KR20120112967A - Poly(butylene terephthalate)/graphene composites and method for preparing the same - Google Patents

Poly(butylene terephthalate)/graphene composites and method for preparing the same Download PDF

Info

Publication number
KR20120112967A
KR20120112967A KR1020110030594A KR20110030594A KR20120112967A KR 20120112967 A KR20120112967 A KR 20120112967A KR 1020110030594 A KR1020110030594 A KR 1020110030594A KR 20110030594 A KR20110030594 A KR 20110030594A KR 20120112967 A KR20120112967 A KR 20120112967A
Authority
KR
South Korea
Prior art keywords
graphene
composite
polybutylene terephthalate
polyurethane
pbt
Prior art date
Application number
KR1020110030594A
Other languages
Korean (ko)
Other versions
KR101234258B1 (en
Inventor
정영규
Original Assignee
금오공과대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 금오공과대학교 산학협력단 filed Critical 금오공과대학교 산학협력단
Priority to KR1020110030594A priority Critical patent/KR101234258B1/en
Publication of KR20120112967A publication Critical patent/KR20120112967A/en
Application granted granted Critical
Publication of KR101234258B1 publication Critical patent/KR101234258B1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Abstract

PURPOSE: A manufacturing method of a polyurethane composite film is provided to provide a moisture-permeable and waterproof polyurethane film by absorbing anions to particle size-controlled hydroxyapatite. CONSTITUTION: A manufacturing method of a polyurethane composite film comprises: a step of manufacturing polyurethane liquid; a step of manufacturing a nanohydroxyapatite dispersion; a step of manufacturing a polyurethane/apatite composite composition by mixing the hydroxyapatite dispersion into the polyurethane liquid; a step of preparing a polyurethane composition by putting a mixture of water and organic solvent into the composite composition; a step of preparing a polyurethane composite film by film casting the polyurethane composition; and a step of absorbing silver ions by impregnating the polyurethane composite film into the silver nitrate solution. [Reference numerals] (AA) Storage elasticity(GPa); (BB) Graphene(weight%)

Description

폴리부틸렌 테레프탈레이트/그래핀 복합체와 그 제조방법{Poly(butylene terephthalate)/Graphene Composites and Method for Preparing the Same}Poly (butylene terephthalate) / Graphene Composites and Method for Preparing the Same}

본 발명은 그래핀(graphene)을 기능성/보강용 나노입자로 하고, 폴리부틸렌 테레프탈레이트 고분자를 매트릭스로 하여 용융혼합 또는 용액혼합방법으로 제조한 폴리부틸렌 테레프탈레이트/그래핀 복합체 및 이를 제조하는 방법에 관한 것이다.The present invention is a polybutylene terephthalate / graphene composite prepared by melt mixing or solution mixing method using a graphene (graphene) as a functional / reinforcement nanoparticles, a polybutylene terephthalate polymer as a matrix and to prepare the same It is about a method.

폴리부틸렌 테레프탈레이트(poly(butylene terephthalate), 이하 “PBT”라고 한다.)는 방향족 폴리에스테르의 일종으로써 테레프탈산 또는 테레프탈산의 디메틸에스테르와 부틸렌글리콜의 중합물질이다. PBT는 아래의 화학식으로 나타낼 수 있다.Poly (butylene terephthalate) (hereinafter referred to as "PBT") is a kind of aromatic polyester and is a polymer of dimethyl ester of terephthalic acid or terephthalic acid and butylene glycol. PBT can be represented by the following formula.

Figure pat00001
Figure pat00001

PBT는 방향족 폴리에스테르인 폴리에틸렌 테레프탈레이트[poly(ethylene terephthalate), PET]와 비교하여 빠른 결정화 속도에 의한 우수한 가공성, 뛰어난 기계적 탄성 등의 잘 조합된 물성을 가지고 있어 엔지니어링 플라스틱, 필름, 섬유소재로 사용되고 있다. 하지만, PBT의 보다 확장된 응용을 위해서는 내열성 및 기계적 물성 향상이 요구된다. 또한 PBT는 본래 절연체이기 때문에, 대전방지 및 전자파차폐 등의 고기능성이 요구되는 응용분야에 있어서는 PBT의 높은 전기저항을 크게 낮추어야 한다.PBT is used in engineering plastics, films, and textile materials because it has a good combination of physical properties such as excellent processability due to fast crystallization rate and excellent mechanical elasticity, compared with aromatic polyester polyethylene terephthalate (poly (ethylene terephthalate), PET). have. However, for more extended applications of PBT, improved heat resistance and mechanical properties are required. In addition, since PBT is an insulator inherently, the high electrical resistance of PBT should be greatly reduced in applications requiring high functionality such as antistatic and electromagnetic shielding.

