KR101679596B1 - Isosorbide-aromatic polycarbonate copolymer and method for preparing the same - Google Patents

Abstract

The present invention relates to an isosorbide-aromatic polycarbonate copolymer and a process for preparing the same, and more particularly, to an isosorbide-aromatic polycarbonate copolymer obtained by copolymerizing an isosorbide, an aromatic diol and a carbonic acid diester, Which is superior in moldability and heat resistance to isosorbide homopolymer and a process for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to an isosorbide-aromatic polycarbonate copolymer and an isosorbide-aromatic polycarbonate copolymer,

The present invention relates to an isosorbide-aromatic polycarbonate copolymer and a process for preparing the same, and more particularly, to an isosorbide-aromatic polycarbonate copolymer obtained by copolymerizing an isosorbide, an aromatic diol and a carbonic acid diester, Which is superior in moldability and heat resistance to isosorbide homopolymer and a process for producing the same.

The polycarbonate resin is a polymer having a carbonate group, which is polymerized using an aromatic or aliphatic dihydroxy compound. A typical commercially used polycarbonate is prepared by using 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). The polymer is excellent in transparency, impact resistance and heat resistance, It is widely used in automotive materials and electronics housing.

However, since conventional polycarbonate is produced mainly by using raw materials obtained from petroleum resources, production and use of such polycarbonate are restricted due to depletion of petroleum resources. Accordingly, there is a demand for the production of polycarbonate from raw materials obtained from renewable resources such as plants, and specifically, polymerization of polycarbonate using isosorbide among plant-derived materials is disclosed in, for example, the following literature .

GB-A-1079686 discloses an isosorbide homopolycarbonate resin synthesized by melt polymerization. However, these polymers lack moldability and heat resistance.

Macromolecules, 1996, vol 29, pp 8077-8082, discloses a homopolycarbonate resin obtained by interfacial polymerization using isosorbide and bischloroformate. However, the polycarbonate resin has a glass transition temperature of 144 캜 and is insufficient in heat resistance.

Accordingly, there is a demand for the development of a new polycarbonate resin having a high content of raw materials obtained from renewable natural resources such as plants, and also having excellent moldability and heat resistance.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems occurring in the prior art, and an object of the present invention is to provide an isosorbide-aromatic polycarbonate copolymer having a high content of isosorbide as a raw material obtained from renewable resources such as plants, And a method of manufacturing the same.

Disclosure of the Invention In order to solve the above-mentioned technical problems, the present invention provides a composition comprising (A) a diol component comprising an isosorbide and an aromatic diol; (A) in an amount of 80 to 98 mol% based on 100 mol% of the total amount of the diol component (A), wherein the diol component (A) Wherein the diol content is from 2 mol% to 20 mol%, based on the total amount of the diisobutyl-aromatic polycarbonate copolymer.

According to another aspect of the present invention there is provided a composition comprising (A) a diol component comprising an isosorbide and an aromatic diol; And (B) melt polycondensing a carbonic acid diester component in the presence of a polymerization catalyst, wherein the diisocyanate component (A) in the diol component (A), based on 100 mol% Aromatic polycarbonate copolymer having a content of 80 mol% to 98 mol% and an aromatic diol content of 2 mol% to 20 mol%.

According to another aspect of the present invention, there is provided a molded article comprising the isosorbide-aromatic polycarbonate copolymer.

The isosorbide-aromatic polycarbonate copolymer according to the present invention has a high content of isosorbide, which is a raw material obtained from renewable resources such as plants, and is low in petroleum resource dependency and environmentally friendly, and also has excellent moldability and heat resistance , Such as automotive interiors and electrical / electronic product housings.

Hereinafter, the present invention will be described in more detail.

The isosorbide-aromatic polycarbonate copolymer of the present invention comprises (A) a diol component comprising an isosorbide and an aromatic diol; And (B) a carbonic acid diester component.

The isosorbide contained in the diol component (A) is a diol-free dihydric alcohol obtained by dehydration of sorbitol, which is an alcohol per C ₆ . In the present invention, isosorbide derived from plants (i.e., isosorbide obtained by dehydration of sorbitol derived from starch) is preferably used.

