JPH06220219A - Polymer film for detection of chemical substance - Google Patents

Abstract

PURPOSE:To obtain a polymer film for detection which can detect distingushingly and safely a plurality of chemical substances by forming a film from a vinyl polymer having specified side chain groups. CONSTITUTION:This film for the detection of chemical substances is made from a homopolymer or copolymer comprising repeating units of the formula [wherein X is H, F, Cl, Br, CH3, CF3, CN, CH2 or CH3; R<1> is R<2> or Z-R<2>; Z is O, S, NH, NR<2>, (C=Y), (C=Y), (C=Y)-Y, Y-(C=Y), (SO2), Y'-(SO2) or the like; Y is O or S; Y' is O or NH; (n) is 0-20; and R<2> and R<2>, are each H, linear alkyl, branched alkyl, cycloalkyl, an unsaturated hydrocarbon group, aryl, a saturated or unsaturated heterocyclic ring or a substituted derivative thereof, provided that R<1> is not H, linear alkyl or branched alkyl].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to polymeric films useful for detecting and distinguishing the presence of gaseous or liquid chemicals. More specifically, the present invention relates to a polymer film capable of distinguishing between gasoline vapor and diesel oil vapor.

[0002]

2. Description of the Related Art At a gas station or the like, when refueling an automobile, an accident of replenishing the wrong kind of fuel often occurs. In order to prevent such an accident, it is strongly demanded to develop a fuel detection system.

As a detector for hydrocarbons such as automobile fuel, there is one that utilizes an electrical or optical detection method. One of the methods utilizing the electrical detection method is that the resistance value or the conductance value of the target substance is changed by the adsorption of the target substance on the semiconductor substance. For example, Japanese Patent Application Laid-Open No. 50-74485 discloses a gas detector in which a counter electrode is provided on an insulating substrate and a silicon rubber resistor containing conductive particles is applied between both electrodes. A detector similar to this is disclosed in JP-A-3-96.
846 and JP-A-3-96847 and German Patent Application Publication No. 2419069 (November 1975).
(6th of a month).

Brown et al. (Proceedings of the Jo) have disclosed a method of detecting a change in ionic conductivity due to adsorption of a gas using a solid electrolyte (ion exchange membrane) by polarography.
int Conferenceon sensing
of Environmental pollutan
ts, AIAA Paper 71-1114 (19)
71) 1-3). A similar method is described in British Patent Application Publication No. 2
It is also disclosed in 185579. In these methods, temperature control for detection is indispensable, and complicated equipment is required for the monitor.

Japanese Unexamined Patent Publication (Kokai) No. 63-285439 discloses a sensor for detecting leakage of hydrocarbons by changing impedance of a coaxial cable. Since these detectors electrically detect hydrocarbons, there is an inherent problem that the hydrocarbons may explode due to malfunctions due to disturbances such as inductive noise and ignition due to sparks.

On the other hand, as a method utilizing an optical detection method, for example, in Japanese Patent Laid-Open No. 55-156838,
A method is disclosed in which the presence of oil or the like is detected by the change in the refractive index due to the absorption of oil or the like by the porous body. A similar method with an optical fiber utilizing the capillarity is also described in EP-A-020282009. Japanese Unexamined Patent Publication No. 60-238746 discloses an apparatus for detecting the concentration of hydrocarbon gas from a change in infrared absorption by providing an infrared detector on the side surface of a duct through which the hydrocarbon gas flows. In addition, JP-A-62
No. 47531 discloses a sensor that utilizes the fact that the propagation mode of an optical fiber is converted into a leakage mode by the adhesion of oil or water on the surface of the optical fiber.

The various detectors described above can detect the presence or absence of hydrocarbons, but it is difficult to individually detect a plurality of types of hydrocarbons. In particular, it is very difficult to distinguish between gasoline and diesel oil, which have very similar properties, and to detect them. Further, hydrocarbons have a risk of ignition, but safety measures cannot be said to be sufficient in the above detectors. Moreover, the above detector requires a large device and is expensive.

[0008]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a detector that can detect a plurality of types of chemical substances safely and individually.

Another object of the present invention is to provide a detector which can detect gasoline and diesel oil safely and separately.

[0010]

[Means for Solving the Problems] In order to solve the above problems,
According to the present invention, a chemical substance detection film containing a vinyl polymer having a specific side chain group is provided. That is,
According to the present invention, there is provided a chemical substance detection film comprising a homopolymer or copolymer having the following repeating unit (I).

[Chemical 2] (In the formula, X is -H, -F, -Cl, -Br, -C.
H _3, represents -CF _3, -CN or -CH ₂ -CH _3, R ¹
Represents -R ² or -Z-R ^2, Z is -O -, - S
-, - NH -, - NR 2 '-, - (C = Y) -, - (C
= Y) -Y -, - Y- (C = Y) -, - (SO 2) -,
_{-Y '- (SO 2) -} , - (SO 2) -Y' -, - Y'-
_{(SO 2) -Y '-,} - NH- (C = O) -, - (C =
O) -NH -, - (C = O) -NR 2 '-, - Y'-
(C = Y) -Y'- or -O- (C = O) - ( CH 2) n
Represents-(C = O) -O-, and Y is the same or different O.
Or S, Y'represents the same or different O or NH, n represents an integer of 0 to 20, R ² and R ² 'represent the same or different hydrogen, linear alkyl group, branched It represents an alkyl group, a cycloalkyl group, an unsaturated hydrocarbon group, an aryl group, a saturated or unsaturated heterocycle, or a substitution product thereof. However, R ¹ is not hydrogen, a linear alkyl group, or a branched alkyl group. )

The inventors of the present invention have conducted diligent research to find out a chemical substance detection film capable of distinguishing and detecting a plurality of chemical substances, particularly organic solvents. As a result, a specific side chain group in a vinyl polymer has a molecular recognition function. The inventors have found that they have, and have completed the present invention. By utilizing the molecular recognition function of such a specific side chain group, different chemical substances such as cycloalkanes and benzenes and linear alkanes can be distinguished from each other. Similarly, hydrocarbons can be distinguished from alcohols, ketones, esters, ethers, and halogenated hydrocarbons.