한편 천연 그래파이트(natural graphite, NG)는 판상의 그래핀(graphene)이 반 데르 발스 인력에 의해 서로 적층되어 이루어진 마이크론 크기의 두께를 갖는 분말 또는 입자이다. 천연 그래파이트(natural graphite, NG)는 104 S/cm 정도의 높은 전기전도도를 가질 뿐만 아니라 탄소나노튜브와 비교하여 가격 또한 매우 저렴하여 우수한 보강제 중의 하나이다. 이러한 천연 그래파이트가 기능성 보강제로서 효과적으로 기능을 발휘하기 위해서는 고분자 매트릭스 내에서 나노 크기의 두께를 가진 입자로 분산되어 있거나, 그래핀(graphen)으로 박리되어 분산되어 있어야 한다. 그래핀(graphene)은 천연 그래파이트를 산처리, 초음파처리 또는 열처리하여 나노크기의 두께로 박리시켜 제조할 수 있다. 그래핀(graphene)은 1060 GPa의 영탄성율을 가지고 있고, 104 S/cm 정도의 전기전도도와 1000 ℃ 이상의 높은 열안정성을 갖는 고기능성 탄소나노입자이다. 이러한 그래핀을 PBT와 같은 고분자 매트릭스에 효과적으로 분산시킬 수 있다면 고분자 매트릭스의 열적, 기계적 및 전기적 물성을 크게 향상시킬 수 있다.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 polymer matrix such as PBT, the thermal, mechanical and electrical properties of the polymer matrix can be greatly improved.

본 발명은 고기능성을 요구하기 위하여 널리 상용화되어 사용되고 있는 폴리부틸렌 테레프탈레이트(PBT)에 우수한 기계적 물성, 내열성 및 전기전도성을 부여한 복합체, 즉 폴리부틸렌 테레프탈레이트(PBT)와 그래핀 탄소나노입자를 복합화한 폴리부틸렌 테레프탈레이트/그래핀 (PBT/graphene) 복합체 및 그 제조방법을 제공하는 것을 목적으로 한다.The present invention is a composite that gives excellent mechanical properties, heat resistance and electrical conductivity to polybutylene terephthalate (PBT), which is widely commercialized and used for high functionality, that is, polybutylene terephthalate (PBT) and graphene carbon nanoparticles An object of the present invention is to provide a polybutylene terephthalate / graphene (PBT / graphene) complex and a method for producing the same.

상기한 과제를 해결하기 위하여 본 발명의 적절한 실시 형태에 따르면, 천연그래파이트를 산처리 및 열처리하여 제조된 그래핀과 폴리부틸렌 테레프탈레이트를 용융혼합 또는 용액혼합하여 폴리부메틸렌 테레프탈레이트/그래핀 복합체를 제조하는 방법을 제공한다.In order to solve the above problems, according to a preferred embodiment of the present invention, a polybutmethylene terephthalate / graphene composite by melting or solution mixing the graphene and polybutylene terephthalate prepared by acid treatment and heat treatment of natural graphite It provides a method of manufacturing.

본 발명의 다른 적절한 실시 형태에 따르며, 상기 복합체에서 그래핀 함량은 복합체 총중량대비 0.01~50.0 중량%인 것을 특징으로 하는 폴리부틸렌 테레프탈레이트/그래핀 복합체의 제조방법을 제공한다.According to another suitable embodiment of the present invention, the graphene content in the composite provides a method for producing a polybutylene terephthalate / graphene composite, characterized in that 0.01 to 50.0% by weight relative to the total weight of the composite.

본 발명의 또 다른 적절한 실시 형태에 따르면, 상기 용융혼합은 220 내지 300 ℃의 온도에서 실시하는 것을 특징으로 하는 폴리부틸렌 테레프탈레이트/그래핀 복합체의 제조방법을 제공한다.According to another suitable embodiment of the present invention, the melt mixing provides a method for producing a polybutylene terephthalate / graphene composite, characterized in that carried out at a temperature of 220 to 300 ℃.

본 발명의 또 다른 적절한 실시 형태에 따르면, 상기 용액혼합은 20~150 ℃의 온도에서 페놀， o-클로로페놀， m-클로로페놀， 니트로벤젠， 페놀 및 사염화에탄으로 이루어진 군에서 선택된 적어도 1종의 용매를 이용하여 실시하는 것을 특징으로 하는 폴리부틸렌 테레프탈레이트/그래핀 복합체의 제조방법을 제공한다.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 polybutylene terephthalate / graphene composite, characterized in that carried out using a solvent.

