KR101093056B1 - Polytrimethylene terephthalate/Graphene Composites with Enhanced Mechanical Property and Electrical Conductivity and Method for Preparing the Same - Google Patents

Polytrimethylene terephthalate/Graphene Composites with Enhanced Mechanical Property and Electrical Conductivity and Method for Preparing the Same Download PDF

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KR101093056B1
KR101093056B1 KR1020100042829A KR20100042829A KR101093056B1 KR 101093056 B1 KR101093056 B1 KR 101093056B1 KR 1020100042829 A KR1020100042829 A KR 1020100042829A KR 20100042829 A KR20100042829 A KR 20100042829A KR 101093056 B1 KR101093056 B1 KR 101093056B1
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graphene
polytrimethylene terephthalate
ptt
composite
electrical conductivity
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KR20110123383A (en
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메이루 리
정영규
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금오공과대학교 산학협력단
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/194After-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides

Abstract

The present invention relates to the preparation of polytrimethylene terephthalate / graphene composites having excellent mechanical properties, thermal stability and electrical conductivity. In the present invention, by using a natural graphite is a graphene (graphene), a functional carbon nanoparticles prepared by acid treatment and heat treatment as a reinforcing agent, using a poly (trimethylene terephthalate) as a polymer matrix melt mixing method Or a method for producing a polytrimethylene terephthalate / graphene composite by a solution mixing method, and various products such as films, fibers, and plastics can be formed from the polytrimethylene terephthalate / graphene composite of the present invention.

Description

Poly (trimethylene terephthalate) / Graphene Composites with Enhanced Mechanical Property and Electrical Conductivity and Method for Preparing the Same}

The present invention is to prepare a graphene (graphene) having a nano-size thickness by acid treatment and heat treatment of natural graphite, and melt-mixed or solution-mixed with a polytrimethylene terephthalate polymer matrix, polytrimethylene terephthalate / It relates to a graphene composite and a method of manufacturing the same.

Polytrimethylene terephthalate (also referred to as "PTT") is a type of aromatic polyester successfully synthesized by Winfield and Dickson in 1941. However, due to the high production price of 1,3-propanediol, a monomer of polytrimethylene terephthalate (PTT), mass production was not achieved. Meanwhile, in the early 1990's, polytrimethylene terephthalate (PTT) began mass production in earnest as Shell Chemical Corp. of the United States developed a technology to mass-produce 1,3-propanediol. Polytrimethylene terephthalate (PTT) combines the excellent properties of aromatic polyester polyethylene terephthalate (PET) with the excellent processability of polybutylene terephthalate (PBT). Has physical properties In particular, polytrimethylene terephthalate (PTT) has an excellent elastic recovery ability has been used mainly as a fiber polymer material for clothing until now.

However, if the thermal and mechanical properties of polytrimethylene terephthalate (PTT) can be improved and the electrical conductivity can be improved, it can be used in various applications as it is used not only as a textile material for clothing but also as an industrial fiber, a film, and an engineering plastic material. .

Polytrimethylene terephthalate is a kind of aromatic polyester and may be represented by the following formula.

Figure 112010029360016-pat00001

On the other hand, natural graphite (NG) is a powder or particles having a micron-sized thickness formed by laminating graphene (graphene) with each other by van der Waals attraction. Natural graphite (NG) not only has a high electrical conductivity of about 10 4 S / cm, but is also one of the excellent reinforcing agents because the price is also very low compared to carbon nanotubes.

In order for the natural graphite to function effectively as a functional reinforcing agent, the natural graphite must be dispersed in particles having a nano-sized thickness in the polymer matrix or peeled and dispersed with graphene. Graphene (graphene) may be prepared by peeling the natural graphite to a nano-sized thickness by acid treatment, sonication or heat treatment. Graphene is a highly functional carbon nanoparticle having a Young's modulus of 1060 GPa and having an electrical conductivity of about 10 4 S / cm and high thermal stability of more than 1000 ° C. If the graphene can be effectively dispersed in a fibrous polymer matrix such as PTT, the thermal, mechanical and electrical properties of the matrix fibrous polymer can be greatly improved.

The present invention is a composite that gives excellent mechanical properties, heat resistance and electrical conductivity to polytrimethylene terephthalate (PTT), which is widely commercialized and used for high functionality, that is, polytrimethylene terephthalate (PTT) and graphene carbon nanoparticles. An object of the present invention is to provide a polytrimethylene terephthalate / graphene complex (PTT / graphene) complex and a manufacturing method thereof.

In order to solve the above problems, according to the preferred embodiment of the present invention, polytrimethylene terephthalate / graphene composite by melting or solution mixing graphene and polytrimethylene terephthalate prepared by acid treatment and heat treatment of natural graphite It provides a method of manufacturing.

