KR20170048298A - Method for preparing rigid poly(1,4:3,6-dianhydrohexitol esters) - Google Patents

Abstract

Disclosed is a method for producing novel 1,4:3,6-dianhydrohexitol (homo)polyester by using in-situ produced acylated 1,4:3,6-dianhydrohexitol. The method comprises the steps of: producing acylated 1,4:3,6-dianhydrohexitol by in-situ acylating 1,4:3,6-dianhydrohexitol and C4 to 16 aliphatic acid anhydride; and producing 1,4:3,6-dianhydrohexitol polyester by in-situ dissolving, condensing, and polymerizing the acylated 1,4:3,6-dianhydrohexitol and C8 to 22 aromatic or loop aliphatic dicarboxylic acid components. The acylated 1,4:3,6-dianhydrohexitol polyester can be used for multiple purposes and have excellent mechanical properties.

Description

Method for preparing rigid poly (1,4: 3,6-dianhydrohexitol esters): A method for preparing rigid poly (1,4: 3,6-dianhydrohexitol ester)

The present invention relates to a process for preparing 1,4: 3,6-dianhydrohexitol polyester (poly (1,4: 3,6-dianhydrohexitol ester)), (homo) poly (1, 2, 3, 4, 5, 6-dianhydrohexitol) using in situ prepared acylated 1,4: 3,6-dianhydrohexitol. The present invention relates to a process for producing (homo) polyester.

Unlike conventional raw materials based on the petrochemical industry, 1,4: 3,6-dianhydrohexitol is a recycled material such as wheat, sugar, corn, etc. having polysaccharide as a constituent is a bio-based material derived from biomass, which is a renewable resource, and is used in various fields such as polymer materials, pharmaceuticals, and cosmetics. 1,4: 3,6-dianhydrohexitol is isomannide (mp: 81-85 DEG C, bp: 123-130 DEG C / 2 mmHg) represented by the following formula (1a) (Isosorbide, mp: 61-62 DEG C, bp: 148-151 DEG C / 2 mmHg) and isoidide (mp: 64 DEG C, bp: 159-162 DEG C / 2 mmHg) represented by the following formula Exist in different stereoisomers and differ in the chemical properties due to the relative configuration differences of the two hydroxyl groups. Particularly, when the 1,4: 3,6-dianhydrohexitol is used as a monomer for polymerization of a polyester, which is one of the polymer materials, the produced polyester has an environment-friendly advantage, and 1,4: 3,6 -Dienhydrohexitol has excellent thermal and optical properties due to its rigidity, which is a molecular structural feature, and its chirality due to the presence of asymmetric hydroxyl groups. Due to such characteristics, the 1,4-3,6-dianhydrohexitol is used as a typical constituent ingredient in the development of eco-friendly materials, and its application range is expanding.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1b]

The following formulas (1d) to (1f) show the molecular structures of isomannide (1d), isosorbide (1e) and isoidide (1f), respectively. Representative 1,4: 3,6-dianhydrohexitol, isosorbide, has a central angle between the two fused rings of 120 degrees and is chemically equivalent to the two fused rings As a secondary diol of a V-shape with a non-hydroxyl group, C2-OH forms an exo orientation in the two fused rings, allowing easy access to other compounds in the three-dimensional , the reactive side sterically eurona because C5-OH is to form the endo orientation (endo orientation) to it hydrogen bonding the oxygen atoms and molecules of the adjacent tetrahydrofuran rings (tetrahydrofuran ring) (intramolecular hydrogen bonding ) forms relative to C2-OH C5-OH is more acidic than C2-OH due to intramolecular hydrogen bonding. In addition, iso sorbitan p K a value of the hydroxyl group of the carbide is because acid is strongly compared with general linear diol to 5.0 ~ 7.5, and in the polyester polycondensation reaction, the oxygen lone pair of hydroxyl groups of isosorbide dicarboxylic It is not easy to attack the carbonyl group of the carboxylic acid, which causes the degradation of the reactivity. According to the above molecular structural approach, the difference in reactivity of 1,4: 3,6-dianhydrohexitol stereoisomers can be predicted as follows: isodide (0 hydrogen bonds in the molecule; endo 0, exo 2) Endo 1, exo 1> isomeride (two intramolecular hydrogen bonds; endo 2, exo 0).