본 발명의 또 다른 적절한 실시 형태에 따르면, 상기 방법으로 제조된 폴리부틸렌 테레프탈레이트/그래핀 복합체를 포함하는 섬유, 필름 또는 플라스틱 제품을 제공한다.According to another suitable embodiment of the present invention, there is provided a fiber, film or plastic article comprising the polybutylene terephthalate / graphene composite prepared by the above method.

본 발명에서 제조된 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체는 폴리부틸렌 테레프탈레이트(PBT) 단독고분자보다 저장탄성률이 우수하여 기계적 물성이 향상된다. 또한 본 발명의 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체는 폴리부틸렌 테레프탈레이트(PBT) 단독고분자보다 우수한 열적 안정성(내열성) 및 전기전도성을 갖는다. 또한 본 발명의 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체는 우수한 내열성, 기계적 강도 및 전기 전도도를 가지기 때문에 우수한 내열성, 기계적 강도 및 전기 전도도를 갖는 섬유, 필름, 플라스틱을 제조할 수 있다. 구제척인 용도로는 의류용/산업용 섬유소재, 대전방지/전자파차폐용 필름, 생활용/산업용 플라스틱(가정용품, 자동차용 내외장재 부품, 토목건축용 부품, 전자제품 및 부품) 등이 있다.The polybutylene terephthalate / graphene (PBT / graphene) composite prepared in the present invention has better storage modulus than the polybutylene terephthalate (PBT) polymer, thereby improving mechanical properties. In addition, the polybutylene terephthalate / graphene (PBT / graphene) composite of the present invention has better thermal stability (heat resistance) and electrical conductivity than the polybutylene terephthalate (PBT) single polymer. In addition, the polybutylene terephthalate / graphene (PBT / graphene) composite of the present invention has excellent heat resistance, mechanical strength and electrical conductivity, it is possible to manufacture fibers, films, plastics having excellent heat resistance, mechanical strength and electrical conductivity. . Remedies include clothing / industrial textile materials, antistatic / electromagnetic shielding films, and household / industrial plastics (home appliances, automotive interior and exterior materials, civil construction parts, electronic products and parts), and the like.

도 1은 본 발명에서 제조된 폴리부틸렌 테레프탈레이트/그래핀 복합체의 저장탄성률을 나타낸 그래프이다.
도 2a 내지 2b는 본 발명에서 제조된 폴리부틸렌 테레프탈레이트/그래핀 복합체의 온도에 따른 질량변화를 나타낸 그래프로서 복합체의 열안정성을 평가할 수 있다. 도 2a는 질소 존재 하에서, 도 2b는 산소 존재 하에서 열안정성을 측정한 결과이다.
도 3은 본 발명에서 제조된 폴리부틸렌 테레프탈레이트/그래핀 복합체의 전기저항을 나타낸 그래프이다.1 is a graph showing the storage modulus of the polybutylene terephthalate / graphene composite prepared in the present invention.
Figure 2a to 2b is a graph showing the mass change with temperature of the polybutylene terephthalate / graphene composite prepared in the present invention can evaluate the thermal stability of the composite. 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 resistance of the polybutylene terephthalate / graphene composite prepared in the present invention.

본 발명에서 사용된 용어 “PBT”는 폴리부틸렌 테레프탈레이트[poly(butylene terephthalate)]를 나타낸다. As used herein, the term “PBT” refers to polybutylene terephthalate.

본 발명에서 사용된 “PBT/graphene”는 그래핀(graphene)과 폴리부틸렌 테레프탈레이트(PBT) 단독고분자를 혼합하여 제조된 물질을 말한다. 여기서 그래핀(graphene)이란 탄소로만 이루어진 판상구조를 가진 탄소입자로써 전기전도성, 내열성, 기계적 강도가 매우 우수하다. As used herein, “PBT / graphene” refers to a material prepared by mixing graphene and polybutylene terephthalate (PBT) 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.

본 발명을 위해 그래핀은 천연 그래파이트(natural graphite, NG)를 산처리와 열처리(열팽창)를 통해 제조하였다. For the present invention, graphene was prepared by acid treatment and heat treatment (thermal expansion) of natural graphite (natural graphite, NG).

