Polyester and methods for preparing these polyesters

Abstract

The present invention relates to a polymer comprising a unit derived from a carboxylic acid or its anhydride containing at least two carboxyl groups and a unit derived from an alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups is of formula (IX): [Chemical formula 1] JPEG2026513356000042.jpg31170(wherein R 1 is ethyl, -CH2-CH2-CH2OH, or -CH(-CH3)-CH2OH, R 2 is H or -CH2OH, but when R 1 is ethyl, R 2 is not H.) a bicyclic aliphatic diol, and a method for preparing a polymer by reacting at least one carboxylic acid or its anhydride or ester containing at least two carboxyl groups with at least one alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups used is the bicyclic aliphatic diol of the above formula (IX), and use of the polymer according to the present invention or the polymer obtained by the method according to the present invention as a lacquer, coating agent, or adhesive, preferably a coating agent for tubes or cans, an enamel for metal decoration, a hot melt lacquer, a hot laminating adhesive, or a primer, or use for producing these, and relates to.

Description

[Technical Field]

[0001] The present invention A polymer comprising units derived from a carboxylic acid or its anhydride containing at least two carboxyl groups, and units derived from an alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups is of formula (IX):

[0002] [ka]

[0003] (In the formula, R 1 R is ethyl, -CH2-CH2-CH2OH, or -CH(-CH3)-CH2OH, 2 is H or -CH2OH, but R 1 If R is ethyl, 2 (It's not H.) A polymer that is a bicyclic aliphatic diol, A method for preparing a polymer by reacting at least one carboxylic acid or its anhydride or ester containing at least two carboxyl groups with at least one alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups used is a bicyclic aliphatic diol of formula (IX). The polymer according to the present invention or the polymer obtained by the method according to the present invention may be used as a lacquer, coating agent, or adhesive, preferably a coating agent for tubes or cans, a metal decorative enamel, a heat-seal lacquer, a hot laminating adhesive, or a primer, or may be used to manufacture these. Regarding. [Background technology]

[0004] Mijolovic et al., in International Publication No. 2011 / 023540 (U.S. Patent Application Publication No. 2012 / 0157548), described formula (II):

[0005] [ka]

[0006] Starting with the (E) / (Z) isomer of , formula (I):

[0007] [ka]

[0008] This document describes the production of a mixture of compounds. This synthesis consists of a two-step process, in which the compound of formula (II) is hydroformed under harsh reaction conditions (temperature: 140°C, CO / H2: 2-60 MPa, 1 / 1) using a rhodium catalyst to produce the corresponding compound of formula (III):

[0009] [ka]

[0010] It is converted into an aldehyde. A mixture of regioisomers of an aldehyde is separated by distillation, and then reduced with RANEY®-Ni at a reaction temperature of 170°C and an H2 pressure of 28 MPa to obtain a mixture of bicyclic diol compounds of formula (I). It has also been mentioned that 5-vinyl-2-norvonene (VNB) of formula (VI) can be used as a starting material.

[0011] Formula (IV):

[0012] [ka]

[0013] Polyesters or polymers using disidol (tricyclodecanedimethanol), represented by , as a monomer have long been known in the art (ACS Sustainable Chem. Eng. 2020, 8, pp. 15199-15208 and J Polym Res (2016) 23:42, DOI 10.1007 / s10965-016-0933-5; European Patent Application Publication No. 0934988, European Patent Application Publication No. 1398337, and European Patent Application Publication No. 2853551). Such polyesters can be used, for example, as coatings for tubes or cans, enamels for metal decoration, heat-seal lacquers, hot-laminate adhesives, or primers, or for the manufacture of these. [Prior art documents] [Patent Documents]

[0014] [Patent Document 1] International Publication No. 2011 / 023540 Pamphlet [Patent Document 2] U.S. Patent Application Publication No. 2012 / 0157548 [Patent Document 3] European Patent Application Publication No. 0934988 [Patent Document 4] European Patent Application Publication No. 1398337 [Patent Document 5] European Patent Application Publication No. 2853551 [Non-patent literature]

[0015] [Non-Patent Document 1] ACS Sustainable Chem. Eng. 2020, 8, pp. 15199-15208 [Non-Patent Document 2] J Polym Res (2016) 23:42, DOI10.1007 / s10965-016-0933-5 [Overview of the project] [Problems that the invention aims to solve]

[0016] The problem that the present invention aims to solve is to provide alternative polyesters that are useful as lacquers, coatings, or adhesives, preferably coatings for tubes, coils, or cans, enamels for metal decoration, heat-seal lacquers, hot-laminate adhesives, or primers, or useful in the manufacture of these. [Means for solving the problem]

[0017] Surprisingly, this problem was found to be solved by the polymer according to the present invention as described in the claims.

[0018] Therefore, the present invention is a polymer comprising units derived from a carboxylic acid or an anhydride containing at least two carboxyl groups, and units derived from an alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups is of formula (IX):

[0019] [ka]

[0020] (In the formula, R 1 R is ethyl, -CH2-CH2-CH2OH, or -CH(-CH3)-CH2OH, 2 is H or -CH2OH, but R 1 If R is ethyl, 2 (It's not H.) This relates to a polymer that is a bicyclic aliphatic diol.

[0021] The present invention further relates to a method for preparing a polymer by reacting at least one carboxylic acid or its anhydride or ester containing at least two carboxyl groups with at least one alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups used is a bicyclic aliphatic diol of formula (IX).

[0022] The present invention further provides the use of the polymer according to the present invention or the polymer obtained by the method according to the present invention as a coating agent for tubes, coils, or cans, a metal decorative enamel, a heat-seal lacquer, a hot laminating adhesive, or a primer, or uses (methods of use) for producing them.

[0023] The polymers of the present invention can exhibit a wide range of glass transition temperatures similar to those of polyesters using disidol as a monomer, without the use of disidol. The polymers of the present invention have the advantage that a broader pool of industrial raw materials can be used to prepare polymers that are useful as coatings for tubes, coils, or cans, enamels for metal decoration, heat-seal lacquers, hot-laminate adhesives, or primers, or useful in the manufacture of these.

[0024] The polymer or its starting material, the diol, according to the present invention can be obtained under more stringent conditions in the manufacturing process than those described in the prior art.

[0025] The polymers, methods, and uses according to the present invention are described below by way of example, but the present invention is not intended to be limited to these exemplary embodiments. When ranges, general formulas, or groups of compounds are specified below, these are intended to include not only the corresponding ranges or groups of compounds explicitly described, but also all sub-ranges and sub-groups of compounds obtained by excluding individual values (ranges) or compounds. When a document is cited in the context of this specification, its content shall be considered as fully constituting a part of the disclosure of the present invention with respect to the matters specifically mentioned. The percentages specified below are weight percentages unless otherwise specified. When average values are reported below, they are numerical averages unless otherwise specified. When referring to material properties such as viscosity below, they are material properties at 25 °C unless otherwise specified. When chemical formulas (empirical formulas) are used in the present invention, the specified indices can be not only absolute values but also average values.

[0026] The present invention relates to a polymer comprising units derived from a carboxylic acid or its anhydride containing at least two carboxyl groups and units derived from an alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups is of formula (IX):

[0027]

Chemical formula

[0028] (wherein R 1 is ethyl, -CH2-CH2-CH2OH, or -CH(-CH3)-CH2OH, and R 2 is H or -CH2OH, provided that when R 1 is ethyl, R 2 is not H.) relates to a polymer which is a bicyclic aliphatic diol of . Preferably, the alcohol containing at least two OH groups is a bicyclic aliphatic diol of formula (I).

[0029] Preferably at least 50 mol%, more preferably 60-100 mol%, and most preferably 70-95 mol% of the units derived from an alcohol containing at least two OH groups in the polymer are based on a bicyclic aliphatic diol of formula (IX).

[0030] The bicyclic aliphatic diol is preferably 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (formula (IXa)):

[0031] [ka]

[0032] , 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (formula (IXb)):

[0033] [ka]

[0034] , 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (formula (IXc)):

[0035] [ka]

[0036] , 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (formula (IXd)):

[0037] [ka]

[0038] , (3-ethylbicyclo[2.2.1]heptane-2,5-diyl)dimethanol (formula (IXe)):

[0039] [ka]

[0040] , (3-ethylbicyclo[2.2.1]heptane-2,6-diyl)dimethanol (formula (IXf)):

[0041] [ka]

[0042] Bicyclic aliphatic diols are 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)-propan-1-ol, 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol, or a mixture of (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol. Bicyclic aliphatic diols or mixtures thereof are available as described in International Publication Brochure No. 2011 / 023540.

[0043] Most preferably, units derived from alcohols containing at least two OH groups are derived from a mixture of 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)-propan-1-ol, 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol, and (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol.

[0044] The units derived from carboxylic acids containing at least two carboxyl groups are preferably derived from phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, malonic acid, 1,2,4-benzenetricarboxylic acid, glutaric acid, adipic acid, 2,2,4-trimethyladipic acid, azelaic acid, succinic acid, undecanediic acid, octadecanediic acid, dimeric fatty acids, itaconic acid, fumaric acid, naphthalene-2,6-dicarboxylic acid, or sebacic acid, or their anhydrides or esters, more preferably from phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, or sebacic acid, most preferably from terephthalic acid.