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

Due to the molecular structural features of the 1,4: 3,6-dianhydrohexitol, the preparation of the homopolyester containing 1,4: 3,6-dianhydrohexitol by the conventional melt polycondensation method It is very difficult. In particular, when an aromatic dicarboxylic acid or a dicarboxylic acid ester is subjected to melt polycondensation with isosorbide, an esterification or esterification exchange reaction temperature of 250 DEG C or higher is required, which causes pyrolysis of isosorbide and polymerization It may cause discoloration of the reaction product, and the reaction time is very slow. Therefore, a linear aliphatic dicarboxylic acid or dicarboxylic acid ester having 4 to 10 carbon atoms can be produced by reacting isosorbide with a dicarboxylic acid ester, such as a binder, a coating, and a toner, which can be produced at a melt polymerization temperature of 250 DEG C or less, The case of melt polycondensation is known to be the most effective isosorbide homopolyester to date. In addition, in the field of commercial plastics, a small amount of isosorbide as a copolymerizable monomer in the production of co-polyester is used to increase the glass transition temperature (Tg) or to be used as a crystallization reducing agent. However, when isosorbide is added The rate of reaction relative to the rate of the conventional melt polycondensation reaction is remarkably slowed and the isosorbide addition amount of about twice as much as the isosorbide content in the target polymer is required to be vaporized or sublimated together with the by- . As a result, there is a disadvantage that another complicated glycol recovery and separation process is required to reuse the lost isosorbide out of the reaction system.

Generally has a lower reactivity during the polycondensation polyester, that is, an aromatic dicarboxylic acid or diol having a lower p K a value can give increased reactivity by giving to activate the respective carboxylic acid or a hydroxyl group. That is, as a method for increasing the reactivity of the aromatic monomers, (i) a method using an activated dicarboxylic acid monomer, (ii) a method using an activated dicarboxylic acid and a diol, and (iii) Is used as a monomer. As the activated dicarboxylic acid monomer, a dicarboxylic acid dichloride may be typically used. In the case of the method (i), the dicarboxylic acid dichloride and the free diol may be condensation-polymerized. The activated diol monomer may be a bissilylated diol or an acylated diol. In the case of the method (ii), the dicarboxylic acid dichloride and bis Bissilylated diols can be condensation-polymerized, and in the case of the (iii) method, the acylated diol can be condensation-polymerized with the free dicarboxylic acid component. However, when dicarboxylic acid dichloride is used as an activating monomer, hydrochloric acid (HCl) is produced as a by-product of condensation polymerization, so there is a limitation in commercial application. When both dicarboxylic acid and diol are activated, (I) and (ii)), both of which are commercially available in that they mainly perform condensation polymerization in solution.

[0003] In a commercial process for preparing aromatic liquid crystalline polyesters, methods have been used for condensation polymerization of acylated aromatic diols or hydroxy acids with free dicarboxylic acid components. If the aromatic diol or hydroxy p K a value of the hydroxy acids are not using an activated monomer because of very low compared to the linear and less hard (rigid) other diol difficult to expect an end product having mechanical properties of high molecular weight and good quality. P K a value of a representative aromatic diol is hydroquinone (hydroquinone) was 10.35, and also hydroxy acids and p- hydroxy p K a value of the benzene acid (hydroxybenzoic acid) is virtually identical to the p K a value of 3.51 to 4.48 terephthalic acid , Especially p-hydroxybenzene acid, has a disadvantage in that some decarboxylation occurs under the conditions of the melt polycondensation reaction of a typical aromatic liquid-crystalline polyester.

The aliphatic acid anhydride, which is mainly used for the monomer activation process of the aromatic liquid-crystalline polyester, that is, the acylation, is easy to use commercially, and in particular, after the activation step, the acylated monomer is separated or purified There is an advantage that it can be directly linked to the melting-condensation polymerization step without any process. In addition, aliphatic acid is formed as a by-product by condensation polymerization of acylated diols or hydroxy acids with free dicarboxylic acid components which are not affected by the acylation process. This is because the condensation polymerization of the three activated monomers mentioned above Among the byproducts generated by the reaction, commercial application and removal are most easy.

Accordingly, an object of the present invention is to provide a process for producing an acrylate 1,4-butanediol derivative capable of improving the reactivity and the reaction rate in the melt polycondensation of polyester through the acylation reaction of 1,4: 3,6-dianhydrohexitol, Dianhydrohexitol in-situ and using the same to prepare a 1,4: 3,6-dianhydrohexitol polyester.

