structural unit represented by formula (2), or both. The molecular chain containing the structural unit represented by formula (1) or (2) may be linear, branched, or cyclic, and may form a crosslinked structure.

[0011]

Chemical formula

Chemical formula

[0012] The structural unit represented by formula (1) can be a divalent group derived from a cyclic ether compound represented by the following formula (10). The structural unit represented by formula (2) can be a divalent group derived from a cyclic ether compound represented by the following formula (20). R in formulas (10) and (20) 1 also represents a methylene group or an ethane-1,2-diyl group. The cyclic ether compounds represented by formula (10) or (20) can be synthesized by converting the carbonyl group of levoglucosenone (LGO) or Cyrene (registered trademark) into an epoxy group or an oxetanyl group, respectively. Therefore, the polymer containing the structural unit represented by formula (1) or (2) can contribute to the effective utilization of raw materials derived from biomass.

[0013]

Chemical formula

Chemical formula

[0014] Formula (10) can be rewritten as the following formula (11) or (12). Formula (20) can be rewritten as the following formula (21) or (22). The compound represented by formula (11) or (21) can be referred to as an epoxy compound. The compound represented by formula (12) or (22) can be referred to as an oxetane compound.

[0015]

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0016] Among some or all of the plurality of structural units represented by formula (1) or (2), some or all may be hydrolyzed. The hydrolyzed structural unit is represented by, for example, the following formula (1A) or (2A). R in formulas (1A) and (2A) 1 is defined in the same manner as R in formulas (1) and (2). By utilizing the reactivity of the hydroxy group in formula (1A) or (1B), etc., the polymer can be modified with various side chains. 1 is defined in the same manner as R in formulas (1) and (2). By utilizing the reactivity of the hydroxy group in formula (1A) or (1B), etc., the polymer can be modified with various side chains.

[0017]

Chemical formula

Chemical formula

[0018] The polymer containing the structural unit represented by formula (1) or (2) may contain, for example, a plurality of structural units represented by the following formula (100) or (200). In formulas (100) and (200), R 1 represents a methylene group or an ethane-1,2-diyl group, and R2 represents a divalent organic group containing a hydrocarbon group bonded to each of the two carbonyl groups in formula (100) or (200).

[0019]

Chemical formula

Chemical formula

[0020] R 2 may be a group represented by the following formula (41) or (42). In formula (41), R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group, and R 11 and R 12 may be bonded to each other to form a cyclic structure. The bond between the carbon atom to which R 11 is bonded and the carbon atom to which R 12 is bonded is a saturated bond or an unsaturated bond. These carbon atoms bonded by an unsaturated bond may form an aromatic group (for example, a benzene ring) together with R 11 and R 12 . In formula (42), R 13 represents a divalent organic group, and R 14 , R 15 , R 16 and R 17 each independently represent a hydrogen atom or a monovalent organic group, and R 15 and R 16 may be bonded to each other to form a cyclic structure. In the portion of R 2 , the molecular chain of the polymer may form a branch.

[0021]

Chemical formula

[0022] R 11 and R 12 , or R 15 and R 16The cyclic structure formed by the combination of them can be an aromatic group which may have a substituent, or an alicyclic group which may have a substituent. R 13 may be a group consisting of a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent (for example, a methylene group), an oxy group (-O-), or a combination thereof.

[0023] Throughout the present disclosure, examples of the monovalent organic group include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an alkylamino group, an alkylaminocarbonyl group, an alkylcarbonylamino group, a hydroxyalkyl group, an arylalkyl group, an aryl group, an alkylaryl group, a halogenated aryl group, a halogeno group, and a hydroxy group.

[0024] Throughout the present disclosure, examples of the substituent that the hydrocarbon group may have include an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, an amino group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an aminocarbonyl group, an alkylcarbonylamino group, an arylcarbonylamino group, a cyano group, an alkylthio group, an arylthio group, a halogeno group, and a hydroxy group.

[0025] Throughout the present disclosure, examples of substituents that an aromatic group or alicyclic group may have include an alkyl group, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an aminocarbonyl group, an alkylcarbonylamino group, an arylcarbonylamino group, a cyano group, an alkylthio group, an arylthio group, a halogeno group, a hydroxy group, a hydroxyalkyl group, an arylalkyl group, an aryl group, an alkylaryl group, a halogenated aryl group, a halogeno group, and a hydroxy group.

[0026] Some or all of the plurality of structural units represented by formula (11) or (12) may be hydrolyzed. The hydrolyzed structural units are represented by, for example, the following formula (100A) or (200A). R in formula (100A) and (200A) 1 and R 2 are defined in the same manner as R 1 and R 2 in formula (100) and (200).

[0027]

Chemical formula

Chemical formula

[0028] The polymer containing a plurality of structural units represented by formula (100) or (200) can be a polyester produced by the polymerization of a cyclic ether compound represented by formula (10) or (20) and one or more acid anhydride compounds having one or more acid anhydride groups. The acid anhydride compound may further have a carboxy group. The acid anhydride compound can ring-open by reacting with a compound having a hydroxyl group or water present in the system to generate a carboxy group. The carboxy group can react with the cyclic ether compound represented by formula (10) or (20). By repeating the generation of a hydroxyl group by the reaction of the carboxy group and the cyclic ether compound and the reaction of the hydroxyl group with another cyclic ether compound, a polyester as a polymer can be produced. From an acid anhydride compound having one acid anhydride group, a linear molecular chain is usually derived. From an acid anhydride compound having a plurality of acid anhydride groups and an acid anhydride compound having one acid anhydride group and a carboxy group, a molecular chain forming a crosslinked structure is usually derived. The acid anhydride compound for producing a polyester by reaction with a cyclic ether compound may include an acid anhydride compound having one acid anhydride group.

[0029] The acid anhydride compound is represented, for example, by the following formula (30). R in formula (30) 2 is defined in the same manner as R in formulas (10) and (20). In the polymer formed, R 2 is usually the residue obtained by removing the acid anhydride group from the acid anhydride compound. 2

[0030]

Chemical formula

[0031] The acid anhydride compound containing one acid anhydride group may be, for example, an acid anhydride derived from an alkyldicarboxylic acid, an alkenyldicarboxylic acid, an aromatic dicarboxylic acid, a hydrogenated product of an aromatic dicarboxylic acid, a halogen-substituted dicarboxylic acid, or a bicyclic dicarboxylic acid. Examples of acid anhydrides derived from alkyldicarboxylic acids and alkenyldicarboxylic acids include maleic anhydride, succinic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride, adipic anhydride, glutaric anhydride, and diglycolic anhydride. Examples of acid anhydrides derived from aromatic dicarboxylic acids include phthalic acid. Examples of acid anhydrides derived from hydrogenated products of aromatic dicarboxylic acids include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples of acid anhydrides derived from halogen-substituted dicarboxylic acids include tetrafluorophthalic anhydride, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride. Examples of acid anhydrides derived from bicyclic dicarboxylic acids include bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, and methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride.

[0032] Examples of acid anhydride compounds having one acid anhydride group and a carboxy group include trimellitic anhydride and hexahydrotrimellitic anhydride.

