WO2012148187A2 - Method for preparing poly(1,4:3,6-dianhydrohexitol ester) - Google Patents

Abstract

Disclosed is a method for preparing 1,4:3,6-dianhydrohexitol (homo)polyester in-situ using acylated 1,4:3,6-dianhydrohexitol. Said method for preparing 1,4:3,6-dianhydrohexitol polyester comprises the steps of: using an acylation reaction of a 1,4:3,6-dianhydrohexitol with an aliphatic acid anhydride having 4 to 16 carbon atoms to prepare the acylated 1,4:3,6-dianhydrohexitol; and using an in-situ melt condensation polymerization reaction of said acylated 1,4:3,6-dianhydrohexitol and an aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 14 carbon atoms to prepare 1,4:3,6-dianhydrohexitol polyester.

Description

Method for preparing poly (1,4: 3,6-dianhydrohexitol ester)

The present invention relates to a method for preparing 1,4: 3,6- dianhydrohexitol polyester (poly (1,4: 3,6- dianhydrohexitol ester)), more specifically, acylate (acylated) 1,4: 3,6-dianhydrohexitol (homo) polyester in-situ using 1,4: 3,6-dianhydrohexitol (homo) polyester).

Unlike conventional raw materials based on the petrochemical industry, 1,4: 3,6-dianhydrohexitol is a renewable resource such as wheat, sugar, corn, etc., which contains polysaccharide as a component. As a bio-based raw material derived from biomass, which is a renewable resource, it is used in various fields such as polymer materials, pharmaceuticals, and cosmetics. 1,4: 3,6-dianhydrohexitol is an isomannide represented by the following formula 1a (isomannide, mp: 81-85 ℃, bp: 123-130 ℃ / 2 mmHg), represented by the formula 1b Isosorbide (mp: 61-62 ° C, bp: 148-151 ° C / 2 mmHg) and isoidide represented by the following formula (1c) (isoidide, mp: 64 ° C, bp: 159-162 ° C / 2 mmHg) There are three stereoisomers of), which differ in their chemical properties due to the relative configuration differences of the two hydroxyl groups. In particular, when the 1,4: 3,6- dianhydrohexitol is used as a monomer in the polymerization of the polyester of one of the polymer materials, the polyester produced has an environmentally friendly advantage, in addition to 1,4: 3,6 Excellent thermal and optical properties are due to the rigidity, the molecular structure of dianhydrohexitol, and the chirality due to the presence of asymmetric hydroxyl groups. Due to such a characteristic, the application range of 1,4: 3,6-dianhydrohexitol is used as a representative constituent raw material for the development of environmentally friendly materials.

[Formula 1a]

[Formula 1b]

[Formula 1c]

The following Chemical Formulas 1d to 1f represent the molecular structures of isomannide (formula 1d), isosorbide (formula 1e), and isoidide (formula 1f), respectively. As shown in Formula 1e, isosorbide, a representative 1,4: 3,6-dianhydrohexitol, has a central angle between two fused rings of 120 ° and two chemically equivalents As a secondary diol of V-shape with an un hydroxyl group, C2-OH forms an exo orientation on two fused rings, making it easier to access stericly different compounds. In addition, C5-OH has an endo orientation and forms an intramolecular hydrogen bond with an oxygen atom of an adjacent tetrahydrofuran ring. It can be said to be very disadvantageous, and as a result, C5-OH becomes 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 carboxylic acid, and it becomes a cause of the reactivity decline. Predicting the difference in reactivity of 1,4: 3,6- dianhydrohexitol stereoisomers according to the above molecular structural approach, isoidide (0 hydrogen bonds in the molecule; endo 0, exo 2)> isosorb High reactivity in the order of Bide (1 hydrogen bond in the molecule; endo 1, exo 1)> Isomannide (2 hydrogen bonds in the molecule; endo 2, exo 0).

