KR20120130402A - A 1,4:3,6-dianhydro-D-hexane-1,2,3,4,5,6-hexol derivative, a preparation method thereof and a polycarbonate prepared by using the same - Google Patents

Abstract

PURPOSE: A dianhydrohexane hexol derivative and a method for preparing the same are provided to replace toxic chemical, bisphenol A and to enhance polymerization rate. CONSTITUTION: A dianhydrohexane hexol derivative is denoted by chemical formula 1. A method for preparing the compound of chemical formula 1 comprises a step of reacting a compound of chemical formula 2 and 4-hydroxybenzoic acid using toluene at 80-120 Deg. C for 3-16 hours. The compound of chemical formula 2 is derived from carbohydrate polymers. A method for preparing a polycarbonate polymer containing a unit of chemical formula 3 comprises a step of polymerizing the compound of chemical formula 1 under the presence of diphosgene.

Description

Dianhydrohexane hexol derivatives, preparation method thereof and polycarbonate prepared using the same {A 1,4: 3,6-dianhydro-D-hexane-1,2,3,4,5,6-hexol derivative, a preparation method according and a polycarbonate prepared by using the same}

The present invention relates to a dianhydrohexanehexol derivative, a preparation method thereof, and a polycarbonate prepared using the same, and more particularly, to a dianhydrohexanehexol derived from biomass (1,4: 3,6-Dianhydro-hexane-1, 2,3,4,5,6-hexol, DHH) is an environmentally friendly biomass-derived compound (isosorbide 2,5-bis (4-hydroxybenzoate, IHB), environmentally friendly bio-polycarbonates prepared by polymerization under a catalyst using the same as a monomer, and a method for producing the same.

Petroleum currently uses 65% of its production as a fuel and converts 35% to raw materials for the production of tens of thousands of compounds. It is no exaggeration to say that most of the chemical materials used by humans are derived from oil. Many researches are underway to replace the petroleum-based chemical materials industry, the most representative of which is the utilization of vegetable biomass. This is because, unlike petroleum resources, fuel and raw materials derived from vegetable biomass can be regenerated through photosynthesis after use. Accordingly, it is necessary to develop chemical / biological reaction / purification / separation processes and related material production process technologies required for the manufacture of core chemical platforms from herbal biomass raw materials and commercialization of functional biopolymer materials using the same.

As part of the development of renewable and sustainable resource-derived chemicals, there is a growing interest in the conversion process to obtain isosorbide from hexasaccharide compounds through hydrogenated sugars such as sorbitol. In particular, the isosorbide conversion process has been developed by advanced companies such as Roquette, and some commercial production has been carried out.However, the conversion reaction itself is an acid catalyst reaction using sulfuric acid developed in the 1940s. There is a disadvantage, and since the production cost of the final product obtained after the separation purification is still expensive, the research and development of a new conversion process to solve this is urgently needed.

In addition, bisphenol A derived from petroleum isosorbide has a chemical structural feature with a solid skeleton, is derived from biomass, has a weak toxicity to the human body, and naturally disappears by biodegradation after disposal. It is expected to replace the compound as a compound.

Therefore, the present inventors studied in view of the above-mentioned dianhydrohexane hexol derived from biomass (1,4: 3,6-Dianhydro-hexane-1,2,3,4,5,6-hexol, DHH) By reacting the compound under optimal reaction conditions to prepare dianhydrohexanehexol derivatives (2,5-bis (4-hydroxybenzoate, IHB)) having ester phenol groups, the conventional petroleum-derived bisphenol A-based compounds with excellent reactivity The present invention has been completed by confirming that the biomass-derived compound can be replaced, and an eco-friendly bio polycarbonate can be prepared by polymerizing under a catalyst using the monomer as a monomer.

An object of the present invention can replace the monomer compound for producing a petroleum-derived bisphenol A-based polycarbonate to generate a conventional harmful substances, and derived from biomass, environmentally friendly biomass-derived DHH derivative (isosorbide 2,5-bis ( It is to provide a compound having a 4-hydroxybenzoate, IHB) skeleton.

Another object of the present invention is to optimize the process conditions, so that not only the monomer compound for preparing polycarbonate in biomass can be produced in an excellent yield, but also the synthetic route is also very economical from the biomass-derived DHH derivative (isosorbide 2,5-bis It is to provide a method for producing a monomer compound for producing a polycarbonate having a (4-hydroxybenzoate, IHB) skeleton.