제조된 그래핀을 폴리부틸렌 테레프탈레이트(PBT) 고분자와 용융혼합 또는 용액혼합 함으로써 폴리부틸렌 테레프탈레이트(PBT) 단독고분자보다 저장탄성률이 우수한 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체를 제조한다. The polybutylene terephthalate / graphene (PBT / graphene) composite having better storage modulus than the polybutylene terephthalate (PBT) polymer by melt-mixing or solution mixing the prepared graphene with a polybutylene terephthalate (PBT) polymer To prepare.

또한 본 발명의 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체는 폴리부틸렌 테레프탈레이트(PBT) 단독고분자보다 우수한 열적 안정성(내열성)과 전기전도도를 갖는다.
In addition, the polybutylene terephthalate / graphene (PBT / graphene) composite of the present invention has better thermal stability (heat resistance) and electrical conductivity than the polybutylene terephthalate (PBT) single polymer.

먼저 본 발명을 위해 사용된 그래핀(graphene)의 제조방법에 대하여 설명한다.First, a method of preparing graphene (graphene) used for the present invention will be described.

천연 그래파이트(natural graphite, NG)는 지름이 수 mm 내지 수백 mm로서 탄소로 이루어진 여러 겹의 판상들이 겹쳐져 있는 형태를 나타내고 있는데, 본 발명에서는 지름이 20~500mm의 천연 그래파이트(NG)를 사용한다. 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.

그래핀(graphene)은 상기 천연 그래파이트(NG)를 황산, 질산 및 염소산칼륨 용액에 침지 시킨 후 교반기를 이용하여 강하게 교반하여 산처리를 실시하여 제조한다. 이 때 염소산칼륨은 산 용액에서 농도가 높으면 폭발 위험성을 가지기 때문에 냉각 수조 안에서 먼저 천연 그래파이트(NG), 황산 및 질산을 넣고 교반 후 온도를 20 ℃이하로 충분이 낮추어 주고 그런 다음 염소산칼륨을 조금씩 천천히 넣어준다. 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.

이때 산의 농도는 90% 이상의 황산, 60% 이상의 질산, 90% 이상의 염소산칼륨을 사용하는 것이 바람직하다. 이는 산의 농도가 높을수록 짧은 시간 안에 높은 산처리 효과를 줄 수 있기 때문이다. 하지만, 산 농도가 높으면 염소산칼륨이 폭발할 위험이 있기 때문에, 반응기의 온도가 37 ℃ 이상 올라가지 않도록 하는 것이 바람직하다. 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.

산처리 반응 시간은 96시간 내지 120시간 동안으로 하고 마그네틱바를 이용하여 충분히 교반하면서 실시하는 것이 바람직하다. 산처리가 완료되면 그래파이트를 과량의 물로 희석하여 준 후 여과하여 걸러준다. 여과된 그래파이트는 여러 번의 수세를 통하여 pH가 6.7 이상이 되도록 조절해준다.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.

상기 방법으로 획득한 그래파이트는 열처리 전에 24시간 동안의 진공건조를 통하여 건조시켜 준다. 건조된 시료는 600 내지 1100 ℃의 용광로에서 30초 내지 1분간 열처리하여 팽창시킴으로써 박리된 그래파이트인 그래핀(graphene)을 제조한다.
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.

다음으로 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체를 제조하는 방법을 설명한다.Next, a method of preparing a polybutylene terephthalate / graphene (PBT / graphene) composite will be described.

상기 방법으로 제조된 그래핀(graphene)을 폴리부틸렌 테레프탈레이트(PBT) 단독고분자와 혼합하여 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체를 제조할 수 있다. 그래핀과 폴리부틸렌 테레프탈레이트(PBT) 단독고분자는 0.001~99.999 : 99.999~0.001의 중량비의 범위에서 다양하게 조합할 수 있지만, 그래핀이 복합체 총 중량대비 0.01~50.00 중량%인 것이 바람직하고, 0.1~10.0 중량%인 것이 보다 바람직하다. 그래핀이 0.01 중량% 이하인 경우는 복합체의 열적/전기적 물성 향상을 기대할 수 없으며, 그래핀이 50.00 중량% 이상인 경우에는 상업적으로 중요한 제조공정인 용융혼합에 의한 복합체 제조가 불가능하다.The graphene prepared by the above method may be mixed with a polybutylene terephthalate (PBT) homopolymer to prepare a polybutylene terephthalate / graphene (PBT / graphene) complex. Graphene and polybutylene terephthalate (PBT) homopolymer can be variously combined in the range of the weight ratio of 0.001 ~ 99.999: 99.999 ~ 0.001, it is preferable that the graphene is 0.01 to 50.00% by weight relative to the total weight of the composite, It is more preferable that it is 0.1-10.0 weight%. 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.