[0033] The acid anhydride compound having a plurality of acid anhydride groups may be, for example, an acid anhydride derived from an aliphatic tetracarboxylic acid, an aromatic tetracarboxylic acid, or an aromatic hexacarboxylic acid. Examples of the acid anhydride derived from an aliphatic tetracarboxylic acid include butanetetracarboxylic dianhydride, dicyclohexyl-3,4,3’,4’-tetracarboxylic dianhydride, hexahydro(tetrahydro, glycerylbis(anhydrotrimellitate monoacetate), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, and 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic 1,4:2,3-dianhydride. Examples of the acid anhydride derived from an aromatic tetracarboxylic acid include pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, 4,4’-biphthalic anhydride, 4,4’-oxydiphthalic anhydride, 4,4’-sulfonyldiphthalic anhydride, 4,4’-carbonyldiphthalic anhydride, 4,4’-(hexafluoropropylidene)diphthalic anhydride, and ethylene glycol bis(trimesic acid ester) anhydride. Examples of the acid anhydride derived from an aromatic hexacarboxylic acid include mellitic trianhydride.

[0034] A polyester may be synthesized by polymerization of one or more acid anhydride compounds selected from the compounds exemplified above and a cyclic ether compound represented by formula (10) or (20). Together with the cyclic ether compound represented by formula (10) or (20), another cyclic ether compound having an epoxy group or an oxetanyl group may be polymerized with the acid anhydride compound.

[0035] For the polymerization of the cyclic ether compound represented by formula (10) or (20) and the acid anhydride compound, an initiator may be used. The initiator is useful, for example, for the efficient initiation of the polymerization reaction and for the control of the molecular weight, molecular weight distribution, or block formation. The initiator can be a compound having one or more reactive groups capable of reacting with one or more functional groups among epoxy groups, oxetanyl groups, or acid anhydride groups to generate hydroxyl groups or carboxyl groups. The reactive groups of the initiator may be, for example, one or more functional groups selected from hydroxyl groups, thiol groups, carboxyl groups, primary amino groups, and secondary amino groups. The hydroxyl group of the initiator can be a phenolic hydroxyl group or an alcoholic hydroxyl group. The thiol group of the initiator can be a primary thiol group or a secondary thiol group. A compound having one or two reactive groups can be the starting point of a linear molecular chain. A compound having three or more reactive groups can be the starting point of a molecular chain having a so-called star structure.

[0036] The compound having one alcoholic hydroxyl group may be an aliphatic monoalcohol, and examples thereof include alkyl alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, stearyl alcohol, and benzyl alcohol, and alkylene glycol monoalkyl ethers such as polyethylene glycol monomethyl ether, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol triacrylate. The compound having two alcoholic hydroxyl groups may be an aliphatic dialcohol, and examples thereof include ethylene glycol, propylene glycol, hexanediol, octanediol, cyclohexanediol, 1,4-benzenedimethanol, cyclohexanedimethanol, glycerin monoethyl ether, glycerin mono(meth)acrylate, pentaerythritol di(meth)acrylate, dimethylolpropionic acid, polyalkylene glycol (for example, polyethylene glycol), and polyester diol (for example, polycaprolactone diol, polycarbonate diol). The compound having three or more alcoholic hydroxyl groups may be an aliphatic polyol, and examples thereof include glycerin, pentaerythritol, and dipentaerythritol.

[0037] The compound having one phenolic hydroxyl group may be an aromatic monoalcohol, and examples thereof include phenol, cresol, ethylphenol, cardanol, butylhydroxytoluene, naphthol, and ethoxyphenol. The compound having two phenolic hydroxyl groups may be an aromatic dialcohol, and examples thereof include hydroquinone, catechol, methylhydroquinone, biphenol, naphthalenediol, and bisphenol (for example, bisphenol A, bisphenol S). The compound having three or more phenolic hydroxyl groups may be an aromatic polyalcohol, and examples thereof include benzenetriol, trihydroxytriphenylmethane, phenol novolak, cresol novolak, tricyclodecane phenol novolak, biphenyl novolak, and bisphenol A novolak.

[0038] Examples of compounds having one thiol group include aliphatic monothiols such as methanethiol and ethanethiol, and aromatic monothiols such as thiophenol. Examples of compounds having two thiol groups include aliphatic dithiols such as ethanedithiol, butanedithiol, decanedithiol, ethylene glycol bis(mercaptopropionate), and bis(mercaptoethyl) sulfide, and aromatic dithiols such as benzenedithiol and biphenyldithiol. Examples of thiol compounds having three or more thiol groups include trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(mercaptopropionate), dipentaerythritol hexakis(mercaptopropionate), tris(mercaptopropionyloxy) isocyanurate, polyethylene glycol bis(mercaptopropionate), pentaerythritol tetrapropanethiol, and tris(mercaptobutanoyloxy) isocyanurate. Examples of compounds having a thiol group and a hydroxyl group include pentaerythritol tripropanethiol.

[0039] Examples of compounds having an amino group include aliphatic monoamines (e.g., ethylamine, diethylamine, piperidine), aliphatic polyamines (e.g., diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, isophoronediamine, and norbornanediamine), (meth)acrylamide, aromatic monoamines (e.g., aniline, methylaniline, benzylmethylaniline), aromatic polyamines (e.g., phenylenediamine, diaminobiphenyl), and heterocyclic polyamines (e.g., aminomethylpiperazine, methylimidazole, ethylmethylimidazole, melamine, methylolated melamine).

[0040] Examples of compounds having a carboxy group include monocarboxylic acids (e.g., acetic acid, propionic acid, butanoic acid, (meth)acrylic acid), dicarboxylic acids (e.g., adipic acid, phthalic acid), and polycarboxylic acids (e.g., trimellitic acid, poly(meth)acrylic acid (co)polymers).

[0041] The polymerization of the cyclic ether compound represented by the formula (10) or (20) and the acid anhydride compound may be, for example, bulk polymerization or solution polymerization. The polymerization may be carried out in the presence of a catalyst. The catalyst can be selected from the ordinary catalysts used for the polymerization of a compound having an epoxy group or an oxetanyl group and an acid anhydride compound. Examples of the catalyst include acid catalysts such as toluenesulfonic acid, methanesulfonic acid, camphorsulfonic acid, and trifluoromethanesulfonate; alkali metal salts of carboxylic acids such as cesium pivalate; tertiary amines such as triethylamine, triethylenediamine, benzyldimethylamine, diazabicycloundecene, diazabicyclononene, and triazabicyclodecene; phosphorus compounds such as triphenylphosphine, trimethoxy triphenylphosphine, trimethyl triphenylphosphine, tetraphenylphosphonium salts, hexafluorophosphate, trifluorotris(pentafluoroethyl) phosphate, and phosphazene bases; boron compounds such as tetraphenylborate salts; and transition metal complexes such as N,N-bis(salicylidene)cyclohexanediamine cobalt, chromium porphyrin, cobalt corrole catalyst, and hexafluoroantimonate salts.

[0042] Polymerization in the presence of a basic or neutral catalyst tends to produce a linear polyester while maintaining the acetal structure of the cyclic ether compound represented by the formula (10) or (20). The basic catalyst therefor may be, for example, an alkali metal salt of a carboxylic acid such as cesium pivalate (e.g., cesium pivalate), or a metal complex (e.g., N,N-bis(salicylidene)cyclohexanediamine cobalt, chromium porphyrin, cobalt corrole catalyst). Polymerization in the presence of an acid catalyst tends to produce a polyester having a molecular chain with a crosslinked structure due to a crosslinking reaction involving the acetal structure.

