Polyester resin

Abstract

To provide a polyester resin which has excellent heat resistance and superior handling performance through non-covalent bonding of polyester polymer chains with the use of a small quantity of a compound having a triptycene structure.SOLUTION: A polyester resin is formed from a dicarboxylic acid and a diol, the polyester resin comprising at least a structural unit derived from a diol represented by formula (1) (where, Ak is a divalent hydrocarbon group having 8 to 20 carbon atoms, and X is a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyester resin and a compound that forms a structural unit of the polyester resin. [Background technology]

[0002] It is known that the elastic modulus increases when molecular chains are linked by chemical bonds. Chemical bonds can be covalent or non-covalent, and when molecular chains are linked by covalent bonds, the elastic modulus increases and wear resistance improves. On the other hand, mechanical flexibility decreases and bending resistance decreases. For certain polymers, when baked at a certain temperature or higher, the ends of the molecules react with other molecules or specific sites within the molecules to form covalent bonds, reducing flexibility. On the other hand, it is known that when the molecules have repeating units that contain a structure that forms non-covalent bonds, non-covalent bonds are formed between molecules and / or with specific sites within the molecules, and the intermolecular interactions provide a moderate elastic modulus and can achieve both abrasion resistance and bending resistance.

[0003] Examples of non-covalent bonds include ionic bonds, π-π stacking, and hydrogen bonds. Hydrogen bonds are preferred because they provide high heat resistance and excellent mechanical properties. The viscosity of some liquid polymers associated by hydrogen bonds can reach about 1,000 times that of the polymer before association.

[0004] However, even such polymers associated by hydrogen bonds may have insufficient heat resistance, and further improvement is desired. Under these circumstances, a compound having a triptycene skeleton has been proposed, and a polyester resin using the compound as a polymerization component of the resin has been disclosed (see Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2019-6685 A Summary of the Invention [Problem to be solved by the invention]

[0006] In the above Patent Document 1, a compound having a triptycene skeleton is used as a dicarboxylic acid component and reacted with a diol to synthesize a polyester resin. In the Examples, it is described that 100 mol % of the dicarboxylic acid units introduced into the polyester resin are derived from triptycene. Patent Document 1 describes that by using a compound having a triptycene structure as the dicarboxylic acid that forms the dicarboxylic acid unit, the composition has excellent optical properties such as a high refractive index, low birefringence, and high transmittance, as well as high heat resistance. However, the heat resistance is insufficient and further improvement is required. In addition, the compound having a triptycene structure is used as one component of a dicarboxylic acid, and in the examples, the dicarboxylic acid component is 100 mol % of the compound having a triptycene structure, thereby ensuring the above performance. Under these circumstances, an object of the present invention is to provide a polyester resin that has excellent heat resistance and easy handling by using a small amount of a compound having a triptycene structure and non-covalently bonding the polymer chains of the polyester. [Means for solving the problem]

[0007] Means for Solving the Problems The inventors of the present invention conducted intensive research to solve the above problems and discovered that by using a compound having a triptycene skeleton with a specific structure, a liquid polyester resin can be converted into a solid polyester resin and excellent heat resistance can be imparted, thereby completing the present invention.

[0008] That is, the present invention relates to the following. [1] A polyester resin formed from a dicarboxylic acid and a diol, the polyester resin including at least a structural unit derived from a diol represented by the following general formula (1):

[0009] [ka]

[0010] (In formula (1), Ak is a saturated or unsaturated divalent hydrocarbon group having 8 to 20 carbon atoms, and X is hydrogen, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group having 1 to 10 carbon atoms which may have a substituent.)

[0011] [2] The polyester resin according to the above [1], wherein the content of the constitutional unit derived from the diol represented by the general formula (1) is 5% by mass or more and 30% by mass or less, based on the polyester resin. [3] The polyester resin according to the above [1] or [2], wherein the X is hydrogen or an alkoxy group having 1 to 10 carbon atoms which may have a substituent. [4] A compound represented by the following general formula (1):

[0012] [ka]

[0013] (In formula (1), Ak is a saturated or unsaturated divalent hydrocarbon group having 8 to 20 carbon atoms, and X is hydrogen, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group having 1 to 10 carbon atoms which may have a substituent.)