[Formula 1d]

[Formula 1e]

[Formula 1f]

Due to the molecular structural characteristics of the 1,4: 3,6-dianhydrohexitol, a homopolyester including 1,4: 3,6-dianhydrohexitol is prepared by a conventional melt condensation polymerization method. Is very difficult. In particular, melt condensation polymerization of aromatic dicarboxylic acid or dicarboxylic acid esters with isosorbide requires an esterification or transesterification reaction temperature of 250 ° C. or higher, which causes isosorbide to thermally decompose and polymerize. Discoloration of the reactants can be caused, and the reaction time is very slow. Therefore, high molecular weight is not required, and linear aliphatic dicarboxylic acid or dicarboxylic acid having 4 to 10 carbon atoms with isosorbide can be used for binders, coatings, toners, and the like which can be produced at a melt polymerization temperature of 250 ° C. or lower. Melt polycondensation is known to be the most effective isosorbide homopolyester to date. In addition, in the commercial plastic field, a small amount of isosorbide is added as a copolymerization monomer to prepare co-polyester, thereby increasing the glass transition temperature (Tg) or reducing the crystallinity. However, when isosorbide is added The reaction rate is significantly slower than the conventional melt polycondensation reaction rate, and due to low reactivity, it is vaporized or sublimed together with the polycondensation reaction by-products, so that isosorbide input of up to twice the amount of isosorbide content in the target polymer must be used. There is. As a result, another complicated glycol recovery and separation process is required to reuse the isosorbide lost out of the reaction system.

In general, aromatic dicarboxylic acids or diols having low reactivity during polyester polycondensation, ie, having low p K a values, may increase reactivity by activating respective carboxylic acid or hydroxyl groups. That is, a method for enhancing the reactivity of the aromatic monomers may include (i) using activated dicarboxylic acid monomers, (ii) using activated dicarboxylic acids and diols, and (iii) activated diols. Is used as a monomer. Dicarboxylic acid dichloride may be typically used as the activated dicarboxylic acid monomer, and in the case of the method (i), dicarboxylic acid dichloride and free diol may be condensation-polymerized. In addition, as the activated diol monomer, a bissilylated diol, an acylated diol, and the like may be used. In the case of the method (ii), dicarboxylic acid dichloride and bissilyl may be used. The bissilylated diols can be condensation polymerized, and in the case of the method (iii) above, the acylated diols can be condensation polymerized with the free dicarboxylic acid component. However, when dicarboxylic acid dichloride is used as an activating monomer, there is a limitation in commercial applications because hydrochloric acid (HCl) is produced as a byproduct of polycondensation reaction, and when both dicarboxylic acid and diol are activated, the reaction is performed before the reaction. It has the disadvantage of being prepared with activated monomers, and both methods ((i) and (ii)) are very low in terms of commercial availability in that they mainly carry out condensation polymerization reactions in solution.

As a commercial method for preparing aromatic liquid crystalline polyesters, a method of condensation polymerization of acylated aromatic diols or hydroxy acids with free dicarboxylic acid components has been used. Because the p K a values of aromatic diols or hydroxy acids are very low compared to other linear and less rigid diols, it is difficult to expect a final product with high molecular weight and good mechanical properties without the use of activated monomers. 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 In particular, p-hydroxybenzene acid has a disadvantage in that some decarboxylation occurs under general aromatic liquid crystal polyester melt polycondensation reaction conditions.

Aliphatic acid anhydride, which is mainly used in the monomer activation process, that is, acylation of aromatic liquid crystalline polyesters, is easy to use commercially, and in particular, the separation or purification of acylated monomers after the activation step It has the advantage of being able to link directly to the melt condensation polymerization step without the process. In addition, polycondensation of the acylated diols or hydroxy acids with free dicarboxylic acid components unaffected in the acylation process produces aliphatic acids as by-products, which are condensation of the three activating monomers mentioned above. Among the by-products produced by the reaction, commercial application and removal are the easiest.

Accordingly, it is an object of the present invention, through the acylation reaction of 1,4: 3,6- dianhydrohexitol, acylate 1,4: which can improve the reactivity and reaction rate during polyester melt condensation polymerization: It is to prepare 3,6- dianhydrohexitol and to use it in-situ to provide a method for producing 1,4: 3,6- dianhydrohexitol polyester.