[0043] The polymer containing the structural unit represented by the formula (1) or (2) may further contain a structural unit represented by the following formula (5). In the formula (5), R 3 represents a methylene group or an ethane-1,2-diyl group, and R 4represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. R 4 is a residue derived from a substituent of another cyclic ether compound used in combination with the cyclic ether compound represented by the formula (10) or (20). R 4 may be, for example, an alkyl group or an alkyloxymethyl group. The alkyl group may have 1 to 20 carbon atoms. The alkyl group in the alkyloxymethyl group may have 1 to 20 carbon atoms. R 4 In the part of, the molecular chain of the polymer may form a branch.

[0044] [Chemical formula]

[0045] The polymer containing the structural unit represented by the formula (1) or (2) and the structural unit represented by the formula (5) can be a polyether produced by polymerization of the cyclic ether compound represented by the formula (10) or (20) and the cyclic ether compound represented by the following formula (50). R in the formula (50) 3 and R 4 are defined in the same manner as R 3 and R 4 in the formula (5). The polyether may have a molecular chain in which the structural unit represented by the formula (1) or (2) and the structural unit represented by the formula (5) are randomly arranged.

[0046] [Chemical formula]

[0047] The cyclic ether compound represented by the formula (50) is not particularly limited and can be appropriately selected according to the required properties and uses. The cyclic ether compound represented by the formula (50) may be a compound having one or more epoxy groups or oxetanyl groups. A compound having one epoxy group or oxetanyl group can usually induce a linear molecular chain. A compound having a plurality of epoxy groups or oxetanyl groups can usually induce a molecular chain containing branches and crosslinked.

[0048] Compounds having one epoxy group can be, for example, aliphatic monoglycidyl ethers, aromatic monoglycidyl ethers, monoepoxy compounds having one epoxy group derived from unsaturated hydrocarbon groups, or combinations thereof. Examples of aliphatic monoglycidyl ethers include butyl glycidyl ether, octyl glycidyl ether, lauryl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl (meth)acrylate, and methylol furfuryl glycidyl ether. Examples of aromatic monoglycidyl ethers include phenyl glycidyl ether and brominated phenyl glycidyl ether. Examples of monoepoxy compounds include ethylene oxide, propylene oxide, 1,2-hexylene oxide, and epoxidized linoleic acid.

[0049] Compounds having two epoxy groups can be, for example, aliphatic diglycidyl ethers, aromatic diglycidyl ethers, diepoxy compounds having two epoxy groups derived from unsaturated hydrocarbon groups, or combinations thereof. Examples of aliphatic diglycidyl ethers include neopentyl glycol diglycidyl ether and hexanediol diglycidyl ether. Examples of aromatic diglycidyl ethers include hydroquinone diglycidyl ether and its alkyl-substituted derivatives, biphenol diglycidyl ether and its alkyl-substituted derivatives, bisphenol A diglycidyl ether and its alkyl-substituted derivatives, brominated bisphenol A diglycidyl ether, and naphthalene diglycidyl ether and its alkyl-substituted derivatives. Examples of diepoxy compounds include epoxidized linolenic acid.

[0050] Compounds having three or more epoxy groups can be, for example, aliphatic polyglycidyl ethers, aromatic polyglycidyl ethers, polyepoxy compounds having three or more epoxy groups derived from unsaturated hydrocarbon groups, or combinations thereof. Examples of aliphatic polyglycidyl ethers include glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and dipentaerythritol hexaglycidyl ether. Examples of aromatic polyglycidyl ethers include polyglycidyl ethers of substituted phenols (e.g., benzene triol glycidyl ether, trihydroxy triphenylmethane glycidyl ether), and novolacs (e.g., phenol novolac glycidyl ether, cresol novolac glycidyl ether, bisphenol A novolac glycidyl ether). Examples of polyepoxy compounds include triallyl isocyanurate, epoxidized soybean oil, and epoxidized linseed oil.

[0051] Examples of compounds having one oxetanyl group include ethyl hydroxymethyloxetane, ethyl hydroxybutyloxetane, and ethyl oxetanylmethyl (meth)acrylate. Examples of compounds having two oxetanyl groups include bis(ethyl oxetanyl)methoxymethylbiphenyl, and bis(ethyl oxetanyl)methyl phthalate.

[0052] The polymerization of the cyclic ether compound represented by formula (10) or (20) and the cyclic ether compound represented by formula (50) may be, for example, bulk polymerization or solution polymerization. The polymerization may be carried out in the presence of a catalyst. The catalyst can be selected from the usual catalysts used for the polymerization of cyclic ether compounds. Examples of the catalyst include acid catalysts, alkali metal salts, alkali metal alkoxides, tertiary amines, phosphorus compounds, boron compounds, and transition metal complexes similar to those exemplified as catalysts for the synthesis of polyesters. The catalyst may be a photoacid generator or a photobase generator.

[0053] Polymerization in the presence of a basic or neutral catalyst tends to produce a linear polyether while maintaining the acetal structure of the cyclic ether compound represented by formula (10) or (20). Basic catalysts for this purpose may be, for example, alkali metal salts of carboxylic acids (such as cesium pivalate) such as cesium pivalate, or metal complexes (such as N,N-bis(salicylidene)cyclohexanediamine cobalt, chromium porphyrin, cobalt corrole catalyst). Polymerization in the presence of an acid catalyst tends to produce a polyether having crosslinked molecular chains by a crosslinking reaction involving the acetal structure. For the control of molecular weight, molecular weight distribution, etc., an alkali metal salt of a carboxylic acid (such as cesium pivalate) may be advantageous.

[0054] The polymer may contain only the structural units represented by formula (1) or (2) as repeating units or monomer units. In that case, the polymer may be a homopolymer of one cyclic ether compound represented by formula (10) or (20), or a copolymer of two or more cyclic ether compounds represented by formula (10) or (20). The conditions for the synthesis of these polymers can be ordinary conditions similar to the conditions for the synthesis of a polymer containing the structural unit represented by formula (1) or (2) and the structural unit represented by formula (5).

[0055] The polymer may form a crosslinked polymer by a ring-opening reaction of an epoxy group, an oxetanyl group or an acetal structure in the structural unit represented by formula (1) or (2), or a crosslinking reaction involving an unsaturated group in the structural unit represented by formula (2).

[0056] The cyclic ether compound represented by formula (10) or (20) can function as a crosslinking agent for forming a crosslinked polymer by a combination of a ring-opening reaction of an epoxy group or an oxetanyl group and a ring-opening reaction of an acetal structure. The crosslinked polymer in that case may contain a structural unit represented by formula (110) or (210). In these formulas, R 1represents a methylene group or an ethane-1,2-diyl group, and * represents a bond. The crosslinked polymer containing the structural unit represented by the formula (110) or (210) may further contain the structural unit represented by the formula (1), (2), (1A), (2A), (110), (200), (100A), (200A) or (5).