Another object of the present invention is to provide a process for producing 1,4: 3,6-dianhydrohexitol homopolyester having a high degree of polymerization and excellent mechanical properties and having rigid polymer repeating units usable in various applications .

In order to achieve the above object, the present invention provides a process for producing an aliphatic acid anhydride of 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, Acylation reaction to produce acylated 1,4: 3,6-dianhydrohexitol represented by the following formula (2); And in-situ melt polycondensation of the acylated 1,4: 3,6-dianhydrohexitol and aromatic or cycloaliphatic dicarboxylic acid component having 8 to 22 carbon atoms to obtain a compound represented by Formula 3 To produce a 1,4: 3,6-dianhydrohexitol polyester having a repeating unit represented by the following formula .

[Chemical Formula 1]

(2)

(3)

) 또는 점쐐기선(dashed-wedge line,

)을 나타내고, R₁은 각각 독립적으로 탄소수 1 내지 7의 지방족 탄화수소기이며, X는 치환 또는 비치환된 탄소수 6 내지 20의 방향족 또는 환지방족 탄화수소기이다.In the above Formulas 1 to 3, the wavy line is a wedge line,

) Or dashed-wedge line,

R ₁ is independently an aliphatic hydrocarbon group having 1 to 7 carbon atoms and X is a substituted or unsubstituted aromatic or cycloaliphatic hydrocarbon group having 6 to 20 carbon atoms.

The process for preparing 1,4: 3,6-dianhydrohexitol polyesters (poly (1,4: 3,6-dianhydrohexitol ester)) according to the present invention is a process for producing 1,4: 3, By activating 6-dianhydrohexitol through an in-situ acylation reaction, it is possible to increase the reaction rate in polyester melt polycondensation reaction, and 1,4: 3,6-dianhydrohexy The reactivity of the unequal hydroxyl groups of the tosyl can be equally activated and the molten polycondensation step is carried out directly without separation or purification of the acylated 1,4: 3,6-dianhydrohexitol The reaction rate and the raw material cost can be reduced.

Hereinafter, the present invention will be described in detail.

The process for the preparation of 1,4: 3,6-dianhydrohexitol polyester according to the invention is characterized in that acylated 1,4: 3,6-dianhydrohexitol is reacted with a diol component by melt polycondensation (A) 1,4: 3,6-dianhydrohexitol represented by the following formula (1) and a substituted or unsubstituted aliphatic acid anhydride having 4 to 16 carbon atoms, preferably 4 to 8 carbon atoms, In-situ acylation reaction to produce acylated 1,4: 3,6-dianhydrohexitol represented by the following formula (2) and (b) reacting the acylated 1,4 : 3,6-dianhydrohexitol and an aromatic or cycloaliphatic dicarboxylic acid component having 8 to 22, preferably 8 to 14, and more preferably 8 to 12 carbon atoms in-situ melting To prepare a 1,4: 3,6-dianhydrohexitol polyester comprising repeating units represented by the following formula (3) It includes the steps:

) 또는 점쐐기선(dashed-wedge line,

)을 나타내고, R₁은 각각 독립적으로 탄소수 1 내지 7, 바람직하게는 1 내지 3의 지방족 탄화수소기이며, X는 치환 또는 비치환된 탄소수 6 내지 20, 바람직하게는 6 내지 12, 더욱 바람직하게는 6 내지 10의 방향족 또는 환지방족 탄화수소기이다. 여기서, 쐐기선은 히드록실기(-OH) 등이 평면(통상적인 선으로 표시된 구조)의 위에서 결합됨을 의미하고, 점쐐기선은 평면의 아래에서 결합됨을 의미하며, 특히, 환지방족 탄화수소기의 trans 함량은 0 내지 100%이다. In the above Formulas 1 to 3, the wavy line is a wedge line,

) Or dashed-wedge line,

R ₁ is independently an aliphatic hydrocarbon group having 1 to 7 carbon atoms, preferably 1 to 3 carbon atoms, and X is a substituted or unsubstituted group having 6 to 20, preferably 6 to 12, 6 to 10 aromatic or cycloaliphatic hydrocarbon groups. Here, the wedge line means that the hydroxyl group (-OH) or the like is bonded above the plane (structure indicated by the normal line), the point wedge line is bonded below the plane, The trans content is 0 to 100%.