[0045] The polymer according to the present invention preferably contains at least 50 mol%, more preferably 60 to 100 mol%, and most preferably 70 to 95 mol%, of phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, or sebacic acid, or mixtures thereof, most preferably units derived from carboxylic acids containing at least two carboxyl groups, based on terephthalic acid.

[0046] The polymer according to the present invention may preferably consist only of units derived from a carboxylic acid or its anhydride containing at least two carboxyl groups, and units derived from a bicyclic aliphatic diol.

[0047] However, the polymer according to the present invention may also include, as monomers, one or more hydroxyl group-based units comprising an organic acid, preferably hydroxystearic acid or glycolic acid. Preferably, the polymer according to the present invention contains, as monomers, one or more hydroxyl group-based units comprising an organic acid, preferably hydroxystearic acid or glycolic acid, in an amount of up to 50 mol%, more preferably 0 to 40 mol%, and most preferably 10 to 30 mol%.

[0048] One or more hydroxyl group-based units containing organic acids may be distributed randomly in the polymer or as one or more oligomeric blocks.

[0049] The composition of the polymer can be determined by hydrolysis of the polymer and subsequent GC analysis.

[0050] The polymer according to the present invention uses a monomer that is different from a bicyclic aliphatic diol, preferably a dihydroxy compound or polyhydroxy compound, such as ethylene glycol, propylene glycol, butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, polyethylene glycol, polytetrahydrofuran, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, hydroxypivalylhydroxypivalic acid, 1,2-propanediol, 2-ethylhexane-1,3-diol, and tri It may be advantageous to further include methylhexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, glycerol, pentaerythritol, trimethylolpropane, di(trimethylolpropane), dimethylolpropionic acid, trimethylolpropane monoallyl ether, disidol(tricyclodecanedimethanol), or 2,2,4,4-tetramethylcyclobutane-1,3-diol, or mixtures thereof, more preferably ethylene glycol or propylene glycol-based units.

[0051] More preferably, the polymer according to the present invention comprises, as monomers, one or more hydroxyl group-based units including an organic acid, preferably hydroxystearic acid or glycolic acid, and as monomers, a dihydroxy compound different from a bicyclic aliphatic diol, preferably ethylene glycol or propylene glycol-based units.

[0052] The polymer according to the present invention preferably has a number-average molecular weight Mn of 8 to 25 kg / mol, as measured by the method shown in the Examples section below.

[0053] The polymer according to the present invention preferably has a weight-average molecular weight Mw of 10 to 75 kg / mol, as measured by the method shown in the Examples section below.

[0054] The polymer according to the present invention preferably has a glass transition temperature Tg of 40 to 110°C, as measured by the method shown in the Examples section below.

[0055] The polymer according to the present invention preferably has a decomposition temperature, as measured by the method shown in the Examples section below, that is greater than 350°C, more preferably greater than 375°C and less than 400°C, and most preferably greater than 377°C and less than 390°C.

[0056] More preferably, the polymer according to the present invention has a number-average molecular weight Mn of 8 to 25 kg / mol, a weight-average molecular weight Mw of 10 to 75 kg / mol, a decomposition temperature greater than 377°C and less than 390°C, and a glass transition temperature Tg of 40 to 110°C, and each parameter is measured by the method shown in the Examples section below.

[0057] The polymers according to the present invention can be prepared by any known method of polymerizing / (trans)esterifying a carboxylic acid having at least two carboxyl groups or its anhydride or ester with a compound having at least two hydroxyl groups. Preferably, the polymers according to the present invention are prepared by the method according to the present invention described below.

[0058] In the method according to the present invention for preparing a polymer by reacting at least one carboxylic acid having at least two carboxyl groups or its anhydride or ester with at least one alcohol having at least two OH groups, the alcohol having at least two OH groups used is a bicyclic aliphatic diol of formula (I). Preferably, the polymer according to the present invention is prepared by the method according to the present invention.

[0059] Preferably, the bicyclic aliphatic diols are 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (formula (IXa)), 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (formula (IXb)), 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (formula (IXc)), 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (formula (IXd)), (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol (formula (IXe)), or (3-ethylbicyclo[2.2.1]heptan-2,6-diyl) Dimethanol (formula (IXf)), or a mixture of two or more of these compounds, more preferably a mixture containing 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol, and (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol.

[0060] Preferably, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, malonic acid, 1,2,4-benzenetricarboxylic acid, glutaric acid, adipic acid, 2,2,4-trimethyladipic acid, azelaic acid, undecanediic acid, octadecanediic acid, dimeric fatty acids, itaconic acid, fumaric acid, naphthalene-2,6-dicarboxylic acid, or sebacic acid, or their anhydrides or esters, more preferably phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, or sebacic acid, or their anhydrides or esters, most preferably dimethyl terephthalate, is used as a carboxylic acid or its anhydride or ester having at least two carboxyl groups.

[0061] At the start of the reaction, it is advantageous to have a molar ratio of a carboxylic acid having at least two carboxyl groups or its anhydride or ester to a bicyclic aliphatic diol of 1:1 to 1:4, preferably 1:1.5 to 1:2.5, and most preferably 1:2.

[0062] In the method according to the present invention, as additional monomers, a hydroxyl group containing the above-mentioned organic acid and a dihydroxy compound or polyhydroxy compound different from a bicyclic aliphatic diol can be used.

[0063] The polymer is preferably prepared at a temperature above 100°C, preferably 120°C to 250°C, while removing water (esterification reaction) and / or alcohol (transesterification reaction) from the reaction mixture. Depending on the composition of the polymer to be prepared, the above-mentioned additional monomers may be added to the reaction mixture. Preferably, the reaction is carried out until no more water or alcohol is produced. The reaction is preferably carried out for 1 to 36 hours, preferably 6 to 30 hours.

[0064] Adding a catalyst to the reaction mixture may be advantageous. Preferably, a catalyst containing Ti is added to the reaction mixture, most preferably Ti(OnBu)4 as the catalyst. The amount of catalyst added is preferably 0.01 to 10 mol%, more preferably 0.5 to 5 mol%, and most preferably 1 mol%, relative to the amount of carboxylic acid used in the reaction mixture.

[0065] The polymer preparation method according to the present invention can be carried out in the presence or absence of oxygen. Preferably, the method is started at atmospheric pressure and finished under reduced pressure.

[0066] It may be advantageous to initially remove most of the released water or alcohol by distillation at standard atmospheric pressure. In subsequent steps, any remaining water or alcohol from the reaction is preferably removed by vacuum distillation, by increasing the surface area, or by introducing a stream of inert gas into the reaction mixture. A preferred inert gas is nitrogen.

[0067] It may be advantageous to further add additives such as antioxidants and color stabilizers, as well as processing aids, to the reaction (esterification) mixture.

[0068] In the method according to the present invention, Formula (V):

[0069] [ka]

[0070] (In the formula, R is vinyl, ethylidene, or acetyl, more preferably vinyl or ethylidene, and most preferably ethylidene.) Preferably, 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (Formula Ia), 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (Formula Ib), 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (Formula Ic), or 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol (Formula Id), (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol (Formula IXe), or (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol (Formula IXf), or a mixture of two or more of these compounds, obtained by a method including a hydroformylation step and a reduction step using the above compounds as starting materials, is used. The hydroformylation and reduction steps may be carried out in a single step. The hydroformylation step can be carried out in the presence of any suitable catalyst, such as a cobalt (carbonyl) catalyst or a rhodium catalyst. Preferably, the hydroformylation step is carried out in the presence of a rhodium-containing catalyst and a phosphorus-containing ligand. Preferably, the catalyst is obtained from bis(1,5-cyclooctadiene)rhodium(I)tetrafluoroborate ([Rh(COD)2]BF4) and triethylphosphan (TEP) or tris(2,4-di-tert-butylphenyl)-phosphite, the latter of which is commercially available from Addivant Corporation under the trade name Alkanox® 240 phosphite. Other possible ligands include, for example, OXOPHOS®, particularly OXOPHOS® 17, available from Evonik Operations GmbH, or (S) available from, for example, Smolecule LLC. ax S,S)-bobphos is one example.

[0071] [ka]

[0072] The hydroformylation process is preferably carried out at a temperature of 50 to 200°C, preferably 60 to 125°C, and at a pressure of 2 to 12 MPa, preferably 4 to 7 MPa, and most preferably 4.5 to 5.5 MPa for the synthesis gas (CO / H2 molar ratio preferably 2 / 1 to 1 / 1).

[0073] When using an ALKANOX® catalyst, the hydroformylation step is preferably carried out at a temperature of 75 to 125°C and a synthesis gas pressure of 4 to 7 MPa, more preferably 4.5 to 5.5 MPa (CO / H2 molar ratio preferably 1 / 1).

[0074] When using an OXOPHOS® catalyst, the hydroformylation step is preferably carried out at a temperature of 120-160°C and a synthesis gas pressure of 8-12 MPa, preferably 10 MPa, with a molar ratio of CO / H2 of 3 / 2.