Still another object of the present invention is to provide a polycarbonate polymer comprising monomer compound units for producing polycarbonate derived from the biomass.

Another object of the present invention is to provide a method for producing a polycarbonate polymer using a monomer compound for producing a polycarbonate derived from the biomass.

In order to solve the above problems, the present invention provides a compound represented by the following formula (1).

The compound represented by the above formula (I) according to the invention is derived from biomass Dian dihydro hexane heksol (1,4: 3,6- D ianhydro- h exane -1,2,3,4,5,6- h exol In order to further improve the reactivity of DHH, it is a compound consisting of a molecular structure having an isosorbide derivative (isosorbide 2,5-bis (4-hydroxybenzoate, IHB) skeleton having two ester phenol groups bonded to the DHH skeleton It is done.

Biomass-derived dianhydrohexanehexole used to provide the DHH backbone in the present invention has a structure of formula (2).

That is, the present invention provides a substance capable of replacing bisphenol A derived from petroleum resources and known as a toxic substance by applying a DHH compound (Formula 2) derived from a carbohydrate-based biomass as a basic skeleton.

Since the DHH compound (Formula 2) has a rigid ring structure, it has a physical property similar to that of bisphenol A derived from a petrochemical process, and may be used as a substitute compound.

In the present invention, by providing an ester phenol group to the DHH compound (Formula 2) to provide a DHH derivative compound (Formula 1) of the present invention having a primary alcohol structure in which two ester phenol groups are bonded to the DHH skeleton, a conventional DHH compound (Formula 2) 2) This secondary alcohol can compensate for the lack of reactivity.

In addition, the present invention provides a method for preparing a compound represented by the following formula (1).

[Reaction Scheme 1]

Specifically, the present invention provides a method for preparing a compound represented by Chemical Formula 1, including the following steps as in Scheme 1.

To react the compound represented by the formula (2) and 4-hydroxybenzoic acid to prepare a compound represented by the formula (1) (step 1):

[Formula 1]

[Formula 2]

Step 1 is a step of preparing a compound represented by the formula 1 by reacting the compound represented by the formula (2) and 4-hydroxybenzoic acid, by reacting the DHH compound represented by the formula (2) and 4-hydroxybenzoic acid It is a step of providing an ester phenol group to the DHH compound. This is a process for effectively binding the ester phenol group to the DHH compound.

In the present invention, the compound represented by Formula 2 may be derived from a carbohydrate polymer.

Specifically, the compound represented by Formula 2 may be prepared from a carbohydrate polymer, as shown in Scheme 2 below.

Scheme 2

In other words, first, a carbohydrate polymer such as cellulose (Cellulose), which contains about 30 to 40% of the carbohydrate polymer, is extracted and then hydrolyzed or treated with an enzyme to perform a saccharification process. (Hexose) compound was obtained, and then the aldehyde group of the hexasaccharide compound was reduced by hydrogenation reaction to prepare hexane-1,2,3,4,5,6-hexol (HH) having 6 hydroxyl groups. By cyclizing the HH compound through a dehydration reaction under an acid catalyst condition, a DHH compound represented by Formula 2, which is a bicyclic compound in which two pentagonal rings are fused, may be obtained.

In the present invention, step 1) may be carried out by reacting the DHH compound (Formula 2) with 4-hydroxybenzoic acid using diethylene glycol dimethyl ether and sulfuric acid as a reaction catalyst. This provides an ester phenol group to DHH compound (Formula 2), which is an existing secondary alcohol, to provide reaction conditions for preparing a compound having a highly reactive primary alcohol structure.

In the present invention, the solvent may be toluene or the like, but is not limited thereto.

The molar ratio of 4-hydroxybenzoic acid to 1 mole of the compound represented by Formula 2 of step 1) is preferably 13.0 mmol to 15.0 mmol, more preferably 13.7 mmol to 14.0 mmol. If the molar ratio of the 4-hydroxybenzoic acid is less than the lower limit, there is a disadvantage in that the ester reaction is reduced, and if more than the upper limit, there is a disadvantage in that the ester reaction is reduced due to the excess acid.

The reaction time of step 1) is preferably 3 to 16 hours, more preferably 4 to 6 hours. If the reaction time is shorter than the lower limit, there is a disadvantage that the reaction yield decreases, and if the reaction time is longer than the upper limit, utility cost increases because there is no change in yield.

The reaction temperature of step 1) is preferably 80 to 120 ° C, more preferably 100 to 110 ° C. If the reaction temperature is lower than the lower limit, the esterification reaction is slow.