The final attainable intrinsic viscosity (IV) of the 1,4: 3,6-dianhydrohexitol polyester comprising the repeating unit represented by the formula (3) prepared by the polyester production method is 0.3 to 1.2 dL / g.

In the present specification, the term dicarboxylic acid component and the like includes dicarboxylic acids such as terephthalic acid, alkyl esters thereof (lower alkyl esters having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl esters) And / or an acid anhydride thereof, and the carbon number of the aromatic or aliphatic dicarboxylic acid component corresponds to a dicarboxylic acid form. In addition, the molten condensation polymerization reaction is a name encompassing esterification and esterification exchange reaction.

The step of producing the acylated 1,4: 3,6-dianhydrohexitol (step (a)) comprises reacting 1,4: 3,6-dianhydrohexitol (isomanide, isosorbide and Isoindide), the reaction temperature of the acylation reaction is 80 to 180 ° C, preferably 120 to 160 ° C, and the reaction time is 5 minutes to 10 hours, preferably 10 minutes to 5 hours.

Representative examples of the aliphatic acid anhydride used in the acylation reaction of 1,4: 3,6-dianhydrohexitol include acetic anhydride, propionic anhydride, But are not limited to, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, 2-ethylhexanoic anhydride, b-bromopropionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, But are not limited to, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, tribromoacetic anhydride, tribromoacetic anhydride, etic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, and the like can be exemplified. The aliphatic acid anhydride may be used in admixture of two or more, and R _{1 in} the formula (2) is determined according to the aliphatic acid anhydride used. From the viewpoint of cost and ease of handling, it is preferable to use acetanhydride, propionic anhydride, butyric anhydride and isobutyric anhydride, more preferably acetanhydride.

The amount of the aliphatic acid anhydride used is preferably 0.9 to 1.2 times the stoichiometric amount of the aliphatic acid anhydride required to acylate all the hydroxyl groups of 1,4: 3,6-dianhydrohexitol, Is 0.97 to 1.13 times. If the amount of the aliphatic acid anhydride is out of the above range, the reaction rate of the linked polyester melt aggregation may become slower or the mixed anhydride impurities may cause the color of the final polymer, such as 1,4: 3, The physical properties of the 6-dianhydrohexitol polyesters may be deteriorated.

In the step of preparing the acylated 1,4: 3,6-dianhydrohexitol, an inert gas purge such as nitrogen or argon is used during the acylation reaction in order to minimize the oxidation of the reactant. ) Can be used. The inert gas purging is preferably continued in the linked polyester melt polycondensation reaction and the acylation reaction and removal and condensation of the aliphatic acid which is a by-product of the melt polycondensation reaction are carried out using conventional methods such as distillation head and condenser It can be easily done. Particularly, acetic acid in the acylation reaction and the melt polycondensation reaction by-products can be easily removed as volatile by-products.

Next, the melt polycondensation reaction step (step (b)) for producing 1,4: 3,6-dianhydrohexitol homopolyester is immediately carried out in conjunction with it. After the in-situ acylation reaction, the initiation of the melt polycondensation reaction is accomplished by selecting a reaction temperature that is higher than the acylation reaction. Here, the amount of the acyl group of the acylated 1,4: 3,6-dianhydrohexitol prepared in-situ is 0.7 to 1.3 times the equivalent amount of the carboxyl group of the dicarboxylic acid component, Preferably 0.9 to 1.1 times, and the temperature raising rate of the melt polycondensation reaction is 0.1 to 60 占 폚 / min, preferably 0.2 to 20 占 폚 / min, more preferably 0.5 to 6 占 폚 / min, Is from 120 to 320 ° C, preferably from 150 to 290 ° C, and the reaction time is from 1 to 10 hours, preferably from 3 to 8 hours.

On the other hand, the aliphatic acid and unreacted aliphatic acid anhydride produced as reaction by-products during the melt polycondensation reaction must be distilled out of the reaction system in order to move the reaction equilibrium in the direction of polyester production. Particularly, when the temperature raising rate is out of the range, the acylated 1,4: 3,6-dianhydrohexitol can be vaporized or sublimated together with the aliphatic acid. The 1,4: 3,6-dianhydrohexitol polyester can be prepared by a batch process or a continuous process.

Representative examples of the aromatic or cycloaliphatic dicarboxylic acid component include monomers represented by the following formula (4).