[0075] (S ax When using an S,S)-bobphos catalyst, the hydroformylation step is preferably carried out at a temperature of 50-70°C and a synthesis gas pressure of 2-10 MPa, preferably 4-7 MPa, and most preferably 4.5-5.5 MPa.

[0076] After the hydroformylation step, the following diarydehyde isomers represented by formulas (Xa), (Xb), and (Xc) are obtained as intermediate products.

[0077] [ka]

[0078] The reduction step is preferably carried out in the presence of NaBH4 or in toluene / H2O using H2 and RANEY®-Ni.

[0079] However, when a compound of formula (V) (wherein R is vinyl (formula VI)) is used as the starting material, the reaction can be carried out as reductive hydroformylation without requiring an additional reduction step. The reaction temperature and synthesis gas pressure are preferably the same as the preferred ranges shown in the hydroformylation step described above.

[0080] [ka]

[0081] When the compound of formula (II) is used as the starting material, the intermediate of formula (VII) is obtained after the first reduction hydroformylation step.

[0082] [ka]

[0083] The polymers of the present invention or polymers obtained by the methods of the present invention can be used, for example, as lacquers, coatings, or adhesives, preferably coatings for tubes, coils, or cans, metal decorative enamels, heat-seal lacquers, hot laminating adhesives, or primers, or for the manufacture of these.

[0084] The present invention is further illustrated by the following non-limiting embodiments illustrating further features, embodiments, aspects, and advantages of the present invention. [Examples]

[0085] 1. Test Method a) Nuclear magnetic resonance spectroscopy (NMR spectroscopy) 1 H and 13 The ¹¹¹ nuclear magnetic resonance spectrum was measured at room temperature (298 K) using a Bruker AV400. The chemical shift is shown in ppm (parts per million), and the residual proton signal (δ) of chloroform-d3 is shown. 1 H) = 7.26 ppm, ( 13The reference was set at C = 77.2 ppm. All coupling constants (J) were reported in Hertz (Hz). The following abbreviations were used for signal multiplicity: s = singlet, d = duplet, dd = duplet of duplets, q = quartet, t = triplet, sept = septet, m = multiplet.

[0086] b) Gas chromatography-mass spectrometry (GC-MS) Gas chromatography-mass spectrometry (GC-MS) was performed using PhMe, THF, DCM, and ÃO solutions on an Agilent GC 7890B with HP-5MS UI columns (0.25 mm, 0.25 μm) and a single quadrupole mass detector MS 5977A. All samples were concentrated at 0.5 mg / mL. The operating temperature range was 45°C to 325°C.

[0087] c) Gel permeation chromatography (GPC) The average molecular weight (Mw and Mn) and polydispersity (Mw / Mn) of polymers were measured using gel permeation chromatography. The concentration range for all samples was 2 mg / mL to 4 mg / mL. Relative measurements were performed using a PL-GPC 50 Plus (Polymer Laboratories) with PLgel 5 μm MIXED-C (2 × 7.5 × 300 mm) and chloroform as the eluent and polystyrene as the standard.

[0088] d) Thermogravimetric analysis (TGA) Thermogravimetric analysis was performed using a TGA Q5000 from TA Instruments. 1 mg to 2 mg of sample was heated under an argon atmosphere at a heating rate of 10 K / min. Time-dependent mass loss was analyzed using TA Universal Software. The starting point indicates the decomposition onset temperature of the substance.

[0089] e) Differential Scanning Calorimetry (DSC) A TA Instruments DSC Q2000 was used for differential scanning calorimetry. 5 mg to 10 mg of sample was placed in an aluminum pan (Tzero) and heated from -100°C to 200°C at a rate of 10 K / min. The reported values ​​were measured by TA Universal Analysis from the third heating cycle. Decomposition temperature and glass transition temperature were also measured using this method.

[0090] 2. Raw materials used All hydroformylation reactions were carried out in a 100 mL steel autoclave equipped with a glass inlay, magnetic stirrer, and oil bath heater, in a mixed atmosphere of carbon monoxide 4.7 (≥99.999%, Westfalen AG) and hydrogen 5.0 (≥99.999%, Westfalen AG), with water and oxygen excluded. Unless otherwise specified, all other experiments were carried out using the standard Schlenk method in an argon 4.6 (≥99.999%, Westfalen AG) atmosphere. Glassware used was heated and dried under a small vacuum before use. Scaled-up hydroformylation and hydrogenation reactions were carried out in a Parr Instrument Company 4530 series 2 L floor stand reactor with a 4848 reactor control device and a Parr Instrument Company 4600 series non-agitated 2 L pressure vessel. Toluene, dichloromethane (DCM), and THF were dried using an MBraun MB SPS 800 solvent purification system and stored in 500 mL Schlenk flasks using a 4A molecular sieve. Toluene was stored in a 500 mL Schott Duran bottle in a glove box using a 4A molecular sieve. EtOH was deoxygenated by circulating argon through the solvent and stored in a 500 mL Schlenk flask using a 3A molecular sieve. ENB and VNB were stored in 500 mL Schlenk flasks using a 4A molecular sieve. All commercially available reagents were purchased from abcr GmbH, Acros Organics, Tokyo Chemical Industry Co., Ltd. (5-acetyl-2-norbornene), and Sigma Aldrich Chemie GmbH (ENB and VNB), respectively, and used without purification.

[0091] Experimental Example 1: Preparation of a diol mixture of formula (V) using ENB of formula (II) as the starting material. Experimental Example 1a: Preparation of dialdehyde according to Scheme 1a as the first step.

[0092] [ka]

[0093] In a snap-cap vial inside an autoclave, 10.14 mg (24.96 micromoles, 0.10 mol%) of [Rh(COD)2]BF4 and 50.06 mg (77.37 micromoles, 0.31 mol%) of Alkanox® (XI) were dissolved in 25 mL (1.00 M) of toluene-25. To this solution, 3.00 g (24.96 mmol, 1.00 equivalent) of formula (II) was added. The autoclave was pressurized with synthesis gas (CO / H2=1:1) at 5 MPa, and the reaction mixture was stirred at a reaction temperature of 100°C for 4 hours. The resulting pale yellow solution was cooled to room temperature and used directly for hydrogenation, or the solvent was removed by concentration. The product was purified by distillation (boiling point: 65-76°C, reduced pressure: 5-6 Pa) to obtain 3.42 g (18.47 mmol, 76%) of (X) as a colorless liquid mixture of (Xa) to (Xc).

[0094] 1 H NMR (500MHz, CDCl3, 298 K): δ (ppm) = 9.78-9.74 (m, 0.24 H, CHO), 9.67-9.53 (m, 1.76 H, CHO), 2.67-2.49 (m, 1.00 H), 2.49-2.38 (m, 1.00 H), 2.38-1.15 (m, 11 H), 1.14-0.99 (m, 3 H), 0.98-0.88 (m, 0.40 H), 0.88-0.63 (m, 0.4 H). 1 Considering the large overlap of aliphatic proton signals in the 1H-NMR spectra, we were able to assign only the resonances of the aldehyde proton signals.

[0095] 13C NMR (400 MHz, CDCl3, 298 K): δ (ppm) = 204.93 (CHO), 204.87 (CHO), 204.72 (CHO), 204.69 (CHO), 204.56 (CHO), 204.54 (CHO), 204.46 (CHO), 203.73 (CHO), 203.21 (CHO), 203.11 (CHO), 203.04 (CHO), 202.99 (CHO), 202.92 (CHO), 202.90 (CHO), 202.87 (CHO), 202.64 (CHO), 202.59 (CHO), 202.57 (CHO), 202.48 (CHO), 202.46 (CHO), 202.25 (CHO), 202.19 (CHO), 201.97 (CHO), 201.78 (CHO), 61.42 (CH), 61.09 (CH), 55.18 (CH), 55.13 (CH), 55.09 (CH), 54.82 (CH), 54.75 (CH), 53.93 (CH), 53.90 (CH), 53.80 (CH), 53.70 (CH), 51.60 (CH), 51.32 (CH), 51.15 (CH), 49.87 (CH), 49.74 (CH), 48.92 (CH), 48.87 (CH), 48.11 (CH), 47.76 (CH), 47.75 (CH), 47.66 (CH) 43.13 (CH2), 43.10 (CH), 43.08 (CH2), 43.04 (CH), 42.90 (CH), 42.84 (CH), 42.62 (CH), 42.50 (CH), 42.36 (CH2), 41.93 (CH), 41.82 (CH), 41.67 (CH), 41.61 (CH), 41.53 (CH), 41.22 (CH), 41.07 (CH), 40.79 (CH), 40.77 (CH), 40.50 (CH), 40.39 (CH), 40.21 (CH), 39.79 (CH), 39.63 (CH), 39.53 (CH), 39.49 (CH), 39.47 (CH), 39.28 (CH) 39.11 (CH), 38.74 (CH), 38.65 (CH), 38.59 (CH), 38.56 (CH), 38.48 (CH), 38.41 (CH), 38.24 (CH), 38.22 (CH), 38.19 (CH), 38.01 (CH), 37.79 (CH2), 37.70 (CH2), 37.60 (CH2), 37.54 (CH2), 37.49 (CH2), 37.48 (CH2), 36.95 (CH2), 36.88 (CH2), 36.85 (CH), 36.76 (CH), 36.65 (CH), 36.55 (CH2), 36.38 (CH2), 36.36 (CH), 36.33 (CH2), 36.28 (CH2), 36.20 (CH), 36.09 (CH), 36.05 (CH2), 35.44 (CH2), 35.27 (CH2), 35.14 (CH2), 35.10 (CH2), 35.03 (CH2), 34.94 (CH2), 33.80 (CH2), 33.73 (CH2), 33.70 (CH2), 33.64 (CH2), 33.28 (CH2), 33.25 (CH2), 30.84 (CH2), 30.82 (CH2), 30.76 (CH2), 30.66 (CH2), 30.60 (CH2), 30.47 (CH2), 29.85 (CH2), 29.54 (CH2), 29.47 (CH2), 29.18 (CH2), 28.55 (CH2), 28.32 (CH2), 25.09 (CH2), 24.90 (CH2), 24.87 (CH2), 24.78 (CH2), 23.65 (CH2), 23.25 (CH2), 22.98 (CH2), 22.91 (CH2), 13.59 (CH3), 13.24 (CH3), 13.14 (CH3), 13.08 (CH3), 12.95 (CH3), 12.89 (CH3), 11.73 (CH3), 11.72 (CH3). . GC-MS: m / z = 180, 150, 136, 107, 91, 79, 55.