Chemical formula

Chemical formula

[0057] The polymer containing the structural unit represented by the formula (110) or (210) can be produced, for example, by ring-opening copolymerization of a cyclic ether compound represented by the formula (10) or (20) and a cyclic acetal compound represented by the formula (60). R in the formula (60) 5 represents a covalent bond or a divalent aliphatic group. In this case, the crosslinked polymer produced may contain a partial structure represented by the formula (120) or (220). m, n and o in the formulas (120) and (220) each independently represent a positive integer, and * represents a bond (such as a single bond). The cyclic acetal compound of the formula (60) may be a 5-membered ring to 8-membered ring compound. Examples of the cyclic acetal compound of the formula (60) include 1,3-dioxane.

Chemical formula

Chemical formula

Chemical formula

[0058] The crosslinked polymer can also be produced by a thiol-ene reaction between an unsaturated group in the structural unit represented by the formula (2) and a polythiol compound having a plurality of thiol groups. In this case, the crosslinked polymer may contain a structural unit represented by the formula (220). R in the formula (230) 1 is R in the formula (2).1 It is defined in the same way. * indicates a bonding hand. The crosslinked polymer containing the structural unit represented by the formula (230) can be obtained, for example, by a method including reacting a polymer containing the structural unit represented by the formula (2) with a polythiol compound. The thiol-ene reaction may proceed by light irradiation in the presence of a photoinitiator. The crosslinked polymer containing the structural unit represented by the formula (230) may further contain the structural unit represented by the formula (1), (2), (1A), (2A), (110), (200), (100A), (200A) or (5). [Chemical formula]

[0059] Examples of the polythiol compound for obtaining the crosslinked polymer include aliphatic dithiols such as ethanedithiol, butanedithiol, decanedithiol, ethylene glycol bis(mercaptopropionate), and bis(mercaptoethyl) sulfide, trimethylolpropane tris mercaptopropionate, pentaerythritol tetrakis mercaptopropionate, dipentaerythritol hexakis mercaptopropionate, tris(mercaptopropionyloxy) isocyanurate, polyethylene glycol bis mercaptopropionate, pentaerythritol tetrapropane thiol, and tris(mercaptobutanoyloxy) isocyanurate.

[0060] The polymer according to the present disclosure can have excellent properties in terms of transparency, heat resistance, flexibility, toughness, adhesiveness, and adhesion. Various properties of the polymer can be adjusted, for example, by appropriately selecting the type of the compound copolymerized with the cyclic ether compound represented by the formula (10) or (20) (for example, the acid anhydride compound of the formula (30) or the cyclic ether compound represented by the formula (50)), and the copolymerization ratio. Examples of the uses to which the polymer according to the present disclosure can be applied include machine parts, containers, optical parts, molded bodies (for example, sheets, films), coating materials, surface coating materials (for example, resists), adhesives, and fibers.

[0061] The cyclic ether compound represented by formula (10) or (20) can be used not only as a monomer for synthesizing a polymer, but also as various synthetic starting materials, additives, modifiers, reactive diluents, etc. that utilize the reactivity of an epoxy group or an oxetanyl group.

[0062] The curable resin composition having thermosetting or photocuring properties may contain the cyclic ether compound represented by formula (10) or (20). The curable resin composition may further contain a polyfunctional epoxy compound having a plurality of epoxy groups, a polyfunctional oxetane compound having a plurality of oxetanyl groups, or a combination thereof. The curable resin composition may further contain other components such as a curing agent for an epoxy resin.

[0063] By reacting the cyclic ether compound represented by formula (10) or (20) with various nucleophiles such as a carboxylic acid compound, an alcohol compound, an amine compound, or a thiol compound, a compound represented by, for example, the following formula (15) or (25) can also be synthesized.

[0064]

Chemical formula

Chemical formula

[0065] In formulas (15) and (25), R 1 represents a methylene group or an ethane-1,2-diyl group, and Z represents a monovalent group represented by the following formula (a), (b), (c), or (d). R 5 in formula (a) represents a monovalent organic group. R 6 in formula (b) represents a monovalent organic group that does not contain a carbonyl group bonded to the oxygen atom in formula (b). R 7 and R 8 in formula (c) each independently represent a hydrogen atom or a monovalent organic group, and R 7 and R 8 may be bonded to each other to form a cyclic structure. R 9represents a monovalent organic group.

[0066] [Chemical formula]

[0067] The compound represented by formula (15) or (25) can be used, for example, as a synthetic intermediate or various additives. R 5 , R 6 , R 7 , R 8 and R 9 may be a hydrocarbon group which may have a substituent. R 5 , R 6 , R 7 , R 8 or R 9 as the hydrocarbon group may be a group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. R 5 , R 6 , R 7 , R 8 or R 9 Examples of the substituent that the hydrocarbon group as R [Examples]

[0068] The present invention is not limited to the following examples.

[0069] 1. Raw materials (a) Reagents The purchased products of the following reagents were used as they were. · Silane (trade name, 99%, Sigma - Aldrich) · Trimethylsulfoxonium iodide ((CH3)3SOI, >98.0%, Tokyo Chemical Industry Co., Ltd.) · Sodium hydride (NaH, 60%, dispersed in liquid paraffin) · Calcium hydride (CaH2, >94%, Junsei Chemical Co., Ltd.) · trans-2-[3-(4-tert-Butylphenyl)-2-methyl-2-propenylidene] malononitrile (DCTB, >98.0%, Tokyo Chemical Industry Co., Ltd.) · Potassium trifluoroacetate (98%, Sigma-Aldrich) · 3-Phenyl-1-propanol (>98.0%, Tokyo Chemical Industry Co., Ltd.) · Cesium pivalate (>97.0%, Tokyo Chemical Industry Co., Ltd.) · Benzoic acid (>99.0%, Tokyo Chemical Industry Co., Ltd.) · Bis(2-methoxyethyl)amine (>98.0%, Tokyo Chemical Industry Co., Ltd.) The following reagents were purified by sublimation, and then recrystallized using acetic anhydride to obtain crystals, which were then purified again by sublimation. The purified products were stored and used in a glove box. · Phthalic anhydride (PA, Tokyo Chemical Industry Co., Ltd., >98%) · 5-Norbornene-endo-2,3-dicarboxylic anhydride (NA, Sigma-Aldrich, 99%) · Succinic anhydride (SA, Tokyo Chemical Industry Co., Ltd., >95.0%) · Glutaric anhydride (GA, Tokyo Chemical Industry Co., Ltd., >98%) The following reagents were dried under vacuum before use. · 1,4-Benzenedimethanol (BDM, Tokyo Chemical Industry Co., Ltd., >99.0%) · Diglycolic anhydride (DGA, Tokyo Chemical Industry Co., Ltd., >98.0%) The following reagents were dried by heating at 100 °C under vacuum for 72 hours or more before use. · Cesium pivalate (CP, Tokyo Chemical Industry Co., Ltd., >97.0%) The following reagents were distilled under reduced pressure in the presence of CaH2 before use, and stored and used in a glove box. · 1,2 - Hexylene Oxide (HO, >96.0%, Tokyo Chemical Industry Co., Ltd.)