The content of the isosbide contained in the diol component (A) is 80 to 98 mol%, preferably 80 to 95 mol%, based on 100 mol% of the total amount of the diol component (A) And preferably 85 to 95 mol%. If the content of isosorbide in the diol component (A) is less than 80 mol%, there is a problem that the use of the raw material (biomass-derived material) obtained from natural resources is not satisfied. The heat resistance can not be improved.

The isosorbide-aromatic polycarbonate copolymer of the present invention includes repeating units derived from the above isosobide. For example, a repeating unit represented by the following formula (1).

[Chemical Formula 1]

The diol component (A) also comprises an aromatic diol. As the aromatic diol, a substituted or unsubstituted polycyclic aromatic diol is used. The polycyclic aromatic diol may be unsubstituted or substituted with at least one selected from an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom and a nitro group.

Preferably, the polycyclic aromatic diol is naphthalene diol, biphenol, or a mixture thereof. Examples of the naphthalene diol include 1,5-naphthalene diol, 2,3-naphthalene diol, 2,5-naphthalene diol, 2,6-naphthalene diol, 2,7- (1,1'bi-2-naphthol), and the like, but the present invention is not limited thereto. Further, examples of the biphenol is 2,2 '- biphenol, 4,4' -, and the like, but non-phenolic, and not also limited to this.

The content of the aromatic diol contained in the diol component (A) is from 2 mol% to 20 mol%, preferably from 5 mol% to 20 mol%, based on 100 mol% of the total amount of the diol component (A) Is from 5 mol% to 15 mol%. If the aromatic diol content in the diol component (A) is less than 2 mol%, there is a problem that the heat resistance can not be improved. If the aromatic diol content is more than 20 mol%, there is a problem that the utilization of the raw material (biomass- Which is a problem in that it does not meet the requirements.

The isosorbide-aromatic polycarbonate copolymer of the present invention includes repeating units derived from the aromatic diol. For example, when the aromatic diol is naphthalene diol, it may include a repeating unit represented by the following formula (2a), and when the aromatic diol is biphenol, it may include a repeating unit represented by the following formula (2b), wherein the aromatic diol is naphthalene diol, It may include all the repeating units of the following formulas (2a) and (2b).

(2a)

(2b)

In the present invention, the diol component (A) may further include an additional diol component (for example, an aliphatic diol or the like), if necessary, in addition to the above-mentioned isosobide and aromatic diol.

As the carbonic acid diester component (B) used in the production of the isosorbide-aromatic polycarbonate copolymer of the present invention, for example, a diorganocarbonate having two organic groups selected from an alkyl group, an aryl group and an aralkyl group can be used And preferably those represented by the following formula (3) can be preferably used.

(3)

In Formula 3, R and R 'are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 25 carbon atoms.

More specifically, the carbonic acid diester component (B) may be selected from diphenyl carbonate, bischlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, and mixtures thereof, more preferably diphenyl carbonate have.

The amount of the carbonic acid diester component (B) used in the production of the isosorbide-aromatic polycarbonate copolymer of the present invention is preferably in a molar ratio [(B) component / (A) Component molar ratio] is preferably 1.02 to 0.98. If the molar ratio of the carbonic acid diester component to 1 mole of the diol component used in the copolymer preparation is more than 1.02, it may be difficult to obtain a copolymer having a sufficient molecular weight because the carbonic ester residue functions as a terminal stopper. On the other hand, It may be difficult to obtain a copolymer having a molecular weight sufficient enough to obtain a sufficient molecular weight.

The isosorbide-aromatic polycarbonate copolymer of the present invention preferably has a viscosity average molecular weight (Mv) of 15,000 to 80,000, more preferably 15,000 to 50,000, and a glass transition temperature of preferably 160 ° C or higher , 160 占 폚 to 250 占 폚), and more preferably 165 占 폚 or more (e.g., 165 占 폚 to 220 占 폚).

The content of the biogenic material in the isosorbide-aromatic polycarbonate copolymer of the present invention is preferably 60% by weight or more (for example, 60% by weight to 80% by weight), more preferably 70% 70% to 80% by weight).

The isosorbide-aromatic polycarbonate copolymer of the present invention is obtained by melt-polymerizing the diol component comprising (A) the isoboside and the aromatic diol and the (B) carbonate diester component described above in the presence of a polymerization catalyst, .