In addition, the present invention provides a polycarbonate polymer comprising a unit of formula (3).

In addition, the present invention provides a method for producing a polycarbonate polymer comprising a unit of formula (3) as shown in Scheme 2.

Scheme 2

Specifically, the present invention provides a method for preparing a polycarbonate polymer comprising a unit of the formula (3) comprising the following steps as in Scheme 2.

To prepare a polycarbonate polymer comprising a unit represented by the formula (3) by polymerizing the compound represented by the formula (1) in the presence of diphosgene (step 2):

[Formula 1]

(3)

Step 2 is a step of polymerizing the compound represented by the formula (1) in the presence of diphosgene (diphosgene) to prepare a polycarbonate polymer comprising a unit of the formula (3), derived from biomass having a DHH skeleton represented by the formula (1) A process for preparing biopolycarbonate polymers by polycondensation of DHH derivative compounds in the presence of diphosgene.

Step 2) may be performed using methylene chloride, dioxane or a mixed solvent thereof, but is not limited thereto.

The reaction time of step 2) is preferably 0.5 to 6 hours, more preferably 1 to 3 hours. If the reaction time is shorter than the lower limit, there is a disadvantage that the reaction yield is not large, and if the reaction time is longer than the upper limit, the size of the molecular weight does not increase, resulting in an increase in manufacturing cost.

The reaction temperature of step 2) is preferably -5 to 10 ° C, more preferably 0 to 5 ° C. If the reaction temperature is lower than the lower limit, there is a disadvantage that the reaction yield is not large, and if the reaction temperature is higher than the upper limit, the size of the molecular weight does not increase, resulting in an increase in manufacturing cost.

In another aspect, the present invention provides an article comprising a polycarbonate polymer comprising a unit of the formula (3).

The article includes an electric and electronic material, an optical material or a building material.

The biomass-derived DHH derivative of the present invention may be used as a monomer for polymerizing polycarbonate by replacing bisphenol A, which is a conventional human harmful substance. It can reduce the environmentally friendly advantages.

In addition, there is an economical advantage of changing the structure of the conventional DHH compound, which is a poorly reactive secondary diol, to a primary diol, thereby increasing the yield of polymerization synthesis.

1 is an H-NMR spectrum of the DHH derivative prepared according to Example 1 of the present invention.
2 is an H-NMR spectrum of the polycarbonate prepared by Example 2 of the present invention.
3 is an FTIR spectrum of the polycarbonate prepared by Example 2 of the present invention.
4 is a high temperature GPC analysis of the polycarbonate prepared by Example 2 of the present invention.
5 is a result of TGA analysis on the polycarbonate prepared by Example 2 of the present invention.
6 is a DSC analysis result of the polycarbonate prepared by Example 2 of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these examples.

Example  1: present invention Dianhydrohexanehexol  Preparation of Derivatives

1 g of a compound of formula 2-1 (6.84 mmol) and 3.1 g of 4-hydroxybenzoic acid (13.7 mmol) were added to a 50 mL round bottom flask, and 10 ml of toluene was added thereto, followed by vigorous stirring. Diethylene glycol dimethyl ether and 1 ml of 50% sulfuric acid solution were added dropwise. After connecting the Dean stark apparatus and the reflux tube, the reaction was performed under an oil bath at 110 ° C. After 3 hours, the temperature was lowered to 80 ° C., and 10 ml of ethylene acetate was added thereto. After another 1 hour, saturated sodium bicarbonate solution was added dropwise to neutralize, and then extracted three times with ethylene acetate and water. Dry with magnesium sulfate and remove solvent by evaporator. The residue was purified by flash column chromatography (Rf = 0.65) (hexanes: ethyl acetate = 2: 3) to afford the title compound as a yellow-white solid. (824 mg, 2.13 mmol) (Yield 31%)

¹ H NMR (400 MHz, DMSO) δ 10.39 (s, 2H), 7.82 (dt, 4H), 6.86 (dt, 4H), 5.31 (t, 1H), 5.28 (s, 1H), 4.93 (t, 1H ), 4.79 (s, 1H), 4.58 (d, 1H), 4.02 (t, 1H), 3.96 (t, 1H), 3.60 (t, 1H)

Example  2: present invention Dianhydrohexanehexol  Polymerization of Polycarbonates Using Derivatives