Another object of the present invention is to provide a method for preparing 1,4: 3,6-dianhydrohexitol homopolyester having high polymerizability and excellent mechanical properties and having a rigid polymer repeating unit that can be used for various purposes. To provide.

In order to achieve the above object, the present invention, by acylation reaction of 1,4: 3,6- dianhydrohexitol and aliphatic acid anhydride having 4 to 16 carbon atoms represented by the following formula (1) Preparing the indicated acylate 1,4: 3,6- dianhydrohexitol; And melt condensation polymerization of the acylated 1,4: 3,6- dianhydrohexitol and an aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 14 carbon atoms in-situ. 1,4: 3,6- dianhydrohexitol polyester comprising the step of preparing a 1,4: 3,6- dianhydrohexitol polyester comprising a repeating unit represented by the formula (3) to provide.

[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3, wavy lines are wedge lines,

) Or dashed-wedge line,

), R ₁ are each 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 12 carbon atoms.

1,4: 3,6- dianhydrohexitol polyester (poly (1,4: 3,6- dianhydrohexitol ester)) according to the present invention is a low reactivity 1,4: 3, 6-dianhydrohexitol is activated via an in-situ acylation reaction. Therefore, it is possible to increase the reaction rate in the polyester melt polycondensation reaction, to activate the reactivity of the non-equivalent hydroxyl groups of 1,4: 3,6- dianhydrohexitol equally, Since the melt condensation polymerization step can be performed immediately without separating or purifying acylated 1,4: 3,6-dianhydrohexitol, there is an advantage in that reaction rate and raw material cost are reduced.

Hereinafter, the present invention will be described in detail.

1,4: 3,6-dianhydrohexitol polyester production method according to the present invention is melt condensation polymerization of acylated 1,4: 3,6-dianhydrohexitol using a diol component Increasing the reactivity, (a) 1,4: 3,6- dianhydrohexitol represented by the following formula (1) and substituted or unsubstituted aliphatic acid anhydride having 4 to 16, preferably 4 to 8 carbon atoms To acylation reaction to prepare an acylate 1,4: 3,6- dianhydrohexitol represented by the following formula (2) and (b) the acylate 1,4: 3,6- dianhydrohex A repeating unit represented by the following Chemical Formula 3 is obtained by melt condensation polymerization of a cytol and an aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 14, preferably 8 to 12, carbon atoms in-situ. Preparing a 1,4: 3,6-dianhydrohexitol polyester comprising;

[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3, wavy lines are wedge lines,

) Or dashed-wedge line,

) And R ₁ is each independently an aliphatic hydrocarbon group having 1 to 7 carbon atoms, preferably 1 to 3, and may be substituted with one or more substituents such as halogen as necessary. X is a substituted or unsubstituted aromatic or cycloaliphatic hydrocarbon group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. Here, the wedge line means that the hydroxyl group (-OH) and the like are coupled on the plane (the structure indicated by the normal line), and the point wedge line means the bottom line is coupled. The content of trans cycloaliphatic hydrocarbon group is 0 to 100%.

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

As used herein, the term "dicarboxylic acid component" refers to dicarboxylic acids such as terephthalic acid, alkyl esters thereof (lower alkyl esters having 1 to 6 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) And an acid anhydride thereof, and the like, and the molten polycondensation reaction is a name encompassing esterification and esterification exchange reaction.

The step of preparing the acylate 1,4: 3,6- dianhydrohexitol (step (a)) is 1,4: 3,6- dianhydrohexitol (isomanide, isosorbide and For equally activating the reactivity of dissimilar hydroxyl groups of isoidide), the reaction temperature of the acylation reaction is 80 to 180 ° C, preferably 120 to 160 ° C, more preferably 120 to 150 ℃, the reaction time is 5 minutes to 10 hours, preferably 10 minutes to 5 hours.