According to another suitable embodiment of the present invention, the graphene content in the composite provides a method for producing a polytrimethylene terephthalate / graphene composite, characterized in that 0.01 to 50.0% by weight relative to the total weight of the composite.

According to another suitable embodiment of the present invention, the melt mixing provides a method for producing a polytrimethylene terephthalate / graphene composite, characterized in that carried out at a temperature of 240 to 300 ℃.

According to another suitable embodiment of the present invention, the solution mixture is at least one selected from the group consisting of phenol, o-chlorophenol, m-chlorophenol, nitrobenzene, phenol and ethane tetrachloride at a temperature of 20-150 ° C. It provides a method for producing a polytrimethylene terephthalate / graphene composite, characterized in that carried out using a solvent.

According to another suitable embodiment of the present invention, there is provided a fiber, film or plastic article comprising the polytrimethylene terephthalate / graphene composite prepared by the above method.

The polytrimethylene terephthalate / graphene (PTT / graphene) composite prepared in the present invention has better storage modulus than the polytrimethylene terephthalate (PTT) polymer, thereby improving mechanical properties. In addition, the polytrimethylene terephthalate / graphene composite of the present invention has better thermal stability (heat resistance) and electrical conductivity than polytrimethylene terephthalate (PTT) polymer alone. In addition, since the polytrimethylene terephthalate (PTT) composite of the present invention has excellent heat resistance, mechanical strength and electrical conductivity, it is possible to prepare fibers, films, and plastics having excellent heat resistance, mechanical strength and electrical conductivity.

1 is a graph showing the storage modulus of the polytrimethylene terephthalate / graphene composite prepared in the present invention.
Figure 2 is a graph showing the thermal stability of the polytrimethylene terephthalate / graphene composite prepared in the present invention, Figure 2a is the result of measuring the thermal stability in the presence of nitrogen, Figure 2b in the presence of oxygen.
Figure 3 is a graph showing the electrical conductivity of the polytrimethylene terephthalate / graphene composite prepared in the present invention.

The term "PTT" as used herein refers to polytrimethylene terephthalate (poly).

“PTT / graphene” used in the present invention refers to a material prepared by mixing graphene and polytrimethylene terephthalate (PTT) homopolymer. Here, graphene (graphene) is a carbon particle having a plate-like structure composed only of carbon, and has excellent electrical conductivity, heat resistance, and mechanical strength.

For the present invention, graphene was prepared by acid treatment and heat treatment (thermal expansion) of natural graphite (natural graphite, NG).

By melting or mixing the prepared graphene with polytrimethylene terephthalate (PTT) polymer, polytrimethylene terephthalate / graphene (PTT / graphene) having better storage modulus than polytrimethylene terephthalate (PTT) polymer Prepare the complex.

In addition, the polytrimethylene terephthalate / graphene composite of the present invention has better thermal stability (heat resistance) and electrical conductivity than the polytrimethylene terephthalate (PTT) polymer.

First, a method of preparing graphene (graphene) used for the present invention will be described.

Natural graphite (NG) has a diameter of several mm to several hundred mm, showing a form in which several layers of carbon are overlapped. In the present invention, natural graphite (NG) having a diameter of 20 to 500 mm is used.

Graphene (graphene) is prepared by immersing the natural graphite (NG) in a sulfuric acid, nitric acid and potassium chlorate solution and then vigorously stirring using a stirrer to perform acid treatment. At this time, potassium chlorate has a high concentration in acid solution, so there is a risk of explosion, so first put natural graphite (NG), sulfuric acid, and nitric acid in the cooling bath, and after stirring, lower the temperature sufficiently to below 20 ℃, and then slowly lower the potassium chlorate slowly. Put it in.

The acid concentration is preferably at least 90% sulfuric acid, at least 60% nitric acid, at least 90% potassium chlorate. This is because the higher the concentration of acid can give a high acid treatment effect in a short time. However, if the acid concentration is high, there is a risk of explosion of potassium chlorate, so it is preferable that the temperature of the reactor does not rise above 37 ° C.

The acid treatment reaction time is preferably 96 hours to 120 hours, and is preferably carried out with sufficient stirring using a magnetic bar. After the acid treatment is completed, the graphite is diluted with excess water and filtered. The filtered graphite is adjusted to a pH above 6.7 by several washings.

The graphite obtained by the above method is dried by vacuum drying for 24 hours before heat treatment. The dried sample is heat-treated and expanded for 30 seconds to 1 minute in a furnace at 600 to 1100 ° C. to produce graphene, which is exfoliated graphite.

