KR20160118033A - Copolymer of furan-type improved viscosity and method for preparing the same - Google Patents
Copolymer of furan-type improved viscosity and method for preparing the same Download PDFInfo
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- KR20160118033A KR20160118033A KR1020150046271A KR20150046271A KR20160118033A KR 20160118033 A KR20160118033 A KR 20160118033A KR 1020150046271 A KR1020150046271 A KR 1020150046271A KR 20150046271 A KR20150046271 A KR 20150046271A KR 20160118033 A KR20160118033 A KR 20160118033A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
Description
The present invention relates to a furan-based copolyamide compound having a viscosity, a molecular weight and a color which are practically applicable to industry, and is excellent in thermal stability and a method for producing the same.
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
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
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 newly proposed furan-based copolyamide and a method for producing the same are required.
It is an object of the present invention to provide a furan-based copolyamide compound having improved viscosity.
Another object of the present invention is to provide a process for producing the furan-based copolyamide compound.
It is still another object of the present invention to provide a bioplastic containing the furan-based copolyamide compound.
In order to achieve the above object, the furan-based copolyamide compound of the present invention can be represented by the following formula (1).
[Chemical Formula 1]
In the above formula (1)
n, m, x and y are the same as or different from each other, each independently an integer of 1 to 10, and a is an integer of 1 to 10,000.
According to another aspect of the present invention, there is provided a process for preparing a furan-based copolyamide compound comprising the steps of: (1) reacting a furan-based dicarboxylate compound and an aliphatic diamine compound Preparing a furan-based diamine compound;
(2) reacting the furan-based diamine compound with an aliphatic dicarboxylic acid compound (adipic acid) to prepare a first polyamide salt;
(3) preparing a second polyamide salt by reacting an aliphatic diamine compound with an aliphatic dicarboxylic acid compound (adipic acid);
(4) reacting the first and second polyamide salts under an inert gas and water-containing condition to prepare a polyamide preliminary polymerized product; And
(5) pulverizing the polyamide prepolymer and subjecting it to solid phase polymerization under an inert gas and water-containing conditions to increase the molecular weight of the copolyamide.
In the step (4), the second polyamide salt may be contained in an amount of 65 to 95 mol%.
In step (4), the reaction may be carried out at 120 to 260 ° C in the presence of 4 to 25 parts by weight of water per 100 parts by weight of the total of the first polyamide salt and the second polyamide salt.
In the step (5), 0.1 to 50 moles of an inert gas are contained per mole of water, and the reaction can be carried out at a temperature of 150 to 300 ° C.
In order to achieve the above-mentioned further object, the bioplastics may include the furan-based copolyamide compound.
The furan-based copolyamide compound having improved viscosity of the present invention has an advantage of being environment-friendly because it is derived from natural polymers and biomass present in nature, and exhibits a molecular weight and color of a level applicable to actual industry and has excellent thermal stability. It can be usefully used as an environmentally friendly bioplastics that can replace synthetic polymeric materials derived from petroleum resources that generate toxic substances.
Particularly, in order to be applied to practical industries, the viscosity should be not less than 0.8 dL / g. The furan-based copolyamide compound of the present invention satisfies the above-mentioned viscosity.
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 with a furan group according to an embodiment of the present invention.
Figure 3 is a 1 H NMR graph of a furan-free polyamide salt according to one embodiment of the present invention.
4 is a 1 H NMR graph of a furan-based copolyamide prepolymer according to an embodiment of the present invention.
Figure 5 is a 1 H NMR graph of the furan-based copolyamide prepared according to one embodiment of the present invention.
6 is a graph showing the intrinsic viscosity of the furan-based copolyamide prepared according to Examples 1-9 of the present invention.
7 is a graph showing the Tm of the furan-based copolyamide produced according to one embodiment of the present invention.
8 is a graph showing the thermal stability of the furan-based copolyamide prepared according to one embodiment of the present invention.
The present invention relates to a furan-based copolyamide compound having improved viscosity, molecular weight and hue at a level applicable to a practical industry, excellent thermal stability, and a method for producing the same.
Hereinafter, the present invention will be described in detail.
The furan-based copolyamide compound of the present invention is represented by the following formula (1) and is produced by the reaction of a first polyamide salt represented by the following formula (2) and a second polyamide salt represented by the following formula (3) do.
[Chemical Formula 1]
In the above formula (1)
n, m, x and y are the same as or different from each other, each independently an integer of 1 to 10,
and a is an integer of 1 to 10,000.
(2)
(3)
In addition, the present invention can provide a process for producing a furan-based copolyamide compound.
