WO2012081966A1 - Heat curable polymer matrix and method of preparation thereof - Google Patents

Heat curable polymer matrix and method of preparation thereof Download PDF

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Publication number
WO2012081966A1
WO2012081966A1 PCT/MY2011/000156 MY2011000156W WO2012081966A1 WO 2012081966 A1 WO2012081966 A1 WO 2012081966A1 MY 2011000156 W MY2011000156 W MY 2011000156W WO 2012081966 A1 WO2012081966 A1 WO 2012081966A1
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Prior art keywords
mgt
copolymer
diamine
polymer matrix
heat curable
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PCT/MY2011/000156
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French (fr)
Inventor
Rais Bin Ahmad Mohd
Yahya Rosiyah
Danial Azzahari Ahmad
Original Assignee
Mimos Berhad
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Publication date
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Publication of WO2012081966A1 publication Critical patent/WO2012081966A1/en

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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
    • C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen

Definitions

  • the present invention relates to heat curable polymer matrix and method for preparation of the same, more particularly to heat curable polymer matrix for use in fabrication of sensing electrode and solid-state reference electrode.
  • Membrane based chemical sensors deployed in harsh environment face serious problem of sensing membrane peeling that causes functional failure of the sensors.
  • Thermosetting polymers exist as viscous liquid prepolymer that irreversibly solidifies upon heat curing treatment. When cured this type of polymers give strong solid material with smooth mirror-like surface. It is ideally used as moulding resin to form a variety of shapes for mechanical purposes. However thermoset materials are not suitable to conduct electrical signal due to its high impedance - this property is unsuitable for use in chemical sensors.
  • a heat curable polymer matrix comprising;
  • MGT copolymer having reactive oxirane and tetrahydrofurfuryl groups to crosslink with diamine molecule and provides low impedance matrix
  • the polymer matrix comprises 40 to 99 percent MGT copolymer and 1 to 60 percent diamine crosslinker, both by weight.
  • the MGT copolymer is MGT 622 having 6 parts of methyl methacrylate, 2 parts of glycidyl methacrylate and 2 parts of tetrahydrofurfuryl acrylate, by volume.
  • the MGT copolymer is MGT 532 having 5 parts of methyl methacrylate, 3 parts of glycidyl methacrylate and 2 parts of tetrahydrofurfuryl acrylate, by volume.
  • a method of preparing low impedance heat curable polymer matrix comprising;
  • step (d) washing the heat cured polymer of step (c) with polar organic solvent;
  • the purifying step (a) further comprising;
  • the curing step (c) is at uniform temperature of 70 to 150 °C.
  • step (b), (c) and (e) are conducted under inert ambient of argon or nitrogen.
  • th c diamine crosslinker molecule has the following structure:
  • the aromatic diamine crosslinker molecule has the following
  • the aromatic diamine crosslinker molecule has the following
  • alkyl diamine crosslinker molecule has the following structure:
  • n 0, 1, 2, 3 or 4
  • thermoforming the heat curable MGT copolymer-diamine product of the above method for the fabrication of sensing electrodes as polymer matrix.
  • thermoforming the heat curable MGT copolymer-diamine product of the above method for the fabrication of solid-state reference electrodes as polymer matrix.
  • the present invention provides low impedance binding matrix suitable for applications in polymeric sensing membrane, cast or printed electrochemical transducer layer, polymeric binder in solid state reference electrode, immobilization of sensing components in Conductometric channel, and screen printing paste for sensor fabrication and packaging.
  • Figure 1 illustrates MGT copolymer crosslinked with meta-xylylenediamine
  • Figure 3 illustrates preferred diamine crosslinkers
  • Figure 4 illustrates MGT 622 crosslinked with meta-xylylenediamine
  • Figure 5 illustrates MGT 532 copolymer crosslinked with meta-xylylenediamine Detailed description of the present invention
  • the present invention relates to heat curable polymer matrix for method for preparation of the same.
  • the heat curable polymer matrix as shown in Figure 1 is usable for the fabrication of solid state sensing electrodes for detection of low quantities or trace-levels of bio-chemical species.
  • the heat curable polymer matrix as shown in Figure 1 is high polarity MGT copolymer (4) based on methyl methacrylate (1), glycidyl methacrylate (2) and tetrahydrofurfuryl acrylate (3) monomers has been prepared earlier.
  • the high polarity MGT copolymer (4) offers economic benefits of low costs of the monomers, the purification method is simple.
  • temperature between 80 to 150 °C and curing time of less than one hour can give practical throughput.
  • the copolymer, crosslinker and the homogenous mixture of the two components are preferably in liquid state, viscous gel or soft paste at room temperature or during prolonged storage temperature prior to heat treatment. This would allow ease of use and simple blending with active electrode components, without the use of additional toner or mechanical stirring.
  • the high polarity MGT copolymer (4) based on methyl methacrylate (1), glycidyl methacrylate (2) and tetrahydrofurfuryl acrylate (3) monomers allow fulfilling the above requirement with appropriate volume ratios of the monomers as well as proper choice of crosslinkers.
  • the MGT copolymers contain reactive oxirane group that can react with primary alkyl diamine or aromatic diamine as shown in Figure 3 thus irreversibly crosslinking the copolymer upon treatment of mild heating.
  • the primary diamines were purified by removing traces of water and acids and were freshly distilled over drying agents such as barium oxide or calcium hydride before use.
  • the heat curing treatment was conducted under continuous flow of argon or purified nitrogen blanket.
  • active sensing components can be blended using the disclosed heat curable polymer in tubular Teflon casing, and the robust sensor surface can be polished, together with the Teflon tubing, to expose fresh surface. This approach provides means of reusing the sensor and removing the worn surface due to fouling.
  • the primary diamine crosslinkers were first refluxed for 5 hours while magnetically stirred over calcium hydride with steady flow of blanket of argon or purified nitrogen gas.
  • the primary diamine crosslinkers were then dried over barium oxide or phosphorus pentoxide by magnetically stirring the mixture under argon or purified nitrogen gas for 1 hour before distillation under reduced pressure.
  • Proton Nuclear Magnetic Resonance (H NMR) of the diamine crosslinkers in deuterated chloroform were carried out to verify absence of proton peaks due to impurities.
  • H NMR Proton Nuclear Magnetic Resonance
  • the nitrogen dried MGT 622 copolymer (10 mg) was taken from the storage glass vial, weighed and transferred to a 2-cm diameter curved glass disc.
  • MGT532 m-Xylylenediamine Crosslinker

