KR20160048338A - Syntheses of alternating copolymer from furane dicarboxyate, diamine, and adipic acid - Google Patents

Abstract

The present invention relates to a preparation method of furane-based copolyamide. More particularly, the preparation method prepares a diamine monomer including a structure of furane by conducting a reaction between at least one kind of furane-based dicarboxylic acid ester and aliphatic diamine on a main chain through solid polymerization, and conducts a reaction of the diamine monomer with an aliphatic dicarboxylic acid compound. The furane-based copolyamide synthesized according to the present invention has molecular weight and color at the level which can be practically applied to industries, and can replace fuel raw materials by having excellent thermal stability, thereby being useful as an eco-friendly bioplastic.

Description

Technical Field [0001] The present invention relates to a furan-based copolyamide,

The present invention relates to a process for producing furan-based copolyamides using solid-state polymerization, and more particularly, to a process for producing furan-based copolyamides by reacting at least one furan-based dicarboxylic acid ester with an aliphatic diamine (diamine) The present invention relates to a process for producing a furan-based copolyamide comprising a furan dicarboxylic acid ester-diamine-dicarboxylic acid by synthesizing a diamine monomer containing a furan structure and reacting it with an aliphatic dicarboxylic acid compound.

In recent years, interest in the development of bioplastics, a polymer synthesized from monomers derived from biomass and natural polymers that exist in nature, can replace fossil raw materials that have been used in the past, as oil instability becomes worse and concerns about environmental pollution increase. Is increasing.

The annual production of biomass on the Earth is estimated to be 10 times the total energy consumed by mankind in a year, and there is a growing desire to use it effectively as renewable energy. As a result, biodegradable plastics have been proposed by using biomass as a recent biotechnology strategy. Particularly, although bioplastics are resource circulating materials produced by biological processes or chemical processes using biomass resources as raw materials, there is a problem that bioplastics are required to be expensive and highly functional.

Natural polymers such as natural rubber and cellulose have been studied for a long time and have already been used in large quantities. However, studies on synthetic polymers derived from biomass have not been relatively long in history, and some of them have been commercialized and applied to actual products have.

The most well-known of these is polylactide, which is currently being mass-produced, and studies are underway to improve properties. In addition, studies have been conducted to synthesize polyolefins using monomers converted from bioethanol, and studies have also been conducted to synthesize polymeric materials from triglycerides, which are the main components of the vegetable oils. Adipic acid, caprolactam, etc., which are used as monomers for polyamides, are currently produced in most petrochemical processes, but recently methods for producing these materials from biomass have been proposed. Polyamide polymers are synthesized from these, but they are still in the research stage because they are less economical than petrochemical processes. Other examples of polyamides synthesized from monomers derived from biomass include polyamide 11 made from castor oil and polyamide 4 made from glucose.

Examples of the method for producing the polyamide include melt polymerization, solution polymerization, solid phase polymerization and the like. The melt polymerization is advantageous in that the polymer can be prepared by a single step process. On the other hand, if the melting temperature of the polymer is high, the quality of the produced polymer is degraded due to the progress of pyrolysis and gelation, It is difficult to control stirring and temperature, and it is difficult to remove by-products which are generated, so that it is difficult to produce a polymer having a high molecular weight. Solution polymerization has a problem that the solvent capable of dissolving the polyamide is very limited, such as concentrated sulfuric acid.

On the other hand, since the solid phase polymerization proceeds between the glass transition temperature and the melting point of the polymer, the side reaction due to the high temperature can be reduced and the solution polymerization can be overcome because no solvent is used. Generally, the solid phase polymerization is carried out by first preparing a preliminary polymerized material having a low molecular weight by melt polymerization, then pulverizing the preliminary polymerized material into a powder form, and subjecting the prepared preliminary polymerized powder to a reactor such as a conductive layer reactor, a fluidized bed reactor, a fixed bed reactor, And a sweep fluid is continuously flowed into the reactor at a temperature between the glass transition temperature and the melting point to polymerize the polymer in a solid state to increase the molecular weight.

The use of aromatic monomers in polyamides has the advantages of high crystallinity, excellent heat resistance, excellent stiffness and dimensional stability, and engineering plastics, which are usually required to have high strength and heat resistance by injection molding. In particular, surface mounting devices (SMT ), LED reflector, I / O connector (I / O connector, etc.), automotive interior and exterior lightweight materials, industrial materials, aviation materials etc. It is applicable to a wide range of fields. Examples of such semi-aromatic polyamides include polyamide 4, prepared from teraphthalic acid and 1,4-butanediamine, polyamide 6, prepared from T, teraphthalic acid and hexamethylene diamine, T and so on.