The interaction of chemicals with the side groups of vinyl polymers occurs in the form of polymer swelling. That is, the presence or absence of a chemical substance can be detected by the swelling of the polymer, and the type of the chemical substance can be specified by the degree of the swelling of the polymer. For example, aromatic hydrocarbons and cycloalkanes interact with a vinyl polymer having an aromatic group and a branched or cycloalkyl group as a side chain group, rather than a vinyl polymer having a straight chain alkyl group as a side chain group. Is big. Therefore, the degree of swelling of the polymer will be different. As a result, in the present invention, it is possible to detect gasoline and diesel oil separately. According to the present invention, it could be sufficiently used in the temperature range of -40 to 80 ° C normally required for detecting gasoline and diesel oil. If a more detailed distinction of chemicals is desired, it is advantageous to use a film formed from two or more polymers with different side groups.

The chemical substance detection film of the present invention comprises a polymer having the above-mentioned repeating unit (I). That is, it may be a homopolymer consisting of only a single repeating unit (I), or a copolymer consisting of another repeating unit and the above repeating unit (I), or a copolymer consisting of two or more kinds of the above repeating unit (I). May be When the chemical substance detection film of the present invention is formed of a copolymer, the repeating units in the copolymer may have any arrangement. For example, the chemical sensing film of the present invention can be formed from random copolymers, alternating copolymers, block copolymers or graft copolymers.

A preferred polymer used in the present invention is, in the above-mentioned repeating unit (I), X represents H or CH ₃ , R ¹ represents a substituted or unsubstituted aryl group or —Z—R ² , and Z represents -O -, - (C = O ) -O- or -O- (C = O) - represents and R ² is a linear alkyl group, branched alkyl group, cycloalkyl group, unsaturated hydrocarbon group, It represents an aryl group, a saturated or unsaturated heterocycle, or a substitution product thereof.

The preferred polymers used in the present invention are polymethacrylic acid esters, polyacrylic acid esters and the like. The side chain group of the ester is preferably a linear or branched alkyl group or a cycloalkyl group, and the carbon number thereof is preferably 4 to 22.

Examples of preferable polymers in the present invention include the following. Poly (dodecyl methacrylate) Poly (isodecyl methacrylate) Poly (2-ethylhexyl methacrylate) Poly (2-ethylhexyl methacrylate-co-methyl methacrylate) Poly (2-ethylhexyl methacrylate-co-styrene) Poly (methacrylic acid Methyl-co-2-ethylhexyl acrylate) Poly (methyl methacrylate-co-2-ethylhexyl methacrylate) Poly (isobutyl methacrylate-co-glycidyl methacrylate) Poly (cyclohexyl methacrylate) Poly (octadecyl methacrylate) Poly ( Octadecyl methacrylate-co-styrene) Poly (vinyl propionate) Poly (dodecyl methacrylate-co-styrene) Poly (dodecyl methacrylate-co-glycidyl methacrylate) Poly (meth Butyl acid) Poly (butyl methacrylate-co-methyl methacrylate) Poly (butyl methacrylate-co-glycidyl methacrylate) Poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) Poly (cyclohexyl methacrylate-co-methacrylic acid) Glycidyl acid) Poly (cyclohexyl methacrylate-co-methyl methacrylate) Poly (benzyl methacrylate-co-methacrylic acid 2-
Ethylhexyl) Poly (2-ethylhexyl methacrylate-co-diacetone acrylamide) Poly (2-ethylhexyl methacrylate-co-benzyl methacrylate-co-glycidyl methacrylate) Poly (2-ethylhexyl methacrylate-co-methyl methacrylate- co-glycidyl methacrylate) poly (vinyl cinnamate) poly (vinyl cinnamate-co-dodecyl methacrylate) poly (tetrahydrofurfuryl methacrylate) poly (hexadecyl methacrylate) poly (2-ethylbutyl methacrylate) poly (methacrylic acid) 2-hydroxyethyl) poly (cyclohexyl methacrylate-co-isobutyl methacrylate) poly (cyclohexyl methacrylate-co-2-ethylhexyl methacrylate) poly (butyl methacrylate-c -2-ethylhexyl methacrylate) poly (butyl methacrylate-co-isobutyl methacrylate) poly (cyclohexyl methacrylate-co-butyl methacrylate) poly (cyclohexyl methacrylate-co-dodecyl methacrylate) poly (butyl methacrylate-co -Ethyl methacrylate) Poly (butyl methacrylate-co-octadecyl methacrylate) Poly (butyl methacrylate-co-styrene) Poly (4-methylstyrene) Poly (cyclohexyl methacrylate-co-benzyl methacrylate) Poly (methacrylic acid Dodecyl-co-benzyl methacrylate) Poly (octadecyl methacrylate-co-benzyl methacrylate) Poly (benzyl methacrylate-co-tetrahydrofurfuryl methacrylate) Poly (methacrylic acid Poly- (hexadecyl methacrylate) poly (dodecyl methacrylate-co-methyl methacrylate) poly (dodecyl methacrylate-co-ethyl methacrylate) poly (2-ethylhexyl methacrylate-co-dodecyl methacrylate) poly (methacrylic acid 2-Ethylhexyl-co-octadecyl methacrylate Poly (2-ethylbutyl methacrylate-co-benzyl methacrylate) Poly (tetrahydrofurfuryl methacrylate-co-glycidyl methacrylate) Poly (4-methoxystyrene) Poly (methacrylic acid 2 -Ethylbutyl-co-glycidyl methacrylate) Poly (styrene-co-tetrahydrofurfuryl methacrylate) Poly (2-ethylhexyl methacrylate-co-propyl methacrylate) Poly (methacrylic acid ester Tadeshiru -co- methacrylic acid isopropyl)

Further, in the above-mentioned methacrylic acid ester polymer or copolymer, it is preferable to use acrylic acid instead of methacrylic acid.