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention relates to heat curable polymer matrix and method for preparation of the same, more particularly to heat curable polymer matrix for use in polymeric sensing membrane, cast or printed electrochemical transducer layer, polymeric binder in solid state reference electrode, immobilization of sensing components in conductometric channel, and screen printing paste for sensor fabrication and packaging.

Description

HEAT CURABLE POLYMER MATRIX AND METHOD OF PREPARATION THEREOF
Field of the invention
The present invention relates to heat curable polymer matrix and method for preparation of the same, more particularly to heat curable polymer matrix for use in fabrication of sensing electrode and solid-state reference electrode.
Background of the invention
Membrane based chemical sensors deployed in harsh environment face serious problem of sensing membrane peeling that causes functional failure of the sensors.
Thermosetting polymers exist as viscous liquid prepolymer that irreversibly solidifies upon heat curing treatment. When cured this type of polymers give strong solid material with smooth mirror-like surface. It is ideally used as moulding resin to form a variety of shapes for mechanical purposes. However thermoset materials are not suitable to conduct electrical signal due to its high impedance - this property is unsuitable for use in chemical sensors.
If the impedance of the polymer matrix is too high or varies significantly from sensor to sensor it is virtually impossible to read the transducer signal or to use a single conversion code for all the sensors. This will make the conversion of the signal in millivolt or milliampere to analyte concentration too complicated because so many dedicated equations (codes) need to be used for each sensor.
Therefore, in view of the above problems, it is desirable to further develop an improved heat curable copolymer that can be cross linked upon mild heat treatment to afford low impedance matrix for chemical sensor applications. Summary of the invention
According to a first aspect of the present invention, there is provided a heat curable polymer matrix comprising;
MGT copolymer having reactive oxirane and tetrahydrofurfuryl groups to crosslink with diamine molecule and provides low impedance matrix;
diamine crosslinker to crosslink between the MGT copolymer strands; and organic chemicals as diluents in preparing the MGT-diamine ink or paste
Preferably, the polymer matrix comprises 40 to 99 percent MGT copolymer and 1 to 60 percent diamine crosslinker, both by weight.
Preferably, the MGT copolymer is MGT 622 having 6 parts of methyl methacrylate, 2 parts of glycidyl methacrylate and 2 parts of tetrahydrofurfuryl acrylate, by volume.
Preferably, the MGT copolymer is MGT 532 having 5 parts of methyl methacrylate, 3 parts of glycidyl methacrylate and 2 parts of tetrahydrofurfuryl acrylate, by volume. According to a second aspect of the invention, there is provided a method of preparing low impedance heat curable polymer matrix comprising;
(a) purifying aromatic and alkyl primary diamine crosslinkers;
(b) adding a volume ratio of MGT copolymer and the diamine crosslinker into a reaction vessel while stirring the mixture;
(c) curing the MGT copolymer-diamine crosslinker;
(d) washing the heat cured polymer of step (c) with polar organic solvent; and
(e) drying the crosslinked polymer. Accordingly, the purifying step (a) further comprising;
(a) diluting the diamine crosslinkers with polar organic solvent
(b) washing with alkaline and brine solutions, (c) drying with sodium sulfate, magnesium sulfate and overnight stirring over barium oxide or calcium hydride; and
(d) distillation under reduced pressure.
Preferably, the curing step (c) is at uniform temperature of 70 to 150 °C.
Also preferably, step (b), (c) and (e) are conducted under inert ambient of argon or nitrogen.
Accordingly, th c diamine crosslinker molecule has the following structure:
Figure imgf000005_0001