그래핀과 폴리부틸렌 테레프탈레이트(PBT)의 혼합은 용액혼합법 또는 용융혼합법으로 각각 행해질 수 있다.The mixing of graphene and polybutylene terephthalate (PBT) may be performed by solution mixing or melt mixing, respectively.

상기 용융혼합은 220 내지 300 ℃의 온도범위에서 용융혼련기를 사용하여 행해진다. 상기 용융혼합은 공지된 방법으로 할 수 있지만, 용융혼련기를 사용하는 것이 바람직하다.The melt mixing is performed using a melt kneader in the temperature range of 220 to 300 ℃. Although the said melt mixing can be made by a well-known method, it is preferable to use a melt kneading machine.

상기 용액혼합은 페놀， o-클로로페놀， m-클로로페놀， 니트로벤젠， 페놀, 사염화에탄과 같은 용매 또는 이들의 혼합용매를 이용하여 실시할 수 있다. 상기 용액혼합은 20~150 ℃의 온도범위에서 실시하는 것이 바람직하며, 이때 용매의 중량은 전체 중량 대비 50.00~99.99 중량%로 하는 것이 바람직하다.
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.

이하에서 실시예를 들어 본 발명을 상세하게 설명하지만, 실시예에 의하여 본 발명의 권리범위가 한정되는 것은 아니다.
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.

제조예 1: 그래핀(graphene) 제조Preparation Example 1 Graphene Preparation

냉각 수조 안에서 먼저 천연 그래파이트 20 g, 황산 320 mL 및 질산 180 mL을 넣고 교반한다. 교반시 온도를 20 ℃이하로 충분이 낮추어 주고 그런 다음 염소산칼륨 220g을 조금씩 천천히 넣어준다. 이때에 온도가 37 ℃ 이상 올라가지 않도록 한다. 반응 시간은 96시간 동안으로 하여 충분히 산처리를 하여준다. 산처리된 그래파이트는 과량을 물로 희석하여 준 후 여과를 통하여 걸러주고 6번 수세를 통하여 pH를 6.7 이상으로 조절해준다. 상기 방법으로 획득한 그래파이트는 열처리 전에 24시간 동안의 진공건조를 통하여 건조시켜 준다. 건조된 시료는 1050 ℃의 용광로에서 30초간 열처리하여 팽창시킴으로써 박리된 그래파이트인 그래핀(graphene)을 제조하였다.
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.

실시예 1~8 및 비교예 1Examples 1-8 and Comparative Example 1

폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체는 표 1에 기재된 바와 같이 다양한 중량의 그래핀을 PBT 고분자와 용융혼합하여 제조하였다. 먼저 표 1에 기재된 비율로 준비한 그래핀과 PBT 단독고분자를 믹서기로 충분히 섞어준 후 용융혼련기를 통하여 230 ~ 245 ℃의 온도범위에서 용융혼합한 후 얻은 복합체 칩(chip)을 0.1 mmHg의 고진공 상태에서 24시간 동안 상온건조하였다. 건조하여 얻은 고분자 PBT/graphene 복합체 칩을 가열프레스를 이용하여 245 ℃ 에서 4분간 녹인 후, 0 ℃로 급냉시켜 0.2 mm의 균일한 두께를 가진 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 필름으로 제조하였다.Polybutylene terephthalate / graphene (PBT / graphene) composites were prepared by melt mixing various weights of graphene with PBT polymer as shown in Table 1. First, the graphene and PBT homopolymers prepared in the ratios shown in Table 1 were sufficiently mixed with a blender, and then melt-mixed at a temperature range of 230 to 245 ° C. through a melt kneader to obtain a composite chip at a high vacuum of 0.1 mmHg. It was dried at room temperature for 24 hours. The polymer PBT / graphene composite chip obtained by drying was melted at 245 ° C. for 4 minutes using a heating press, and then quenched to 0 ° C. to form a polybutylene terephthalate / graphene (PBT / graphene) film having a uniform thickness of 0.2 mm. It was prepared by.