In the present invention, by using a combination of certain specific monomers to form a copolymer and adjusting the composition thereof, effects such as enhancing the selectivity for certain chemical substances can be obtained.

The polymer for forming the chemical substance detection film of the present invention can be crosslinked by itself, or can be crosslinked by introducing a compound having a reactive group for crosslinking into the polymer. It is possible to Such reactive groups for crosslinking include, for example, amino groups, hydroxyl groups, carboxyl groups, epoxy groups, carbonyl groups and urethane groups and their derivative groups. Other examples are eg C = C double bonds. As the compound having such a double bond, for example, maleic acid,
There are fumaric acid, sorbic acid, itaconic acid and cinnamic acid and their derivatives. A substance having a chemical structure capable of forming carbene or nitrene by irradiation with visible light, ultraviolet light or high-energy radiation can also be used as a crosslinking agent. The advantage of cross-linking the polymer is that the film formed from the cross-linked polymer is insoluble and thus has increased stability. The crosslinking method is not particularly limited, and conventionally known crosslinking methods such as heating and irradiation with light or radiation can be used.

When forming a film from the above-mentioned polymer, any known film forming method can be used. For example, spin coating, polymer solution casting, melt extrusion, and the like can be used. Since it is preferable that the film thickness is as small as possible in order to enhance the detection sensitivity, it is preferable to use a film forming method, especially a spin coating method, which can reduce the film thickness.

In the chemical substance detection film of the present invention, when it is desired to shorten the response time, it is desirable that the glass transition temperature of the film forming polymer is lower than the temperature of the detection environment.

Further, according to the present invention, there is provided a chemical substance detector having a chemical substance detection film made of the above polymer. As described above, the chemical substance detection film of the present invention swells by interacting with the chemical substance, and therefore it is possible to detect the chemical substance by utilizing this swelling. That is, the chemical substance can be detected from a physical change associated with the swelling of the film, such as a weight change, a film thickness change or a refractive index change. Therefore,
The chemical substance detector of the present invention comprises a chemical substance detection film, and further comprises detection means for detecting a physical change in the chemical substance detection film. As the detection means,
Optical means are preferred.

As the optical means, for example, an interference amplification reflection method, a surface plasmon resonance method, a Mach-Zehnder interferometer having different top coatings, a change of a propagation mode in a waveguide due to swelling or the like can be used. In the chemical substance detector of the present invention, it is particularly preferable to use the interference amplification reflection method measuring means as the detecting means because the sensitivity becomes higher.

It is of course possible to use a detecting means other than the optical means, for example, an electric detecting means, a detecting means using a crystal oscillator, or the like can be used.

Interference amplification reflection method (Interferenc)
e Enhanced Reflection: IER
Method) is a method utilizing the reflection characteristics of a polymer film on a highly reflective substrate. The light reflected on the surface of the polymer film and the light reflected on the interface between the polymer film and the substrate interfere with each other. The intensity of the reflected light largely depends on the thickness and refractive index of the polymer film. That is, a change in the thickness or the refractive index of the polymer film or a change in both of them appears as a change in the intensity of reflected light.
Further, even when the swelling behaviors of a plurality of polymer films are different, the swelling of each polymer film can be easily discriminated from each change of the intensity of reflected light. That is, in the IER method, changes in film thickness and refractive index are used as physical changes in the chemical substance detection film.

Surface plasmon resonance method (Surface)
In the Plasmon Resonance (SPR method), the light such that the momentum and energy of photons at the metal-dielectric interface coincide with those of surface plasmons is incident on the metal-dielectric interface at a critical angle. Can be excited. As a result, the photon energy is coupled with the surface plasmons, and a sharp decrease in the intensity of the reflected light is observed. Such surface plasmon couplings are very sensitive to the thickness of the metal film and the properties of the dielectric on one side of the metal film. That is, in the SPR method, changes in film thickness and refractive index are used as physical changes in the chemical substance detection film.

The chemical substance detection film of the present invention is preferably used together with a substrate supporting the film. The type of such substrate depends on the type of detection means for detecting physical changes in the film. For example, when using the IER method, a silicon wafer,
Glass, polymers and metals can be used.
On the other hand, when the SPR method is used, a metal thin film applied on glass or a transparent polymer, preferably a silver thin film or a gold thin film can be used.

[0028]

EXAMPLE 1 Preparation of poly (2-ethylhexyl methacrylate) 19.83 grams (0.1 mole) of 2-ethylhexyl methacrylate and 164 milligrams of azobisisobutyronitrile (AIBN) in 100 milliliters of tetrahydrofuran. It was dissolved at 20 ° C. The solution was purged with nitrogen for 1 hour. The solution is then heated to 6
Refluxed at 5 ° C for 7 hours. During reflux, the solution was purged with nitrogen to keep out oxygen. The solution was cooled to 20 ° C. and subsequently poured into 1 liter of methanol to precipitate poly (2-ethylhexyl methacrylate). To further increase the purity of the poly (2-ethylhexyl methacrylate), the poly (2-ethylhexyl methacrylate) was dissolved in 50 milliliters of tetrahydrofuran and subsequently precipitated with 1 liter of methanol. Finally, viscous poly (2-ethylhexyl methacrylate) was collected and dried at 60 ° C. in vacuum.
After drying, a thin layer chromatography test was performed to detect residual monomers in the resulting poly (2-ethylhexyl methacrylate), but no residual monomers were found in the poly (2-ethylhexyl methacrylate). It was not included at all.