The process for preparing the furan-based copolyamide compound according to the present invention comprises the steps of (1) reacting a furan-based dicarboxylate compound and an aliphatic diamine compound to obtain a furan-based copolyamide compound Preparing a diamine compound;
(2) reacting the furan-based diamine compound with an aliphatic dicarboxylic acid compound (adipic acid) to prepare a first polyamide salt represented by
(3) reacting an aliphatic diamine compound with an aliphatic dicarboxylic acid compound (adipic acid) to prepare a second polyamide salt represented by
(4) reacting the first and second polyamide salts under an inert gas and water-containing condition to prepare a polyamide preliminary polymerized product; And
(5) a step of pulverizing the polyamide preliminary polymer, and subjecting the polyamide preliminary polymer to a solid phase polymerization under an inert gas and water-containing conditions to increase the molecular weight of the copolyamide, which can be represented by the following reaction formula.
[Reaction Scheme]
In step (1), the furan dimethyl dicarboxylate compound and the aliphatic diamine compound are reacted at 15 to 50 ° C, preferably 20 to 50 ° C, in an inert gas atmosphere using a low- And reacted at 35 DEG C for 1 to 8 hours to prepare a furan-based diamine compound represented by the formula (4).
The aliphatic diamine used in the reaction may be a compound represented by
[Chemical Formula 8]
The low-priced alcohol may be at least one selected from the group consisting of methanol, ethanol, propanol, butanol and isopropanol, preferably methanol.
The inert gas is not particularly limited as long as it does not participate in the chain extension reaction of the polymer. Preferably, the inert gas may be selected from nitrogen, helium, argon, and carbon dioxide.
Next, in step (2), the furan-based diamine compound (Formula 4) prepared in the step (1) is reacted with an aliphatic dicarboxylic acid compound (adipic acid) in an organic solvent, To prepare a first polyamide salt represented by the above formula (2) having a precipitated furan group.
The aliphatic dicarboxylic acid compound (adipic acid) may be a compound represented by the formula (5).
Next, in step (3), an aliphatic diamine compound represented by the formula (6) and an aliphatic dicarboxylic acid compound represented by the formula (5) ≪ / RTI > is prepared.
Next, in step (4), the first and second polyamide salts are dissolved in an organic solvent, and reacted under an inert gas and water-containing condition to prepare a copolyamide prepolymer.
According to the present invention, in order to produce a polymer having a high viscosity, it is preferable to add a second polyamide salt represented by the above formula (3) to the first polyamide salt represented by the above formula (2) Do. When the first polyamide salt or the second polyamide salt is used alone, both the prepolymer and the solid polymer may exhibit a low viscosity of 0.1-0.3 dL / g.
The first polyamide salt is preferably contained in an amount of 5 to 35 mol% and the second polyamide salt is contained in an amount of 65 to 95 mol% in order to obtain a highly viscous furan-based copolyamide compound. Can be obtained. When the content of the first and second polyamide salts is out of the above range, a furan-based copolyamide compound having a low viscosity is obtained.
Examples of the organic solvent include at least one selected from the group consisting of a lower alcohol, tetrahydrofuran, N, N-dimethylformamide, acetonitrile, toluene, dichloromethane and dimethylsulfoxide, And more preferably methanol.
In the step (4), the reaction can be carried out by using a stirring reactor capable of maintaining high temperature and high pressure.
The reaction temperature in the step (4) is 120 to 260 ° C, preferably 160 to 220 ° C. When the temperature is lower than the lower limit, the reaction temperature is too low to cause an effective chain extension reaction, so that a prepolymer having a high molecular weight can not be produced. When the temperature is higher than the upper limit, a side reaction such as a cyclization reaction, It is impossible to produce a high quality prepolymer.
Further, the reaction is carried out in the presence of 4 to 25 parts by weight, preferably 8 to 20 parts by weight, of water per 100 parts by weight of the total of the first polyamide salt (formula 2) and the second polyamide salt (formula 3) Is performed.
When the water content is less than the lower limit, the amount of water is insufficient and the precipitation rate of the prepolymer is increased. Therefore, it may be difficult to prepare a prepolymer having a high molecular weight. When the water content exceeds the upper limit, It is difficult to proceed with a proper reaction and it may be difficult to prepare a prepolymer having a high molecular weight.
Next, in the step (5), the copolyamide prepolymer prepared in the step (4) is pulverized, and a fluid containing an inert gas and water is used to form a solid phase at 150 to 300 ° C, preferably 180 to 200 ° C. A furan-based copolyamide compound represented by the following formula (1) is prepared by polymerization reaction to increase the molecular weight of the copolyamide.