[0096] Experimental Example 1b: Hydrogenation of Toluene / H2O with RANEY®-Ni

[0097] [ka]

[0098] To the reaction mixture obtained in Experimental Example 1a (Table 1), various amounts of the hydroformylation reaction product of formula (II), various amounts of RANEY®-Ni, and water were added. Subsequently, the autoclave was flushed three times with 5 MPa of H2, and finally repressurized at room temperature with 50 MPa of H2. The reaction mixture was stirred at various reaction temperatures for various times (Table 1). After the autoclave was cooled to room temperature, the resulting reaction mixture was redissolved in RINKAN and filtered to remove nickel. The solvent was concentrated and removed, and the product was purified by distillation (boiling point: 105-120°C, reduced pressure: 5 Pa) to obtain 3.09 g (16.74 mmol, 67%) of (IX) as a colorless, viscous liquid mixture of diols of formulas (IXa) to (IXf). Table 1: Various reaction parameters for hydrogenating the reaction mixture obtained in Experimental Example 1a in toluene / H2O using RANEY®-Ni as a catalyst.

[0099] [Table 1]

[0100] The weight percentages (H2O) and (Ni) represent the proportions of the reaction materials added in the first hydroformylation step. on = overnight (20 hours or more) rt=room temperature (II) indicates the amount of (II) used in the corresponding experimental example 1a. Δp indicates the pressure drop during the reaction. yes = complete transformation, no = complete transformation of the poison The diols obtained in experiments #2, #4, #5, and #7 were recovered and used together in Experimental Example 8.

[0101] Experimental Example 1c: Reduction of MeOH by NaBH4:

[0102] [ka]

[0103] Following the hydroformylation reaction of (II), 125 mL of MeOH (0.20 M) was added to the reaction mixture obtained in Experimental Example 1a, and the mixture was then cooled to 0°C. 2.83 g (74.9 mmol, 3.00 equivalents) of NaBH4 was added in small increments, and the resulting mixture was stirred at room temperature for 3 hours. The reaction mixture was then reduced by half and acidified with hydrochloric acid (37 wt%, 1.00 M) until the pH was 6-7. The organic phase was extracted with DCM (3 × 100 mL), dried over Na₂SO₄, filtered, and the remaining solvent was removed under reduced pressure. The product was purified by silica gel chromatography using n-pentane and HCl (using a gradient of 10-50% HCl) to obtain 3.49 g (19.40 mmol, 73%) of (IX) as a colorless, viscous liquid mixture of diols of formulas (IXa) to (IXf).

[0104] 1 H NMR (500 MHz, CDCl3, 298 K): δ (ppm) = 3.70-3.54 (m, 1.43 H, CH2OH), 3.46-3.26 (m, 2.57 H, CH2OH), 2.23-2.06 (m, 1.80 H), 2.04-1.87 (m, 0.47 H), 1.86-1.70 (m, 0.61 H), 1.70-0.83 (m, 11 H), 0.83-0.54 (m, 0.53 H). 1 Considering the large overlap of aliphatic proton signals in the 1H-NMR spectra, we were able to assign resonance only to the CH2 group signal adjacent to the hydroxyl group.

[0105] 13C NMR (400 MHz, CDCl3, 298 K): δ (ppm) = 68.12 (CH2OH), 67.95 (CH2OH), 67.92 (CH2OH), 67.39 (CH2OH), 67.20 (CH2OH), 67.01 (CH2OH), 66.96 (CH2OH), 66.93 (CH2OH), 66.92 (CH2OH), 66.90 (CH2OH), 66.71 (CH2OH), 66.62 (CH2OH), 66.47 (CH2OH), 66.44 (CH2OH), 66.40 (CH2OH), 66.31 (CH2OH), 63.30 (CH2OH), 63.25 (CH2OH), 63.23 (CH2OH), 63.19 (CH2OH), 52.88 (CH), 52.04 (CH), 46.16 (CH), 46.04 (CH), 45.68 (CH), 45.64 (CH), 45.59 (CH), 45.57 (CH), 45.36 (CH), 45.33 (CH), 45.24 (CH), 45.23 (CH), 44.63 (CH), 44.54 (CH), 44.34 (CH), 44.13 (CH), 43.05 (CH), 43.02 (CH), 43.00 (CH), 42.52 (CH), 42.24 (CH), 41.70 (CH), 41.55 (CH), 41.12 (CH), 41.05 (CH), 40.89 (CH), 40.82 (CH), 40.75 (CH), 40.66 (CH), 40.45 (CH), 40.25 (CH), 40.18 (CH), 40.14 (CH), 40.11 (CH), 39.67 (CH), 39.28 (CH), 39.12 (CH), 39.00 (CH), 38.95 (CH), 38.69 (CH), 38.66 (CH), 38.57 (CH), 38.54 (CH), 38.47 (CH), 38.46 (CH), 38.40 (CH), 38.31 (CH2), 38.03 (CH), 37.62 (CH), 37.53 (CH2), 37.48 (CH2), 37.10 (CH), 37.06 (CH), 36.99 (CH), 36.96 (CH), 36.91 (CH2), 36.89 (CH2), 36.65 (CH), 36.62 (CH2), 36.60 (CH), 36.54 (CH), 36.48 (CH2), 36.39 (CH), 36.37 (CH2), 36.34 (CH), 36.31 (CH), 36.23 (CH2), 36.16 (CH2), 36.04 (CH2), 35.61 (CH2), 35.41 (CH2), 34.88 (CH2), 34.87 (CH2), 34.85 (CH2), 34.74 (CH2), 34.42 (CH2), 34.38 (CH2), 33.96 (CH2), 33.81 (CH2), 33.25 (CH2), 33.16 (CH2), 33.04 (CH2), 32.91 (CH2), 32.89 (CH2), 32.67 (CH2), 32.59 (CH2), 32.50 (CH2), 32.31 (CH2), 32.28 (CH2), 32.07 (CH2), 31.91 (CH2), 31.28 (CH2), 31.19 (CH2), 28.90 (CH2), 28.25 (CH2), 27.42 (CH2), 27.15 (CH2), 27.11 (CH2), 26.68 (CH2), 24.87 (CH2), 24.17 (CH2), 16.79 (CH3), 16.53 (CH3), 16.40 (CH3), 16.29 (CH3), 16.24 (CH3), 16.18 (CH3), 14.98 (CH3), 14.68 (CH3), 13.25 (CH3), 13.23 (CH3). . GC-MS: m / z = 184, 166, 135, 107, 95, 79, 67, 55.

[0106] Experimental Example 2: Preparation of a mixture of diols of formula (IXc) and formula (IXd) using VNB of formula (VI) as the starting material. Example 2a: Preparation of dialdehyde according to Scheme 1a as the first step.

[0107] [ka]

[0108] In a snap-cap vial in an autoclave, 10.14 mg (24.96 μmol, 0.10 mol%) of [Rh(COD)2]BF4 and 21.60 mg (27.46 μmol, 0.11 mol%) of Oxophos® (XII) were dissolved in 25 mL of toluene (1.00 M). To this solution, 3.00 g (24.96 mmol, 1.00 equivalent) of VNB (formula (VI)) was added. The reaction mixture was heated to 80°C, then pressurized with synthesis gas (CO / H2=3:2) at 5 MPa, and further heated to 140°C, where it was stirred for 4 hours. The resulting pale yellow solution was cooled to room temperature and either used directly for hydrogenation, or the solvent was removed by concentration. The product was then purified by distillation (boiling point: 74-76°C, reduced pressure: 3.5 Pa) to obtain 1.25 g (3.45 mmol, 14%) of the dialdehyde of formula (Xc) as a colorless liquid.