Finally, colorless and transparent poly (methacrylic acid 2
-Ethylhexyl) was obtained. When the refractive index of this poly (2-ethylhexyl methacrylate) was measured using an Abbe refractometer, it was 1.
It was 482.

Elemental analysis of this poly (2-ethylhexyl methacrylate) gave the following results. Incidentally, poly (2-ethylhexyl methacrylate) was represented by C ₁₂ H ₂₂ O ₂ , and its molecular weight was calculated as 198.31.

Further, the gel permeation chromatography of this poly (2-ethylhexyl methacrylate) was measured. Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, the weight average molecular weight Mw of this poly (2-ethylhexyl methacrylate) was 63,100,
The number average molecular weight Mn was 30,400. The molecular weight distribution Mw / Mn was 2.08.

[0032]

Example 2 Poly (2-ethylhexyl methacrylate-co-methac)
Preparation of Methyl Phosphate 18.428 g (0.1 mol) of 2-ethylhexyl acrylate, 20.024 g (0.2 mol) of methyl methacrylate and 164 mg of AIBN in 100 ml of tetrahydrofuran. Dissolved at 20 ° C. The solution was purged with nitrogen for 1 hour. The solution was then heated to reflux at 65 ° C. for 7 hours.
During reflux, the solution was purged with nitrogen to keep out oxygen. Cool the solution to 20 ° C. and then add 8
When poured into 00 ml of methanol, poly (2-ethylhexyl methacrylate-co-methyl methacrylate) was precipitated. To further increase the purity of the poly (2-ethylhexyl methacrylate-co-methyl methacrylate), the poly (2-ethylhexyl methacrylate-co-methyl methacrylate) was dissolved in 100 ml of tetrahydrofuran and subsequently 800 ml. Of methanol. Finally, the obtained poly (2-ethylhexyl methacrylate-co-methyl methacrylate) was collected and dried in vacuum at 60 ° C. A thin layer chromatography test was performed to detect residual monomers in the resulting poly (2-ethylhexyl methacrylate-co-methyl methacrylate) after drying. No residual monomer was contained in (co-methyl methacrylate).

Finally, colorless and transparent poly (methacrylic acid 2
-Ethylhexyl-co-methyl methacrylate) is 1
5.3 grams were obtained. When the refractive index of this poly (2-ethylhexyl methacrylate-co-methyl methacrylate) was measured using an Abbe refractometer, it was 1.457 at 24 ° C.

Further, by using a differential scanning calorimeter (DSC7 manufactured by Perkin-Elmer Co.), this poly (methacrylic acid 2-
The glass transition temperature of ethylhexyl-co-methyl methacrylate) was measured and found to be 22 ° C. (heating rate 10 ° C./min).

Elemental analysis of this poly (2-ethylhexyl methacrylate-co-methyl methacrylate) revealed that carbon was 64.65% and hydrogen was 9.41%. From these results, the proportions of the two comonomers in poly (2-ethylhexyl methacrylate-co-methyl methacrylate) were 0.29 for 2-ethylhexyl methacrylate and 0.71 for methyl methacrylate. I understood.

Further, gel permeation chromatography of this poly (2-ethylhexyl methacrylate-co-methyl methacrylate) was measured. Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, the poly (2-ethylhexyl methacrylate-co-methyl methacrylate) had a weight average molecular weight Mw of 57,800 and a number average molecular weight Mn of 32,500. Also,
The molecular weight distribution Mw / Mn was 1.8.

[0037]

Example 3 Preparation of Polydodecyl Methacrylate 50.882 grams (0.2 mole) of dodecyl methacrylate and 164 milligrams of AIBN were dissolved in 100 milliliters of tetrahydrofuran at 20 ° C. The solution was purged with nitrogen for 1 hour. The solution was then heated to reflux at 65 ° C. for 7 hours. During reflux, the solution was purged with nitrogen to keep out oxygen. The solution was cooled to 20 ° C and subsequently poured into 800 ml of methanol to give poly (dodecyl methacrylate).
Was precipitated. To further increase the purity of the poly (dodecyl methacrylate), the poly (dodecyl methacrylate) was dissolved in 100 milliliters of tetrahydrofuran and subsequently precipitated with 800 milliliters of methanol. Finally, the viscous poly (dodecyl methacrylate) was collected and dried in vacuum at 60 ° C. After drying,
A thin layer chromatography test was performed to detect residual monomers in the resulting poly (dodecyl methacrylate), but no residual monomers were included in the poly (dodecyl methacrylate).

Finally, 23.6 g of colorless and transparent poly (dodecyl methacrylate) was obtained. When the refractive index of this poly (dodecyl methacrylate) was measured using an Abbe refractometer, it was 1.474 at 24 ° C.

Elemental analysis of this poly (dodecyl methacrylate) gave the following results. In addition, poly (dodecyl methacrylate) is represented by C ₁₆ H ₃₀ O ₂ ,
The molecular weight was calculated as 254.41.

Further, this poly (dodecyl methacrylate)
Was measured by gel permeation chromatography. Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, the weight average molecular weight Mw of this poly (dodecyl methacrylate) was 111,100, and the number average molecular weight Mn was
Was 49,000. In addition, the molecular weight distribution Mw / Mn
Was 2.3.