Representative examples of the aliphatic acid anhydrides used in the acylation reaction of 1,4: 3,6-dianhydrohexitol include acet anhydride, propionic anhydride, Butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride ( 2-ethylhexanoic anhydride, b-bromopropionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride Trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride cetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride and the like. Two or more aliphatic acid anhydrides may be mixed and used, and R ₁ of Chemical Formula 2 is determined according to the aliphatic acid anhydride to be used. In terms of cost and ease of handling, it is preferable to use acet anhydride, propionic anhydride, butyric anhydride and isobutyric anhydride, more preferably acet anhydride can be used.

The amount of aliphatic anhydride used is 0.9 to 1.2 times the stoichiometric amount of aliphatic anhydride required to acylate all the hydroxyl groups of 1,4: 3,6-dianhydrohexitol, preferably Is 0.97 to 1.13 fold. When the amount of the aliphatic anhydride is out of the above range, the reaction rate of the associated polyester melt condensation polymerization may be slowed, or 1,4: 3, including the color of the final polymer, may be caused by mixed anhydride impurities. There is a fear that the physical properties of 6-dianhydrohexitol polyesters are lowered.

In preparing the acylate 1,4: 3,6-dianhydrohexitol, purge an inert gas such as nitrogen or argon during an acylation reaction to minimize the oxidation of the reactants. ) Can be used. The inert gas purge is preferably continued in the associated polyester melt polycondensation reaction, and the removal and condensation of the acylation and melt polycondensation by-product aliphatic acids is carried out using conventional methods such as distillation heads and condensers. It can be done easily. In particular, acetic acid in the acylation and melt polycondensation reaction by-products is a volatile by-product and is very easy to remove.

Next, the melt condensation polymerization step (step (b)) for the preparation of 1,4: 3,6-dianhydrohexitol homopolyester is carried out directly in conjunction. After the in-situ acylation reaction, the initiation of the melt polycondensation reaction is achieved by selecting a higher reaction temperature than the acylation reaction. Here, the amount of acyl groups of in-situ prepared acylated 1,4: 3,6-dianhydrohexitol is 0.7 to 1.3 times the equivalent amount of the carboxyl groups of the free dicarboxylic acid component. , Preferably 0.9 to 1.1 times, and the temperature increase rate of the melt polycondensation reaction is 0.1 to 60 ℃ / min, preferably 0.2 to 20 ℃ / min, more preferably 0.5 to 6 ℃ / min, the reaction The temperature is from 120 to 320 ° C, preferably from 150 to 290 ° C, more preferably from 170 to 280 ° 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 shift the reaction equilibrium in the polyester production direction. In particular, when out of the temperature increase rate range, the acylated 1,4: 3,6-dianhydrohexitol may be vaporized or sublimed together with the aliphatic acid. The 1,4: 3,6- dianhydrohexitol polyester can be prepared by a batch process or by a continuous process.

Representative examples of the aromatic or cycloaliphatic dicarboxylic acid component may be exemplified by the monomer represented by the following formula (4).

[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 above. Also, representative examples of X are

,

,

,

,

,

,

,

,

,

,

,

,

,

Etc. can be illustrated. Where * represents a bonding site and Y is an oxygen atom (O), a sulfur atom (S), an alkylene group, a carbonyl group or a sulfonyl group. In addition, X may be substituted by an alkyl group, an aryl group, an alkoxy group, a halogen group, etc. as needed.