[0109] 1 H NMR (500 MHz, CDCl3, 298 K): δ (ppm) = 9.76-9.71 (m, 1 H, CHO), 9.62-9.57 (m, 1 H, CHO), 2.58-2.51 (m, 0.50 H), 2.49 (d, 3 J = 4.8 Hz, 0.50 H), 2.31-2.18 (m, 2 H), 2.05 (d, 3 J = 4.2 Hz, 0.15 H), 1.95-1.83 (m, 1.50 H), 1.82-1.70 (m, 1.50 H), 1.69-1.54 (m, 2.50 H), 1.54-1.39 (m, 1 H), 1.32-1.13 (m, 2.50 H), 1.13-1.07 (m, 0.30 H), 1.07-0.98 (m, 0.60 H), 0.72 (ddd, 3 J = 4.8 Hz, 0.40 H), 0.65 (ddd, 3 J = 5.1 Hz (0.30 H). 1Considering the large overlap of aliphatic proton signals in the 1H-NMR spectra, we were able to assign only the resonances of the aldehyde proton signals.

[0110] 13 C NMR (400 MHz, CDCl3, 298 K): δ (ppm) = 203.70 (CHO), 203.18 (CHO), 202.96 (CHO), 202.89 (CHO), 202.57 (CHO), 202.47 (CHO), 202.44 (CHO), 202.23 (CHO), 55.06 (CH), 54.79 (CH), 53.86 (CH), 47.63 (CH), 43.10 (CH2), 43.04 (CH2), 42.46 (CH), 42.32 (CH2), 41.63 (CH), 41.58 (CH), 41.50 (CH), 40.76 (CH), 39.46 (CH), 39.43 (CH), 39.08 (CH), 38.70 (CH), 38.37 (CH), 37.67 (CH2), 37.56 (CH2), 37.50 (CH2), 37.45 (CH2), 36.82 (CH), 36.52 (CH2), 36.33 (CH), 36.30 (CH2), 33.24 (CH2), 33.22 (CH2), 30.62 (CH2), 30.56 (CH2), 29.44 (CH2), 28.52 (CH2), 28.29 (CH2), 24.87 (CH2), 24.74 (CH2), 22.88 (CH2). GC-MS: m / z = 180, 150, 136, 107, 91, 79, 55. Experimental Example 2b: Hydrogenation of Toluene / H2O with RANEY®-Ni

[0111] [ka]

[0112] After the hydroformylation reaction of (VI), 2 wt% RANEY®-Ni and 10 wt% water were added in varying amounts to the reaction mixture obtained in Experimental Example 2a (relative to the total mass of the reaction mixture). Subsequently, the autoclave was flushed three times with 5 MPa H2 and finally repressurized at room temperature with 5 MPa H2. The reaction mixture was stirred at 80°C for 3 hours. After the autoclave was cooled to room temperature, the pressure was 4.7 MPa. The product in the reaction mixture was redissolved in ELISA and filtered to remove nickel. The solvent was removed by concentration, and the product was purified by vacuum distillation (boiling point: 130°C, partial pressure: 8 Pa) to obtain 0.99 g (5.49 mmol, 22%) of (IX) as a colorless, viscous liquid mixture mainly containing only (IXc) and (IXd). Experimental Example 2c: Reduction of MeOH by NaBH4:

[0113] [ka]

[0114] After the hydroformylation reaction of (VI), 125 mL of MeOH (0.20 M) was added to the reaction mixture obtained in Experimental Example 2a, and the mixture was then cooled to 0°C. 2.83 g (74.9 mmol, 3.00 equivalents) of NaBH4 was added in small increments, and the resulting mixture was stirred at room temperature for 3 hours. The reaction mixture was then reduced by half and acidified with hydrochloric acid (37 wt%, 1.00 M) until the pH was 6-7. The organic phase was extracted with DCM (3 × 100 mL), dried over Na₂SO₄, filtered, and the residual solvent was removed under reduced pressure. The product was purified by silica gel chromatography using n-pentane and HCl (using a gradient of 10-50% HCl) to obtain 2.02 g (10.98 mmol, 44%) of (IX) as a mixture of (IXc) and (IXd) as a colorless viscous liquid.

[0115] 1 H NMR (500 MHz, CDCl3, 298 K): δ (ppm) = 3.61 (q, 3J = 6.5 Hz, 2 H, CH2OH), 3.38-3.30 (m, 2 H), 2.19-2.07 (m, 2 H), 1.95-1.92 (m, 0.75 H), 1.85-1.75 (m, 2 H), 1.67 (ddd, 3 J = 8.5 Hz, 0.50 H), 1.57-1.49 (m, 4 H), 1.24-1.17 (m, 1.40 H), 1.16-1.10 (m, 1 H), 1.07-1.01 (m, 0.50 H), 1.01-0.95 (m, 0.50 H), 0.89-0.80 (m, 1H), 0.65-0.61 (m, 0.30H), 0.59-0.55 (m, 0.20H). 1 Considering the large overlap of aliphatic proton signals in the 1H-NMR spectra, we were able to assign resonance only to the CH2 group signal adjacent to the hydroxyl group.

[0116] 13C NMR (400 MHz, CDCl3, 298 K): δ (ppm) = 66.92 (CH2OH), 66.88 (CH2OH), 66.79 (CH2OH), 66.61 (CH2OH), 63.20 (CH2OH), 63.15 (CH2OH), 63.13 (CH2OH), 63.08 (CH2OH), 45.60 (CH), 45.29 (CH), 44.30 (CH), 42.99 (CH), 41.68 (CH), 41.47 (CH), 41.10 (CH), 40.25 (CH), 40.24 (CH), 40.07 (CH), 39.65 (CH), 38.98 (CH), 38.51 (CH), 38.29 (CH2), 37.52 (CH2), 37.46 (CH2), 36.92 (CH), 36.88 (CH2), 36.83 (CH2), 36.62 (CH2), 36.55 (CH), 36.37 (CH), 34.71 (CH2), 34.41 (CH2), 33.24 (CH2), 32.87 (CH2), 32.66 (CH2), 32.28 (CH2), 32.24 (CH2), 32.05 (CH2), 31.88 (CH2), 31.25 (CH2), 31.17 (CH2), 28.89 (CH2), 28.25 (CH2), 27.09 (CH2). GC-MS: m / z = 184, 166, 135, 107, 95, 79, 67, 55. Experimental Example 3: Preparation of a mixture of diols of formula (IXa) and formula (IXb) The diol was prepared according to Scheme 3 below.

[0117] [ka]

[0118] Experimental Example 3a: First step according to Scheme 3a

[0119] [ka]

[0120] The reaction was carried out using the Schlenk process (Schlenk flask). The phosphonium salt [Ph3PCH2OCH3]Cl(methoxymethylidene(triphenyl)-λ) was reacted in dry THF (239 mL). 5 To a suspension of 16.4 g (47.7 mmol, 1.30 equivalents) of phosphan (Sigma Aldrich, CAS: 4009-98-7), 6.18 mg (55.1 mmol, 1.50 equivalents) of tert-butanolate potassium (KOtBu) was added in small increments at 0°C. The reaction mixture, which was dark red, was stirred at 0°C for 45 minutes, and then 5.00 g (37.3 mmol, 1.00 equivalent) of (Va) in THF (187 mL) was added dropwise via cannula. The reaction mixture was stirred at room temperature for 2 hours. Distilled water (300 mL) was added to the orange suspension, and the organic phase was extracted with n-pentane (3 × 150 mL). The recovered organic phase was washed with water and NH4Cl, dried over Na2SO4, filtered, and the solvent was removed under vacuum. Finally, the crude product was purified by silica gel column chromatography (n-pentane / Et2O = 50 / 1) to obtain 6.01 g (36.6 mmol, 98%) of (VIIIa) as a colorless liquid.

[0121] 1 H NMR (400 MHz, CDCl3): δ (ppm) = 6.22-5.83 (m, 2 H), 5.83-5.60 (m, 1 H), 3.57-3.50 (m, 3 H), 2.88-2.62 (m, 2 H), 1.88 (dd, 3 J = 8.5, 4.9 Hz, 1 H), 1.64-1.52 (m, 3 H), 1.45-1.22 (m, 4 H). 13 ¹³C NMR (400 MHz, CDCl3): (VIIIa) (principal component): δ (ppm) = 141.54, 137.49, 136.80, 117.67 59.41, 46.10, 45.58, 42.57, 42.22, 30.74, 13.49. Since there are many isomer compounds produced by the olefinization of (Va), only the main product is shown. GC MS: m / z = 164, 131, 115, 98, 91, 83, 55. Experimental Example 3b: Second step according to Scheme 3b

[0122] [ka]

[0123] 6.01 g (36.6 mmol, 1.00 equivalent) of product (VIIIa) obtained in Experimental Example 3a was dissolved in toluene (73 mL), and water (6.60 mL, 10.0 equivalent) was added. This solution was cooled to 0°C, and 1.40 g (7.32 mmol, 0.20 equivalent) of p-toluenesulfonic acid monohydride (p-TsOH × H2O) was added in small amounts. The reaction mixture was refluxed for 1 hour, cooled to room temperature, and then saturated NaHCO3 solution was added. The organic phase was extracted with Et2O (3 × 150 mL), dried with Na2SO4, filtered, and the solvent was removed under vacuum. Finally, the product was purified by silica gel chromatography (n-pentane / Et2O = 10 / 1) to obtain 4.34 g (28.9 mmol, 79%) of product (VIIIb) as a colorless liquid. Three different isomers were identified using NMR spectroscopy.