To a 50 ml 2-neck round bottom flask was placed 366 mg of the compound of formula 1-1 (0.95 mmol) prepared in Example 1. 5 ml of methylene chloride and dioxane mixed solution (1: 1, v / v) were added dropwise thereto to completely dissolve the compound of Formula 1-1, and then 0.17 ml of diphosgene (1.14 mmol) was slowly added dropwise at 0 ° C. . Using a dropping funnel, 0.3 mL of pyridine was made light with 5 ml of methylene chloride and dioxane mixed solution (1: 1, v / v) and then added to the reaction mixture at 0 ° C. Added slowly. After 1 hour, 30 ml of methanol was added to terminate the reaction, and the resulting precipitate was filtered through filtration. It was then dried in a vacuum oven at 50 ° C. for 5 hours to afford the title compound as an off white solid. (150 mg) (conversion rate: 41%)

¹ H NMR (400 MHz, DMSO) δ 8.10-8.02 (br, 4H), 7.59-7.53 (br, 4H), 5.42 (br, 1H), 5.40 (br, 1H), 5.28 (br, 1H), 5.01 (br, 1H), 4.87 (br, 1H), 4.64 (br, 1H), 4.06-3.90 (br, 1H), 3.86-3.82 (br, 1H)

Experimental Example  1: present invention Dianhydrohexanehexol  GPC Analysis of Polycarbonates Using Derivatives

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by performing GPC (Gel Permeation Chromatography) analysis on the polycarbonate using the dianhydrohexanehexol derivative of the present invention prepared in Example 2.

As a result, as shown in FIG. 4, the number average molecular weight (Mn) was 5728 and the weight average molecular weight (Mw) was 7209.

Experimental Example  2: present invention Dianhydrohexanehexol  Thermogravimetric Analysis of Polycarbonate Using Derivatives ( TGA )

Thermogravimetric analysis (TGA) was performed on the polycarbonate using the dianhydrohexanehexol derivative of the present invention prepared in Example 2.

The results are shown in Fig.

5, it can be seen that the weight loss due to pyrolysis is less than 10% at 400 ° C or less, and rapid pyrolysis occurs in the 400 to 450 ° C section.

Experimental Example  3: present invention Dianhydrohexanehexol  Thermal Analysis of Polycarbonates Using Derivatives

Thermal characteristics of the polycarbonate using the dianhydrohexanehexol derivative of the present invention prepared in Example 2 were analyzed using a differential scanning calorimeter (DSC).

The results are shown in FIG.

6, it can be seen that T _g of the present invention polycarbonate is 115 ° C.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is clear that the present invention can be suitably modified and applied in the same manner. Therefore, the above description does not limit the scope of the present invention, which is defined by the limitations of the following claims.

Claims (15)

A compound represented by the following formula (1):
[Formula 1]

Method for preparing a compound represented by the following formula (1) comprising the following steps:
To react the compound represented by the formula (2) and 4-hydroxybenzoic acid to prepare a compound represented by the formula (1) (step 1):
[Formula 1]

(2)

The method of claim 2, wherein the compound represented by Chemical Formula 2 is derived from a carbohydrate polymer.
The method of claim 2, wherein step 1) is performed using diethylene glycol dimethyl ether and sulfuric acid as reaction catalysts.
The method of claim 2, wherein step 1) is performed using toluene as a solvent.
The method of claim 2, wherein the molar ratio of 4-hydroxybenzoic acid to 1 mole of the compound represented by Formula 2 of step 1) is 13.0 mmol to 15.0 mmol.
The method of claim 2, wherein the reaction time of step 1) is 3 to 16 hours.
The method of claim 2, wherein the reaction temperature of step 1) is 80 to 120 ° C. 4.
A polycarbonate polymer comprising a unit of formula
(3)

A process for preparing a polycarbonate polymer comprising a unit of formula 3 comprising the following steps:
To prepare a polycarbonate polymer comprising a unit represented by the formula (3) by polymerizing the compound represented by the formula (1) in the presence of diphosgene (step 2):
[Formula 1]

(3)

The method of claim 10, wherein step 2) is performed using methylene chloride, dioxane or a mixed solvent thereof as a solvent.
The method of claim 10, wherein the reaction time of step 2) is 0.5 to 6 hours.
The method of claim 10, wherein the reaction temperature of step 2) is -5 to 10 ° C.
An article comprising the polycarbonate polymer of claim 9.
The article of claim 14, wherein the article is an electrical and electronic material, an optical material, or a building material.

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