Examples of the polymerization catalyst include alkali metal salt compounds such as sodium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate and the like; Alkaline earth metal salt compounds such as calcium hydroxide, barium oxide, and magnesium oxide; Nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylamine and the like; These may be used singly or in combination of two or more kinds. Among them, it is more preferable to use a combination of a nitrogen-containing basic compound and an alkali metal salt compound. The amount of the polymerization catalyst to be used is preferably 1 * 10 ^-9 to 1 * 10 ^-3 equivalents, more preferably 1 * 10 ^-8 to 5 * 10 ^-4 equivalents, per 1 mole of the carbonic acid diester .

The molten polymerization may be carried out under elevated temperature conditions, for example, 180 ° C to 280 ° C, at normal pressure or reduced pressure (for example, 0.1 torr to 50 torr). According to one embodiment of the present invention, the melt polymerization process comprises mixing and heating the reactants at atmospheric pressure and reacting at a temperature of from 180 DEG C to 280 DEG C, and then heating the reaction mixture at a temperature of from 180 DEG C to 280 DEG C And removing the phenol, which is a minor reactant, at a temperature. Thereafter, the reaction can be terminated by removing the remaining phenol by further reducing the pressure to 0.1 torr or less.

The isosorbide-aromatic polycarbonate copolymer according to the present invention is environmentally friendly, and at the same time, since it has excellent moldability and heat resistance, it can be suitably used for molded articles such as automobile interior materials and electric / electronic product housings.

Accordingly, in accordance with another aspect of the present invention, there is provided a molded article comprising the isosorbide-aromatic polycarbonate copolymer of the present invention.

The method of molding the isosorbide-aromatic polycarbonate copolymer of the present invention into a molded article is not particularly limited, and a molded article can be manufactured by a method generally used in the plastic molding field.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Example  One

325 g of diphenyl carbonate, 208 g of isosorbide, 9.31 g of 2,2'-biphenol and 0.0001 g of cesium carbonate (cesium carbonate) were placed in a 2L three-neck condenser, and the mixture was slowly heated at 180 DEG C under a nitrogen gas atmosphere. The pressure was gradually lowered to 50 torr over 1 hour and the temperature was raised to 260 ° C to remove the side reaction phenol and continue the reaction. The reaction was terminated by removing the remaining phenol while further reducing the pressure to 0.1 torr for 1 hour. As a result, an isosorbide-aromatic polycarbonate copolymer having a viscosity average molecular weight of 25,420 was obtained. The physical properties of the prepared copolymer were evaluated, and the results are shown in Table 1 below.

Example  2

An isosorbide-aromatic polycarbonate copolymer having a viscosity average molecular weight of 18,675 was prepared in the same manner as in Example 1, except that 328 g of diphenyl carbonate, 186 g of isosorbide and 36 g of 2,5-naphthalene diol were used. The physical properties of the prepared copolymer were evaluated, and the results are shown in Table 1 below.

Example  3

Aromatic polycarbonate copolymer having a viscosity average molecular weight of 32,564 was obtained in the same manner as in Example 1 by using 321 g of diphenyl carbonate, 186 g of isosorbide, 14 g of 2,2 'biphenol and 24 g of 2,5-naphthalenediol. . The physical properties of the prepared copolymer were evaluated, and the results are shown in Table 1 below.

Comparative Example  One

328 g of diphenyl carbonate and 219 g of isosorbide were used to prepare isosoboid homopolycarbonate having a viscosity average molecular weight of 15,820 in the same manner as in Example 1. The properties of the prepared homopolycarbonate were evaluated, and the results are shown in Table 1 below.

Comparative Example  2

An isosorbide-aromatic polycarbonate copolymer having a viscosity average molecular weight of 19,487 was prepared in the same manner as in Example 1, except that 328 g of diphenyl carbonate, 132 g of isosorbide and 96 g of 2,5-naphthalene diol were used. The physical properties of the prepared copolymer were evaluated, and the results are shown in Table 1 below.

Comparative Example  3

Aromatic polycarbonate copolymer having a viscosity average molecular weight of 31,547 was obtained in the same manner as in Example 1 by using 321 g of diphenyl carbonate, 142 g of isosorbide, 84 g of 2,2'-biphenol and 12 g of 2,5-naphthalenediol. . The physical properties of the prepared copolymer were evaluated, and the results are shown in Table 1 below.