[0070] (b) Solvent The purchased products of the following solvents were used as they were. · Methanol (>99.8%, Sigma - Aldrich) · Dichloromethane (CH2Cl2, >98.0%, Junsei Chemical Co., Ltd.) · Deuterated Chloroform (CDCl3, with 0.03% added Tetramethylsilane (TMS), 99.8%, Kanto Chemical Co., Inc.) · Chloroform (CHCl3, >99.0%, Junsei Chemical Co., Ltd.) · Tetrahydrofuran (THF, >99.0%, Junsei Chemical Co., Ltd.) · Ultra - dehydrated Dimethyl Sulfoxide (>99.0%, water content: <0.001%, Fujifilm Wako Pure Chemical Corporation)

[0071] The following solvents were purified with a Solvent purification system (MBRAUN, MS - SPSCompact) before use. · Dehydrated Tetrahydrofuran (>99.5%, water content: <0.001%, Kanto Chemical Co., Inc.) · Dehydrated Toluene (>99.5%, water content: <0.001%, Kanto Chemical Co., Inc.)

[0072] 2. Measurement Method 2 - 1. 1 1H NMR, 13 13C NMR Equipment: JEOL JNM - ECS400 (400 MHz), and JEOL JNM - ECX400 (400 MHz) Solvent: CDCl3 Internal Standard Substance: TMS (0.03%) Measurement Temperature: 25 °C Number of Integrations: 1 1H NMR: 16 times or 32 times, 13 13C NMR: 128 times

[0073] 2-2. Size Exclusion Chromatography (SEC) From the chromatogram obtained by SEC under the following conditions, the number average molecular weight (M n,SEC ) and the molecular weight distribution D of the polymer were calculated based on the molecular weight calibration curve prepared with standard polystyrene. Autosampler: Jasco AS-4550 Guard column: Shodex KF-G 4A (4.6 mm × 10 mm) Solvent separation column: Shodex KF-800D, (8.0 mm × 100 mm), Column: Shodex KF-804L (linear, 8 mm × 300 mm), Exclusion limit molecular weight: 300,000, Particle size: 7 μm Shodex KF-806L (linear, 8 mm × 300 mm), Exclusion limit molecular weight: 20,000,000, Particle size: 10 μm Column oven: Jasco CO-2065 Plus Differential refractive index detector: Jasco RI-4030 Liquid delivery pump: Jasco PU-4180 Degassing device: Jasco DG-4000-04 Solvent: THF Measurement temperature: 40 °C Flow rate: 1.0 mL / min Standard substance: Polystyrene (Molecular weight: 2,170; 3,070; 4,430; 7,210; 19,600; 55,100; 133,000; 275,000; 815,000; 1,320,000)

[0074] 2-3. Preparative SEC The polymer was purified by preparative SEC under the following apparatus and conditions. Apparatus: LaboACE LC-7080 (Nippon Bunko Kogyo Co., Ltd.) Column: JAIGEL-2HR (linear, 20 mm × 600 mm), Exclusion limit molecular weight: 5,000 JAIGEL-2.5HR (linear, 20 mm × 600 mm), Exclusion limit molecular weight: 20,000 Measurement temperature: Room temperature Solvent: CHCl3 Flow rate: 10 mL / min

[0075] 2-4. SEC with multi-angle light scattering and viscosity detector (SEC-MALS-Visco) The polymer was analyzed by SEC-MALS-Visco under the following conditions. The number average molecular weight (absolute molecular weight, M n,MALS ) was calculated by the light scattering method. Guard column: Shodex K-800D (8.0 mm × 100 mm) Column: Shodex K-804L (linear, 8 mm × 100 mm), and Shodex K-806L (linear, 8 mm × 100 mm), particle size: 10 μm Column oven: Jasco CO-2065 Plus Differential refractive index detector: Shodex RI-501 Light scattering meter: DAWN 8 Viscosity meter: Viscostar viscosity detector Liquid delivery pump: PU-4180 Autosampler: Jasco AS-4550 Solvent: CHCl3 Measurement temperature: 40 °C Flow rate: 1.0 mL / min

[0076] 2-5. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) A THF solution of the polymer (concentration 5 mg / mL), a THF solution of the matrix (concentration 20 mg / mL), and a THF solution of the cationizing agent (concentration 10 mg / mL) were mixed at a volume ratio of 1 / 4 / 2. 1.0 μL of the resulting mixed solution was dropped onto a sample plate and air-dried to form a measurement sample. Apparatus: Bruker Daltonics, ultraflex III (Nd: YAG laser; 355 nm) Measurement method: Reflector Positive Matrix: DCTB Cationizing agent: Potassium trifluoroacetate

[0077] 2-6. Differential scanning calorimetry (DSC) The DSC of the second heating process of the polymer was recorded by measurement under the following conditions. The glass transition temperature Tg of the polymer was determined from the obtained DSC. Apparatus: DSC7000X (Hitachi High-Tech Science) Measurement range: -100 °C to 200 °C (2nd heating) Heating rate: 10 °C / min Cooling rate: 20 °C / min Nitrogen atmosphere

[0078] 2-7. Thermogravimetric (TGA) measurement The thermal decomposition temperature (5% weight loss temperature, T d,5% ) of the polymer was determined by TGA measurement under the following conditions. Apparatus: STA200RU (Hitachi High-Tech Science) Measurement range: 30 to 550 °C Heating rate: 10 °C / min Nitrogen atmosphere

[0079] 3. Synthesis of cyclic ether compounds Synthesis Example 3-1 Synthesis of (1S,5R)-7,8-dioxaspiro[bicyclo[3.2.1]octane-2,2’-oxirane] (DBOO) [Chemical formula]

[0080] (CH3)3SOI (58.5 g, 254 mmol, 1.1 eq.) and NaH (7.03 g, 293 mmol, 1.3 eq.) were placed in a flask, and the system was purged with argon. Dry THF (300 mL) was added to the mixture in the flask under an argon atmosphere. Subsequently, while cooling the flask in an ice bath, dry DMSO (225 mL) was further added to form a reaction solution. The system was gradually heated to 40 °C, and after the generation of gas from the reaction solution completely ceased, silene (trade name, 30.0 g, 234 mmol, 1 eq.) was added to the reaction solution in an ice bath. Thereafter, the flask was taken out of the ice bath, and the reaction was allowed to proceed at room temperature for 5 hours. The reaction was stopped by adding water. Five extraction operations were performed with ethyl acetate (300 mL). The organic layer was washed with brine (300 mL), and then the solvent was distilled off under reduced pressure from the organic layer. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 1 / 1, 1 / 2 (v / v), Rf = 0.39, 0.49). The obtained crude product was distilled in the presence of CaH2 to obtain DBOO as a colorless transparent viscous substance (yield: 7.09 g, yield: 21.3%). Figures 1 and 2 are the 1 1H NMR spectrum and 13 13C NMR spectrum, respectively. Each spectrum was the same as that reported in Non-Patent Document 4. The diastereoselectivity (dr) was approximately 1:1.