Accordingly, the aromatic diamine crosslinker molecule has the following
structure:
Figure imgf000005_0002
Accordingly, the aromatic diamine crosslinker molecule has the following
structure:
Figure imgf000005_0003
Accordingly, the alkyl diamine crosslinker molecule has the following structure:
H2N NH2
where n = 0, 1, 2, 3 or 4
According to a third aspect of the present invention, there is provided use of the heat curable MGT copolymer-diamine product of the above method for the fabrication of sensing electrodes as polymer matrix. According to a fourth aspect of the present invention, there is provided use of the heat curable MGT copolymer-diamine product of the above method for the fabrication of solid-state reference electrodes as polymer matrix.
Advantageously, the present invention provides low impedance binding matrix suitable for applications in polymeric sensing membrane, cast or printed electrochemical transducer layer, polymeric binder in solid state reference electrode, immobilization of sensing components in Conductometric channel, and screen printing paste for sensor fabrication and packaging.
Brief description of the drawings
Figure 1 : illustrates MGT copolymer crosslinked with meta-xylylenediamine
Figure 2 : illustrates MGT copolymer
Figure 3 : illustrates preferred diamine crosslinkers
Figure 4 : illustrates MGT 622 crosslinked with meta-xylylenediamine
Figure 5 : illustrates MGT 532 copolymer crosslinked with meta-xylylenediamine Detailed description of the present invention
The present invention relates to heat curable polymer matrix for method for preparation of the same. The heat curable polymer matrix as shown in Figure 1 is usable for the fabrication of solid state sensing electrodes for detection of low quantities or trace-levels of bio-chemical species.
The heat curable polymer matrix as shown in Figure 1 is high polarity MGT copolymer (4) based on methyl methacrylate (1), glycidyl methacrylate (2) and tetrahydrofurfuryl acrylate (3) monomers has been prepared earlier. The high polarity MGT copolymer (4) offers economic benefits of low costs of the monomers, the purification method is simple.
For manufacturing purposes temperature between 80 to 150 °C and curing time of less than one hour can give practical throughput.
Yet another requirement is the form and texture of the MGT copolymer and crosslinkers. The copolymer, crosslinker and the homogenous mixture of the two components are preferably in liquid state, viscous gel or soft paste at room temperature or during prolonged storage temperature prior to heat treatment. This would allow ease of use and simple blending with active electrode components, without the use of additional toner or mechanical stirring.
The high polarity MGT copolymer (4) based on methyl methacrylate (1), glycidyl methacrylate (2) and tetrahydrofurfuryl acrylate (3) monomers allow fulfilling the above requirement with appropriate volume ratios of the monomers as well as proper choice of crosslinkers.
The MGT copolymers contain reactive oxirane group that can react with primary alkyl diamine or aromatic diamine as shown in Figure 3 thus irreversibly crosslinking the copolymer upon treatment of mild heating. In order to ensure good reactivity of the crosslinkers, the primary diamines were purified by removing traces of water and acids and were freshly distilled over drying agents such as barium oxide or calcium hydride before use. Moreover, the heat curing treatment was conducted under continuous flow of argon or purified nitrogen blanket.
In bio-chemical sensor application active sensing components can be blended using the disclosed heat curable polymer in tubular Teflon casing, and the robust sensor surface can be polished, together with the Teflon tubing, to expose fresh surface. This approach provides means of reusing the sensor and removing the worn surface due to fouling.
The invention now being generally described, the same will be better understood by reference to the following detailed examples which are provided for purposes of illustration only and are not to be limiting of the invention unless so specified.