[0014] [5] The compound according to the above [4], wherein Ak is a saturated or unsaturated divalent hydrocarbon group having 8 to 20 carbon atoms, and X is hydrogen or an alkoxy group having 1 to 10 carbon atoms which may have a substituent. Effect of the Invention

[0015] According to the present invention, by using a compound having a triptycene skeleton, a liquid polyester resin can be converted into a solid polyester resin, and excellent heat resistance can be imparted to the polyester resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Hereinafter, the embodiments of the present invention will be described in detail. Note that the following description is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to the contents thereof as long as it does not depart from the gist of the present invention.

[0017] [Polyester resin] The polyester resin of the present invention is a polyester resin formed from a dicarboxylic acid and a diol, and is characterized by including at least a constituent unit derived from a diol represented by the following general formula (1).

[0018] [ka]

[0019] In formula (1), Ak is a saturated or unsaturated divalent hydrocarbon group having 8 to 20 carbon atoms, and X is hydrogen, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Examples of the saturated or unsaturated divalent hydrocarbon group having 8 to 20 carbon atoms constituting Ak include saturated or unsaturated aliphatic hydrocarbon groups having 8 to 20 carbon atoms which may have a branch, and aromatic hydrocarbon groups having 8 to 20 carbon atoms which may have a substituent. Among these, linear aliphatic hydrocarbon groups having 8 to 20 carbon atoms are preferred, and linear aliphatic hydrocarbon groups having 8 to 14 carbon atoms are more preferred from the viewpoints of ease of synthesis and inexpensive procurement of raw materials. The substituent that the alkoxy group having 1 to 10 carbon atoms or the alkyl group having 1 to 10 carbon atoms for X may have is not particularly limited, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a group containing a silicon atom such as a silanol group, a group containing an oxygen atom such as a hydroxyl group, a group containing a sulfur atom such as a sulfate group, a nitro group, and a cyano group.

[0020] X is preferably hydrogen or an alkoxy group having 1 to 10 carbon atoms which may have a substituent, more preferably hydrogen or an alkoxy group having 1 to 6 carbon atoms which may have a substituent, still more preferably hydrogen or an alkoxy group having 1 to 3 carbon atoms which may have a substituent, and particularly preferably hydrogen or a methoxy group from the viewpoints of ease of synthesis and inexpensive procurement of raw materials.

[0021] The content of the constitutional unit derived from the diol represented by formula (1) is preferably 5% by mass or more and 30% by mass or less with respect to the total amount of the polyester resin. When the content is 5% by mass or more, the polymer chain of the polyester resin can be sufficiently crosslinked by non-covalent bonds, and the polyester resin can be solidified without increasing the molecular weight. Being solid, the polyester resin of the present invention has improved heat resistance and is extremely easy to handle depending on the application. Since it is only crosslinked by non-covalent bonds, the difference in the properties of the polymer itself between the liquid and solid forms is small, and there is no significant change in the basic physical properties. In addition, if necessary, the crosslinks can be removed by heating or the like, and the original liquid state can be restored. Therefore, liquid polyester resins and solid polyester resins can be used separately depending on the application. On the other hand, when the content is 30 mass% or less, the effects of other diol components can be maintained, and the inherent physical properties, performance, etc. of the polyester resin are not impaired. Thus, the polyester resin of the present invention can change from a liquid state to a solid state by adding a small amount of compound (1) having a triptycene skeleton represented by formula (1). From the above viewpoints, the content of the constitutional unit derived from the diol represented by formula (1) is more preferably 8% by mass or more, and even more preferably 10% by mass or more, and more preferably 28% by mass or less, and even more preferably 25% by mass or less.

[0022] [Dicarboxylic acid] Examples of the dicarboxylic acid that forms the polyester resin of the present invention include an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid.

[0023] (Aliphatic dicarboxylic acids) Examples of the aliphatic dicarboxylic acid include saturated dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid, as well as unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid.

[0024] (alicyclic dicarboxylic acid) Examples of alicyclic dicarboxylic acids include di- or tricycloalkane dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid, decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, and tricyclodecane dicarboxylic acid, and di- or tricycloalkene dicarboxylic acids such as cyclohexene dicarboxylic acid and norbornene dicarboxylic acid.