[0124] 1 1H NMR (400 MHz, CDCl3): VIIIb 1 (principal component): δ (ppm) = 9.56 (d, 3 J = 3.1 Hz, 1 H, CHO), 6.14-5.89 (m, 2 H), 2.75-2.56 (m, 2 H). 2.15 (dddp, 3 J = 13.9, 10.6, 6.8, 3.6 Hz, 1 H), 1.37-1.20 (m, 5 H), 1.14 (d, 3 J = 6.8 Hz, 3 H, CH3). VIIIb 2 (principal component): δ (ppm) = 9.59 (d,3 J = 3.6 Hz, 1 H, CHO), 6.14 - 5.89 (m, 2 H), 2.86 - 2.80 (m, 2 H), 2.15 (dddp, 3 J = 13.9, 10.6, 6.8, 3.6 Hz, 1 H), 1.37 - 1.20 (m, 5 H), 1.08 (d, 3 J = 6.9 Hz, 3 H, CH3). VIIIb 3 (minor component): δ (ppm) = 9.63 (d, 3 J = 3.1 Hz, 0.10 H, CHO), 1.00 (d, 3 J = 6.8, 0.35 H, CH3). 13 C NMR (400 MHz, CDCl3): VIIIb 1 (major component): δ (ppm) = 204.91 (CHO), 52.01, 45.32, 43.56, 42.31, 40.11, 31.38, 13.04 (CH3). VIIIb 2 (major component): δ (ppm) = 205.23 (CHO), 51.66, 45.51, 44.75, 41.92, 40.32, 30.41, 13.47 (CH3). VIIIb 3 (minor component): δ (ppm) = 205.30 (CHO), 50.86, 49.66, 44.50, 42.48, 41.92, 41.15, 30.41, 25.89, 13.33 (CH3). GC MS: m / z = 150, 132, 117, 106, 94, 79, 66, 55. Experimental Example 3c: The third step according to Scheme 3c

[0125]

Chemical Structure

[0126] This step was performed using a round-bottom flask. 4.34 g (28.9 mmol, 1.00 equivalent) of the product (VIIIb) obtained in Experimental Example 3b was dissolved in MeOH (142 mL), and the reaction mixture was cooled to 0°C. 1.09 g (28.9 mmol, 1.00 equivalent) of NaBH4 was added to this solution in small increments, and the reaction mixture was stirred for 2 hours. The resulting mixture was reduced to half its volume and acidified with hydrochloric acid (37 wt%, 1.00 M) until the pH was 6-7. The organic phase was extracted with DCM (3 × 100 mL), dried over Na₂SO₄, filtered, and the residual solvent was removed under reduced pressure. The product was purified by silica gel chromatography (n-pentane / Et₂O = 8 / 2) to obtain 4.09 g (26.9 mmol, 93%) of the product of formula (VIIIc) as a colorless liquid.

[0127] 1 H NMR (400 MHz, CDCl3): δ (ppm) = 6.05 (ddd, 3 J = 5.7, 2.9 Hz, 2 H, CHO), 3.75 (ddd, 3 J = 25.1, 10.5, 3.7 Hz, 1 H), 3.50 (dd, 3 J = 10.6, 6.8 Hz, 0.5 H), 3.37 (dd, 3 J = 10.5, 7.3 Hz, 0.5 H), 2.84-2.73 (m, 2 H), 1.44 (dtq, 3 J = 13.7, 6.9, 3.3 Hz, 1 H), 1.33-1.24 (m, 5 H), 1.06 (d, 3 J = 6.5 Hz, 1.5 H, CH3), 0.99 (d, 3 J = 6.7 Hz, 1.5 H, CH3). 13 ¹³C NMR (400 MHz, CDCl3): VIIIc-1: δ (ppm) = 136.59, 67.88, 45.29, 43.75, 42.13, 41.88, 41.27, 31.90. VIIIc-2: δ (ppm) = 137.1 (d), 67.51, 45.65, 43.83, 42.21, 41.82, 40.76, 31.65. 13 Three isomerized compounds were revealed by 13C NMR, and so far, two major isomers of VIIIc have been identified. GC MS: m / z = 152, 134, 119, 105, 91, 77, 66, 55. Experimental Example 3d: Fourth Step using Scheme 3d

[0128] [ka]

[0129] This process was carried out in a manual autoclave using the Schlenk process. 109 mg (269 μmol, 1.00 mol%) of [Rh(COD)2]BF4 and 794 mg (1.34 mmol, 5.00 mol%) of PEt3 (20 wt%) in EtOH were dissolved in EtOH (16 mL), and 4.09 g (26.9 mmol, 1.00 equivalent) of the product (VIIIc) obtained in Experimental Example 3c was added to the suspension. The reaction mixture was pressurized with synthesis gas (CO / H2=1 / 1) at 5 MPa and stirred at a reaction temperature of 60°C for 16 hours. The resulting dark red reaction mixture was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography (n-pentane / Et2O = 1 / 1), and after removing the solvent, 3.82 g (20.7 mmol, 77%) of (VIIId), a mixture of (IXa) and (IXb), was obtained as a colorless, viscous liquid. Two distinct isomers were identified by NMR spectroscopy.

[0130] 1 1H NMR (400 MHz, CDCl3): VIIId-1: δ (ppm) = 3.73-3.58 (m, 1 H, CH2O), 3.45-3.29 (m, 3 H, CH2O), 2.24-2.09 (m, 2 H), 1.67-1.57 (m, 1 H), 1.45-1.15 (m, 7 H), 1.04-0.96 (m, 3H, CH3), 0.88 (d, 3 J = 6.7 Hz, 0.66 H). VIIId-2: δ (ppm) = 3.75-3.60 (m, 1 H, CH2O), 3.54-3.33 (m, 3 H, CH2O), 2.26-2.15 (m, 2 H), 1.70-1.49 (m, 2 H), 1.44-1.29 (m, 3.5 H), 1.29-1.14 (m, 2.8 H), 1.02-0.94 (m, 1 H), 0.92 (d, 3 J = 6.5 Hz, 0.88 H, CH3), 0.89 (d, 3 J = 6.5 Hz, 1.4 H, CH3). GC MS: m / z = 184, 166, 153, 135, 125, 107, 95, 79, 67, 55. Experimental Example 4: Preparation of the intermediate of formula (VII) The intermediate was prepared according to Scheme 4 below.

[0131] [ka]

[0132] 16.9 mg (41.6 μmol, 0.10 mol%) of [Rh(COD)2]BF4 (bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate, CAS: 35138-22-8, manufactured by Tokyo Chemical Industry Co., Ltd.) and 123 mg (208 μmol, 0.50 mol%) of TEP (20 wt%) in EtOH were dissolved in EtOH (24 mL), and 5.00 g (41.6 mmol, 1.00 equivalent) of 5-ethylidene-2-norvonene (ENB) was added to this suspension. The reaction mixture was pressurized with synthesis gas (CO / H2 = 1 / 1) at 5 MPa and stirred at 100°C for 17 hours. The yellowish reaction mixture was cooled to room temperature, and the solvent was removed by vacuum distillation at room temperature. The crude product was purified by silica gel column chromatography (Et2O), and after removing the solvent, 5.82 g (38.2 mmol, 92%) of the intermediate of formula (VII) was obtained as a colorless liquid. This intermediate consisted mainly of the (E)-isomer (formula (VIIa)) and contained the (Z)-isomer (formula (VIIb)) as a minor component.

[0133] [ka]

[0134] 1 1H NMR (400 MHz, CDCl3): (VIIa) Principal component: δ (ppm) = 5.27 (dqd, 3 J = 6.5 Hz, 0.76 H, H8), 3.38 (dd, 3 J = 6.9, 2 H, H 10), 1.50 (d, 3 J = 6.8 Hz, 3 H, H 9) (VIIb) Subcomponent: δ (ppm) = 5.05 (dq, 3 J = 7.0 Hz, 0.24 H, H 8'), 3.38 (dd, 3 J = 6.9 Hz, 2 H, H 10'), 1.62 (tt, 3 J = 7.1 Hz, 0.64 H, H 9') 2.92 (d, 3J = 3.8 Hz, 0.20 H), 2.59 (t, 3 J = 7.7 Hz, 0.75 H), 2.40 - 2.29 (m, 0.87 H), 2.28 - 2.19 (m, 0.16 H), 2.12 (tq, 3 J = 21.2, 16.2, 5.0, 2.6 Hz), 1.88 - 1.66 (m, 2.17 H), 1.62 (tt, 3 J = 7.1, 2.0 Hz, 0.64 H), 1.48 - 1.38 (m, 1 H), 1.38 - 1.29(m, 1 H), 1.24 (t, 3 J = 8.2 Hz, 1 H), 1.09 (ddt, 3 J = 12.5, 8.0, 4.1 Hz, 1 H).