[0081] Synthesis Example 3-2 (1R,5S)-7,8-dioxaspiro[bicyclo[3.2.1]octane-2,2'-oxetane] (DBOO 4 ) synthesis

Chemical Structure

[0082] (CH3)3SOI (95.25 g, 433 mmol, 1.04 eq.) and NaH (12.21 g, 509 mmol, 1.23 eq.) were placed in a flask, and the system was purged with argon. Dry THF (500 mL) was added to the mixture in the flask under an argon atmosphere. Subsequently, while cooling the flask in an ice bath, dry DMSO (100 mL) was further added to form a reaction solution. The system was gradually heated to 40 °C, and after the generation of gas from the reaction solution completely ceased, silene (trade name, 53.17 g, 415 mmol, 1 eq.) was added to the reaction solution in an ice bath. The flask was taken out of the ice bath, and the reaction was allowed to proceed at room temperature for 20 hours. The reaction was stopped by adding water. Extraction was performed three times with ethyl acetate (300 mL). The organic layer was washed with water (300 mL), and then the solvent was distilled off under reduced pressure from the organic layer. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 1 / 1, 1 / 2 (v / v), Rf = n.d., 0.28). 4 The crude product, which is a fraction containing 4 DBOO, was distilled to obtain DBOO as a colorless transparent viscous substance 4 (yield: 2.35 g, yield rate: 4.2%). Since the fraction containing DBOO, which is a by-product, obtained by silica gel column chromatography was small, isolation by distillation from there was not performed. Figures 3 and 4 are the 1 1H NMR spectrum and 13 13C NMR spectrum of the obtained DBOO, respectively.

[0083] Synthesis Example 3-3 (1R,5S)-7,8-dioxaspiro[bicyclo[3.2.1]octane-2,2'-oxiran]-3-ene (DBOE) Synthesis [Chemical formula]

[0084] DBOE was obtained (yield: 16.4%) in substantially the same procedure as in Synthesis Example 3-1, except that levoglucosenone (LGO) was used instead of sirene and (CH3)3SI was used instead of (CH3)3SOI. Figures 5 and 6 are the 1 1H NMR spectrum and 13 13C NMR spectrum of the obtained DBOE, respectively.

[0085] 4. Synthesis of Polymer Synthesis Example 4-1 P(PA-alt-DBOO)

Chemical formula

[0086] In a dry box, phthalic anhydride (PA, 1.51 g, 10.2 mmol, 70 eq.), DBOO (4.11 g, 28.9 mmol, 200 eq.), 1,4-benzenedimethanol (BDM, 20.4 mg, 0.148 mmol, 1 eq.), and cesium pivalate (CP, 35 mg, 0.150 mmol, 1 eq.) were placed in a needle flask. The mixture in the flask was stirred while heating to 60 °C to allow the polymerization reaction to proceed. After 120 hours, the polymerization reaction was stopped by lowering the temperature in the flask to room temperature. The product was dissolved in a small amount of CH2Cl2, and a solid crude product was obtained by reprecipitation into methanol. The crude product was purified by preparative SEC, and the solvent was distilled off under reduced pressure from the fraction containing the product to obtain the target polyester P(PA-alt-DBOO) as a yellowish-brown powder (yield: 557 mg, yield: 23.6%). Figure 7 is the 1 1H NMR spectrum of the obtained P(PA-alt-DBOO).

[0087] Synthesis Example 4-2 P(PA-alt-DBOO)

Chemical formula

[0088] PA (383 mg, 2.59 mmol, 30 eq.), DBOO (370 mg, 2.60 mmol, 30 eq.), BDM (12.0 mg, 86.8 μmol, 1 eq.), CP (20.0 mg, 85.5 μmol, 1 eq.), and dehydrated toluene (517 μL) were placed in a flask. The mixture in the flask was stirred while heating to 100 °C to allow the polymerization reaction to proceed. After 8 hours, the polymerization reaction was stopped by lowering the temperature in the flask to room temperature. Thereafter, the target polyester P(PA-alt-DBOO) was obtained as a yellowish-brown powder by the same purification operation as in Synthesis Example 4-1 (yield: 136 mg, yield rate: 25.1%).

[0089] Synthesis Example 4-3

Chemical Structure

Chemical Structure

[0090] P(GA-alt-DBOO) In a dry box, glutaric anhydride (GA, 460 mg, 4.03 mmol, 100 eq.), DBOO (570 mg, 4.01 mmol, 100 eq.), BDM (5.5 mg, 39.8 μmol, 1 eq.), CP (9.4 mg, 40.2 μmol, 1 eq.), and dehydrated toluene (800 μL) were placed in a test tube. The mixture in the flask was stirred while heating to 100 °C to allow the polymerization reaction to proceed. After 72 hours, the polymerization reaction was stopped by adding a small amount of CH2Cl2. Thereafter, the target polyester P(GA-alt-DBOO) was obtained as a white powder by the same purification operation as in Synthesis Example 4-1 (yield: 291 mg, yield rate: 33.1%). Figure 8 is the 1 1H NMR spectrum of the obtained P(GA-alt-DBOO).

[0091] P(SA-alt-DBOO) In a dry box, succinic anhydride (SA, 400 mg, 4.00 mmol, 100 eq.), DBOO (570 mg, 4.00 mmol, 100 eq.), BDM (5.5 mg, 39.8 μmol, 1 eq.), CP (9.4 mg, 40.1 μmol, 1 eq.), and dehydrated toluene (800 μL) were placed in a test tube. The mixture in the test tube was stirred while heating to 100 °C to proceed with the polymerization reaction. After 96 hours, the polymerization reaction was stopped by lowering the temperature in the test tube to room temperature. Thereafter, by the same purification operation as in Synthesis Example 4-1, the target alternating polymer P(SA-alt-DBOO) was obtained as a brown powder (yield: 207 mg, yield: 24.0%). Figure 9 is the 1 1H NMR spectrum of.

[0092] P(DGA-alt-DBOO) In a dry box, diglycolic anhydride (DGA, 465 mg, 4.00 mmol, 100 eq.), DBOO (569 mg, 4.00 mmol, 100 eq.), BDM (5.5 mg, 39.8 μmol, 1 eq.), CP (9.4 mg, 40.2 μmol, 1 eq.), and dehydrated toluene (800 μL) were placed in a test tube. The mixture in the test tube was stirred while heating to 100 °C to proceed with the polymerization reaction. After 96 hours, the polymerization reaction was stopped by lowering the temperature in the test tube to room temperature. Thereafter, by the same purification operation as in Synthesis Example 4-1, the target polyester P(DGA-alt-DBOO) was obtained as a pale orange powder (yield: 327 mg, yield: 31.5%). Figure 10 is the 1 1H NMR spectrum of.

[0093] P(NA-alt-DBOO) In a dry box, 5-norbornene-endo-2,3-dicarboxylic anhydride (NA, 660 mg, 4.02 mmol, 100 eq.), DBOO (570 mg, 4.01 mmol, 100 eq.), BDM (5.5 mg, 39.8 μmol, 1 eq.), CP (9.4 mg, 40.2 μmol, 1 eq.), and dehydrated toluene (800 μL) were placed in a test tube. The mixture in the test tube was stirred while heating to 80 °C to allow the polymerization reaction to proceed. After 620 hours, the polymerization reaction was stopped by lowering the temperature in the test tube to room temperature. Thereafter, by the same purification operation as in Synthesis Example 4-1, the target polyether P(NA-alt-DBOO) was obtained as a brown powder (yield: 366 mg). Figure 11 is the 1 1H NMR spectrum of the obtained P(NA-alt-DBOO).

[0094] Synthesis Example 4-4-1 P(PA-alt-DBOO 4 ) [Chemical formula]

[0095] In a dry box, PA (365 mg, 2.46 mmol, 70 eq.), DBOO 4 (1155 mg, 7.40 mmol, 210 eq.), BDM (4.9 mg, 35.5 μmol, 1 eq.) and CP (8.3 mg, 35.5 μmol, 1 eq.) were placed in a needle flask. The mixture in the flask was stirred while heating to 130 °C to allow the polymerization reaction to proceed. After 165 hours, the polymerization reaction was stopped by lowering the temperature in the flask to room temperature. By reprecipitation into cooled methanol, the target polyester P(PA-alt-DBOO 4 ) was obtained (yield: 522 mg, yield: 77.3%).