[0025] (Aromatic dicarboxylic acids) Aromatic dicarboxylic acids can be roughly classified into arene dicarboxylic acids, dicarboxylic acids having a diaryl skeleton, dicarboxylic acids having a fluorene skeleton, and the like. Examples of arene dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; alkyl benzene dicarboxylic acids such as methyl terephthalic acid, 4-methylisophthalic acid, and 5-methylisophthalic acid; naphthalene dicarboxylic acids such as 1,2-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid; condensed polycyclic arene dicarboxylic acids such as anthracene dicarboxylic acid and phenanthrene dicarboxylic acid; and biarene dicarboxylic acids such as 2,2'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, and 4,4'-biphenyl dicarboxylic acid.

[0026] Examples of dicarboxylic acids having a diaryl skeleton include diarylalkanedicarboxylic acids such as 4,4'-diphenylmethanedicarboxylic acid, and diarylketonedicarboxylic acids such as 4,4'-diphenylketonedicarboxylic acid.

[0027] Examples of dicarboxylic acids having a fluorene skeleton include 9,9-bis(carboxyalkyl)fluorenes such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene, and 9-(dicarboxyalkyl)fluorenes such as 9-(1,2-dicarboxyethyl)fluorene and 9-(2,3-dicarboxypropyl)fluorene. 2-8 9,9-bis(carboxyaryl)fluorenes such as 9,9-bis(4-carboxyphenyl)fluorene, and 2,7-dicarboxy-9,9-dimethylfluorene.

[0028] These dicarboxylic acid units may be used alone or in combination of two or more kinds.

[0029] [Diol] The diol other than the formula (1) is not particularly limited, but specific examples thereof include linear or branched alkanediols such as ethylene glycol, propylene glycol, trimethylene glycol (1,3-propanediol), 1,2-butanediol, 1,3-butanediol, tetramethylene glycol (1,4-butanediol), 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol; polyalkanediols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol; and dialkanediols such as diethylene glycol, triethylene glycol, and dipropylene glycol. Of the above diols, linear or branched alkanediols such as ethylene glycol, propylene glycol, and 1,4-butanediol are preferred, and polyalkanediols such as polyethylene glycol and polypropylene glycol are preferred.

[0030] Silicone diol is also a preferred embodiment. As the silicone diol, a polyorganosiloxane compound having reactive hydroxyl groups at both ends of the polysiloxane as shown in the following formula is preferably used. The number average molecular weight of the silicone diol used in the present invention is preferably 100 or more, more preferably 300 or more, and even more preferably 500 or more. The upper limit of the number average molecular weight is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less.

[0031] [ka]

[0032] The repeat numbers n and m in the above formula correspond to the molecular weight. The above diols can be used alone or in combination of two or more kinds.

[0033] [Method of manufacturing polyester resin] The polyester resin of the present invention can be produced by reacting the dicarboxylic acid component, the compound represented by formula (1) according to the present invention, and the diol component, and can be prepared by a conventional method, for example, a melt polymerization method such as an ester exchange method or a direct polymerization method, a solution polymerization method, an interfacial polymerization method, etc., and the melt polymerization method is preferred. The reaction may be carried out in the presence or absence of a solvent depending on the polymerization method.

[0034] The reaction may be carried out in the presence of a catalyst. As the catalyst, a conventional esterification catalyst, for example, a metal catalyst, etc., can be used. As the metal catalyst, for example, a metal compound containing an alkali metal (such as sodium); an alkaline earth metal (such as magnesium, calcium, barium), a transition metal (such as manganese, zinc, cadmium, lead, cobalt, titanium); a metal of Group 13 of the periodic table (such as aluminum); a metal of Group 14 of the periodic table (such as germanium); a metal of Group 15 of the periodic table (such as antimony) and the like can be used. As the metal compound, for example, an alkoxide, an organic acid salt (such as acetate, propionate), an inorganic acid salt (such as borate, carbonate), a metal oxide, etc., or a hydrate thereof may be used. Representative metal compounds include, for example, germanium compounds (germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, germanium-n-butoxide, etc.); antimony compounds (antimony trioxide, antimony acetate, antimony ethylene glycolate, etc.); titanium compounds (tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium oxalate, potassium titanium oxalate, etc.); manganese compounds (manganese acetate tetrahydrate, etc.); calcium compounds (calcium acetate monohydrate, etc.), and the like.