1,4: 3,6-dianhydrohexitol polyester production method according to the present invention may further use a catalyst for improving the reactivity of the melt polycondensation reaction. As the catalyst, metal catalysts commonly used in polyester melt condensation polymerization may be mainly used. For example, salts of titanium (Ti) or antimony (Sb), lithium (Li), sodium (Na), and the like. ), Acetate salts of potassium (K), magnesium (Mg), manganese (Mn), tin (Sn), lead (Pb), calcium (Ca), cobalt (Co), zinc (Zn) and antimony (Sb) (acetate salt), titanium (Ti), cobalt (Co), zinc (Zn), manganese (Mn), tin (Sn), lead (Pb), antimony (Sb), germanium (Ge) oxide Or alkanoate salts of cobalt (Co) or antimony (Sb), ortho titanate esters, and the like may be used. On the other hand, an organic catalyst such as methyl imidazole (N-methylimidazole) or dimethylaminopyridine (N, N-dimethylamino pyridine) may also be used. The content of the catalyst is 1 to 500 ppm, preferably 10 to 300 ppm relative to the total reactant weight. The catalyst can be applied irrespective of the melt polycondensation reaction step, but is preferably added before the start of the melt polycondensation reaction.

In addition, the method for producing 1,4: 3,6-dianhydrohexitol polyester according to the present invention quickly induces by-product removal in a molten state having a high viscosity as the degree of polymerization increases as the melt polycondensation reaction proceeds. Reduced pressure may be applied to accelerate the rate of polymerization. Upon decompression to increase the degree of polymerization, the decompression conditions are 0.2 to 2 Torr, preferably 0.5 to 1 Torr, and the reaction time under reduced pressure may be performed for 1 to 10 hours, preferably 1 to 5 hours.

In addition, the 1,4: 3,6- dianhydrohexitol polyester manufacturing method which concerns on this invention can further add various additives as needed. For example, antioxidants and heat stabilizers, resorcinol, such as hindered phenol, hydroquinone, phosphite, and substituted compounds thereof, Additives include UV absorbers such as salicylate, color protection agents such as phosphite and hydrophosphite, lubricants such as montanic acid and stearyl alcohol, and the like. Can be used as In addition, dyes and pigments may be used as the coloring agent, and carbon black may be used as the conductive agent, the colorant, or the nucleation agent. Fire retardants, plasticizers, antistatic agents and the like can be used. Here, all the above-mentioned additives should not impair thermal stability, especially among the final polymer properties.

In the method for preparing 1,4: 3,6-dianhydrohexitol polyester according to the present invention, a solid-sate polymerization may be further performed after the melt condensation polymerization reaction. The polymer obtained from the melt condensation polymerization is collected in a solid state such as crushed or flakes 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 ° C /. At a minute, preferably 0.1 to 0.2 ° C./minute, the reaction temperature may be heat-treated at a reaction temperature of 30 to 350 ° C., preferably at 100 to 280 ° C., for a reaction time of 1 to 30 hours, preferably 2 to 24 hours. 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 solid phase polymerization, the obtained polymer can be molded immediately to meet the end purpose according to the application by conventional methods. The final attainable intrinsic viscosity (IV) of the 1,4: 3,6- dianhydrohexitol polyester produced by the solid phase polymerization is from 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, but the scope of the present invention is not limited by the following examples.

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

(A) acetylation reaction

In order to completely remove the air present in the 1 L flask before the reaction, the flask was emptied with nitrogen and washed five times, and then the flask was equipped with a distillation head, a cooling condenser, a thermometer, a nitrogen input tube, and a mechanical stirrer. 200 g (1.20 mole) of terephthalic acid and 176 g (1.20 mole) of isosorbide were added to the flask, and the temperature was raised to 60 to 70 ° C, followed by stirring for 10 to 20 minutes, followed by a dropping funnel. 250 g (2.45 mole) of acet anhydride were added slowly to a terephthalic acid / isosorbide slurry. Acetic anhydride was all added, then under normal pressure, immediately raised to 120 ° C., and then stirred and maintained for 1 hour. After again raising the temperature to 145 ℃, stirred and maintained for 3 hours to 1,4: 3,6- dianhydr-D-glucitol-2,5- diacetate (1,4: 3,6-dianhydro-D -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 which is an acetylation reaction by-product. Next, an additional acetic acid by-product was removed by raising the temperature to 250 ° C. at a rate of 1 ° C./min and then stirring and maintaining at 250 ° C. for 3 hours. After stopping the nitrogen purge, the melt condensation polymerization is carried out for 2 hours under 1 Torr decompression, and then cooled to room temperature to include a repeating unit represented by the following Chemical Formula 3a in the form of a polymer chunk (chunk) 1, 4: 3,6- dianhydrohexitol (homo) polyester (IV = 0.55) was obtained.