[0041]

Example 4 Poly (2-ethylhexyl methacrylate-co-styrene)
2-ethylhexyl methacrylate 10.4 grams of the preparation of emissions) 19.83 g (0.1 mol) of styrene and 164 mg (0.1 mol) and AIBN in tetrahydrofuran 120 ml by dissolving at 20 ° C. It was The solution was purged with nitrogen for 1 hour. The solution was then heated to reflux at 65 ° C. for 7 hours. During reflux, the solution was purged with nitrogen to keep out oxygen. The solution was cooled to 20 ° C. and subsequently poured into 800 ml of hexane to precipitate poly (2-ethylhexyl methacrylate-co-styrene). To further increase the purity of the poly (2-ethylhexyl methacrylate-co-styrene), the poly (2-ethylhexyl methacrylate-co-styrene) was dissolved in 50 ml of tetrahydrofuran and subsequently precipitated with 800 ml of hexane. I'm sorry. Finally, the obtained poly (2-ethylhexyl methacrylate-co-styrene) was collected and dried at 60 ° C. in vacuum. After drying,
Obtained poly (2-ethylhexyl methacrylate-co
-Styrene) to detect residual monomers in
This poly (2-ethylhexyl methacrylate-co-styrene) was tested by thin layer chromatography.
The residual monomer was not contained at all.

Finally, colorless and transparent poly (methacrylic acid 2
19.8 grams of -ethylhexyl-co-styrene) was obtained. When the refractive index of this poly (2-ethylhexyl methacrylate-co-styrene) was measured using an Abbe refractometer, it was 1.522 at 23 ° C.

Further, by using a differential scanning calorimeter (DSC7 manufactured by Perkin-Elmer Co.), this poly (methacrylic acid 2-
The glass transition temperature of ethylhexyl-co-styrene was measured and found to be 13 ° C (rate of temperature increase 10 ° C /
Minutes).

Elemental analysis of this poly (2-ethylhexyl methacrylate-co-styrene) revealed that carbon was 79.58% and hydrogen was 9.96%. From this result, poly (2-ethylhexyl methacrylate-
The proportions of the two comonomers in (co-styrene) were found to be 0.49 for 2-ethylhexyl methacrylate and 0.51 for styrene.

Further, gel permeation chromatography of this poly (2-ethylhexyl methacrylate-co-styrene) was measured. Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, the weight average molecular weight Mw of this poly (2-ethylhexyl methacrylate-co-styrene) was 50,300, and the number average molecular weight Mn was 29,300. The molecular weight distribution Mw / Mn was 1.73.

[0046]

Example 5 Poly (isobutyl methacrylate-co-methacrylate)
Preparation of 30.0 g (0.21 mol) of isobutyl methacrylate, 1.58 g (0.00222 mol) of glycidyl methacrylate and 164 mg of AIBN.
It was dissolved in 00 ml of tetrahydrofuran at 20 ° C. The solution was purged with nitrogen for 1 hour.
The solution was then heated to reflux at 65 ° C. for 7 hours. During reflux, the solution was purged with nitrogen to keep out oxygen. The solution is cooled to 20 ° C. and then 800
Pouring into milliliters of hexane precipitated poly (isobutyl methacrylate-co-glycidyl methacrylate). To further increase the purity of the poly (isobutyl methacrylate-co-glycidyl methacrylate), the poly (isobutyl methacrylate-co-glycidyl methacrylate) was dissolved in 50 ml of tetrahydrofuran and subsequently precipitated with 800 ml of methanol. I'm sorry. Finally, the obtained poly (isobutyl methacrylate-co-glycidyl methacrylate) was collected,
Dried in vacuum at 60 ° C. A thin layer chromatography test was performed to detect residual monomers in the resulting poly (isobutyl methacrylate-co-glycidyl methacrylate) after drying. This poly (isobutyl methacrylate-co-methacrylic acid) was tested. Glycidyl)
The residual monomer was not contained at all.

Finally, 16 g of colorless and transparent poly (isobutyl methacrylate-co-glycidyl methacrylate) was obtained. This poly (isobutyl methacrylate-co
The refractive index of (glycidyl methacrylate) was 1.475 at 22 ° C. when measured using an Abbe refractometer.

Further, the glass transition temperature of this poly (isobutyl methacrylate-co-glycidyl methacrylate) was measured by a differential scanning calorimeter (DSC7 manufactured by Perkin-Elmer Co.) and found to be 29.0 ° C. (increase). Temperature rate 10 ° C / min).

This poly (isobutyl methacrylate-co
Elemental analysis of (glycidyl methacrylate) showed that carbon was 66.97% and hydrogen was 9.92%. From this result, poly (isobutyl methacrylate-
The molar fractions of the two comonomers in (co-glycidyl methacrylate) were found to be 0.93 for isobutyl methacrylate and 0.07 for glycidyl methacrylate.

Further, gel permeation chromatography of this poly (isobutyl methacrylate-co-glycidyl methacrylate) was measured. Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, this poly (isobutyl methacrylate-co-glycidyl methacrylate) had a weight average molecular weight Mw of 61,000 and a number average molecular weight Mn of 40,500. The molecular weight distribution Mw / Mn was 1.55.

[0051]

Example 6 Detection of Hydrocarbon Vapor by Interference Amplification Reflection Method Gasoline and diesel oil vapor and other hydrocarbons at room temperature by interference amplification reflection method (IER method) using the polymer film for chemical substance detection of the present invention Optically detected.

The polymers used in the IER method are shown in Table 1. The polymer is dissolved in cyclohexanone to a concentration of 5
A 10 wt% solution was prepared and then spin-coated on a silicon substrate. After spin coating, the film was baked under vacuum near its glass transition temperature for about 1.5 hours. The thickness of the film thus obtained was measured by a 3030ST surface texture analysis system manufactured by DEKTAK. For maximum detection sensitivity, the polymer film thickness should be less than 1 μm, typically around 130 nm.

During the measurement of the IER method, the silicon substrate having the polymer film was sealed in a flow-through cell.
Gasoline vapor and diesel oil vapor and other chemicals can be introduced into the flow-through cell along with air or nitrogen. The vapors were obtained by bubbling air or nitrogen into liquid gasoline or the like. The chemicals used in this example were hexane and toluene.

The polymer film was irradiated with He—Ne laser light at an incident angle of 70 °. This laser light was linearly polarized in the direction perpendicular to the plane of incidence. The intensity of the reflected light was monitored by a photo detector. The output of the photodetector is converted to the chart recorder and personal computer (Comp
aq 386 PC).

