WO2008080201A1 - Copolymer of methyl methacrylate and anthracenyl methacrylate - Google Patents
Copolymer of methyl methacrylate and anthracenyl methacrylate Download PDFInfo
- Publication number
- WO2008080201A1 WO2008080201A1 PCT/BR2007/000007 BR2007000007W WO2008080201A1 WO 2008080201 A1 WO2008080201 A1 WO 2008080201A1 BR 2007000007 W BR2007000007 W BR 2007000007W WO 2008080201 A1 WO2008080201 A1 WO 2008080201A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- methacrylate
- copolymer
- anthracenyl
- methyl methacrylate
- mdcpac
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
Definitions
- the present patent application for invention has for object an innovative synthesis of a derived of a methyl polymetacrilate.
- a polymer has a methyl methacrylate backbone with pendent chromophoric units derived of anthracene, to which an original constructive disposition was given in order to improve usage and performance in comparison to other models available at the market. Therefore, this polymer product has been especially projected and developed in order to be uncomplicated and to offer great advantages in its use and production.
- conjugated polymers make possible the combination of the inherent characteristics to the polymeric systems and the properties of semiconductors in general, or even those of metals, in specific cases. Therefore, they are especially suitable to be used in the production of several electronic and optoelectronic devices such as transistors and light emitter diodes.
- this product was designed seeking a minimum number of stages, conveniently configured and arranged to allow the copolymer to carry out its functions with efficiency and unparalleled versatility, without the inconveniences already mentioned.
- This product is an innovative and practical copolymer with all desired qualities, projected and developed according to the most modern techniques. It can be used for different purposes including the industrial ones.
- the innovative structure of this material provides unique properties such as resistance and conductivity combined with the attributes of elastomers, for instance, flexibility, solubility and mechanical resistance. It has an excellent functionality and possesses great durability.
- the problem related to the size of the effective conjugation can be solved through the separation of the exciton units in the main chain of the polymer, by the incorporation of no conjugated spacers to its backbone.
- the confinement of the conjugation was obtained by attaching pendent anthracene chromophoric units to the non-conjugated polymeric main chain.
- the distance among the chromophoric units can be altered. Also, an interaction among the chromophoric units can be make possible, depending solely on the distance that they are kept when placed on the non-conjugated polymer chain.
- the distance among the chromophoric units can be controlled, and so is the interaction among them. It was also determined that the degree of interaction among the chromophoric units is responsible for the variation in the optoeletronic and mechanic behavior of the material.
- the polymer light emission can shift to other regions of the spectrum, what can be achieved, for instance, through the use of naphtyl methacrylate, estilbenyl methacrylate and others compounds.
- a methyl methacrylate and anthracenyl methacrylate copolymer was synthesized via free radical route.
- This copolymer has intrinsic homogeneity and its chromophores can recrystallized, which are desirable traits that the copolymers obtained with the incorporation of chromophores into an inert matrix do not own.
- this product has an extremely simple synthesis, is easily obtained and offers excellent practical and functional qualities that are innovative when compared to the other existent models.
- FIG. 1 Chemical representation of MDCPAC.
- FIG. 2 Graphic representation of the absorption spectrum of MDCPAC using chloroform and dichloromethane as solvents.
- FIG. 3 Graphic representation of the curve of calibration of MDCPA.
- FIG 4 Graphic representation of I(V) profiles - AI/MDCPAC (5:1)/AI.
- FIG 5 Graphic representation of I(V) profiles -AI/MDCPAC (5:1)/AI.
- FIG 6 Graphic representation of I(V) profiles - AI/MDCPAC (5:1)/AI.
- FIG 7 Graphic representation of I(V) profiles - AI/MDCPAC (6:1)/AI.
- FIG 8 Graphic representation of I(V) profiles - AI/MDCPAC (6:1)/AI.
- FIG 9 Graphic representation of I(V) profiles -AI/MDCPAC (10:1)/AI.
- FIG 10 Graphic representation of I(V) profiles - AI/MDCPAC (10:1)/AI.
- FIG 11 Graphic representation of I(V) profiles - AI/MDCPAC (10:1)/AI.