[Formula 3a]

1,4: 3,6-dianhydrohexitol (homo) polyester comprising a repeating unit represented by Formula 3a is amorphous, and glass transition temperature (Tg) is intrinsic viscosity 0.5 In the above, it was 203 to 205 ℃, the asymmetric (isosymmetrical) isosorbide unit, the polymer chain statistically random (statistically random) in the form of head-to-head, head-to-tail, and tail-to-tail chain Since it is included in the glass transition temperature is high, but the mechanical properties are expected to be lower than the polymer that is expected to have a linear structure using isoidide as a monomer, is expected to be similar to the polymer using isomannide as a monomer. The reactivity of 1,4: 3,6-dianhydride-D-glucitol-2,5-diacetate with isosorbide can be compared as follows. The loss rate of 1,4: 3,6- dianhydr-D-glucitol-2,5-diacetate vaporized or sublimed with acetic acid was up to 0.5% of the dose. This loss rate is very low compared to the loss rate of isosorbide. Thus, the reactivity of 1,4: 3,6-dianhydride-D-glucitol-2,5-diacetate is markedly improved compared to isosorbide. The same result was obtained in the following examples.

Example 2 Preparation of a (cyclic aliphatic) 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 having a cis / trans ratio of 77/23% Add 1,4-cyclohexanedicarboxylic acid (manufactured by SK NJC) and 212 g (1.45 mole) of isosorbide, and add 300 g of acet anhydride instead of 250 g (2.45 mole). 2.93 mole) 1,4: 3,6-dianhydrohexitol (homo) polyester (IV = 0.58) containing a repeating unit represented by the following Formula 3b in the same manner as in Example 1 except that )

[Formula 3b]

1,4: 3,6- dianhydrohexitol (homo) polyester comprising a repeating unit represented by the formula (3b) is amorphous, and as a characteristic result is the first monomer 1,4-cyclohexanedica The cis / trans ratio of carboxylic acid, 77/23%, was changed to 44/64% in the polymer through acetylation and polycondensation reaction, which isomerized by acid catalysis of acetic acid, a byproduct of acetylation and polycondensation reaction. Judging from the effect of isomerization, a constant cis / trans ratio was obtained at a given reaction temperature and reaction time. As a result, the glass transition temperature of the polymer is affected by the cis / trans ratio in the final polymer, and when the intrinsic viscosity is cis / trans 44/64% at 0.5 or more, the glass transition temperature is 151 to 153 ° C.

Example 3 Preparation of (angled aromatic) 1,4: 3,6-dianhydrohexitol polyester comprising a repeating unit represented by Chemical Formula 3c

In the step (A), 200 g (1.20 mole) of terephthalic acid (terephthalic acid), instead of 200 g (1.20 mole) of isophthalic acid (isophthalic acid) except that in the same manner as in Example 1 1,4: 3,6- dianhydrohexitol (homo) polyester (IV = 0.56) containing the repeating unit represented by 3c was obtained.

 [Formula 3c]

1,4: 3,6-dianhydrohexitol (homo) polyester comprising a repeating unit represented by Formula 3c is more than an amorphous polymer structure of a polyester comprising a repeating unit represented by Formula 3a. It is close to linear and exhibits a zig-zag or helical chain conformation with a gentle curve.

Example 4 Preparation of a (angular cycloaliphatic) 1,4: 3,6- dianhydrohexitol polyester containing a repeating unit represented by the formula (3d)

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 with a cis / trans ratio of 46/54% Add 1,3-cyclohexanedicarboxylic acid (Aldrich) and 212 g (1.45 mole) of isosorbide, and 300 g (2.93 mole) instead of 250 g (2.45 mole) of acet anhydride. mole) 1,4: 3,6-dianhydrohexitol (homo) polyester (IV = 0.57) containing a repeating unit represented by the following formula (3d) in the same manner as in Example 1 except that: Got.