The measurement results are shown in Table 1. The sensitivity in Table 1 is a percentage obtained by dividing the change in the intensity of reflected light by the absolute value of the intensity of reflected light.

As is apparent from Table 1, the measurement sensitivity was different depending on the type of hydrocarbon. In particular, it should be noted that the difference in sensitivity between gasoline and diesel oil is very large.

[0057]

[Table 1] The symbols in the table represent the following polymers. PMMA: poly (methyl methacrylate) PiDMA: poly (isodecyl methacrylate) CoP (EHMA-St): poly (2-ethylhexyl methacrylate-co-styrene) (2-ethylhexyl methacrylate: styrene = 0.4)
9: 0.51) PEHMA: poly (ethylhexyl methacrylate) CoP (MMA-EHA): poly (methyl methacrylate-co-2-ethylhexyl acrylate) (methyl methacrylate: 2-ethylhexyl acrylate = 0.71: 0.29) CoP (MMA-EHMA): poly (methyl methacrylate-co-2-ethylhexyl methacrylate) (methyl methacrylate: 2-ethylhexyl methacrylate = 0.62: 0.38) PCHA: poly (acrylic acid Cyclohexyl) PDDMA: Poly (dodecyl methacrylate) PVP: Poly (vinyl propionate)

[0058]

Comparative Example Instead of the thin film used in Example 6, poly (ethylene adipate), poly (ethylene terephthalate),
Using a thin film of poly (1,4-butylene terephthalate), poly (ethylene succinate), poly (ε-caprolactam), nylon 66, cellulose and polyacrylonitrile, a hydrocarbon vapor is produced in the same manner as in Example 6. Was detected, but sufficient sensitivity was not obtained.

[0059]

Example 7 Preparation of Polytetrahydrofurfuryl Methacrylate 17.21 grams (0.1 mole) of tetrahydrofurfuryl methacrylate and 164 milligrams of AIBN were dissolved in 100 milliliters of tetrahydrofuran at 20 ° C. The solution was purged with nitrogen for 1 hour. The solution was then heated to reflux at 65 ° C. for 4 hours.
During reflux, the solution was purged with nitrogen to keep out oxygen. Cool the solution to 20 ° C. and then add 8
When poured into 00 ml of methanol, poly (tetrahydrofurfuryl methacrylate) was precipitated. To further increase the purity of the poly (tetrahydrofurfuryl methacrylate), the poly (tetrahydrofurfuryl methacrylate) was dissolved in 100 ml of tetrahydrofuran and subsequently precipitated with 1.0 liter of methanol. Finally, poly (tetrahydrofurfuryl methacrylate) was collected and dried in vacuum at 60 ° C.
After drying, a thin layer chromatography test was performed to detect residual monomers in the resulting poly (tetrahydrofurfuryl methacrylate). It was not included at all.

Finally, 12.53 g of colorless and transparent poly (tetrahydrofurfuryl methacrylate) was obtained.
5 of this poly (tetrahydrofurfuryl methacrylate)
A wt% THF solution is prepared and spin-coated on a silicon substrate to form a thin film, and the refractive index is adjusted by a three-wavelength automatic ellipsometer Auto EL IV NIRIII manufactured by Rudolph Research.
It was 1.503 at 23 ° C.

The glass transition temperature of this poly (tetrahydrofurfuryl methacrylate) was measured with a differential scanning calorimeter (DSC7 manufactured by Perkin Elmer Co., Ltd.) (temperature rising rate: 20 ° C./min) to find that it was 49 ° C. .

Further, gel permeation chromatography of this poly (tetrahydrofurfuryl methacrylate) was measured. Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, the weight average molecular weight Mw of this poly (tetrahydrofurfuryl methacrylate) was 95,800.
And the number average molecular weight Mn was 45200. The molecular weight distribution Mw / Mn was 2.12.

[0063]

Example 8 Poly (2-ethylhexyl methacrylate-co-methac)
Preparation of 19.83 grams (0.1 mole) 2-ethylhexyl methacrylate, 14.22 grams (0.1 mole) glycidyl methacrylate and 164 milligrams AIBN in 120 milliliters of tetrahydrofuran. Dissolved at 0 ° C. The solution was purged with nitrogen for 1 hour. The solution was then heated to reflux at 65 ° C. for 7 hours.
During reflux, the solution was purged with nitrogen to keep out oxygen. The solution was cooled to 20 ° C. and subsequently poured into 1.2 liters of methanol to precipitate poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate). To further increase the purity of the poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate), the poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) was dissolved in 100 milliliters of tetrahydrofuran, followed by 1. Precipitated with 5 liters of methanol. Finally,
Obtained poly (2-ethylhexyl methacrylate-co
-Glycidyl methacrylate) was collected and dried in vacuum at 60 ° C. After drying, the resulting poly (methacrylic acid 2
-Ethylhexyl-co-glycidyl methacrylate) was tested by thin layer chromatography to detect residual monomers in the poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate).
The residual monomer was not contained at all.

Finally, colorless and transparent poly (methacrylic acid 2
29.7 grams of -ethylhexyl-co-glycidyl methacrylate) was obtained. This poly (methacrylic acid 2-
Ethylhexyl-co-glycidyl methacrylate) 1
A 0 wt% cyclohexanone solution was prepared and spin-coated on a silicon substrate to form a thin film, and the refractive index was adjusted to three wavelengths by a Rudolph Research auto-ellipsometer Auto EL IV.
When measured by NIR III, it was 1.
It was 498.

Further, by using a differential scanning calorimeter (DSC7 manufactured by Perkin-Elmer Co.), this poly (methacrylic acid 2-
The glass transition temperature of ethylhexyl-co-glycidyl methacrylate was measured and found to be 29 ° C. (heating rate 10 ° C./min).