,

,

,

,

,

,

,

,

,

,

,

등을 예시할 수 있다. 여기서, *는 결합부위를 나타내며, Y는 산소 원자(O), 황 원자(S), 알킬렌기, 카르보닐기 또는 술포닐기이다. 또한, X는 필요에 따라, 알킬기, 아릴기, 알콕시기, 할로겐기 등에 의해 치환될 수 있다.In Formula 4, R ₂ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and X is as defined in Formula 3. Representative examples of X include

,

,

,

,

,

,

,

,

,

,

,

And the like. Here, * represents a bonding site, and Y represents an oxygen atom (O), a sulfur atom (S), an alkylene group, a carbonyl group, or a sulfonyl group. Further, X may be optionally substituted with an alkyl group, an aryl group, an alkoxy group, a halogen group or the like.

In the process for producing a 1,4: 3,6-dianhydrohexitol polyester according to the present invention, a catalyst may be further used for improving the reactivity of the melt polycondensation reaction. As the catalyst, catalysts commonly used in polyester melt condensation polymerization can be used. For example, salts of titanium (Ti) or antimony (Sb), cobalt (Co), zinc (Zn) An alkanoate salt of an acetate salt of antimony (Sb), an oxide of antimony (Sb) or germanium (Ge) or an oxide of cobalt (Co) or antimony (Sb) , Ortho titanate ester, and the like can be used. The content of the catalyst is 1 to 500 ppm, preferably 10 to 300 ppm, based on the total weight of reactants. The catalyst may be applied irrespective of the stage of the melt polycondensation reaction, but is preferably introduced before the initiation of the melt polycondensation reaction.

In addition, the process for preparing 1,4: 3,6-dianhydrohexitol polyester according to the present invention induces the removal of by-products in a molten state having a high viscosity as the degree of polymerization increases with the progress of the melt polycondensation reaction, A reduced pressure may be applied to promote the polymerization reaction rate. Under reduced pressure for increasing the degree of polymerization, the reduced pressure condition is 0.2 to 2 Torr, preferably 0.5 to 1 Torr, and the reaction time under reduced pressure is 1 to 10 hours, preferably 1 to 5 hours.

Further, in the process for producing a 1,4: 3,6-dianhydrohexitol polyester according to the present invention, various additives may be further added, if necessary. For example, antioxidants and heat stabilizers such as hindered phenol, hydroquinone, phosphite, and substituted compounds thereof, resorcinol, A UV absorber such as salicylate, a color protection agent such as a phosphite or a hydrophosphite, a lubricant such as montanic acid or stearyl alcohol, . In addition, dyes and pigments may be used as the coloring agent, carbon black may be used as the conductive agent, the coloring agent or the nucleation agent, A fire retardant, a plasticizer, an antistatic agent and the like can be used. Here, all the above-mentioned additives should not interfere particularly with the thermal stability among the final polymer properties.

In the process for producing 1,4: 3,6-dianhydrohexitol polyester according to the present invention, solid-sate polymerization can be further performed after the melt polycondensation reaction. The polymer obtained from the melt polycondensation is collected in a solid state such as a crushed product or a flake or a small pellet outside the reactor and then heated under an inert environment such as nitrogen or argon gas at a temperature raising rate of 0.1 to 0.5 DEG C / At a reaction temperature of 30 to 350 ° C, preferably 100 to 280 ° C, for a reaction time of 1 to 30 hours, preferably 2 to 24 hours. The solid phase polymerization can be carried out with or without stirring and can be carried out continuously in the same reactor as the melt polymerization. After the solid-phase polymerization, the obtained polymer can be directly molded into a final product according to the application by a conventional method. The final attainable intrinsic viscosity (IV) of the 1,4: 3,6-dianhydrohexitol polyester produced by the solid phase polymerization is 0.5 to 2.5 dL / g.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The following examples are intended to illustrate the present invention, and the scope of the present invention is not limited by the following examples.

[Example 1] Preparation of 1,4: 3,6- dianhydrohexitol polyester containing repeating unit represented by formula (3a)

(A) Acetylation reaction

The flask was equipped with a distillation head, a cooling condenser, a thermometer, a nitrogen inlet tube and a mechanical stirrer, after which the flask was purged with nitrogen and washed 5 times to completely remove the air present in the 1 L flask before the reaction. 200 g (1.20 moles) of terephthalic acid and 176 g (1.20 moles) of isosorbide were added to the flask, and the mixture was heated to 60 to 70 DEG C, stirred for 10 to 20 minutes, and then dropped into a dropping funnel 250 g (2.45 mole) of acetanhydride was slowly added to the terephthalic acid / isosorbide slurry. After all of the acetanhydride was added, the temperature was immediately raised to 120 ° C at normal pressure, and then the mixture was stirred and maintained for 1 hour. The mixture was heated to 145 DEG C again and stirred and maintained for 3 hours to obtain 1,4: 3,6-dianhydro-D (D-glucitol-2,5-diacetate -glucitol-2,5-diacetate).

