KR20120121477A - Method for preparing rigid poly1,4:3,6-dianhydrohexitol esters - Google Patents

Abstract

PURPOSE: A manufacturing method of poly(1,4:3,6-dianhydrdohexitol ester) is provided to improve reactivity and reaction rate at melt polycondensation polymerization of polyester through an acrylation of 1,4:3,6-dianhydrdohexitol ester. CONSTITUTION: A manufacturing method of poly(1,4:3,6-dianhydrdohexitol ester) comprises: a step of in-situ acrylation of 1,4:3,6-dianhydrdohexitol and C4-16 aliphatic anhydride to manufacture acylated 1,4:3,6-dianhydrohexitol in chemical formula 2; and a step of manufacture poly(1,4:3,6-dianhydrohexitol ester) comprising a repeating unit represented by chemical formula 3 by in-situ melt-polycondensating the acylated 1,4:3,6-dianhydrohexitol and C8-22 aromatic or cyclic aliphatic free dicarboxylic acid component.

Description

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

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

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 isomannide represented by the following formula 1a (isomannide, mp: 81-85 ℃, bp: 123-130 ℃ / 2mmHg), iso represented by the formula 1b Sorbide (mp: 61-62 ℃, bp: 148-151 ℃ / 2mmHg) and isoidide (mpoid: 64 ℃, bp: 159-162 ℃ / 2mmHg) represented by the formula (1c) It exists in three stereoisomers, which differ in chemical properties due to the relative configuration difference of each 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]

[Chemical Formula 1b]

[Chemical Formula 1b]

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 chemical equivalents. As a secondary diol of V-shape having a non-hydroxyl group, C2-OH forms an exo orientation on two fused rings, thereby facilitating access to other compounds in three dimensions. , C5-OH has an endo orientation and forms intramolecular hydrogen bonds with oxygen atoms of adjacent tetrahydrofuran rings. It is very disadvantageous, and as a result, 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 a 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).

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

Due to the molecular structural characteristics of the 1,4: 3,6-dianhydrohexitol, the production of homopolyester containing 1,4: 3,6-dianhydrohexitol by the conventional melt polycondensation method 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 existing melt polycondensation reaction rate, and due to low reactivity, it is vaporized or sublimed together with the polycondensation reaction by-products, so that the isosorbide input of up to twice the amount of isosorbide in the target polymer is required. 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 having to be prepared with activated monomers, and both methods ((i) and (ii)) are very low in terms of commercial availability in that they mainly carry out polycondensation reactions in solution.

As a commercial method for producing aromatic liquid crystalline polyesters, a method of condensation polymerization of acylated aromatic diols or hydroxy acids with free dicarboxylic acid components has been used. The p K a values of aromatic diols or hydroxy acids are very low compared to other linear and less rigid diols, so 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 There is an advantage that can be directly linked to the melt condensation polymerization step without a 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 provide a method for preparing 1,4: 3,6-dianhydrohexitol polyester using 3,6-dianhydrohexitol in-situ.

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, in-situ 1,4: 3,6- dianhydrohexitol represented by the following formula (1) and aliphatic acid anhydride having 4 to 16 carbon atoms Preparing the acylate 1,4: 3,6-dianhydrohexitol represented by the following Chemical Formula 2 by acylation reaction; And an in-situ melt polycondensation reaction of the acylated 1,4: 3,6- dianhydrohexitol and an aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 22 carbon atoms. It provides a 1,4: 3,6- dianhydrohexitol polyester manufacturing method comprising the step of preparing a 1,4: 3,6- dianhydrohexitol polyester comprising a repeating unit represented by 3. do.

[Formula 1]

[Formula 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 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 20 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, By activating 6-dianhydrohexitol through in-situ acylation reaction, the reaction rate can be increased in polyester melt polycondensation reaction, and 1,4: 3,6-dianhydrohex It is possible to equally activate the reactivity of non-equivalent hydroxyl groups of the toll, and perform the melt condensation polymerization step immediately without separating or purifying acylated 1,4: 3,6-dianhydrohexitol. Since it can be, there is an advantage that the reaction rate and raw material costs 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 prepare an acylate 1,4: 3,6- dianhydrohexitol represented by the following formula 2 by in-situ acylation reaction and (b) the acylate 1,4 In-situ is an aromatic or cycloaliphatic free dicarboxylic acid component of 3,6-dianhydrohexitol and 8 to 22 carbon atoms, preferably 8 to 14 carbon atoms, more preferably 8 to 12 carbon atoms. 1,4: 3,6-dianhydrohexitol polyester comprising a repeating unit represented by the following Chemical Formula 3 by melt condensation polymerization: Manufacturing step.

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

) Or dashed-wedge line,

), R ₁ is each independently an aliphatic hydrocarbon group having 1 to 7, preferably 1 to 3, X is substituted or unsubstituted 6 to 20, preferably 6 to 12, more preferably 6-10 aromatic or cycloaliphatic hydrocarbon group. Here, the wedge means that the hydroxyl group (-OH) and the like are bonded above the plane (structure represented by the normal line), and the point wedge means the bond below the plane, in particular, of the cycloaliphatic hydrocarbon group trans content is from 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.