[0035] Furthermore, the reaction may be carried out, if necessary, in the presence of a stabilizer such as a heat stabilizer (for example, a phosphorus compound such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phosphorous acid, trimethyl phosphite, or triethyl phosphite) or an antioxidant.

[0036] The reaction may be carried out in air, or generally in an inert gas (e.g., nitrogen; rare gases such as helium and argon, etc.) atmosphere. The reaction may also be carried out under reduced pressure (e.g., 1×10 2 ~1×10 4 The reaction temperature can be selected depending on the polymerization method, and for example, the reaction temperature in the melt polymerization method may be about 150 to 300°C, preferably 180 to 290°C, and more preferably 200 to 280°C.

[0037] The weight average molecular weight Mw of the polyester resin of the present invention can be selected from the range of about 5,000 to 200,000 in terms of polystyrene conversion, preferably 6,000 to 80,000, and more preferably 6,000 to 50,000. The number average molecular weight Mn of the polyester resin can be selected from the range of, for example, about 500 to 50,000 in terms of polystyrene conversion, preferably 800 to 20,000, and more preferably 1,000 to 15,000. Even if the polyester resin of the present invention is in a molecular weight range that is usually liquid, it exhibits a solid state by forming an associated structure with the compound represented by the formula (1). The weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution Mw / Mn can be measured in terms of polystyrene conversion by gel permeation chromatography (GPC).

[0038] [Compound forming the structural unit of the polyester resin] As described above, the polyester resin of the present invention contains a structural unit derived from the compound represented by the formula (1) as an essential constituent. The compound represented by the formula (1) is as described above, and the compound itself represented by the general formula (1) is also within the scope of the present invention. In the production process of the polyester resin of the present invention, by using the compound represented by the formula (1) as a part of the diol, the structure derived from the compound represented by the formula (1) can be added into the polyester resin.

Examples

[0039] The present invention will be described in more detail in the following examples and comparative examples, but the present invention is not limited thereto.

[0040] (Evaluation method) <Measurement of XRD> An X-ray device (manufactured by Rigaku, NANOPIX, X-ray source: Cu, λ = 1.54 Å), a detector (manufactured by Rigaku, HyPix-6000), an X-ray beam diameter of approximately 0.4 mm, a standard sample (silver behenate), a camera length of 92 mm, a temperature of room temperature (20 °C), an irradiation time of 10 minutes, and a measurement range of 2θ: 0° to 38°. The measurement was carried out under these device conditions. As the measurement operation, the sample was filled in a capillary (φ1.5 mm), the capillary was set on a hot stage, and the XRD measurement device was set up. The XRD image was obtained in such a way, and the two-dimensional image was one-dimensionalized and analyzed. It was confirmed whether peaks derived from a regular structure were detected instead of the halo derived from the amorphous part.

[0041] <Mw and Mn> The weight-average molecular weight Mw, the number-average molecular weight Mn, and the molecular weight distribution Mw / Mn were measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

[0042] (Synthesis Example 1) Synthesis of 1,8TUDO To a solution of pentacycloicosa-(4),1(5),2(6),3(7),8(14),9(15),10,12(16),13(17)-nonaene-14,15-diol (12 g, 41.91 mmol) in acetonitrile (720 mL) was added potassium carbonate (23.17 g, 167.64 mmol), and the mixture was stirred at 80 °C for 30 minutes. Then, 11-bromoundecan-1-ol (52.64 g, 209.55 mmol) was dissolved in acetonitrile (320 mL), and the solution was added dropwise. The mixture was aged at this temperature for 24 hours. The reaction solution was cooled to room temperature, filtered, concentrated under reduced pressure to obtain a residue, which was purified by flash column chromatography on silica gel (ISCO (registered trademark); 120 g, SepaFlash (registered trademark) Silica Flash Column, 0 to 5% CH3OH / CH2Cl2 gradient, 60 mL / min) to obtain the crude product (23 g, 34.49 mmol, yield 82%) as a white solid. The crude product (2.78 g) and (5.8 g) obtained in the same manner were combined and suspended and washed in a mixed solvent of ethyl acetate:n-heptane = 1:5 (300 mL) at 25 ° C for 16 hours. As a result, 11-[[37-(11-hydroxyundecoxy)-36-pentacycloicosa-(4),1(5),2(6),3(7),8(36),9(37),32,34(38),35(39)-nonaenyl]oxy]undecan-1-ol (29.79 g, 46.57 mmol) was obtained as a white solid.