Polyamide 4, T and polyamide 6, T are high in crystallinity and excellent in heat resistance, but have melting temperatures of 430 ° C. and 370 ° C., respectively, which are higher than the decomposition temperatures of conventional polyamides, . Thus, in order to produce a high heat-resistant polyamide-based polymer capable of injection molding by controlling the melting temperature of polyamide 4, T, polyamide 6, and T to 300-330 ° C, it is usually prepared from adipic acid and 1,4-butane diamine T / 4,6, copolyamide 4, T / 4,6, copolyamide 6, T / 4,6, copolyamide 4, polyamide 4,6 and polyamide 4, T or polyamide 6, T / 6, and T / 4,6.

However, efforts have been made to prepare furan-based copolyamides capable of replacing semi-aromatic copolyamides by introducing FDCA instead of terephthalic acid. However, there is a problem in that the color of the polymerized polymer is not changed or the molecular weight is not sufficiently increased However, no successful examples have been reported so far, and a novel furan-based copolyamide and a process for producing the same are required.

Korean Patent No. 1,310,302 Korean Patent No. 1,116,450 US Patent No. 6,153,724

The object of the present invention is to provide a novel furan-based copolyamide compound prepared from a natural polymer existing in nature and a monomer derived from biomass, which can replace conventional fossil raw materials.

Another object of the present invention is to provide a process for preparing the novel furan-based copolyamide compound.

In order to achieve the above object, the present invention provides a furan-based copolyamide compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula 1,

n and m are the same as or different from each other, each independently an integer of 1 to 10,

And X is an integer of 1 to 10,000.

The present invention also provides a process for producing a furan-based copolyamide compound represented by the above formula (1), which comprises the following steps.

(1) reacting a furan-based dicarboxylate compound and an aliphatic diamine compound to prepare a furan-based diamine compound;

(2) reacting the furan-based diamine compound with an aliphatic dicarboxylic acid to prepare a polyamide salt;

(3) reacting the polyamide salt in an inert gas and moisture-containing condition to prepare a polyamide prepolymer; And

(4) pulverizing the polyamide prepolymer and subjecting it to solid phase polymerization under inert gas and water-containing conditions to increase the molecular weight of the copolyamide.

The present invention also provides a bioplastic comprising the furan-based copolyamide compound.

The furan-based copolyamide produced according to the present invention has an environmental friendliness due to natural polymers and biomass present in nature, exhibits a molecular weight and color at a level suitable for practical industry, and has excellent thermal stability. And can be usefully used as environmentally friendly bioplastics that can replace synthetic polymeric materials derived from petroleum resources that generate substances.

1 is a ¹ H NMR graph of a furan-based diamine compound according to an embodiment of the present invention.
2 is a ¹ H NMR graph of a polyamide salt according to an embodiment of the present invention.
3 is a ¹ H NMR graph of the furan-based copolyamide prepolymer according to an embodiment of the present invention.
4 is a ¹ H NMR graph of a furan-based copolyamide compound according to an embodiment of the present invention.
FIG. 5 is a graph showing the intrinsic viscosity of the furan-based copolyamide compound according to an embodiment of the present invention, according to the solid-state polymerization temperature (intrinsic viscosity of the preliminary polymer: 0.16 dL / g).
6A and 6B are graphs showing a melting point (Tm) and a crystallinity of a furan-based copolyamide compound according to an embodiment of the present invention measured by a differential scanning calorimeter. FIG. 6A is a graph showing the measurement of the melting point, and FIG. 6B is a graph showing the crystallization temperature.
7 is a graph showing the thermal stability of a furan-based copolyamide compound measured by a thermogravimetric analyzer according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides a furan-based copolyamide compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

n and m are the same as or different from each other, each independently an integer of 1 to 10,

And X is an integer of 1 to 10,000.

Preferably, n and m are the same as or different from each other, and each independently may be an integer of 2 to 6.

According to the present invention, the furan-based copolyamide compound represented by the above formula (1) can be produced through a production process comprising the following steps.

(1) reacting a furan-based dicarboxylate compound and an aliphatic diamine compound to prepare a furan-based diamine compound;

(2) reacting the furan-based diamine compound with an aliphatic dicarboxylic acid to prepare a polyamide salt;

(3) reacting the polyamide salt in an inert gas and moisture-containing condition to prepare a polyamide prepolymer; And

(4) pulverizing the polyamide prepolymer and subjecting it to solid phase polymerization under inert gas and water-containing conditions to increase the molecular weight of the copolyamide.