PBT (중량%)PBT (% by weight) 그래핀 (중량%)Graphene (wt%) 비교예1Comparative Example 1 100.0100.0 0.00.0 실시예1Example 1 99.999.9 0.10.1 실시예2Example 2 99.799.7 0.30.3 실시예3Example 3 99.599.5 0.50.5 실시예4Example 4 99.399.3 0.70.7 실시예5Example 5 99.099.0 1.01.0 실시예6Example 6 97.097.0 3.03.0 실시예7Example 7 95.095.0 5.05.0 실시예8Example 8 93.093.0 7.07.0

시험예 1-저장탄성률 분석Test Example 1-Storage Modulus Analysis

폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체 필름의 기계적 물성인 저장탄성률을 측정하여 도 1에 나타내었다. 저장탄성률은 동적기계적 물성측정 장치(dynamic mechanical analyzer, DMA)를 사용하여 측정하였다. 도 1에 나타난 바와 같이, 폴리부틸렌 테레프탈레이트(PBT) 단독고분자의 저장탄성률(storage modulus)는 약 2.47 GPa인 반면, 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체의 경우 그래핀 함량이 증가함에 따라 복합체의 저장탄성률가 증가하였다. 그래핀 함량이 1.0 중량%(실시예 5)일 경우 복합체의 저장탄성률이 3.31 GPa로 약 34% 증가하였으며, 그래핀 함량 7.0 중량%(실시예 8)에서는 4.11 GPa으로 약 66% 향상된 기계적 물성을 보였다.
The storage modulus of mechanical properties of the polybutylene terephthalate / graphene (PBT / 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 polybutylene terephthalate (PBT) homopolymer is about 2.47 GPa, whereas the graphene content is in the case of the polybutylene terephthalate / graphene (PBT / graphene) composite. With this increase, the storage modulus of the composite increased. When the graphene content is 1.0% by weight (Example 5), the storage modulus of the composite is increased by about 34% to 3.31 GPa. In the graphene content of 7.0% by weight (Example 8), by about 4.11 GPa, the mechanical properties are improved by about 66%. Seemed.

시험예 2-열안정성 측정Test Example 2-Measurement of Thermal Stability

폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체의 열안정성을 측정하여 도 2 및 표 2에 나타내었다. 열안정성 측정은 열중량분석기(thermogravimetric analyzer, TGA)를 이용하여 질소(도 2a) 및 산소(도 2b) 존재 하에서 실험하였다. 도 2와 표 2에 나타난 바와 같이, PBT 단독고분자는 각각 질소와 산소 기류조건에서 443.8℃와 416.0℃에서 30%의 중량 감소를 나타내었다. 하지만 1.0 중량%의 비교적 적은 그래핀(graphene) 함량을 갖는 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체(실시예 5)의 경우 30%의 중량 감소가 일어나는 온도는 질소와 산소 기류조건에서 각각 PBT 단독고분자보다 약 1℃와 6℃이상 높았다. 7 중량%의 그래핀을 함유한 복합체(실시예 8)의 경우는 질소와 산소 조건에서 PBT 단독고분자보다 각각 2℃와 13℃정도 높은 온도에서 30%의 중량감소가 일어났다.The thermal stability of the polybutylene terephthalate / graphene (PBT / graphene) composite was measured and shown in Figure 2 and Table 2. Thermostability measurements were performed in the presence of nitrogen (FIG. 2A) and oxygen (FIG. 2B) using a thermogravimetric analyzer (TGA). As shown in FIG. 2 and Table 2, the PBT homopolymer showed a weight loss of 30% at 443.8 ° C and 416.0 ° C under nitrogen and oxygen airflow conditions, respectively. However, in the case of polybutylene terephthalate / graphene (PBT / graphene) composite (Example 5) having a relatively low graphene content of 1.0% by weight, the temperature at which a weight loss of 30% occurs occurs under nitrogen and oxygen airflow conditions. Were about 1 ℃ and 6 ℃ higher than PBT single polymer, respectively. In the case of the composite containing 7% by weight of graphene (Example 8), a weight loss of 30% occurred at temperatures of about 2 ° C. and 13 ° C. higher than the PBT single polymer under nitrogen and oxygen conditions, respectively.

No.No. 그래핀 (중량%)Graphene (wt%) 30%의 중량감소가 일어나는 열분해온도, T30% (℃)Pyrolysis temperature with 30% weight loss, T 30% (℃) 질소(N2) 조건Nitrogen (N 2 ) Condition 산소(O2) 조건Oxygen (O 2 ) Conditions 실시예1Example 1 0.10.1 443.8443.8 416.0416.0 실시예2Example 2 0.30.3 443.6443.6 416.2416.2 실시예3Example 3 0.50.5 443.8443.8 419.5419.5 실시예4Example 4 0.70.7 444.0444.0 418.7418.7 실시예5Example 5 1.01.0 444.2444.2 421.7421.7 실시예6Example 6 3.03.0 444.2444.2 426.0426.0 실시예7Example 7 5.05.0 445.0445.0 426.5426.5 실시예8Example 8 7.07.0 445.7445.7 428.1428.1 비교예1Comparative Example 1 0.00.0 443.6443.6 415.4415.4