Elemental analysis of this poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) revealed that carbon was 66.53% and hydrogen was 9.54.
%Met. From this result, the ratio of the two types of comonomers in poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) was 0.5 for 2-ethylhexyl methacrylate and 0.5 for glycidyl methacrylate.
It turned out that

The gel permeation chromatography of this poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) was also measured. Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, the weight average molecular weight Mw of this poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) was 95,000.
And the number average molecular weight Mn was 42,000.
The molecular weight distribution Mw / Mn was 2.26.

[0068]

[Example 9]Poly (benzyl methacrylate-co-methacrylic acid 2-
Preparation of ethylhexyl)  24.67 grams (0.14 mole) of methacrylic acid benzene
Jill and 13.88 grams (0.07 moles) methacryl
2-ethylhexyl acid and 164 mg AIBN
To 100 ml of tetrahydrofuran at 20 ° C
I let it dissolve. Purge the solution with nitrogen for 1 hour
It was The solution was then heated to reflux at 65 ° C. for 6 hours.
During the reflux, purge the solution with nitrogen to avoid oxygen contamination.
I'm sorry. Cool the solution to 20 ° C. and then add 1
When poured into 1 liter of methanol, poly (methacrylic acid)
-Co-2-ethylhexyl methacrylate)
I got it. This poly (benzyl methacrylate-co-meta
To further improve the purity of 2-ethylhexyl acrylate)
This poly (benzyl methacrylate-co-methacrylate)
2-Ethylhexyl acid chloride) 50 ml of tetra
Dissolve in hydrofuran and continue to add 1 liter of meta
Precipitated with nol. Finally, the resulting poly (methac
Benzyl phosphate-co-2-ethylhexyl methacrylate
And was dried at 60 ° C. in vacuum. After drying,
The resulting poly (benzyl methacrylate-co-methacrylate)
Residual monomer in 2-ethylhexyl acetate)
Was tested by thin layer chromatography
This poly (benzyl methacrylate-co-methacrylate)
2-Ethylhexyl acetate) contains no residual monomer.
It wasn't rare.

Finally, the colorless and transparent poly (benzyl methacrylate-co-2-ethylhexyl methacrylate) was converted into 3
4.5 grams were obtained. A 10 wt% cyclohexanone solution of this poly (benzyl methacrylate-co-2-ethylhexyl methacrylate) was prepared and spin-coated on a silicon substrate to form a thin film. N
1.53 at 23 ° C as measured by IR III
It was 4.

Further, the glass transition temperature of this poly (benzyl methacrylate-co-2-ethylhexyl methacrylate) was measured with a differential scanning calorimeter (DSC7 manufactured by Perkin-Elmer Co.), and it was 36.0 ° C. (Raising rate 10 ° C./min).

This poly (benzyl methacrylate-co-
Elemental analysis of 2-ethylhexyl methacrylate) showed that carbon was 74.56% and hydrogen was 8.62%.
Met. From this result, the molar fraction of the two kinds of comonomer in poly (benzyl methacrylate-co-2-ethylhexyl methacrylate) was 0.
73 and 2-ethylhexyl methacrylate is 0.2
It turned out to be 7.

Further, this poly (benzyl methacrylate-
Gel permeation chromatography of co-2-ethylhexyl methacrylate) was measured. Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, the weight average molecular weight Mw of this poly (benzyl methacrylate-co-2-ethylhexyl methacrylate) was 88,800, and the number average molecular weight Mn was 37,100. The molecular weight distribution Mw / Mn was 2.42.

[0073]

Example 10 Preparation of Polybutyl Methacrylate 14.22 grams (0.1 mole) of butyl methacrylate and 164 milligrams of AIBN were dissolved in 100 milliliters of tetrahydrofuran at 20 ° C.
The solution was purged with nitrogen for 1 hour. The solution was then heated to reflux at 65 ° C. for 7 hours. During reflux, the solution was purged with nitrogen to keep out oxygen. 20 solution
After cooling to 0 ° C. and then pouring the solution into 1 liter of methanol, poly (butyl methacrylate) was precipitated. To further increase the purity of the poly (butyl methacrylate), the poly (butyl methacrylate) was dissolved in 50 milliliters of methylene chloride and subsequently precipitated with 800 milliliters of methanol. Finally, the viscous poly (butyl methacrylate) was collected and dried at 60 ° C. in vacuum. After drying, a thin layer chromatography test was performed to detect the residual monomers in the resulting poly (butyl methacrylate), which did not contain any residual monomers. There wasn't.

Finally, 8.44 g of colorless and transparent poly (butyl methacrylate) was obtained. A 5 wt% cyclohexanone solution of this poly (butyl methacrylate) was prepared and spin-coated on a silicon substrate to form a thin film, and the refractive index was adjusted to three-wavelength automatic ellipsometer Au manufactured by Rudolph Research.
When measured with to EL IV NIR III, 23
It was 1.480 at ° C.

Elemental analysis of this poly (butyl methacrylate) gave the following results. The poly (butyl methacrylate) is represented by C ₈ H ₁₄ O ₂ , and its molecular weight was calculated as 142.2.

Further, gel permeation chromatography of this poly (butyl methacrylate) was measured.
Calibration was carried out using tetrahydrofuran as the solvent and polystyrene as the standard. As a result, this poly (butyl methacrylate) had a weight average molecular weight Mw of 45,000 and a number average molecular weight Mn of 22,
It was 500. The molecular weight distribution Mw / Mn is 2.0.
Met.

[0077]

Example 11 Poly (2-ethylhexyl methacrylate-co-methac)
Preparation of Glycidyl Phosphate) Thin Film 1.0 g of poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) and 0.201 g of 4,4′-diaminodiphenylmethane (1.015 mmol) were dissolved in cyclohexanone. The total amount was 20 grams. This solution was dropped on a silicon substrate and 4000
Spin coated by spinning at rpm for 30 seconds.
After drying the film in a vacuum at 60 ° C. for 2 hours,
The polymer was crosslinked by heating at 150 ° C. for 2 hours. Thus, a thin film of insoluble poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) having a thickness of 165.0 nm was obtained.