According to the present invention, the furanic dicarboxylic acid ester may be a compound represented by the following formula (5), and the aliphatic diamine may be a compound represented by the following formula (6).

[Chemical Formula 5]

[Chemical Formula 6]

In the above formula (6)

n is an integer of 1 to 10;

According to the present invention, the furan-based diamine compound produced by reacting the furan-based dicarboxylic acid ester compound and the aliphatic diamine compound may be a compound represented by the following formula (2).

(2)

In the above formula (2)

n is an integer of 1 to 10;

According to the present invention, the step (1) may be carried out by stirring with an inexpensive alcohol solvent at 15 to 50 ° C for 1 to 8 hours under an inert gas atmosphere, preferably at 20 to 35 ° C. have.

The lower alcohol may be any one selected from methanol, ethanol, propanol, butanol and isopropanol, and preferably methanol.

In the present invention, the inert gas is not limited to the gas surface which does not participate in the chain extension reaction of the polymer, and specifically, can be selected from nitrogen, helium, argon and carbon dioxide.

According to the present invention, the polyamide salt is prepared by reacting the furan-based diamine compound with an aliphatic dicarboxylic acid compound represented by the following formula (3) in an organic solvent, and then adding diethyl ether to form a precipitate And can be represented by the following formula (4).

(3)

[Chemical Formula 4]

In the above Chemical Formula 3 or Chemical Formula 4,

The organic solvent may be at least one selected from the group consisting of lower alcohol, tetrahydrofuran, N, N-dimethylformamide, acetonitrile, toluene, dichloromethane and dimethylsulfoxide, Alcohol, more preferably methanol.

Next, the step (3) may be carried out by performing the reaction using a stirring reactor in which high temperature and high pressure can be maintained,

If the reaction temperature is lower than 120 ° C, the reaction temperature is too low to effectively chain extension reaction. Thus, a prepolymer having a high molecular weight can not be produced. When the reaction temperature exceeds 260 ° C, There is a problem that a high quality prepolymer can not be produced due to side reaction. Therefore, it can be carried out at 120 to 260 ° C, preferably at 160 to 220 ° C.

In the step (3), the reaction is carried out in the presence of 5-50 wt% of water relative to the polyamide salt, preferably in the presence of 10 to 33 wt% of water relative to the polyamide salt.

Particularly, when the reaction temperature is outside the above range, if the amount of water is less than 5 wt%, the amount of water is insufficient and the precipitation rate of the prepolymer is increased, so that it is difficult to prepare a prepolymer having a high molecular weight. %, There is a problem that it is difficult to proceed with the reaction due to an increase in the amount of reaction by-products, and it is difficult to prepare a prepolymer having a high molecular weight.

Next, the step (4) is a solid-phase polymerization reaction using a fluid mixed with an inert gas and water, and may be contained in an amount of 0.1 to 50 moles of an inert gas relative to 1 mole of water, 1 to 30 moles of an inert gas relative to moles.

When the inert gas is contained in an amount of less than 0.1 mole per mole of the above-mentioned water, the amount of water is too large to increase the reaction byproducts, and the chain extension reaction is difficult to proceed efficiently, so that a high molecular weight furan- If the inert gas is more than 50 moles, the water content is too small to cause a side reaction such as a cyclization reaction or a coloring reaction, and thus it is difficult to produce a high quality furan-based copolyamide.

The reaction may be carried out at 150 to 300 ° C, preferably at 200 to 180 ° C.

When the reaction temperature is lower than 150 ° C, the temperature of the solid phase polymerization is too low to effectively effect the chain extension reaction. Thus, it is impossible to prepare a furan-type copolyamide having a high molecular weight. In order to prepare a high molecular weight copolyamide, Which is not economical. When the reaction temperature is higher than 300 ° C, besides the chain extension reaction, a side reaction such as a cyclization reaction or a coloring reaction may occur, and a low molecular weight prepolymer can be melted, making it difficult to produce high quality furan copolyamide .

On the other hand, the above production method is shown in the following Reaction Scheme 1.

[Reaction Scheme 1]

The present invention also provides a bio-plastic comprising the furan-based copolyamide produced by the above-described method.