Example 1
Purification of Primary Diamine Crosslinkers
All chemicals were procured from Sigma-Aldrich Chemical Company and were subject o the following purification method. The primary diamine crosslinkers were first refluxed for 5 hours while magnetically stirred over calcium hydride with steady flow of blanket of argon or purified nitrogen gas. The primary diamine crosslinkers were then dried over barium oxide or phosphorus pentoxide by magnetically stirring the mixture under argon or purified nitrogen gas for 1 hour before distillation under reduced pressure. Proton Nuclear Magnetic Resonance (H NMR) of the diamine crosslinkers in deuterated chloroform were carried out to verify absence of proton peaks due to impurities. Example 2
Preparation of Heat Curable Methyl Methacrylate-Tetrahydrofurfuryl Acrylate Copolymer
(MGT622) and m-Xylylenediamine Crosslinker
Freshly prepared MGT 622 copolymer with purified methyl methacrylate (6 mL, 1), 2 mL of glycidyl methacrylate (2) and 2 mL of tetrahydrofurfuryl acrylate (3) monomers and 2mg of benzoyl peroxide affords viscous slightly yellowish liquid. The use of extra amounts of benzoyl peroxides tends to give solid copolymer in the form of soft gel that is not suitable for thermoset application. The nitrogen dried MGT 622 copolymer (10 mg) was taken from the storage glass vial, weighed and transferred to a 2-cm diameter curved glass disc. Purified and freshly distilled m-xylylenediamine (10 μΐ) was added to the MGT 622 copolymer and the two liquid components were mixed thoroughly with Teflon rod for 5 minutes under stream of purified nitrogen atmosphere. The mixture became thicker and appeared as more viscous or soft gel after mixing. The viscous mixture was treated with heating at 100 °C under nitrogen environment for 10 minutes. The m-xylylenediamine crosslinked MGT 622 appeared as hard white solid and slightly sticky upon touching with solid materials such as Teflon, plastic or metal spatula. The heat cured polymer matrix was washed with polar solvent preferably ethanol and dried in the oven at 100 °C under nitrogen environment for another 10 minutes. The washed and dried polymer matrix remained hard white solid but no longer sticking to spatula as shown in Figure 4.
Example 3
Preparation of Heat Curable Methyl Methacrylate-Tetrahydrofurfuryl Acrylate Copolymer
(MGT532) and m-Xylylenediamine Crosslinker Freshly prepared MGT532 copolymer with purified methyl methacrylate (5 mL, 1),
3mL of glycidyl methacrylate (2) and 2 mL of tetrahydrofurfuryl acrylate (3) monomers and 2mg of benzoyl peroxide affords viscous slightly yellowish liquid. The use of extra amounts of benzoyl peroxides tends to give solid copolymer in the form of soft gel that is not suitable for thermoset application. The nitrogen dried MGT532 copolymer (10 mg) was taken from the storage glass vial, weighed and transferred to a 2-cm diameter curved glass disc. Purified and freshly distilled m-xylylenediamine (10 μΐ) was added to the MGT532 copolymer and the two liquid components were mixed thoroughly with Teflon rod for 5 minutes under stream of purified nitrogen atmosphere. The mixture became thicker and appeared as more viscous or soft gel after mixing. The viscous mixture was treated with heating at 100 °C under nitrogen environment for 10 minutes. The m-xylylenediamine crosslinked MGT532 appeared as hard white solid. The heat cured polymer matrix was washed with polar solvent preferably ethanol and dried in the oven at 100 °C under nitrogen environment for another 10 minutes. The washed and dried polymer matrix afforded hard and shiny solid as shown in Figure 5.
The invention being thus described, it will be apparent that the same may be varied in many ways. Such variations are to be regarded as within the scope of the invention, and all such modifications as would be apparent to one skilled in the art are intended to be within the scope of the following claims.