- FIG 12 Graphic representation of I(V) profiles of an Au/SAN/MDCPAC/PEDOT/AI sandwich.
- FIG 13 Graphic representation of I(V) profiles of Au / SPAN / MDCPAC / AL.
- FIG 14 Graphic representation of I(V) profiles of Au/SPAN/MDCPAC/AL
- the solution should be stirred and refluxed for some hours. Then, the reaction should be neutralized and the resulting solution, filtered. Next, the mixture is poured in methanol. The necessary amount of methanol will be 10 times the amount of methanol initially used. The resulting precipitate should be collect and dried in vacuum.
- VIS spectrum VIS spectrum. Solutions with distinct concentration of the anthracenyl methacrylate monomer were utilized in order to establish a calibration curve. Then, a UV-VIS spectrum of a 1g of MDCPAC copolymer solution was obtained in chloroform and presented an anthracene band with a peak at 375 nm. The solution UV-VIS spectrum was compared to the calibration curve. The absorption spectrums of films obtained from a solution of MDCPAC in chloroform and in dichloromethane are depicted in fig. 2.
- the curve of calibration from the MDCPA is depicted in fig. 3.
- the MDCPAC is soluble in both solvents. Although the absorption spectra of both solutions do not exhibit any difference, the electric characteristics of the solutions are different.
- the I(V) profile of an Au/SPAN/MDCPAC/PEDOT/AI sandwich is depicted in fig 12
- the fig. 13 and fig. 14 show the I (V) profile of an Au/SPAN/MDCPAC/PEDOT/AI sandwich
Abstract
The Copolymer of Methyl Methacrylate and AntHracenyl Methacrylate is the object of an innovative synthesis of a derived of a methyl polymethacrylate, with pendent chromophoric units derived of anthracene. It is a polymeric compound, with elastomeric characteristics and differential traits, such as resistance and conductivity.
Description
Copolymer of Methyl Methacrylate and Anthracenyl Methacrylate
FIELD OF THE INVENTION
The present patent application for invention has for object an innovative synthesis of a derived of a methyl polymetacrilate. The subject matter, a polymer, has a methyl methacrylate backbone with pendent chromophoric units derived of anthracene, to which an original constructive disposition was given in order to improve usage and performance in comparison to other models available at the market. Therefore, this polymer product has been especially projected and developed in order to be uncomplicated and to offer great advantages in its use and production.
It is also an objective of this request, to present a methyl methacrylate and anthracenyl methacrylate copolymer with low industrial costs but with desirable traits such as robustness, safety and great applicability. It will be an additional option in the polymer market, offering countless possibilities and benefits to users in comparison to the other available products, thus, becoming a model of great acceptance in the consumer market.
BACKGROUND OF THE INVENTION
As it is known, conjugated polymers make possible the combination of the inherent characteristics to the polymeric systems and the properties of semiconductors in general, or even those of metals, in specific cases. Therefore, they are especially suitable to be used in the production of several electronic and optoelectronic devices such as transistors and light emitter diodes.
DEFICIENCIES OF THE TECHNIQUE
Since 1990, when PPVs electro luminescent characteristics were first established by de Cambridge Group, in England, a great deal of effort was made world wide in order to develop new electroluminescent polymers and understand the photophysics phenomena related to light emission. The main advantage of
PPV on the totally conjugated polymers (polyphenylene and polyacethylene) is its solubility. The PPVs synthesis via a non-conjugated polymer precursor route is what differentiates this polymer from its counterparts. The principal flaw of this compound, that still remains, is the impossibility to determine the effective conjugation.
SUMMARY OF THE INVENTION
Extensive research and studies were carried out in search for the answer to those inconveniences. The synthesis of a methyl methacrylate and anthracenyl methacrylate polymer through a free radical reaction in solution solved some of these problems.
Therefore, this product was designed seeking a minimum number of stages, conveniently configured and arranged to allow the copolymer to carry out its functions with efficiency and unparalleled versatility, without the inconveniences already mentioned.
This product is an innovative and practical copolymer with all desired qualities, projected and developed according to the most modern techniques. It can be used for different purposes including the industrial ones.