[0043] The identification results by NMR are as follows: 1 H-NMR (400MHz, DMSO-d6): δ=7.45-7.39(m, 1H), 7.32-7.26(m, 1H), 7.04(d, J=4.0Hz, 2H), 7.00-6.94(m, 2H), 6.93-6.90(m, 2H), 6.66(d, J =12.0Hz, 2H), 6.25(s, 1H), 5.58(s, 1H), 4.36-4.34(m, 2H)), 3.99-3.92(m, 4H), 1.82-1.73(m, 4H), 1.58-1.47(m, 4H), 1.27(m, 32H). 1 H-NMR (400MHz, CDCl3): δ=7.44-7.42(m, 1H), 7.40-7.32(m, 1H), 7.04(d, J=8.0Hz, 2H), 6.99-6.97(m, 2H), 6.93-6.89(m, 2H), 6.58(d, J=8.0Hz, 2H), 6.41(s, 1H), 5.41(s, 1H), 4.05-3.92(m, 4H), 3.67-3.64(m, 4H), 1.94- 1.81(m, 4H), 1.78-1.69(m, 2H), 1.59-1.55(m, 8H), 1.46-1.31(m, 24H).

[0044] The reaction scheme is shown below. [ka]

[0045] (Synthesis Example 2) Synthesis of 1,8TUDM To 16-methoxypentacyclo[6.6.6.02,7.09,14.015,20]icosa-2(7),3,5,9(14),10,12,15(20),16,18-nonaene-3,13-diol (4.7 g, 14.86 mmol) in acetonitrile (200 mL) was added potassium carbonate (8.21 g, 59.43 mmol). The mixture was stirred at 80 °C for 30 min, then 11-bromoundecan-1-ol (18.66 g, 74.28 mmol) dissolved in acetonitrile (200 mL) was added dropwise and aged at 80 °C for 24 h. The solution was concentrated under reduced pressure to give a white residue, which was triturated in purified water (200 mL) at 25 °C for 30 min and filtered to give a white solid. The white solid was then triturated in acetonitrile (100 mL) at 25 °C for 2 h and filtered to obtain the crude product (7.5 g) as a white solid, which was purified by short-path column chromatography in a mixture of dichloromethane (DCM) and methanol (220 mL, DCM / methanol = 10 / 1) and triturated in acetonitrile (25 mL) at 0 °C for 30 min to obtain the desired product 11-[[13-(11-hydroxyundecoxy)-16-methoxy-3-pentacyclo[6.6.6.02,7.09,14.015,20]icosa-2(7),3,5,9(14),10,12,15(20),16,18-nonaenyl]oxy]undecan-1-ol (1,8-TUDM, 5.71 g, 8.32 mmol, 56% yield) as a white solid.

[0046] The identification results by NMR are as follows: 1 H-NMR (400MHz, DMSO-d6): δ=7.06-7.01(m, 3H), 6.95-6.87(m, 3H), 6.72(s, 1H), 6.69-6.62(m, 3H)), 5.55(s, 1H), 4.34(t, J=5 .2Hz, 2H), 4.01-3.90(m, 4H), 3.78(s, 3H), 3.40-3.36(m, 4H), 1.80-1.71(m, 4H), 1.62-1.48(m, 4H), 1.43-1.24(m, 28H).