(a) Viscosity average molecular weight (Mv): The viscosity of the methylene chloride solution was measured at 20 占 폚 using a Ubbelohde Viscometer, and the intrinsic viscosity [?] was calculated from the following formula.

^{[η] = 1.23x10 -5 Mv 0} .83

(b) Glass transition temperature (Tg): Using a differential scanning calorimeter (DSC Q100, TA Instrument), the temperature was raised from 20 ° C to 200 ° C at a heating rate of 10 ° C / min, And the temperature was raised to 200 ° C.

(c) content of biogenic material: isosorbide content (% by weight)

(d) Moldability: Injection molding was performed, and the shape of a 2 mm molded plate was visually evaluated (mold temperature: 80 to 110 占 폚, molding temperature: 230 to 280 占 폚). The evaluation criteria are as follows.

O: HAZE, silver phenomenon due to shrinkage and decomposition (water, air, or plastic particles in the form of pellet-like silver-white lines in the flow direction of the resin due to disintegrated plastic particles) are not seen.

X: HAZE, shrinkage, and silver phenomenon due to decomposition.

As shown in Table 1, the isosobaid-aromatic polycarbonate copolymer produced according to the present invention had an elevated glass transition temperature than the isosoboid homopolycarbonate prepared according to Comparative Example 1, As a result, it can be confirmed that the heat resistance is improved. In addition, the isosorbide-aromatic polycarbonate copolymer prepared according to the embodiment of the present invention has a higher biocompatibility than Comparative Examples 2 and 3, and thus exhibits a better environmental compatibility.

Claims (13)

(A) a diol component comprising an isosorbide and an aromatic diol; And (B) a carbonic acid diester component,
Wherein the aromatic diol is 2,5-naphthalenediol, 2,2'-biphenol or a mixture thereof,
(A) is 85 to 95 mol% and the aromatic diol content is 5 to 15 mol%, based on 100 mol% of the total amount of the diol component (A)
Having a viscosity average molecular weight of 15,000 to 80,000 and a glass transition temperature of 165 to 190 DEG C,
Isosorbide-aromatic polycarbonate copolymer. The isosorbide-aromatic polycarbonate copolymer according to claim 1, wherein the isosorbide is derived from a plant. The isosorbide-aromatic polycarbonate copolymer according to claim 1, which comprises a repeating unit represented by the following formula (1) as a repeating unit derived from isosobide:

[Chemical Formula 1]

delete delete The isosorbide-aromatic polycarbonate copolymer according to claim 1, wherein the repeating unit derived from an aromatic diol is a repeating unit represented by the following formula (2a), a repeating unit represented by the following formula (2b) coalescence:
(2a)

(2b)

The isosorbide-aromatic polycarbonate copolymer according to claim 1, wherein the (B) carbonate diester component is represented by the following formula (3):

(3)

In Formula 3, R and R 'are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 25 carbon atoms. The isosorbide-aromatic polycarbonate copolymer according to claim 1, wherein the amount of the (B) carbonate diester component is 1.02 to 0.98 in a molar ratio with respect to 1 mole of the (A) diol component. delete A process for producing an isosorbide-aromatic polycarbonate copolymer,
(A) a diol component comprising an isosorbide and an aromatic diol; And (B) a carbonic acid diester component, in the presence of a polymerization catalyst,
Wherein the aromatic diol is 2,5-naphthalenediol, 2,2'-biphenol or a mixture thereof,
(A) is 85 to 95 mol% and the aromatic diol content is 5 to 15 mol%, based on 100 mol% of the total amount of the diol component (A)
Wherein the copolymer has a viscosity average molecular weight of 15,000 to 80,000 and a glass transition temperature of 165 to 190 ° C,
A process for producing an isosorbide-aromatic polycarbonate copolymer. The process according to claim 10, wherein the polymerization catalyst is an alkali metal salt compound, an alkaline earth metal salt compound, a nitrogen-containing basic compound or a mixture thereof. 11. The process according to claim 10, wherein the melt polymerization is carried out at a pressure of from 180 DEG C to 280 DEG C at atmospheric pressure or from 0.1 torr to 50 torr. A molded article comprising the isosorbide-aromatic polycarbonate copolymer of any one of claims 1 to 3 and 6 to 8.