Claims

Claims
1. Heat curable polymer matrix comprising;
MGT copolymer having reactive oxirane and tetrahydrofurfuryl groups to crosslink with diamine molecule and provides low impedance matrix;
diamine crosslinker to crosslink between the MGT copolymer strands; and organic chemicals as diluents in preparing the MGT-diamine ink or paste
2. The heat curable polymer matrix according to Claim 1, wherein the polymer matrix comprises 40 to 99 percent MGT copolymer and 1 to 60 percent diamine crosslinker, both by weight.
3. The heat curable polymer matrix according to Claim 1, wherein the MGT copolymer is MGT 622 having 6 parts of methyl methacrylate, 2 parts of glycidyl methacrylate and 2 parts of tetrahydrofurfuryl acrylate, by volume.
4. The heat curable polymer matrix according to Claim 1, wherein the MGT copolymer is MGT 532 having 5 parts of methyl methacrylate, 3 parts of glycidyl methacrylate and 2 parts of tetrahydrofurfuryl acrylate, by volume.
5. A method of preparing low impedance heat curable polymer matrix comprising;
(a) purifying aromatic and alkyl primary diamine crosslinkers;
(b) adding a volume ratio of MGT copolymer and the diamine crosslinker into a reaction vessel while stirring the mixture;
(c) curing the MGT copolymer-diamine crosslinker;
(d) washing the heat cured polymer of step (c) with polar organic solvent; and
(e) drying the crosslinked polymer.
6. A method according to Claim 5, characterized in that step (a) further comprising;
(a) diluting the diamine crosslinkers with polar organic solvent;
(b) washing with saturated alkaline and brine solutions, (c) drying with sodium sulfate, magnesium sulfate and overnight stirring over barium oxide or calcium hydride; and
(d) distillation under reduced pressure.
7. A method according to Claim 5, characterized in that the curing step (c) is at uniform temperature of 70 to 150 °C.
8. A method according to Claim 5 or Claim 7, characterized in that step (b),(c) and (e) are conducted under inert ambient of argon or nitrogen.
9. A method according to Claim 5 or Claim 6 wherein the diamine crossiinker is at least one or combination of the following molecules; meta-xylylenediamine, para
xylylenediamine, para-phenylenediamine, 1,3-diaminopropane and 1,4-diaminobutane.
10. Use of the heat curable MGT copolymer-diamine according to Claim 5 for at least one of the following applications; polymeric sensing membrane, cast or printed electrochemical transducer layer, polymeric binder in solid state reference electrode, immobilization of sensing components in Conductometric channel, screen printing paste for sensor fabrication and packaging.
PCT/MY2011/000156 2010-12-13 2011-06-23 Heat curable polymer matrix and method of preparation thereof WO2012081966A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4068061A (en) * 1975-03-20 1978-01-10 Mitsui Toatsu Chemicals Inc. Process for the continuous preparation of reactive copolymers
JPH0593047A (en) * 1991-03-29 1993-04-16 Osaka Organic Chem Ind Ltd Thermosetting polymer composition
EP0999436A1 (en) * 1998-05-22 2000-05-10 Matsushita Electric Industrial Co., Ltd. Temperature sensor and electronic apparatus containing the same
WO2006091088A1 (en) * 2005-02-25 2006-08-31 National Starch & Chemical B.V. Pressure sensitive adhesive composition as well as a method of applying it and a method for the preparation thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4068061A (en) * 1975-03-20 1978-01-10 Mitsui Toatsu Chemicals Inc. Process for the continuous preparation of reactive copolymers
JPH0593047A (en) * 1991-03-29 1993-04-16 Osaka Organic Chem Ind Ltd Thermosetting polymer composition
EP0999436A1 (en) * 1998-05-22 2000-05-10 Matsushita Electric Industrial Co., Ltd. Temperature sensor and electronic apparatus containing the same
WO2006091088A1 (en) * 2005-02-25 2006-08-31 National Starch & Chemical B.V. Pressure sensitive adhesive composition as well as a method of applying it and a method for the preparation thereof

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