(B) melt polycondensation reaction

After the acetylation reaction, the temperature was raised to 200 ° C and stirred and maintained at 200 ° C for 1 hour to remove acetic acid as a by-product of the acetylation reaction. Next, the temperature was raised to 250 DEG C at a heating rate of 1 DEG C / min, and then additional acetic acid by-products were removed by stirring and holding at 250 DEG C for 3 hours. After the nitrogen purge was stopped, the melt polycondensation was carried out for 2 hours under a reduced pressure of 1 Torr, and the mixture was cooled to room temperature to obtain a polymer chunk-like 1, 4: 3,6-dianhydrohexitol (homo) polyester (IV = 0.55) was obtained.

[Chemical Formula 3]

The 1,4: 3,6-dianhydrohexitol (homo) polyester containing the repeating unit represented by the above-mentioned general formula (3a) is amorphous and its glass transition temperature (Tg) is intrinsic viscosity 0.5 And 203 to 205 ° C. and the unsymmetrical isosorbide units were statistically random in the form of head-to-head, head-to-tail, and tail- , The glass transition temperature is high but the mechanical properties are lower than those expected to have a linear structure using isodide as a monomer and are expected to be similar to polymers using isomanide as a monomer. On the other hand, in the comparison of the reactivity of 1,4: 3,6-dianhydro-D-glucitol-2,5-diacetate with isosorbide, it was found that 1,4: 3,6-dianhydride The loss rate of -D-glucitol-2,5-diacetate was about 0.5% with respect to the input amount. This shows a remarkable increase in the reactivity compared to the loss ratio of the maximum times or more, which was the limit of isosorbide. The same results were obtained in the examples.

[Example 2] Production of ( cycloaliphatic ) 1,4: 3,6-dianhydrohexitol polyester containing a repeating unit represented by the formula (3b )

In step (A), instead of 200 g (1.20 mole) of terephthalic acid and 176 g (1.20 mole) of isosorbide, 250 g (1.45 mole) of 1,4- 212 g (1.45 moles) of isosorbide was added to 300 g (2.93 mole) of acetic anhydride instead of 250 g (2.45 mole) of 1,4-cyclohexanedicarboxylic acid (manufactured by SK NJC) Dianhydrohexitol (homo) polyester (IV = 0.58) containing a repeating unit represented by the following formula (3b) was obtained in the same manner as in Example 1, except that

(3b)

The 1,4: 3,6-dianhydrohexitol (homo) polyester containing the repeating unit represented by the above formula (3b) is amorphous, and as a characteristic result, 1,4-cyclohexanediol The cis / trans ratio, 77/23%, of the carboxylic acid was changed to 44/64% in the polymer as a result of the condensation polymerization with the acetylation. This is because the acetic acid and isomerization of acetic acid, (cis / trans ratio) at a given reaction temperature and reaction time. As a result, the glass transition temperature of the polymer was influenced by the cis / trans ratio in the final polymer. When the intrinsic viscosity was 0.5 or more and the cis / trans 44/64%, the glass transition temperature was 151 to 153 ° C.

[Example 3] Production of (angled aromatic) 1,4: 3,6-dianhydrohexitol polyester containing repeating units represented by formula (3c)

The procedure of Example 1 was repeated except that 200 g (1.20 mole) of isophthalic acid was used instead of 200 g (1.20 mole) of terephthalic acid in the step (A) To obtain 1,4: 3,6-dianhydrohexitol (homo) polyester (IV = 0.56) containing the repeating units to be displayed.

 [Chemical Formula 3c]

The 1,4: 3,6-dianhydrohexitol (homo) polyester containing the repeating unit represented by the above-described formula (3c) has a structure similar to that of the amorphous polymer structure of the polyester containing the repeating unit represented by the above formula Zig-zag or helical chain conformation, which is close to linear and has a gentle curve.