시험예 3 - 전기전도성 측정Test Example 3-Conductivity Measurement

폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체의 전기저항을 측정하여 도 3에 나타내었다. 복합체의 전기저항은 고저항 측정기를 이용하여 측정하였다. 도 3에 나타낸 바와 같이, PBT 단독고분자 필름은 ~1016 Ωcm 정도의 높은 전기저항값을 나타낸다. 하지만 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체 필름의 경우 그래핀 함량에 3~5 중량% 사이에서 급격하게 낮은 전기저항값을 나타내며, 그래핀 함량이 7 중량%일 경우(실시예 7)에는 ~106 Ωcm의 낮은 전기저항을 나타낸다. The electrical resistance of the polybutylene terephthalate / graphene (PBT / graphene) composite was measured and shown in FIG. 3. The electrical resistance of the composite was measured using a high resistance meter. As shown in Fig. 3, the PBT homopolymer film exhibits a high electrical resistance value of about 10 < 16 > However, in the case of polybutylene terephthalate / graphene (PBT / graphene) composite film, the graphene content shows a sharply low electrical resistance value between 3 to 5 wt%, and the graphene content is 7 wt% (Example 7) shows a low electrical resistance of ~ 10 6 dBm.

본 발명에서 제시하는 방법에 따라 제조된 폴리부틸렌 테레프탈레이트/그래핀(PBT/graphene) 복합체는 상기 시험예의 결과로부터 입증되듯이 기존의 폴리부틸렌 테레프탈레이트 단독고분자보다 우수한 기계적 물성, 열안정성, 전기전도성을 가진다. 따라서 필름, 섬유, 플라스틱 등 다양한 분야에서 유용하게 적용될 수 있다. Polybutylene terephthalate / graphene (PBT / graphene) composite prepared according to the method proposed in the present invention has excellent mechanical properties, thermal stability, It has electrical conductivity. Therefore, it can be usefully applied in various fields such as film, fiber, plastic.

Claims (5)

그래핀 및 폴리부틸렌 테레프탈레이트를 용융혼합 또는 용액혼합하여 폴리부틸렌 테레프탈레이트/그래핀 복합체를 제조하는 방법.Method for preparing a polybutylene terephthalate / graphene composite by melt mixing or solution mixture of graphene and polybutylene terephthalate. 청구항 1에 있어서,
상기 복합체에서 그래핀 함량은 복합체 총중량대비 0.01~50.0중량%인 것을 특징으로 하는 폴리부틸렌 테레프탈레이트/그래핀 복합체의 제조방법.The method according to claim 1,
Graphene content in the composite is a method for producing a polybutylene terephthalate / graphene composite, characterized in that 0.01 to 50.0% by weight relative to the total weight of the composite. 청구항 1에서 있어서,
상기 용융혼합은 220 내지 300 ℃의 온도에서 실시하는 것을 특징으로 하는 폴리부틸렌 테레프탈레이트/그래핀 복합체의 제조방법. The method according to claim 1,
The melt mixing is a method for producing a polybutylene terephthalate / graphene composite, characterized in that carried out at a temperature of 220 to 300 ℃. 청구항 1에 있어서,
상기 용액혼합은 20~150 ℃의 온도에서 페놀， o-클로로페놀， m-클로로페놀， 니트로벤젠， 페놀 및 사염화에탄으로 이루어진 군에서 선택된 적어도 1종의 용매를 이용하여 실시하는 것을 특징으로 하는 폴리부틸렌 테레프탈레이트/그래핀 복합체의 제조방법.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 butylene terephthalate / graphene composite. 청구항 1의 방법으로 제조된 폴리부틸렌 테레프탈레이트/그래핀 복합체를 포함하는 섬유, 필름 또는 플라스틱 제품.Fiber, film or plastic article comprising the polybutylene terephthalate / graphene composite prepared by the method of claim 1.
KR1020110030594A 2011-04-04 2011-04-04 Poly(butylene terephthalate)/Graphene Composites and Method for Preparing the Same KR101234258B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020110030594A KR101234258B1 (en) 2011-04-04 2011-04-04 Poly(butylene terephthalate)/Graphene Composites and Method for Preparing the Same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020110030594A KR101234258B1 (en) 2011-04-04 2011-04-04 Poly(butylene terephthalate)/Graphene Composites and Method for Preparing the Same

Publications (2)

Publication Number Publication Date
KR20120112967A true KR20120112967A (en) 2012-10-12
KR101234258B1 KR101234258B1 (en) 2013-02-18