[0135] 13 C NMR (400 MHz, CDCl 3 ): (VIIa) Main component: δ (ppm) = 145.89 (C 5), 145.88 (C 5), 111.88 (C 8), 111.44 (C 8), 66.93 (C 10), 66.51 (C 10), 14.01 (C 9), 13.95 (C 9), 47.00 (CH), 45.12 (CH), 45.03 (CH), 44.41 (CH), 38.40 (CH), 36.41 (CH), 36.17 (CH2), 35.89 (CH2), 35.84 (CH2), 35.13 (CH2), 34.15 (CH2), 33.14 (CH2). (VIIb) Subcomponents: δ (ppm) = 145.03 (C 5'), 144.97 (C 5'), 112.67 (C 8'), 112.02 (C 8'), 66.95 (C 10'), 66.47 (C 10'), 14.58 (C 9'), 14.56 (C 9'), 44.44 (CH), 44.18 (CH), 41.47 (CH), 39.67 (CH), 38.99 (CH2), 38.32, 38.23 (CH2), 36.33, 36.00 (CH2), 35.52 (CH2), 33.28 (CH2), 32.90 (CH2). Due to the large overlap of aliphatic signals, only the characteristic methyl, methylidene, and ethylidene group resonances could be assigned. Furthermore, clear distinction between positional isomers and diastereomers was not possible. GC MS: m / z = 152, 134, 121, 108, 93, 79, 67. Experimental Example 5: Preparation of the diol of formula (I) The diol was prepared according to Scheme 5 below.

[0136] [ka]

[0137] 13.3 mg (32.8 μmol, 0.10 mol%) of [Rh(COD)2]BF4 and 106 mg (164 μmol, 0.50 mol%) of Alkanox® were dissolved in toluene (66 mL, 0.50 M), and 5.00 g (32.8 mmol, 1.00 equivalent) of the intermediate obtained in Experimental Example 4 was added to this suspension. The reaction mixture was pressurized with synthesis gas (CO / H2 = 1 / 1) at 5 MPa and stirred at 100°C for 18 hours. The yellowish reaction mixture was cooled to room temperature, dissolved in MeOH (164 mL, 0.20 M), and 3.72 g (98.4 mmol, 3.00 equivalent) of NaBH4 was added little by little at 0°C. The reaction mixture was stirred at room temperature for 16 hours. The resulting mixture was reduced to half its volume under vacuum, and aqueous HCl (37 wt%, 100 mL) was added. The organic phase was extracted using DCM (3 × 150 mL), dried over Na₂SO₄, filtered, and the solvent was removed under vacuum. The crude product was purified by silica gel chromatography (DCM / Et₂O=3 / 1 and siRNA), and after solvent removal, 3.42 g (18.6 mmol, 56%) of a mixture of the compound of formula (I) was obtained as a colorless, viscous liquid.

[0138] (I) 1 H NMR (400 MHz, CD2Cl2): δ (ppm) = 3.68-3.53 (m, 1.20 H, CH2OH), 3.44-3.21 (m, 2.80 H, CH2OH). (I) 13 C NMR (400 MHz, CD2Cl2): δ (ppm) = 67.73 (CH2OH), 66.71 (CH2OH), 66.53 (CH2OH), 66.50 (CH2OH), 66.47(CH2OH), 66.14 (CH2OH), 62.98 (CH2OH), 62.97 (CH2OH). Due to the large overlap of aliphatic signals, only the characteristic aldehyde and methylidene group resonances could be assigned. (Aldehyde intermediate) GC-MS: m / z = 182, 164, 123, 107, 93, 79, 67, 55. (I) GC MS: m / z = 184, 166, 153, 135, 125, 107, 93, 79, 67, 55. Experimental Example 6: Preparation of the diol of formula (I) The diol was prepared according to Scheme 6 below.

[0139] [ka]

[0140] 84.5 mg (208 μmol, 1.00 mol%) of [Rh(COD)2]BF4 and 614 mg (1.04 mmol, 5.00 mol%) of TEP (20 wt%) in EtOH were dissolved in EtOH (12 mL), and 2.50 g (20.8 mmol, 1.00 equivalent) of 5-vinyl-2-norvonene (VNB) was added to this suspension. The reaction mixture was pressurized with synthesis gas (CO / H2=1 / 1) at 5 MPa and stirred at 100°C for 18 hours. The yellowish reaction mixture was cooled to room temperature, and the solvent was removed by vacuum distillation at room temperature. The crude product was purified by silica gel chromatography (DCM / Et2O=3 / 1 and ethyl), and after solvent removal, 3.63 g (19.7 mmol, 95%) of a mixture of the compound of formula (I) was obtained as a colorless viscous liquid.

[0141] 1 H NMR (400 MHz, CDCl3): δ (ppm) = 3.70-3.55 (m, 1.70 H, CH2OH), 3.44-3.26 (m, 2.30 H, CH2OH). 13 C NMR (400 MHz, CDCl3): δ (ppm) = 68.16 (CH2OH), 67.96 (CH2OH), 67.94 (CH2OH), 67.21 (CH2OH), 67.02 (CH2OH), 66.98 (CH2OH), 66.94 (CH2OH), 66.74 (CH2OH), 63.32 (CH2OH), 63.27 (CH2OH), 63.26 (CH2OH), 63.21 (CH2OH). Due to the large overlap of aliphatic signals, only the characteristic methylidene group resonances could be assigned. GC MS: m / z = 184, 166, 153, 135, 125, 107, 93, 79, 67, 55. Experimental Example 7: (S ax Hydroformylation using S,S)-bobphos

[0142] [ka]

[0143] [Rh(COD)2]BF4 and (S ax S,S)-bobphos (formula (XIII)) and ENB(II) were dissolved in 25 mL of toluene (1.00 M) in a snap-cap vial in an autoclave (Table 2). The autoclave was pressurized with synthesis gas (CO / H2 = 1 / 1) at 5 MPa, and then heated to 60°C and stirred for 16 hours. The reaction mixture was then cooled to room temperature, and the solvent was removed by concentration. The product was purified by distillation (boiling point: 65-70°C, reduced pressure: 2.5 Pa) to obtain 0.68 g (4.52 mmol, 18%) of (X) as a colorless liquid mixture of (Xa), (Xb), and (Xc). The synthesis was carried out using various parameters shown in Table 2. Table 2: [Rh(COD)2]BF4 and S ax Summary of the amount of S,S-bobphos (XIII) used in the isoselective hydroformylation of (II).

[0144] [Table 2]

[0145] 1H NMR (500 MHz, CDCl3, 298 K): δ (ppm) = 9.64-9.52 (m, 2 H, CHO), 2.63-2.51 (m, 1 H), 2.40 (bs, 0.25 H), 2.37-2.17 (m, 2 H), 2.17-2.14 (m, 0.30 H), 2.13-2.02 (m, 0.70 H), 2.00-1.73 (m, 2 H), 1.73-1.60 (m, 1 H), 1.59-1.46 (m, 1 H), 1.40-1.33 (m, 0.50 H), 1.33-1.14 (m, 3 H), 1.13-1.05 (m, 2 H), 1.03-0.98 (m, 1 H), 0.95-0.85 (m, 0.35 H), 0.85-0.78 (m, 0.15 H). 13C NMR (400 MHz, CDCl3, 298 K): δ (ppm) = 204.87 (CHO), 204.81 (CHO), 204.67 (CHO), 204.63 (CHO), 204.51 (CHO), 204.48 (CHO), 204.40 (CHO), 203.05 (CHO), 202.98 (CHO), 202.92 (CHO), 202.86 (CHO), 202.84 (CHO), 202.81 (CHO), 202.58 (CHO), 202.52 (CHO), 202.51 (CHO), 202.42 (CHO), 202.14 (CHO), 201.91 (CHO), 201.73 (CHO), 66.81 (CH), 66.66 (CH), 61.37 (CH), 61.05 (CH), 55.14 (CH), 55.09 (CH), 54.77 (CH), 54.71 (CH), 53.88 (CH), 53.75 (CH), 53.66 (CH), 51.75 (CH), 51.55 (CH), 51.28 (CH), 51.10 (CH), 49.82 (CH), 49.69 (CH), 48.87 (CH), 48.82 (CH), 48.06 (CH), 47.70 (CH), 45.06 (CH), 44.95 (CH), 44.33 (CH), 44.03 (CH), 43.06 (CH), 43.05 (CH), 43.00 (CH), 42.86 (CH), 42.80 (CH), 42.57 (CH), 42.45 (CH), 41.89 (CH), 41.78 (CH), 41.18 (CH), 41.03 (CH), 40.75 (CH), 40.73 (CH), 40.46 (CH), 40.35 (CH), 40.17 (CH), 39.75 (CH), 39.59 (CH), 39.49 (CH), 38.61 (CH), 38.55 (CH), 38.52 (CH), 38.20 (CH), 38.15 (CH), 37.97 (CH), 37.75 (CH2), 37.44 (CH2), 36.91 (CH2), 36.84 (CH2), 36.72 (CH), 36.61 (CH), 36.34 (CH2), 36.24 (CH2), 36.16 (CH), 36.09 (CH2), 36.05 (CH), 36.01 (CH2), 35.22 (CH2), 35.10 (CH2), 35.06 (CH2), 34.98 (CH2), 34.90 (CH2), 33.76 (CH2), 33.69 (CH2), 33.65 (CH2), 33.59 (CH2), 30.79 (CH2), 30.71 (CH2), 30.43 (CH2), 29.49(CH2), 29.14 (CH2), 25.04 (CH2), 23.61 (CH2), 23.20 (CH2), 22.94 (CH2), 13.94 (CH3), 13.88 (CH3), 13.55 (CH3), 13.19 (CH3), 13.10 (CH3), 13.04 (CH3), 12.91 (CH3), 12.86 (CH3), 11.69 (CH3), 11.68 (CH3). GC MS: m / z = 180, 150, 136, 107, 91, 79, 55.