[0047] The reaction scheme is shown below. [ka]

[0048] [Example 1] Carbinol (Hydroxyl) Terminated Polydimethylsiloxane (trade name: DMS-C16) (0.87g, 1.2mmol, Mn600-850) and 1,8-TUDO (0.19g, 0.30mmol) were charged into a flask and placed under nitrogen. Then, it was dissolved in chloroform (1.8mL), the internal temperature was raised to 58°C, and triethylamine (0.42ml, 3.0mmol) was added. Dodecane dioyl dicarbonate dichloride (0.37ml, 1.5mmol) was added dropwise with a syringe over 4 hours. Chloroform (1mL) was added 3 hours after the start of the dropwise addition of dodecane dioyl dicarbonate dichloride, and chloroform (1mL) was added 7 hours later, and maturation was completed 10 hours later. Then, chloroform (4 mL) was added, 1N HCl (1.0 mL), and water (4.0 mL) were added and stirred, and the aqueous layer was removed. Further, water (5 mL) was added and stirred, and the aqueous layer was removed. This operation was carried out a total of four times. The reaction solution was dropped into methanol (200 mL) to carry out reprecipitation. Then, it was dried under reduced pressure at 50°C to obtain a resin (0.3 g). The results of evaluation using the above methods are shown in Table 1.

[0049] [Example 2] Carbinol (Hydroxyl) Terminated Polydimethylsiloxane (trade name: DMS-C16) (1.1 g, 1.5 mmol) and 1,8-TUDM (0.25 g, 0.37 mmol) were charged in a flask and placed under nitrogen. Then, it was dissolved in chloroform (2.3 mL), the internal temperature was raised to 58°C, and triethylamine (0.54 ml, 3.8 mmol) was added. Dodecane dioyl dicarboxylic acid dichloride (0.46 ml, 1.9 mmol) was added dropwise with a syringe over 3 hours. The maturation was completed 3.5 hours after the start of the dropwise addition of dodecane dioyl dicarboxylic acid dichloride. Then, 1N HCl (2.0 mL) and water (8.0 mL) were added, stirred, and the aqueous layer was removed. Further water (8 mL) was added, stirred, and the aqueous layer was removed. This operation was carried out a total of six times. The reaction solution was dropped into methanol (200 mL) to perform reprecipitation, and then dried under reduced pressure at 50° C. to obtain a resin (0.3 g). The results of evaluation using the above methods are shown in Table 1.

[0050] [Comparative Example 1] Carbinol (Hydroxyl) Terminated Polydimethylsiloxane (trade name: DMS-C16) (1.8g, 2.4mmol) was charged into a flask and placed under nitrogen. Then, it was dissolved in chloroform (3.0mL), the internal temperature was raised to 58°C, and triethylamine (0.70ml, 4.9mmol) was added. Dodecane dioyl dicarboxylic acid dichloride (0.60ml, 2.4mmol) was added dropwise with a syringe over 4 hours. After 4 hours from the start of the dropwise addition of dodecane dioyl dicarboxylic acid dichloride, chloroform (1mL) was added, and after 11 hours, chloroform (4mL) was added to complete the maturation. 1N HCl (1.0mL), water (19.0mL), and chloroform (10mL) were added, and the reaction solution was dropped into methanol (150mL) to perform reprecipitation. Thereafter, the mixture was dried under reduced pressure at 50° C. to obtain a resin (0.3 g). The results of evaluation using the above methods are shown in Table 1.

[0051] [Table 1]

[0052] In Table 1, Si diol is Carbinol (Hydroxyl) Terminated PolyDimethylsiloxane, 1,10DC represents dodecane dioyl dicarboxylic acid dichloride, and "-" for the XRD peaks in Example 2 represents not measured.

[0053] [Example 3] Polyethylene glycol (molecular weight 400) (0.64g, 1.6mmol) and 1,8-TUDM (0.18g, 0.28mmol) were charged in a flask and placed under nitrogen. Then, it was dissolved in chloroform (1.7mL), the internal temperature was raised to 58°C, and triethylamine (0.52ml, 3.7mmol) was added. Dodecane dioyl dicarboxylic acid dichloride (0.46ml, 1.9mmol) was added dropwise with a syringe over 4 hours. The maturation was completed 10 hours after the start of the dropwise addition of dodecane dioyl dicarboxylic acid dichloride. Then, 1N HCl (2.0mL) and water (8.0mL) were added, stirred, and the aqueous layer was removed. Further water (8mL) was added, stirred, and the aqueous layer was removed. This operation was carried out a total of six times. The reaction solution was dropped into methanol (200mL) and reprecipitation was carried out. Thereafter, the mixture was dried under reduced pressure at 50° C. to obtain a resin (0.3 g). The results of evaluation using the above methods are shown in Table 2.