Family

ID=47282680

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020110030594A KR101234258B1 (en) 2011-04-04 2011-04-04 Poly(butylene terephthalate)/Graphene Composites and Method for Preparing the Same

Country Status (1)

Country Link
KR (1) KR101234258B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105331058A (en) * 2015-11-17 2016-02-17 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing conductive polyester master batch with in-situ polymerization method
CN107129601A (en) * 2017-06-09 2017-09-05 深圳领护运动防护科技有限公司 A kind of athletic protective vibration-absorptive material and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100384482B1 (en) * 2000-07-26 2003-05-22 주식회사 엘지생명과학 Growth promoting composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100031981A (en) * 2008-09-17 2010-03-25 엔바로테크 주식회사 A composite of graphene and polymer and a method for preparation thereof
KR101131964B1 (en) * 2009-07-06 2012-03-29 (주)삼박 Thermal conductive resin and LED heat sink, LED lighting case and SMPS case comprising same
KR20110059130A (en) * 2009-11-27 2011-06-02 연세대학교 산학협력단 Composite composition and bipolar plate for fuel cell using the same
KR101021805B1 (en) * 2010-07-21 2011-03-17 권원현 Method for manufacturing conductive polymer compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105331058A (en) * 2015-11-17 2016-02-17 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing conductive polyester master batch with in-situ polymerization method
CN107129601A (en) * 2017-06-09 2017-09-05 深圳领护运动防护科技有限公司 A kind of athletic protective vibration-absorptive material and preparation method thereof

Also Published As

Publication number Publication date
KR101234258B1 (en) 2013-02-18

Similar Documents

Publication Publication Date Title
US9017805B2 (en) Polyimide-graphene composite material and method for preparing same
CN105177745A (en) Novel electromagnetic shielding nanocarbon conductive fibrous material and preparation method thereof
CN103710790A (en) Antistatic, antibacterial and graphene-reinforced composite polyester fiber and preparation method thereof
Khan et al. Reinforcement effect of acid modified nanodiamond in epoxy matrix for enhanced mechanical and electromagnetic properties
KR101279017B1 (en) Cellulose derivatives/Graphene Composites and Method for Preparing the Same
KR102125401B1 (en) Method for preparing carbon nano materials/PEDOT:PSS hybrid conductive polymer based on In-situ process, hybrid conductive polymer made therefrom and anti-static coating agent using the same
KR101234258B1 (en) Poly(butylene terephthalate)/Graphene Composites and Method for Preparing the Same
CN114957855B (en) Wave-absorbing heat-conducting thermoplastic composite material and preparation method thereof
KR101093056B1 (en) Polytrimethylene terephthalate/Graphene Composites with Enhanced Mechanical Property and Electrical Conductivity and Method for Preparing the Same
CN103059345B (en) Composite flame retardant based on carbon microspheres and preparation method thereof
KR102180930B1 (en) Graphene oxide filler with flame retardant and compatibilizer, and polypropylene nanocomposite using the same
KR102198383B1 (en) Method for preparation of carbon-benzoxazine complex and its carbon-polymer composite material
CN108864622A (en) A kind of preparation method of polymer-based dielectric composite material
KR20170001340A (en) Electrically Conductive Polyetherimide Nanofibers and Method for Manufacturing the same
KR101234257B1 (en) Aramid/Graphene Composites and Method for Preparing the Same
KR20140108360A (en) Graphene-reinforced Poly(p-phenylene benzobisoxazole) composites and process for producing the same
KR101151737B1 (en) Method for preparating of chemically treated carbon nanotube/polyvinylidene fluoride nanocomposite
JPS63286437A (en) Fiber-resin composite composition
KR20050075858A (en) Synthesis of carbon nanotube/polyethyleneterephthalate composites with high elastic modulus, conductivity and electromagnetic interference shielding property
CN109575405B (en) Modified ultrahigh molecular weight polyethylene and preparation method thereof, and polyethylene composite material and preparation method thereof
CN115141439A (en) Foamed PVC composite material with electromagnetic shielding performance and preparation method and application thereof
KR101025681B1 (en) Barium titanate particles attached with polyimide precursor, a method for preparation thereof and a composition of barium titanate particles/polyimide complex prepared by using the same
CN106519668A (en) Method for preparing conductive polyamideimide composite material
CN108219270B (en) Antistatic PP modified material and preparation method thereof
CN115584059B (en) Preparation and application of intumescent halogen-free flame retardant

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20160212

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20180102

Year of fee payment: 6