The innovative structure of this material provides unique properties such as resistance and conductivity combined with the attributes of elastomers, for instance, flexibility, solubility and mechanical resistance. It has an excellent functionality and possesses great durability.
The problem related to the size of the effective conjugation can be solved through the separation of the exciton units in the main chain of the polymer, by the incorporation of no conjugated spacers to its backbone. In the present case, the confinement of the conjugation was obtained by attaching pendent anthracene chromophoric units to the non-conjugated polymeric main chain.
Through this technique, the distance among the chromophoric units can be altered. Also, an interaction among the chromophoric units can be make possible, depending solely on the distance that they are kept when placed on the non-conjugated polymer chain.
With all the previous concepts in mind, a derived of methyl
polymethacrylate was synthesized with pendent chromophoric units derived of anthracene attached to the main chain of methyl methacrylate.
Through this synthetic route the distance among the chromophoric units can be controlled, and so is the interaction among them. It was also determined that the degree of interaction among the chromophoric units is responsible for the variation in the optoeletronic and mechanic behavior of the material. Through of changes in the synthetic route and modifications in the structure of the chromophoric monomer the polymer light emission can shift to other regions of the spectrum, what can be achieved, for instance, through the use of naphtyl methacrylate, estilbenyl methacrylate and others compounds.
A methyl methacrylate and anthracenyl methacrylate copolymer was synthesized via free radical route.
This copolymer has intrinsic homogeneity and its chromophores can recrystallized, which are desirable traits that the copolymers obtained with the incorporation of chromophores into an inert matrix do not own.
Hence, this product has an extremely simple synthesis, is easily obtained and offers excellent practical and functional qualities that are innovative when compared to the other existent models.
BRIEF DESCRIPTIONS OF THE DRAWINGS:
FIG. 1 - Chemical representation of MDCPAC.
FIG. 2 - Graphic representation of the absorption spectrum of MDCPAC using chloroform and dichloromethane as solvents.
FIG. 3 - Graphic representation of the curve of calibration of MDCPA.
FIG 4 - Graphic representation of I(V) profiles - AI/MDCPAC (5:1)/AI.
FIG 5 - Graphic representation of I(V) profiles -AI/MDCPAC (5:1)/AI.
FIG 6 - Graphic representation of I(V) profiles - AI/MDCPAC (5:1)/AI. FIG 7 - Graphic representation of I(V) profiles - AI/MDCPAC (6:1)/AI.
FIG 8 - Graphic representation of I(V) profiles - AI/MDCPAC (6:1)/AI.
FIG 9 - Graphic representation of I(V) profiles -AI/MDCPAC (10:1)/AI.
FIG 10 - Graphic representation of I(V) profiles - AI/MDCPAC
(10:1)/AI.
FIG 11 - Graphic representation of I(V) profiles - AI/MDCPAC (10:1)/AI.
FIG 12 - Graphic representation of I(V) profiles of an Au/SAN/MDCPAC/PEDOT/AI sandwich.
FIG 13 - Graphic representation of I(V) profiles of Au / SPAN / MDCPAC / AL.
FIG 14 - Graphic representation of I(V) profiles of Au/SPAN/MDCPAC/AL
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A solution of anthracenyl methacrylate monomer and methyl methacrylate in toluene was stirred and heated to reflux. The benzoyl peroxide was used as initiator of polymerization. Through of changes in the charge of the monomers utilized in the synthesis, it has become possible to establish the concentration of anthracene in the compound.
The solution should be stirred and refluxed for some hours. Then, the reaction should be neutralized and the resulting solution, filtered. Next, the mixture is poured in methanol. The necessary amount of methanol will be 10 times the amount of methanol initially used. The resulting precipitate should be collect and dried in vacuum.
METHOD OF CALIBRATION
The chemical structure of the copolymer was confirmed through UV-
VIS spectrum. Solutions with distinct concentration of the anthracenyl methacrylate monomer were utilized in order to establish a calibration curve. Then, a UV-VIS spectrum of a 1g of MDCPAC copolymer solution was obtained in chloroform and presented an anthracene band with a peak at 375 nm. The solution UV-VIS spectrum was compared to the calibration curve. The absorption spectrums of films obtained from a solution of MDCPAC in chloroform and in
dichloromethane are depicted in fig. 2.