The furan-based copolyamide according to the present invention has excellent thermal stability and can be used as an environment-friendly bioplastic since it can replace fossil raw materials.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. , And it is natural that such variations and modifications fall within the scope of the appended claims.

Example

Production Example 1. Preparation of furan-based diamine

10 g (57 mmol) of 2,5-furan dicarboxylate and 19.1 g (218 mmol) of 1,4-butanediamine were stirred at room temperature under nitrogen atmosphere for 6 hours. The reaction mixture was washed with 20 ml of toluene 4 to 5 times to remove unreacted raw materials and then dried in a vacuum oven at 60 ° C to prepare a furan-type diamine compound, which was analyzed and shown in FIG.

15.9 g (54 mmol), yield 94.7%

Analytical values: C (23.6%), H (7.9%), N (14.3%), theoretical values were C (56.7%), H (8.1%) and N (28.3%).

Production Example 2. Preparation of polyamide salt

15.9 g (54 mmol) of the furan-type diamine synthesized in Preparation Example 1 was dissolved in 50 ml of methanol, 7.9 g (54 mmol) of adipic acid was added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 30 ml of diethyl ether was added to form a precipitate, and the resulting precipitate was filtered and dried in a vacuum oven at 60 ° C to prepare a polyamide salt, which was analyzed and shown in FIG.

23.5 g (53 mmol), yield 97.9%

Analytical values: C (53.6%), H (7.8%), N (13.3%), theoretical values were C (54.3%), H (7.6%) and N (12.6%).

Preparation Example 3. Preparation of furan-based copolyamide prepolymer

30 g (67 mmol) of the polyamide salt prepared in Preparation Example 2 was dissolved in 150 g of tertiary distilled water and then charged into a 500 ml high-temperature high-pressure stirred reactor made of stainless steel (Grade 316), stirred under a nitrogen atmosphere During the first hour of the reaction, the mixture was stirred while increasing the temperature from 25 ° C to 170 ° C. After that, the mixture was stirred for 4 hours while gradually increasing the temperature from 170 ° C to 220 ° C. And the mixture was stirred to prepare a prepolymer, which was analyzed and shown in FIG.

The prepared furan-based copolyamide prepolymer had a Tg of 85 ° C, a Tm of 216 ° C and an IV of 0.16 (dL / g).

Example 1 Preparation of furan-based copolyamide compound 1

The preliminary polymerizate prepared in Preparation Example 3 was pulverized into particles having a size of 250 to 500 μm, and then 1.5 g of pulverized preliminary polymer powder was introduced into a tube solid-phase polymerization reactor made of stainless steel (Grade 316). Thereafter, while the molar ratio of nitrogen and water was maintained at 2: 1, the reaction temperature was raised to 150 ° C with the flow rate of 2 L / min into the solid-phase polymerization reactor, and the solid phase polymerization reaction was carried out for 24 hours, A copolyamide compound was prepared and analyzed to show it in Fig.

Example 2: Preparation of furan-based copolyamide compound 2

The furan-based copolyamide compound was prepared in the same manner as in Example 1, except that the reaction temperature was raised to 170 ° C instead of 150 ° C.

Example 3: Preparation of furan-based copolyamide compound 3

A furan-based copolyamide compound was prepared in the same manner as in Example 1 except that the reaction temperature was raised to 200 ° C instead of 150 ° C

Example 4: Preparation of furan-based copolyamide compound 4

A furan-based copolyamide compound was prepared in the same manner as in Example 1 except that the reaction temperature was raised to 220 ° C instead of 150 ° C

Test Example 1. Characterization of polymer

The furan-based copolyamide compounds prepared in Examples 1 to 4 were used by drying in a vacuum oven at 80 DEG C for 24 hours. The polymer properties of the dried furan-based copolyamide compounds were analyzed.

Test Example 1. Measurement of intrinsic viscosity

The intrinsic viscosity was measured using a Schott instrument AVS370 viscometer using a Ubbelohde viscometer under ISO307 conditions and is shown in Figure 5 and Table 1 below.

As shown in Fig. 5, the intrinsic viscosity of the copolyamides according to Examples 1 to 4 prepared by performing the solid phase polymerization for 24 hours using a prepolymer having an intrinsic viscosity of 0.16 dL / g was 0.258, 0.280, 0.299 And 0.310 dL / g, respectively, which were 60.2%, 73.9%, 85.7% and 92.5% higher than the intrinsic viscosity of the preliminary polymer, respectively. As a result, it was confirmed that the molecular weight of the copolyamide was greatly increased through the solid-state polymerization reaction. Particularly, it was confirmed that polymerization at a temperature of 200 ° C or higher was effective in producing a high molecular weight copolyamide compound.