[Example 4] Preparation of (angular ring aliphatic ) 1,4: 3,6-dianhydrohexitol polyester containing repeating unit represented by the formula (3 )

In step (A), 250 g (1.45 mole) of 1,3-propanediol having a cis / trans ratio of 46/54% instead of 200 g (1.20 mole) of terephthalic acid and 176 g (2.93 moles) instead of 250 g (2.45 moles) of acetic anhydride was added to a solution containing 212 g (1.45 mole) of isosorbide and 1,3-cyclohexanedicarboxylic acid (manufactured by Aldrich) Dianhydrohexitol (homo) polyester (IV = 0.57) containing the repeating unit represented by the following formula (3) was obtained in the same manner as in Example 1,

 (3d)

The 1,4: 3,6-dianhydrohexitol (homo) polyester containing the repeating unit represented by the above-mentioned formula (3d) is the same as the result obtained in the production of the polyester containing the repeating unit represented by the above formula (3b) The cis / trans ratio of the first monomer, 1,3-cyclohexane dicarboxylic acid, was changed from 46/54% to 5/95%, which was prepared by using trans 100% 1,3-cyclohexane dicarboxylic acid And have properties similar to those of the polymer.

From the above examples, it has been found that in accordance with the present invention, acylated 1,4: 3,6-dianhydrohexitol (e.g., 1,4: 3,6-dianhydrohexitol- Diacetate) is in-situ produced and from which an aromatic or cycloaliphatic 1,4: 3,6-dianhydrohexitol polyester is prepared, the conventional dicarboxylic acid and 1,4 : It is found that the reaction rate is significantly faster than that of the melt polycondensation of 3,6-dianhydrohexitol, and the isosorbide input amount almost equal to the isosorbide content in the polymer can be used due to the increase of the reactivity have. Therefore, a complicated glycol recovery and separation process for reusing the lost isosorbide outside the reaction system is not necessary, which is economical.

Claims (8)

In-situ acylation reaction of 1,4: 3,6-dianhydrohexitol represented by the following formula (1) and an aliphatic acid anhydride having 4 to 16 carbon atoms to produce an acyl Lt; / RTI > 1,4: 3,6-dianhydrohexitol; And
In-situ melt polycondensation of the acylated 1,4: 3,6-dianhydrohexitol and the aromatic or cycloaliphatic dicarboxylic acid component having 8 to 22 carbon atoms, A process for producing a 1,4: 3,6-dianhydrohexitol polyester comprising preparing a 1,4: 3,6-dianhydrohexitol polyester comprising a repeating unit to be displayed.
[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3, the wavy line is a wedge line,

) Or dashed-wedge line,

R ₁ is independently an aliphatic hydrocarbon group having 1 to 7 carbon atoms and X is a substituted or unsubstituted aromatic or cycloaliphatic hydrocarbon group having 6 to 20 carbon atoms. The process according to claim 1, wherein the aromatic or cycloaliphatic dicarboxylic acid component is a monomer represented by the following formula (4).
[Chemical Formula 4]

In Formula 4, R ₂ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and X is as defined in Formula 3. 2. The compound according to claim 1,

,

,

,

,

,

,

,

,

,

,

And

(Wherein * denotes a bonding site and Y is an oxygen atom, a sulfur atom, an alkylene group, a carbonyl group or a sulfonyl group). Lt; / RTI > The process according to claim 1, wherein the reaction temperature of the acylation reaction is from 80 to 180 ° C and the reaction time is from 5 minutes to 10 hours. The process according to claim 1, wherein the temperature elevation rate of the melt polycondensation reaction is 0.1 to 60 캜 / min, the reaction temperature is 120 to 320 캜, and the reaction time is 1 to 10 hours. Dianhydrohexitol polyester. The process according to claim 1, wherein, in the melt polycondensation reaction, the decompression condition is 0.2 to 2 Torr and the reaction time under reduced pressure is 1 to 10 hours under reduced pressure for increasing polymerization degree. Dianhydrohexitol polyester. The process according to claim 1, further comprising a solid phase polymerization step in which the 1,4: 3,6-dianhydrohexitol polyester is subjected to a heat treatment in an inert environment in a solid state, 1,4: 3,6-dianhydrohexoxy Tallow polyester. The method according to claim 7, wherein the solid-state polymerization is carried out at a temperature raising rate of 0.1 to 0.5 占 폚 / min, a reaction temperature of 30 to 350 占 폚, and a reaction time of 1 to 30 hours. Hexitol polyester.