[0146] Experimental Example 8: Polymer Preparation The polycondensation reaction was carried out at atmospheric pressure and standard atmosphere in a three-neck flask equipped with a magnetic coupling bmd075 (manufactured by Buchi AG) and a stainless-steel propeller stirrer. In each polymerization, 1.00 mol% of Ti(OnBu)4 catalyst, 1.00 equivalent of dimethyl terephthalate (DMT), and 2.00 equivalents of the corresponding diol obtained in Experimental Examples 1, 3, and 4 were added to the three-neck flask, and the temperature was adjusted to 160 °C. As soon as methanol began to separate, the temperature was gradually raised to 210 °C. If necessary, the temperature was further increased until the prepolycondensation reaction was completely completed (until no more MeOH was produced). Finally, the reaction mixture was stirred overnight under reduced pressure, the residual diol was recovered, dissolved in DCM or THF, and precipitated in cold MeOH. It was observed that not only a colorless solid but also a fibrous residue was obtained. This fibrous residue was dissolved in THF and precipitated again in cold MeOH. This step was repeated if necessary. In Table 3 below, the product obtained after the first precipitation was designated as -1, the product obtained after the second precipitation was designated as -2, and so on. Table 3: Evaluation in the synthesis of polyesters from the diols obtained in Experimental Examples 1, 2, 3, 5, and 6 (M n : number-average molecular weight, M w : weight-average molecular weight, D M : polydispersity index, T g : glass transition temperature, T dec : decomposition temperature).

[0147]

Table 3

[0148] * Poly(tricyclodecane dimethylene terephthalate), cited from J Polym Res (2016) 23: 42, Table 1 ** Poly(tricyclodecane dimethylene terephthalate), cited from ACS Sustainable Chem. Eng. 2020, 8, 15199 - 15208, Table 1

[0149] When the alicyclic diol compounds obtained in Experimental Examples 1, 2, 3, 5, and 6 were evaluated as monomers for polyester synthesis, promising results were obtained as components of polyesters having amorphous properties and a high glass transition temperature. All the synthesized polyesters were dissolved in THF and precipitated in cold MeOH. They were divided into a plurality of fractions (described as "-X" in Table 3, X = 1 to 2, 1 to 4) and analyzed by gel permeation chromatography (GPC), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) (Table 3).

[0150] The polyesters made from the diols of Experimental Example 1 and Experimental Example 2 showed the highest polydispersity. When compared with known polyesters (Table 3) based on dicyclodecanol (tricyclodecane dimethanol) as the diol monomer, the polyesters made from the diols of Experimental Example 5 (T g = 84 °C, Table 3, Example 5-1) and Experimental Example 6 (T g = 69 °C, Table 3, Example 6-2) showed the lowest achievable glass transition temperature compared to PDT and PTA-TCDM (T g = 118 °C, 115 °C, Table 3), respectively. When the diol of Experimental Example 3 was additionally evaluated as a monomer in polyester synthesis, it showed the highest achievable glass transition temperature (T g = 118 °C, Table 3) compared to PDT (T g = 103, Table 3, Example 3-4). The number average molecular weight and polydispersity index of the polymers according to the present invention were in a range almost equivalent to the values of the known polyester PTA-TCDM.

Claims

1. A polymer comprising units derived from a carboxylic acid or an anhydride containing at least two carboxyl groups, and units derived from an alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups is of formula (IX): 【Chemistry 1】 (wherein, R １ is ethyl, -CH ２ -CH ２ -CH ２ OH, or -CH(-CH ３ )-CH ２ OH, and R ２ is H or -CH ２ OH, but when R １ is ethyl, R ２ is not H.) A polymer that is a bicyclic aliphatic diol.

2. The polymer according to claim 1, wherein at least 50 mol%, more preferably 60 to 100 mol%, and most preferably 70 to 95 mol%, of the units derived from an alcohol containing at least two OH groups in the polymer are based on a bicyclic aliphatic diol of formula (IX).

3. The bicyclic aliphatic diol is preferably 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)-propan-1-ol, 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol, or (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol, or a mixture thereof. The polymer according to claim 1 or claim 2, which is a mixture of 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol, and (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol.

4. The polymer according to any one of claims 1 to 3, wherein the number average molecular weight Mn measured by the method described herein is 8 to 25 kg / mol.

5. The polymer according to any one of claims 1 to 4, wherein the weight-average molecular weight Mw measured by the method described herein is 10 to 75 kg / mol.

6. The polymer according to any one of claims 1 to 5, wherein the glass transition temperature Tg measured by the method described herein is 40 to 110°C.

7. The polymer according to any one of claims 1 to 6, wherein the units derived from a carboxylic acid containing at least two carboxyl groups are derived from phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, malonic acid, succinic acid, 1,2,4-benzenetricarboxylic acid, glutaric acid, adipic acid, 2,2,4-trimethyladipic acid, azelaic acid, undecanediic acid, octadecanediic acid, dimeric fatty acid, itaconic acid, fumaric acid, naphthalene-2,6-dicarboxylic acid, or sebacic acid, or their anhydride or ester, more preferably phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, or sebacic acid, most preferably terephthalic acid.

8. The polymer according to claim 7, wherein at least 50 mol%, more preferably 60 to 100 mol%, and most preferably 70 to 95 mol%, of the units derived from a carboxylic acid containing at least two carboxyl groups in the polymer are based on phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, malonic acid, succinic acid, 1,2,4-benzenetricarboxylic acid, glutaric acid, adipic acid, 2,2,4-trimethyladipic acid, azelaic acid, undecanediic acid, octadecanediic acid, dimeric fatty acid, itaconic acid, fumaric acid, naphthalene-2,6-dicarboxylic acid, or sebacic acid, or a mixture thereof.

9. A method for preparing a polymer by reacting at least one carboxylic acid or its anhydride or ester containing at least two carboxyl groups with at least one alcohol containing at least two OH groups, wherein the alcohol containing at least two OH groups used is of formula (IX): 【Chemistry 2】 (In the formula, R １ is ethyl, -CH ２ -CH ２ -CH ２ OH, or -CH(-CH ３ ) - CH ２ OH and R ２ is H or -CH ２ OH, but R １ If R is ethyl, ２ (It's not H.) A method for determining a bicyclic aliphatic diol.

10. The method according to claim 9 for preparing the polymer according to any one of claims 1 to 8.

11. As bicyclic aliphatic diols, these include 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)-propan-1-ol, 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol, or (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol, or mixtures of two or more of these compounds. The method according to claim 9 or 10, preferably using a mixture of 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)-propan-1-ol, 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol, and (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol.

12. The method according to any one of claims 9 to 11, wherein the carboxylic acid containing at least two carboxyl groups or its anhydride or ester is phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, malonic acid, succinic acid, 1,2,4-benzenetricarboxylic acid, glutaric acid, adipic acid, 2,2,4-trimethyladipic acid, azelaic acid, undecanediic acid, octadecanediic acid, dimeric fatty acid, itaconic acid, fumaric acid, naphthalene-2,6-dicarboxylic acid, or sebacic acid, or its anhydride or ester, more preferably phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, or sebacic acid, or its anhydride or ester, most preferably dimethyl terephthalate.

13. Formula (II): 【Transformation 3】 (In the formula, R is vinyl, ethylidene, or acetyl, more preferably vinyl or ethylidene, and most preferably vinyl.) The method according to any one of claims 9 to 12, using 2-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 2-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(5-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, 3-(6-hydroxymethylbicyclo[2.2.1]hept-2-yl)propan-1-ol, (3-ethylbicyclo[2.2.1]heptan-2,5-diyl)dimethanol, or (3-ethylbicyclo[2.2.1]heptan-2,6-diyl)dimethanol, or a mixture of two or more of these compounds, obtained by a method comprising a hydroformylation step and a reduction step using the compound as a starting material.

14. The method according to claim 13, wherein the hydroformylation step is carried out in the presence of a rhodium-containing catalyst and a phosphorus-containing ligand.

15. Use of a polymer according to any one of claims 1 to 8, or a polymer obtained by the method according to any one of claims 9 to 14, as a lacquer, coating agent, or adhesive, preferably a coating agent for tubes, coils, or cans, a metal decorative enamel, a heat-seal lacquer, a hot laminating adhesive, or a primer, or for the manufacture of such uses.

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