Test Example 2. Crystallinity Measurement

Glass transition temperature (Tg), melting point (Tm), and crystallinity were measured using a differential scanning calorimeter (DSC) from Texas Instrument, which is shown in Table 1 and FIG.

As shown in FIG. 6, melting point and melting heat were measured using differential scanning calorimetry. As a result, after the solid-state polymerization at 220 ° C for 24 hours, the first scan was not usually used because the thermal history was reflected, Was measured at a melting point of 218 캜 and a heat of fusion of 31.0 J / g, and in a temperature-sensitive scanning, the crystallization temperature was 158 캜 and the crystallization heat was 24.8 J / g, indicating that semi-crystalline copolyamide was obtained.

division Polymerization temperature (캜) Polymerization time (h) DSC analysis Intrinsic viscosity (dL / g) Tg (占 폚) Secondary Tm (캜) Example 1 150 24 87.6 211 0.258 Example 2 170 24 88.7 213 0.280 Example 3 200 24 88.1 215 0.299 Example 4 220 24 81.6 218 0.310

Test Example 3. Measurement of thermal stability

10 mg of the copolyamide sample prepared in Examples 1 to 4 was introduced into a pan and then heated at 40 ° C to 300 ° C at a rate of 10 ° C / min under the nitrogen atmosphere of 50 ml / min. The temperature was again lowered to 50 ° C at a heating rate of 10 ° C / min, and then the temperature was immediately raised to 300 ° C at a heating rate of 10 ° C / min. Melting point and melting heat were measured based on the data measured at the second temperature elevation condition. Thermogravimetric analysis (TGA) from Texas Instrument was also used to measure the 5% and 10% weight loss temperatures. 5 mg of the copolyamide sample was introduced into a pan, and then the temperature was measured at 30 ° C at a heating rate of 10 ° C / min under a nitrogen atmosphere of 50 ml / min to 800 ° C.

As shown in FIG. 7, the thermal stability of the copolyamide polymerized in Example 2 at 220 ° C for 24 hours was evaluated using TGA. As a result, it was found that the 5% weight reduction temperature was 375 ° C and the 10% weight reduction temperature was 391 Lt; 0 > C, indicating that the copolyamide according to the present invention has excellent thermal stability.

As a result, the bifunctional copolyamide according to the present invention has an intrinsic viscosity of 0.310 dL / g and has excellent thermal stability. Therefore, it can be used as an environment-friendly bioplastic in place of fossil raw materials. Respectively.

Claims (8)

A furan-based copolyamide compound represented by the following formula 1:
[Chemical Formula 1]

In the above formula (1)
n and m are the same as or different from each other, each independently an integer of 1 to 10,
And X is an integer of 1 to 10,000. The method according to claim 1,
n and m are the same as or different from each other, and each independently is an integer of 2 to 6. (1) reacting a furan-based dicarboxylate compound and an aliphatic diamine compound to prepare a furan-based diamine compound;
(2) reacting the furan-based diamine compound with an aliphatic dicarboxylic acid to prepare a polyamide salt;
(3) reacting the polyamide salt in an inert gas and moisture-containing condition to prepare a polyamide prepolymer; And
(4) a step of pulverizing the polyamide prepolymer, and subjecting the polyamide prepolymer to solid phase polymerization under an inert gas and water-containing conditions to increase the molecular weight of the copolyamide, thereby producing a furan-based copolyamide compound : ≪
[Chemical Formula 1]

In the above formula (1)
n and m are the same as or different from each other, each independently an integer of 1 to 10,
And X is an integer of 1 to 10,000. The method of claim 3,
Wherein the furan-based diamine compound is a compound represented by the following formula (2): < EMI ID =
(2)

In the above formula (2)
n is an integer of 1 to 10; The method of claim 3,
Wherein the aliphatic dicarboxylic acid compound is a compound represented by the following formula (3): < EMI ID =
(3)

In the above formula 3,
m is an integer of 1 to 10; The method of claim 3,
Wherein the step (3) is carried out at 120 to 260 ° C in the presence of 5-50 wt% of water relative to the polyamide salt. The method of claim 3,
Wherein the step (4) is carried out at a rate of 0.1 to 50 moles of an inert gas relative to 1 mole of water, and is carried out at 150 to 300 占 폚. A bioplastic comprising the furan-based copolyamide compound according to claim 1 or 2.

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