The inert gas and the fluid containing water contain 0.1 to 50 mol, preferably 1 to 30 mol, of inert gas per mol of water. When the content of the inert gas is less than the lower limit, the amount of water is too much to increase the reaction byproducts, and the chain extension reaction is difficult to proceed effectively, so that it may be difficult to produce a high molecular weight furan-based copolyamide In the case of the upper limit value of the super light, the water content is too small to cause a side reaction such as a cyclization reaction and a coloring reaction, so that it may be difficult to produce high quality furan copolyamide.
When the reaction temperature is lower than the lower limit, the temperature of the solid phase polymerization is too low to effectively cause the chain extension reaction. Thus, furan-type copolyamides having a high molecular weight can not be produced. In order to prepare a high molecular weight copolyamide, Which is not economical; If the upper limit is exceeded, a side reaction such as a cyclization reaction or a coloring reaction may occur in addition to the chain extension reaction, and a low molecular weight prepolymer can be melted, making it difficult to produce high quality furan copolyamide.
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 present invention. Such variations and modifications are intended to be within the scope of the appended claims.
<Examples>
Synthetic example 1. A compound represented by the formula [4-1] Furan system Diamine Synthesis of compounds
[Formula 4-1]
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 and then, Washed with 20 ml of
The compound of Formula 4-1 was analyzed and shown in FIG.
Analytical values: C (23.6%), H (7.9%), N (14.3%), theoretical values were C (56.7%), H (8.1%) and N (28.3%).
Synthetic example 2. (2-1) Furan giga Of a polyamide salt
[Formula 2-1]
15.9 g (54 mmol) of the compound of the formula [4-1] 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. The resulting precipitate was filtered and dried in a vacuum oven at 60 ° C to obtain 23.5 g (53 mmol, yield: 97.9% ≪ / RTI >
The compound of Formula 2-1 was analyzed and shown in FIG.
Analytical values: C (53.6%), H (7.8%), N (13.3%), theoretical values were C (54.3%), H (7.6%) and N (12.6%).
Synthetic example 3. [Formula 3-1] Furan giga Manufacture of polyamide salts without
[Formula 3-1]
Adipic acid (10.0 g, 68 mmol) was dissolved in 50 ml of methanol, and then 5.9 g (6 mmol) of 1,4-butanediamine was added thereto, followed by stirring at room temperature for 1 hour. After completion of the reaction, the resulting precipitate was filtered and dried in a vacuum oven at 60 ° C to obtain a compound of the formula (3-1).
The compound of Formula 3-1 was analyzed and shown in FIG.
Synthetic example 4-12. Furan system Copolyamide Preparation of preliminary polymerizates
The compound of formula (2-1) and the compound of formula (3-1) are reacted at a ratio of 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80 and 10:90 mol%, and dissolved in 100 g of high-purity methanol. The resulting mixture was poured into a 500-ml high-temperature high-pressure stirred reactor made of stainless steel (Grade 316), stirred under nitrogen atmosphere, And the temperature was gradually increased from 170 DEG C to 220 DEG C for 4 hours. Then, the reaction temperature was increased from 220 DEG C to 260 DEG C over 3 hours, A polyamide prepolymer was prepared and analyzed to show it in FIG. At this time, the reaction was carried out with 4 to 25 parts by weight of water per 100 parts by weight of the compound of the formula (2-1) and the compound of the formula (3-1).
The prepared furan-based copolyamide prepolymer has a Tg of 78.5 ° C, a Tm of 262 ° C and an IV value of 0.58 (dL / g).
Example 1 to 9. Furan system Copolyamide Preparation of compounds
Nine kinds of prepolymer prepared in Synthesis Example 4-12 were each pulverized into particles having a size of 250 to 500, and 1.5 g of pulverized preliminary polymer powder was introduced into a tube solid-state polymerization reactor made of stainless steel (Grade 316) Respectively. Thereafter, while the molar ratio of nitrogen to water was maintained at 2: 1, the reaction temperature was raised to 240 while flowing the mixture into the solid-state polymerization reactor at a rate of 2 L / min, and then subjected to solid phase polymerization reaction for 24 hours to obtain the desired furan- Amide compound.
The furan-based copolyamide compound was analyzed and shown in FIG.
<Test Example>
The polymer properties are The furan-based copolyamide compounds prepared in Examples 1 to 9 were dried in a vacuum oven at 80 DEG C for 24 hours, and polymer characteristics of the dried furan-based copolyamide compounds were analyzed.