Next, a method of preparing a polytrimethylene terephthalate / graphene (PTT / graphene) complex will be described.

The graphene prepared by the above method may be mixed with a polytrimethylene terephthalate (PTT) homopolymer to prepare a polytrimethylene terephthalate / graphene (PTT / graphene) complex. Graphene and polytrimethylene terephthalate (PTT) alone polymer can be variously combined in the weight ratio (wt%) of 0.001 to 99.999: 99.999 to 0.001, but the graphene is 0.01 to 50.00% by weight of the total weight of the composite It is preferable. If the graphene is less than 0.01% by weight can not be expected to improve the thermal / electrical properties of the composite, if the graphene is more than 50.00% by weight it is impossible to produce a composite by melt mixing, a commercially important manufacturing process.

The mixing of graphene and polytrimethylene terephthalate (PTT) may be performed by solution mixing or melt mixing, respectively.

The melt mixing is performed using a melt kneader in the temperature range of 240 to 300 ℃. It is preferable to use a melt kneader for the melt mixing.

The solution mixing can be carried out using a solvent such as phenol, o-chlorophenol, m-chlorophenol, nitrobenzene, phenol, ethane tetrachloride or a mixed solvent thereof. The solution mixing is preferably carried out at a temperature range of 20 ~ 150 ℃, the weight of the solvent is preferably 50.00 ~ 99.99% by weight relative to the total weight.

Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited by Examples.

Preparation Example 1 Graphene Preparation

In a cooling bath, 20 g of natural graphite, 320 mL of sulfuric acid and 180 mL of nitric acid are added and stirred. When stirring, lower the temperature sufficiently below 20 ℃, and then slowly add 220g of potassium chlorate little by little. At this time, the temperature should not rise above 37 ℃. The reaction time is 96 hours, and the acid treatment is sufficiently performed. Acid treated graphite is diluted with water and filtered through filtration, and the pH is adjusted to 6.7 or more through 6 washes. The graphite obtained by the above method is dried by vacuum drying for 24 hours before heat treatment. The dried sample was heat-treated in a 1050 ° C. furnace for 30 seconds to expand, thereby preparing graphene (graphene) that was exfoliated graphite.

Examples 1-8 and Comparative Example 1

Polytrimethylene terephthalate / graphene (PTT / graphene) composites were prepared by melt mixing various weights of graphene with PTT polymer as shown in Table 1. First, the graphene and PTT homopolymers prepared in the ratios shown in Table 1 were sufficiently mixed with a blender, and then subjected to a kneading mixer at a temperature range of 250 to 270 ° C., followed by drying at room temperature for 24 hours at a high vacuum of 0.1 mmHg. The polymer PTT / graphene powder samples obtained by drying were melted at 270 ° C. for 3 minutes using a heating press, and then quenched to 0 ° C. to form polytrimethylene terephthalate / graphene (PTT / graphene) film having a uniform thickness of 0.2 mm. It was prepared by.

PTT (wt%) Graphene (wt%) Comparative Example 1 100.0 0.0 Example 1 99.9 0.1 Example 2 99.7 0.3 Example 3 99.5 0.5 Example 4 99.3 0.7 Example 5 99.0 1.0 Example 6 97.0 3.0 Example 7 95.0 5.0 Example 8 93.0 7.0

Test Example 1-Storage Modulus Analysis

The storage modulus of mechanical properties of the polytrimethylene terephthalate / graphene (PTT / graphene) composite film was measured and shown in FIG. 1. Storage modulus was measured using a dynamic mechanical analyzer (DMA). As shown in FIG. 1, the storage modulus of the polytrimethylene terephthalate (PTT) homopolymer is about 3.71 GPa, whereas the graphene content is in the case of the polytrimethylene terephthalate / graphene (PTT / graphene) complex. With this increase, the storage modulus of the composite increased. When the graphene content is 1.0 wt% (Example 5), the storage modulus of the composite is increased by about 19% to 4.42 GPa, and the mechanical properties of the graphene content is increased by about 57% to 5.84 GPa at 7.0 wt% (Example 8). Seemed.

Test Example 2-Measurement of Thermal Stability

Thermal stability of the polytrimethylene terephthalate / graphene (PTT / graphene) composite was measured and shown in FIG. 2 and Table 2. FIG. Thermostability measurements were performed in the presence of nitrogen (FIG. 2A) and oxygen (FIG. 2B) using a thermogravimetric analyzer (TGA). As shown in Figure 2 and Table 2, the PTT homopolymer showed a weight loss of 30% at 428.5 and 421.2 ° C under nitrogen and oxygen airflow conditions, respectively. However, for polytrimethylene terephthalate / graphene (PTT / graphene) composites (Example 5) having a relatively low graphene content of 1.0 wt%, the temperature at which the weight loss of 30 wt% occurs is nitrogen and oxygen airflow. Under the conditions, it was about 4 ℃ and 7 ℃ higher than the PTT single polymer, respectively. In the case of the composite containing 7 wt% of graphene (Example 8), a weight loss of 30 wt% occurred at a temperature of about 7 ° C. and 14 ° C. higher than PTT single polymer under nitrogen and oxygen conditions, respectively.