[0096] Synthesis Example 4-4-2 P(PA-alt-DBOO 4 )(Resynthesis) In the dry box, PA (245 mg, 1.65 mmol, 70 eq.), DBOO 4 (780 mg, 4.99 mmol, 210 eq.), BDM (3.3 mg, 23.9 μmol, 1 eq.) and CP (5.5 mg, 23.5 μmol, 1 eq.) were added to the needle flask. The mixture in the flask was stirred while heating to 150 °C to allow the polymerization reaction to proceed. After 59 hours, the polymerization reaction was stopped by lowering the temperature in the flask to room temperature. By reprecipitation into cooled methanol, the target polyester P(PA-alt-DBOO 4 ) was obtained as a brown powder (yield: 161 mg, yield: 54.8%). Figure 12 shows the 4 1H NMR spectrum of the obtained P(PA-alt-DBOO 1 ).

[0097] Synthesis Example 4-5 P(PA-alt-DBOE)

Chemical formula

[0098] Synthesis Example 4-6 P(DBOO-co-HO)

Chemical formula

[0099] In a dry box, HO (155 mg, 1.55 mmol, 40 eq.), DBOO (220 mg, 1.55 mmol, 40 eq.), BDM (5.3 mg, 38.4 μmol, 1 eq.), and CP (9.1 mg, 38.9 μmol, 1 eq.) were placed in a flask. The mixture in the flask was stirred while heating to 100 °C to allow the polymerization reaction to proceed. After 2 hours, it was returned to room temperature to stop the polymerization reaction. A small amount of CH2Cl2 was added, and the target polyether P(DBOO-co-HO) was obtained as a pale yellow powder by reprecipitation into cooled methanol (yield: 169 mg, yield rate: 53.8%). Figure 14 shows the 1 1H NMR spectrum of the obtained P(DBOO-co-HO).

[0100] Synthesis Example 4-7-1 P(DBOE-co-HO)

Chemical Structure

[0101] In a dry box, HO (135 eq.), DBOE (15 eq.), BDM (1 eq.), and CP (1 eq.) were placed in a flask. The mixture in the flask was stirred while heating to 100 °C to allow the polymerization reaction to proceed. After 9 hours, it was returned to room temperature to stop the polymerization reaction. A small amount of CH2Cl2 was added, and the target polyether P(DBOE-co-HO) was obtained.

[0102] Synthesis Example 4-7-2 P(DBOE-co-HO) (Resynthesis) In a dry box, HO (125 eq.), DBOE (40 eq.), BDM (1 eq.), and CP (1 eq.) were placed in a flask. The mixture in the flask was stirred while heating to 100 °C to allow the polymerization reaction to proceed. After 11.5 hours, it was returned to room temperature to stop the polymerization reaction. A small amount of CH2Cl2 was added, and the target polyether P(DBOE-co-HO) was obtained. Figure 15 shows the 11H NMR spectrum.

[0103] Synthesis Examples 4-8 PDBOO

Chemical formula

[0104] In a reaction vessel under an argon atmosphere, DBOO (2.64 mmol) was dissolved in anisole (660 μL) to form a reaction solution. A THF solution of potassium tert-butoxide (concentration: 1 M) and 16-crown-6-ether (18C6) were added thereto. The reaction solution was stirred while heating to 100 °C to allow the polymerization reaction to proceed. The molar ratio of the charged amounts of DBOO / tBuOK / 18C6 was 50 / 1 / 1. After 4.5 hours, heating of the reaction solution was stopped. The target PDBOO was obtained from the reaction solution by a conventional method. PDBOO was obtained in the same procedure except that the molar ratio of the charged amounts of DBOO / tBuOK / 18C6 was changed to 100 / 1 / 1 and the reaction time was changed to 2.5 hours. Figure 16 is the 1 1H NMR spectrum. PDBOO was obtained in the same procedure except that the molar ratio of the charged amounts of DBOO / tBuOK / 18C6 was changed to 200 / 1 / 1 and the reaction time was changed to 4.5 hours.

[0105] Synthesis Example 4-9 PDBOE

Chemical formula

[0106] In a reaction vessel under an argon atmosphere, DBOE (4.46 mmol) was dissolved in anisole (1115 mL) to form a reaction solution. CP was added thereto. The reaction solution was stirred while heating to 100 °C to allow the polymerization reaction to proceed. The molar ratio of the charged amounts of DBOE / CP was 100 / 1. After 40 hours, heating of the reaction solution was stopped. The target polyether, PDBOE (a homopolymer of DBOE), was obtained from the reaction solution by a conventional method. Figure 17 is the1 It is an H NMR spectrum.

[0107] 5. Evaluation 5-1. Copolymer The number average molecular weight (M n,NMR and M n,SEC ), molecular weight dispersity D, glass transition temperature Tg, and thermal decomposition temperature T d,5% were measured. The results are shown in Table 1. Some physical properties were not measured.

[0108]

Table 1

[0109] 5-2. Homopolymer The number average molecular weight (M n,SEC ) and molecular weight dispersity D of PDBOO obtained in Synthesis Example 4-8 were measured. The glass transition temperature Tg and thermal decomposition temperature T d,5% of PDBOE obtained in Synthesis Example 4-9 were also measured. The results are shown in Table 2.

[0110]

Table 2

[0111] PDBOO obtained in Synthesis Example 4-8 was analyzed by MALDI-TOF MS. In the obtained mass spectrum, peaks attributed to the fragment ions of the following formula were confirmed. Table 3 shows the measured values of the molecular weights of each peak together with the theoretical values.

[0112]

Chemical formula

[0113]