Test Example 1. Measurement of intrinsic viscosity
The intrinsic viscosity was measured using an AVS370 viscometer from Schott Instruments using Ubbelohde viscometer under ISO307 conditions and is shown in Figure 6 and Table 1 below.
As shown in Table 1 and FIG. 6, the intrinsic viscosity of the copolyamide according to Example 8, which was prepared by performing solid phase polymerization for 24 hours using a prepolymer having an intrinsic viscosity of 0.58 dL / g, was 0.95 dL / g , And it was confirmed that the intrinsic viscosity of the prepolymer was increased by 68.9%. Thus, it was confirmed that the molecular weight of the copolyamide was significantly increased through the solid-state polymerization reaction. Particularly, it was found that polymerization at a temperature of 240 ° C or higher was effective in producing a high molecular weight copolyamide compound.
Further, it is preferable that the intrinsic viscosity is 0.8 dL / g or more in order to be applied to practical industries, and it is confirmed that Examples 7 to 9 satisfy the above-mentioned viscosity.
Time (h)
Test Example 2. Determination of crystallinity
Example 7 was measured for melting point (Tm) using a differential scanning calorimeter (DSC) manufactured by Texas Instrument, which is shown in Table 1 and FIG.
As shown in Table 1 and FIG. 7, according to the result of examination of the melting point and melting heat using a differential scanning calorimeter, after the solid-state polymerization at 240 ° C for 24 hours, the melting point was 288 ° C and the melting heat was 108 J / g in the first scan , And in the second scan, the melting point was 277 ° C and the heat of fusion was 61.7 J / g, confirming that the semi-crystalline copolyamide compound was obtained.
Test Example 3. Thermal stability Measure
10 mg of the copolyamide sample prepared in Examples 1 to 9 was introduced into a pan and the temperature was increased from 40 ° C. to 320 ° C. at a rate of 10 ° C./min under the first temperature elevation condition under a nitrogen atmosphere of 50 mL / min After the temperature was lowered to 50 ° C at a heating rate of 10 ° C / min, the temperature was immediately heated to 320 ° C at a rate of 10 ° C / min. Melting point and melting heat were measured based on the data measured at the second temperature elevation condition and Thermogravimetric analysis (TGA) from Texas Instrument was used to measure the 5% and 10% weight reduction temperatures . 5 mg of the copolyamide sample was introduced into the pan and the temperature was measured at 30 DEG C at a rate of 10 DEG C / min under a nitrogen atmosphere of 50 mL / min while increasing the temperature to 800 DEG C.
As shown in FIG. 8, the thermal stability of the copolyamide polymerized in Example 7 at 240 ° C. for 24 hours was evaluated using TGA. As a result, 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.
From the above results, it can be seen that the furan-based copolyamide according to the present invention has an intrinsic viscosity of 0.82 dL / g and has excellent thermal stability, so that it can be used as an environment-friendly bioplastic in place of fossil raw materials Respectively.
Claims (9)
[Chemical Formula 1]
In the above formula (1)
n, m, x and y are the same as or different from each other, each independently an integer of 1 to 10,
and a is an integer of 1 to 10,000.
(2) reacting the furan-based diamine compound with an aliphatic dicarboxylic acid compound (adipic acid) to prepare a first polyamide salt;
(3) preparing a second polyamide salt by reacting an aliphatic diamine compound with an aliphatic dicarboxylic acid compound (adipic acid);
(4) reacting the first and second polyamide salts under an inert gas and water-containing condition to prepare a polyamide preliminary polymerized product; And
(5) a step of pulverizing the polyamide preliminary polymer and subjecting it 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 represented by the following formula ;
[Chemical Formula 1]
In the above formula (1)
n, m, x and y are the same as or different from each other, each independently an integer of 1 to 10,
and a is an integer of 1 to 10,000.
[Chemical Formula 4]
In the above formula (4), n is an integer of 1 to 10.
(2)
In the above formula (2), n is an integer of 1 to 10.
(3)
In the above formula (3), n is an integer of 1 to 10.
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| CN105985302A (en) * | 2015-02-05 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | 2,5-furandicarboxamidediamine compound, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985302A (en) * | 2015-02-05 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | 2,5-furandicarboxamidediamine compound, and preparation method and application thereof |
| CN105985302B (en) * | 2015-02-05 | 2019-06-07 | 中国科学院宁波材料技术与工程研究所 | One kind 2,5- furans diformamide diamine compound, preparation method and application |
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