No. Graphene (wt%) Pyrolysis temperature at 30 wt% weight loss, T 30% (℃) Nitrogen (N 2 ) Condition Oxygen (O 2 ) Conditions Example 1 0.1 430.8 423.6 Example 2 0.3 431.8 425.7 Example 3 0.5 432.0 426.5 Example 4 0.7 432.0 428.1 Example 5 1.0 432.6 428.5 Example 6 3.0 432.7 432.8 Example 7 5.0 433.6 435.6 Example 8 7.0 435.4 435.4 Comparative Example 1 0.0 428.5 421.2

Test Example 3-Conductivity Measurement

The electrical conductivity of the polytrimethylene terephthalate / graphene (PTT / graphene) composite was measured and shown in FIG. 3. The electrical conductivity of the composite was measured using a high resistance meter. As shown in FIG. 3, the PTT homopolymer film exhibits a high electrical resistance value of about 10 16 Pa · cm. However, in the case of polytrimethylene terephthalate / graphene (PTT / graphene) composite film, the graphene content shows a sharply low electrical resistance value between 3 and 5 wt%, and the graphene content is 7 wt% (Example 7) shows a low electrical resistance of ˜10 6 Ω · cm.

Polytrimethylene terephthalate / graphene (PTT / graphene) composite prepared according to the method proposed in the present invention has excellent mechanical properties, thermal stability, superior to conventional polytrimethylene terephthalate homopolymer, as evidenced from the results of the test example It has electrical conductivity. Therefore, it can be usefully applied in various fields such as film, fiber, plastic.

Claims (5)

  1. Method of producing a polytrimethylene terephthalate / graphene composite by melting or solution mixing the graphene and polytrimethylene terephthalate prepared by acid treatment and heat treatment of natural graphite.
  2. The method according to claim 1,
    Graphene content in the composite is a method for producing a polytrimethylene terephthalate / graphene composite, characterized in that 0.01 to 50.0% by weight relative to the total weight of the composite.
  3. The method according to claim 1,
    The melt mixing is a method for producing a polytrimethylene terephthalate / graphene composite, characterized in that carried out at a temperature of 240 to 300 ℃.
  4. The method according to claim 1,
    The solution mixing is carried out using at least one solvent selected from the group consisting of phenol, o-chlorophenol, m-chlorophenol, nitrobenzene, phenol and ethane tetrachloride at a temperature of 20 ~ 150 ℃ Method for preparing trimethylene terephthalate / graphene complex.
  5. Fiber, film or plastic article comprising the polytrimethylene terephthalate / graphene composite prepared by the method of claim 1.
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WO2012151433A2 (en) * 2011-05-03 2012-11-08 The Board Of Regents For Oklahoma State University Polyethylene terephthalate-graphene nanocomposites
PT107398B (en) * 2014-01-12 2018-06-26 Octavio Adolfo Romao Viana Ethylene and polypheneetalate filter and / or graffen oxide
CN103881336A (en) * 2014-04-09 2014-06-25 中国科学院理化技术研究所 Adipic acid-terephthalic acid-butanediol ternary copolyester/graphene oxide composite material and preparation method thereof

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US20040077771A1 (en) 2001-02-05 2004-04-22 Eisuke Wadahara Carbon fiber reinforced resin composition, molding compounds and molded article therefrom
JP2007169461A (en) 2005-12-22 2007-07-05 Sato Light Kogyo Kk Semi-electroconductive structure, electroconductive and/or thermo-conductive structure, and method for production thereof and use thereof
EP2071654A1 (en) 2006-10-05 2009-06-17 DIC Corporation Separator for fuel batteries and fuel batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040077771A1 (en) 2001-02-05 2004-04-22 Eisuke Wadahara Carbon fiber reinforced resin composition, molding compounds and molded article therefrom
JP2007169461A (en) 2005-12-22 2007-07-05 Sato Light Kogyo Kk Semi-electroconductive structure, electroconductive and/or thermo-conductive structure, and method for production thereof and use thereof
EP2071654A1 (en) 2006-10-05 2009-06-17 DIC Corporation Separator for fuel batteries and fuel batteries

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