Table 3

[0114] 6. Synthesis of low molecular weight compounds Synthesis Example 6-1 [Chemical formula] 3-Phenyl-1-propanol (105.5 mg, 0.77 mmol), DBOO (100.0 mg, 0.70 mmol) and cesium pivalate (16.5 mg, 0.070 mmol) were mixed in a test tube. Toluene (0.77 mL) was added thereto. The mixture in the test tube was heated at 80 °C for 30 hours. The crude product obtained by the reaction was purified by silica gel column chromatography (hexane / ethyl acetate = 2 / 1 (v / v), Rf = 0.13, 0.23) to obtain low molecular weight compound 6-1 as two colorless liquids containing diastereomers (yield = 143 mg, yield = 70%, dr = about 68:32). For each of the major and minor components of the diastereomers, 1 1H NMR spectrum and 13 13C NMR spectrum were measured. Major component (Rf = 0.23) 1 1H NMR (400 MHz, CDCl3): δ(ppm)7.31 - 7.25 (m, 2H), 7.21 - 7.15 (m, 3H), 5.26 (s, 1H), 4.56 - 4.52 (m, 1H),3.85 (d, J = 6.8 Hz, 1H), 3.79 (ddd, J = 7.2, 5.2, 1.2 Hz, 1H), 3.48 (t, J =6.4 Hz, 2H),3.45 (d, J = 9.6 Hz, 1H), 3.23 (d, J = 9.6 Hz, 1H), 2.71 (s, 1H),2.68 (t, J =8.0 Hz, 2H), 2.21 - 2.10 (m, 1H), 1.96 - 1.87 (m, 2H), 1.66 - 1.44 (m,3H). 13 13C-NMR (100 MHz, CDCl3): δ(ppm)141.8, 128.4, 128.3, 125.8, 102.1, 74.1, 73.0, 71.0, 70.8, 67.0, 32.2,31.0,25.1, 24.9 Minor component (Rf = 0.13) 1 1H NMR (400 MHz, CDCl3): δ (ppm) 7.31 - 7.25 (m, 2H), 7.21 - 7.15 (m, 3H), 5.27 (s, 1H), 4.56 - 4.50 (m, 1H), 3.89 (d, J = 7.2 Hz, 1H), 3.82 (ddd, J = 7.2, 5.2, 1.6 Hz, 1H), 3.63 (d, J = 9.6 Hz, 1H), 3.49 (t, J = 6.4 Hz, 2H), 3.37 (d, J = 9.6 Hz, 1H), 2.69 (t, J = 8.0 Hz, 2H), 2.51 (s, 1H), 1.96 - 1.79 (m, 3H), 1.76 - 1.70 (m, 2H), 1.59 - 1.51 (m, 1H) 13 13C-NMR (100 MHz, CDCl3): δ (ppm) 141.8, 128.4, 128.3, 125.8, 102.9, 73.2, 73.0, 72.8, 70.8, 67.8, 32.3, 31.0, 27.1, 26.9

[0115] Synthesis Example 6-2

Chemical formula

[0116] Synthesis Example 6-3

Chem.

[0117] 7. Crosslinked polymer Synthesis Example 7-1 Crosslinking of P(DBOE-co-HO) by thiol-ene reaction

Chem.

[0118] P(DBOE-co-HO) (60 eq.) obtained in Synthesis Example 4-7-1 or Synthesis Example 4-7-2, dipentaerythritol hexakis(3-mercaptopropionate) (crosslinking agent, 10 eq.), 2,2-dimethoxy-2-phenylacetophenone (photoinitiator, 1 eq.), and dimethylformamide were mixed to form a reaction solution. The amount of dimethylformamide was 5 mL per 1 mmol of P(DBOE-co-HO). The reaction solution was irradiated with light having a wavelength of 365 nm at room temperature for 4 hours. By the light irradiation, a liquid product was formed from the P(DBOE-co-HO) of Synthesis Example 4-7-1, and a solid product was formed from the P(DBOE-co-HO) of Synthesis Example 4-7-2. The solid product recovered from the reaction solution of the P(DBOE-co-HO) of Synthesis Example 4-7-2 was insoluble in chloroform and THF. It was suggested that a crosslinked polymer with a high crosslinking density was formed from the P(DBOE-co-HO) of Synthesis Example 4-7-2 which contains a relatively large amount of structural units derived from DBOE.

[0119] Synthesis Example 7-2 Crosslinking by cationic ring-opening copolymerization of DBOO and 1,3-dioxolane

Chemical formula

[0120] DBOO (10 eq.), 1,3-dioxolane (90 eq.), and boron trifluoride diethyl ether complex (1 eq.) were mixed to form a reaction solution. After standing at room temperature for within 1 minute, 100 equivalents of piperidine were added to the boron trifluoride diethyl ether complex to stop the reaction. Since the product was insoluble in dichloromethane and swelled, it was suggested that a crosslinked polymer (P(DBOO-co-DXL)) was formed. For a control experiment, 1,3-dioxolane (90 eq.) and boron trifluoride diethyl ether complex (1 eq.) were mixed to form a reaction solution that did not contain DBOO. After standing at room temperature for less than 1 minute, 100 equivalents of piperidine were added to the boron trifluoride diethyl ether complex to terminate the reaction. The resulting poly(1,3-dioxolane) was dissolved in dichloromethane, suggesting that no crosslinking reaction had occurred. This result also supports the idea that in the above synthesis example where DBOO was introduced into the reaction solution, a crosslinked polymer insoluble in dichloromethane was produced by the crosslinking reaction involving DBOO.

Claims

1. The following formula (1) or (2): 【Chemical 1】 【Chemical 2】 A polymer comprising a plurality of structural units represented by R １ wherein R represents a methylene group or an ethane-1,2-diyl group.

2. The following formula (100) or (200): [Chemical 3] 【Chemical Formula 4】 comprising a plurality of structural units represented by R １ represents a methylene group or an ethane-1,2-diyl group, and R ２ is a divalent organic group containing a hydrocarbon group bonded to each of two carbonyl groups in formula (100) or (200), the polymer according to claim 1.

3. The following formula (5): 【Chemical Formula 5】 further includes a structural unit represented by, and R ３ represents a methylene group or an ethane-1,2-diyl group, and R ４ represents a monovalent hydrocarbon group which may have a substituent, the polymer according to claim 1.

4. The following formula (1A) or (2A): [Chemical Formula 6] 【Chemical Formula 7】 A polymer comprising a plurality of structural units represented by R １ wherein R represents a methylene group or an ethane-1,2-diyl group.

5. The following formula (100A) or (200A): 【Chemical 8】 【Chemical Formula 9】 comprising a plurality of structural units represented by R １ represents a methylene group or an ethane-1,2-diyl group, and R ２ represents a divalent organic group containing a hydrocarbon group bonded to each of two carbonyl groups in formula (100A) or (200A), the polymer according to claim 4.

6. The following formula (5): 【Chemical 10】 further includes a structural unit represented by R ３ represents a methylene group or an ethane-1,2-diyl group, and R ４ represents a monovalent hydrocarbon group which may have a substituent, the polymer according to claim 4.

7. The polymer according to claim 1, comprising only the structural unit represented by formula (1) or (2) as a repeating unit.

8. The following formula (110) or (210): 【Chemical Formula 11】 【Chemical 12】 A polymer comprising a plurality of structural units represented by R １ wherein R represents a methylene group or an ethane-1,2-diyl group, and * represents a bond, and which is a crosslinked polymer.

9. The following formula (220): 【Chemical Formula 13】 A polymer comprising a plurality of structural units represented by R １ wherein R represents a methylene group or an ethane-1,2-diyl group, and * represents a bond, and which is a crosslinked polymer.

10. The following formula (12) or (22): 【Chemical Formula 14】 【Chemical Formula 15】 An oxetane compound represented by

11. The following formula (10) or (20): 【Chemical 16】 【Chemical 17】 A curable resin composition containing a cyclic ether compound represented by R １ wherein R represents a methylene group or an ethane-1,2-diyl group.

12. The following formula (15) or (25): 【Chemical Formula 18】 【Chemical Formula 19】 represented by R １ represents a methylene group or an ethane-1,2-diyl group, and Z is represented by the following formula (a), (b), (c) or (d): 【Chemical 20】 represents a monovalent group, and R ５ represents a monovalent organic group, and R ６ represents a monovalent organic group that does not contain a carbonyl group bonded to the oxygen atom in formula (b), and R ７ and R ８ each independently represent a hydrogen atom or a monovalent organic group, and R ７ and R ８ may be bonded to each other to form a cyclic structure, and R ９ represents a monovalent organic group, a compound.

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