 [Formula 3d]

1,4: 3,6-dianhydrohexitol (homo) polyester comprising a repeating unit represented by Formula 3d is the same as the result obtained in preparing a polyester including a repeating unit represented by Formula 3b. The cis / trans ratio of the original monomeric 1,3-cyclohexanedicarboxylic acid changed from 46/54% to 5/95%, which was prepared using trans 100% of 1,3-cyclohexanedicarboxylic acid. It has similar properties to the polymers.

As disclosed in the above examples, acylated 1,4: 3,6- dianhydrohexitol (eg, 1,4: 3,6- dianhydrohexitol-2,5-diacetate ) Is prepared in-situ, and when the aromatic or cycloaliphatic 1,4: 3,6-dianhydrohexitol polyester is prepared therefrom, 1,4: 3 Compared to melt polycondensation of, 6-diandianhexitol, the reaction rate is significantly faster and the reactivity is increased. Therefore, the amount of isosorbide (reactant) used can be reduced to be almost equal to the isosorbide content contained in the final polymer. Thus, no complicated process or apparatus for reusing excess isosorbide is required, and 1,4: 3,6-dianhydrohexitol polyester can be economically produced.

This application claims priority to Korean Patent Application No. 10-2011-0039316, filed April 27, 2011, the entire contents of which are incorporated herein by reference.

Claims (8)

1. The acylate 1,4: 3, represented by the following formula (2) by acylation reaction of 1,4: 3,6- dianhydrohexitol and aliphatic acid anhydride having 4 to 16 carbon atoms Preparing 6-dianhydrohexitol; And

   The polycondensation reaction of the acylated 1,4: 3,6- dianhydrohexitol and an aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 14 carbon atoms in-situ is performed to 1,4: 3,6-dianhydrohexitol polyester production method comprising the step of preparing a 1,4: 3,6- dianhydrohexitol polyester comprising a repeating unit represented by 3.

   [Formula 1]

   

   [Formula 2]

   

   [Formula 3]

   

   In Chemical Formulas 1 to 3, wavy lines are wedge lines,

   

   ) Or dashed-wedge line,

   

   ), R ₁ are each 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 12 carbon atoms.
2. The method of claim 1, wherein the aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 14 carbon atoms is a monomer represented by the following general formula (4): 1,4: 3,6-dianhydrohexitol polyester production method .

   [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 above.
3. The method of claim 1, wherein X is

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   ,

   

   , And

   

   1,4: 3,6-dianhydrohexitol poly, which is selected from the group consisting of: wherein * represents a bonding site and Y is an oxygen atom, a sulfur atom, an alkylene group, a carbonyl group or a sulfonyl group Ester production method.
4. According to claim 1, The reaction temperature of the acylation reaction is 80 to 180 ℃, the reaction time is 5 minutes to 10 hours, 1,4: 3,6- dianhydrohexitol polyester production method.
5. According to claim 1, wherein the temperature increase rate of the melt polycondensation reaction is 0.1 to 60 ℃ / min, the reaction temperature is 120 to 320 ℃, the reaction time is 1,4: 3,6- Method for preparing dianhydrohexitol polyester.
6. The method of claim 1, wherein in the melt condensation polymerization, under reduced pressure to increase the degree of polymerization, the reduced pressure is 0.2 to 2 Torr, the reaction time under reduced pressure is 1 to 10 hours, 1,4: 3,6- Method for preparing dianhydrohexitol polyester.
7. The method of claim 1, further comprising a solid phase polymerization step of heat-treating the 1,4: 3,6- dianhydrohexitol polyester in a solid state in an inert environment. Tall polyester production method.
8. According to claim 7, Temperature rise rate of the solid phase polymerization is 0.1 to 0.5 ℃ / min, the reaction temperature is 30 to 350 ℃, the reaction time is 1, 30 hours, 1,4: 3,6- dianhydro Hexitol polyester production method.