[0054] [Example 4] Polyethylene glycol (molecular weight 400) (0.69 g, 1.7 mmol) and 1,8-TUDM (0.093 g, 0.14 mmol) were charged in a flask and placed under nitrogen. Then, the mixture was dissolved in chloroform (1.6 mL), the internal temperature was raised to 58°C, and triethylamine (0.52 ml, 3.7 mmol) was added. Dodecane dioyl dicarboxylic acid dichloride (0.46 ml, 1.9 mmol) was added dropwise with a syringe over 3 hours. The maturation was completed 3.5 hours after the start of the dropwise addition of dodecane dioyl dicarboxylic acid dichloride. Then, 1N HCl (2.0 mL) and water (8.0 mL) were added, stirred, and the aqueous layer was removed. Further water (8 mL) was added, stirred, and the aqueous layer was removed. This operation was carried out a total of six times. The reaction solution was dropped into methanol (200 mL) and reprecipitation was carried out. Thereafter, the mixture was dried under reduced pressure at 50° C. to obtain a resin (0.2 g). The results of evaluation using the above methods are shown in Table 2.

[0055] [Comparative Example 2] Polyethylene glycol (molecular weight 400) (1.2 g, 3.0 mmol) was charged in a flask and placed under nitrogen. Then, it was dissolved in chloroform (2.5 mL), the internal temperature was raised to 58 ° C, and triethylamine (0.84 ml, 6.0 mmol) was added. Dodecane dioyl dicarboxylic acid dichloride (0.74 ml, 3.0 mmol) was added dropwise with a syringe over 4 hours. Two hours after the start of the dropwise addition of dodecane dioyl dicarboxylic acid dichloride, chloroform (2.2 mL) was added, six hours later, chloroform (4 mL) was added, and aging was completed after 10 hours. Then, 1N HCl (1.0 mL) and water (4.0 mL) were added, and the reaction solution was dropped into methanol (200 mL) to perform reprecipitation. Then, it was dried under reduced pressure at 50 ° C, and a resin (0.2 g) was obtained. The results of evaluation using the above methods are shown in Table 2.

[0056] [Table 2]

[0057] In Table 2, PEG stands for polyethylene glycol, and 1,10DC stands for dodecandioyldicarboxylic acid dichloride.

[0058] From the results of Tables 1 and 2, it can be seen that the polyester resin of the present invention can be converted from a liquid to a solid without changing the molecular weight. This makes it easier to handle depending on the application. It is also expected that the heat resistance will be improved. [Industrial Applicability]

[0059] The polyester resin of the present invention can be changed from liquid to solid by adding a small amount of the compound (1) having a triptycene skeleton represented by formula (1). By making it solid, the heat resistance can be improved and the handleability can be greatly improved. In addition, since it can be easily returned from solid to liquid by heating or the like, it can be used in either solid or liquid form depending on the application without impairing the basic physical properties of the polyester resin, making it an industrially valuable invention.

Claims

1. A polyester resin formed from a dicarboxylic acid and a diol, the polyester resin containing at least a structural unit derived from a diol represented by the following general formula (1): 【Chemistry 1】 (In formula (1), Ak is a saturated or unsaturated divalent hydrocarbon group having 8 to 20 carbon atoms, and X is a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group having 1 to 10 carbon atoms which may have a substituent.)

2. The polyester resin according to claim 1, wherein the content of the constitutional unit derived from the diol represented by the general formula (1) is 5% by mass or more and 30% by mass or less based on the polyester resin.

3. 3. The polyester resin according to claim 1, wherein X is hydrogen or an alkoxy group having 1 to 10 carbon atoms which may have a substituent.

4. A compound represented by the following general formula (1): 【Chemistry 2】 (In formula (1), Ak is a saturated or unsaturated divalent hydrocarbon group having 8 to 20 carbon atoms, and X is a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group having 1 to 10 carbon atoms which may have a substituent.)

5. The Ak is a saturated or unsaturated divalent hydrocarbon group having 8 to 20 carbon atoms, 5. The compound according to claim 4, wherein X is hydrogen or an alkoxy group having 1 to 10 carbon atoms which may have a substituent.

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