In the present specification, terms such as dicarboxylic acid component is dicarboxylic acid such as terephthalic acid, alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) And / or acid anhydrides thereof, wherein the carbon number of the aromatic or cycloaliphatic free dicarboxylic acid component corresponds to the dicarboxylic acid form. 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 Is a step for equally activating the reactivity of dissimilar hydroxyl groups of isoidide), the reaction temperature of the acylation reaction is 80 to 180 ℃, preferably 120 to 160 ℃, 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 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 etic 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, it may be 0.9 to 1.1 times, 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 120 to 320 ° C, preferably 150 to 290 ° C, and the reaction time is 1 to 10 hours, preferably 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).

,

,

,

,

,

,

,

,

,

,

,

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 above. Also, representative examples of X are

,

,

,

,

,

,

,

,

,

,

,

And the like. 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, catalysts commonly used in polyester melt condensation polymerization may be used. For example, salts of titanium (Ti) or antimony (Sb), cobalt (Co), zinc (Zn), Acetate salt of antimony (Sb), oxide of antimony (Sb) or germanium (Ge), or alkanoate salt of cobalt (Co) or antimony (Sb) Ortho titanate esters and the like can 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, after the melt condensation polymerization, solid-sate polymerization may be further performed. The polymer obtained from the melt condensation polymerization is crushed out of the reactor or collected in a solid state such as flakes or pellets, 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 invention, but the scope of the 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 then heated to 60 to 70 ° C., stirred for 10 to 20 minutes, and then placed in a dropping funnel. 250 g (2.45 mole) of acet anhydride was slowly added to the terephthalic acid / isosorbide slurry. All of the acet anhydride was added and then immediately raised to 120 ° C. under atmospheric pressure, 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- dianhydride-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, additional acetic acid by-products were removed by raising the temperature to 250 ° C. at a rate of 1 ° C./min, then stirring and holding 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.

[Chemical Formula 3]

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 range, the unsymmetrical isosorbide unit is statistically random in the form of head-to-head, head-to-tail, and tail-to-tail chains. 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. Meanwhile, 1,4: 3,6-dianhydride vaporized or sublimed together with acetic acid in the reactivity comparison of 1,4: 3,6-dianhydride-D-glucitol-2,5-diacetate with isosorbide The loss rate of -D-glucitol-2,5-diacetate was up to 0.5% of the dose, which shows a remarkably remarkable improvement in reactivity compared to the loss ratio of more than twice the maximum of isosorbide. The same result was shown in the 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 1,4- cis / trans ratio of 77/23% 1,4-cyclohexanedicarboxylic acid (manufactured by SK NJC) and 212 g (1.45 mole) of isosorbide were added, and 300 g (2.93 mole) of acetic anhydride was added instead of 250 g (2.45 mole). Except that 1,4: 3,6-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.

(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 influenced 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 was 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), 200g (1.20mole) of terephthalic acid (terephthalic acid), instead of 200g (1.20mole) isophthalic acid (isophthalic acid) except that in the same manner as in Example 1 to the formula 3c 1,4: 3,6- dianhydrohexitol (homo) polyester (IV = 0.56) containing the indicated repeating unit 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 (angular cycloaliphatic ) 1,4: 3,6 - dianhydrohexitol polyester containing a repeating unit represented by Chemical 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 1,3- cis / trans ratio is 46/54%. 1,3-cyclohexanedicarboxylic acid (manufactured by Aldrich) and 212 g (1.45 mole) of isosorbide were added, and 300 g (2.93 mole) of acetic anhydride was added instead of 250 g (2.45 mole). Except for the 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.

 [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%, prepared using trans 100% 1,3-cyclohexanedicarboxylic acid. It has similar properties to the polymers.

From the above examples, according to the invention, acylate 1,4: 3,6- dianhydrohexitol (eg, 1,4: 3,6- dianhydrohexitol-2,5- Diacetate) is prepared in-situ, and when an aromatic or cycloaliphatic 1,4: 3,6-dianhydrohexitol polyester is prepared therefrom, the existing dicarboxylic acid and 1,4 Compared to the melt condensation polymerization of: 3,6-dianhydrohexitol, the reaction rate is significantly faster, and the increase in the reactivity leads to the advantage of using an isosorbide input which is almost equal to the isosorbide content in the polymer. have. Thus, there is no need for complicated glycol recovery and separation processes to reuse the isosorbide lost out of the reaction system, making it economical.

Claims (8)

The acyl represented by the following formula (1) by 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 Preparing rated 1,4: 3,6-dianhydrohexitol; And
The acylated 1,4: 3,6- dianhydrohexitol and an aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 22 carbon atoms are subjected to in-situ melt polycondensation reaction to the following Chemical Formula 3 1,4: 3,6- dianhydrohexitol polyester manufacturing method comprising the step of preparing a 1,4: 3,6- dianhydrohexitol polyester comprising a repeating unit.
[Formula 1]

(2)

(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 20 carbon atoms. According to claim 1, wherein the aromatic or cycloaliphatic free dicarboxylic acid component is a 1,4: 3,6-dianhydrohexitol polyester manufacturing method that 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 above. 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. 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. The method of 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 to 10 hours, 1,4: 3,6- Method for preparing dianhydrohexitol polyester. 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. 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. The method of claim 7, wherein the temperature increase 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.