The curve of calibration from the MDCPA is depicted in fig. 3. The MDCPAC is soluble in both solvents. Although the absorption spectra of both solutions do not exhibit any difference, the electric characteristics of the solutions are different.
The graphs of the different concentrations are depicted from fig 4 through fig 11.
The I(V) profile of an Au/SPAN/MDCPAC/PEDOT/AI sandwich is depicted in fig 12 The fig. 13 and fig. 14 show the I (V) profile of an
Au/SPAN/MDCPAC/AL sandwich.
With Ovshinsky's observations in mind, symmetrical I(V) profiles graphs were selected. After a polarity reversal, it was possible to obtain a V(d) graph, that clearly demonstrated the space charge transport mechanism, indicative of the ON state and an OFF state with high density of traps.
Several film samples were originated by using solutions with different concentrations of anthracene, with 4:1 , 5:1 , 6:1 , 9:1, 20:1 anthracene to PMMA ratio. All the other variables such as thickness, mg/ml concentration and centrifugation velocity were held constant. However the films obtained have shown differences in appearance, texture and even in electric measurements. The electric measurements demonstrated differences in the charge transport means.
The films obtained in different temperatures and atmospheres (nitrogen and ambient) have demonstrated a difference in electric behavior. The phenomenon was baffling and morphological problems were deemed as the culprit. Still, a X-Ray diffraction spectrum and photos from the microscopy analysis have later demonstrated that the copolymer may have a semicrystalline structure after cure.
Therefore, the Copolymer of Methyl Methacrylate and Anthracenyl Methacrylate is a compound with outstanding qualities, great applicability that without any doubts justify the present patent application for invention.
Claims
What is claimed is:
1 The Copolymer of Methyl Methacrylate and AntHracenyl Methacrylate, characterized for the fact as being a solution of anthracenyl methacrylate monomer and methyl methacrylate in toluene. Benzoyl peroxide is the initiator of choice. The reflux temperature was reached with the help of silicone oil bath and a stirring hotplate. The concentration of anthracene is controlled by modifications in the charge of the monomers utilized in the synthesis. The solution should be stirred and refluxed for some hours. Then, the reaction should be neutralized and the resulting solution, filtered. Next, the mixture is poured in methanol. The necessary amount of methanol will be 10 times the amount of methanol initially used. The resulting precipitate should be collect and dried in vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/BR2007/000007 WO2008080201A1 (en) | 2007-01-05 | 2007-01-05 | Copolymer of methyl methacrylate and anthracenyl methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/BR2007/000007 WO2008080201A1 (en) | 2007-01-05 | 2007-01-05 | Copolymer of methyl methacrylate and anthracenyl methacrylate |
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| Publication Number | Publication Date |
|---|---|
| WO2008080201A1 true WO2008080201A1 (en) | 2008-07-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BR2007/000007 WO2008080201A1 (en) | 2007-01-05 | 2007-01-05 | Copolymer of methyl methacrylate and anthracenyl methacrylate |
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| WO (1) | WO2008080201A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886102A (en) * | 1996-06-11 | 1999-03-23 | Shipley Company, L.L.C. | Antireflective coating compositions |
| US6309790B1 (en) * | 1999-03-15 | 2001-10-30 | Hyundai Electronics Industries Co., Ltd. | Organic anti-reflective coating material and its preparation |
| US20010043992A1 (en) * | 1999-12-30 | 2001-11-22 | Min-Ho Jung | Organic polymer for anti-reflective coating layer and preparation thereof |
-
2007
- 2007-01-05 WO PCT/BR2007/000007 patent/WO2008080201A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886102A (en) * | 1996-06-11 | 1999-03-23 | Shipley Company, L.L.C. | Antireflective coating compositions |
| US6309790B1 (en) * | 1999-03-15 | 2001-10-30 | Hyundai Electronics Industries Co., Ltd. | Organic anti-reflective coating material and its preparation |
| US20010043992A1 (en) * | 1999-12-30 | 2001-11-22 | Min-Ho Jung | Organic polymer for anti-reflective coating layer and preparation thereof |
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