[0078]

Example 12 Detection of Organic Chemical Vapor by Interference Amplification Reflection Method Using the polymer film for chemical substance detection of the present invention, the same method as in Example 6 was carried out by the interference amplification reflection method (IER method), and gasoline, diesel and Other organic solvents were detected optically at room temperature. The polymers used are listed in Table 2.
Shown in. The organic chemicals used in this example were gasoline, diesel, acetone, dichloromethane, diethyl ether, ethanol, hexane and toluene. In addition, poly (2-ethylhexyl methacrylate-
The response to gasoline using a thin film of (co-glycidyl methacrylate) was recorded every 0.2 seconds and is shown in FIG.

[0079]

[Table 2] The symbols in the table represent the following polymers.

CoP (BZMA-EHMA): poly (benzyl methacrylate-co-2-ethylhexyl methacrylate) (benzyl methacrylate: 2-ethylhexyl methacrylate = 0.73: 0.27) CoP (EHMA-GLMA): Poly (2-ethylhexyl methacrylate-co-glycidyl methacrylate) (2-ethylhexyl methacrylate: glycidyl methacrylate = 0.5: 0.5) PBMA: poly (butyl methacrylate) PTHFMA: poly (tetrahydrofurfuryl methacrylate )

As can be seen from FIG. 1, gasoline could be detected within a very short time of less than 1 second.

As is clear from the results shown in Table 2, the measurement sensitivity differs depending on the type of chemical substance. Therefore, it is possible to simultaneously measure various chemical substances by using a combination of a plurality of films.

[0083]

Example 13 Detection of Hydrocarbon Vapor by Surface Plasmon Resonance Method In order to obtain optimum coupling between incident light of wavelength 632.8 nm and surface plasmon, silver with a thickness of 50 nm was formed on a slide glass substrate by vacuum evaporation. A thin film was formed. The surface of the silver thin film was spin-coated with poly (2-ethylhexyl methacrylate-co-styrene) having a concentration of 2.5 wt% dissolved in cyclohexanone. The resulting polymer film had a thickness of about 50 nm. The thickness of the polymer film depended on the spin speed. After the spin coating was completed, the polymer film was dried under vacuum near the glass transition temperature of the polymer.

An outline of the SPR measuring device is shown in FIG. He
The -Ne laser beam 1 is split by the beam splitter 2 and then P-polarized by the polarizer 3, and then enters the flint glass right-angle prism 4 (n = 1.745) and is coupled with the silver thin film 5. The prism 4 was arranged on a slide glass (n = 1.5143). Immersion oil (n = 1.514) was filled between the prism 4 and the slide glass in order to match the refractive index. The prism-glass / silver thin film / polymer film assembly was placed in the cell with the side of the polymer film 6 facing the inside of the flow-through cell (not shown). The critical angle of the surface plasmon was determined by changing the incident angle of the laser beam 1. The angle of incidence was set to a value approximately corresponding to the half maximum intensity on one side of the resonance. This state is shown in FIG. The intensity of the reflected light was monitored by a photodetector at room temperature while allowing vapors of gasoline and other hydrocarbons to flow through the flow-through cell. The hydrocarbons used were toluene, gasoline, hexane and diesel oil. In this way, the change in the thickness of the polymer film or the change in the refractive index due to the interaction between the hydrocarbon vapor and the polymer film 6 could be measured with high sensitivity. The results are shown in Table 3. The numerical values in the table represent the relative change in the intensity of reflected light as a percentage.

As is clear from Table 3, the measurement sensitivity differs depending on the type of hydrocarbon. In particular, it should be noted that gasoline and diesel oil have different sensitivities even by one order.

[0086]

[Table 3]

[Brief description of drawings]

FIG. 1 Poly (2-ethylhexyl methacrylate-co
-Glycidyl methacrylate) is a diagram showing a response to gasoline when the gasoline is detected by an IER method using a thin film.

FIG. 2 is a schematic diagram of a chemical substance detector according to the SPR method.

FIG. 3 is a diagram showing a relationship between an incident angle and an intensity of reflected light in the SPR method.

[Explanation of symbols]

 1 He-Ne laser light 2 Beam splitter 3 Polarizer 4 Right-angle prism 5 Silver thin film 6 Polymer film 7 Photodetector for reference light 8 Photodetector for signal light 9 Electronic circuit 10 Recording means

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08F 20/18 MMC 7242-4J 26/02 MNL 7242-4J C08L 101/00 LTB 7242-4J // G01N 33 / 22 D 7055-2J (72) Shizuo Ogura Shizuo Ogura 1384-123 (72) Injured in Tsurugashima City, Saitama Prefecture Satoshi Yamamoto 1982-11 Toyodamoto, Kawagoe City, Saitama Prefecture Happy Heights 201 (72) Akihiko Tsuneda Saitama Prefecture 3-1-11 Isehara-cho, Kawagoe City (72) Inventor Kenji Motosugi 13-5 Wakita Shinmachi, Kawagoe-shi, Saitama Shuttle Brown Room 202

Claims (10)

[Claims] 1. A chemical substance detection film comprising a homopolymer or copolymer having the following repeating unit (I). [Chemical 1] (In the formula, X is -H, -F, -Cl, -Br, -C.
H _3, -CF ₃ represents -CN or -CH ₂ -CH _3, R ¹ represents -R ² or -Z-R ^2, Z is -O-, -S-, -NH-, -NR ² '-,-
(C = Y)-,-(C = Y) -Y-, -Y- (C = Y)
_{-, - (SO 2) -} , -Y '- (SO 2) -, - (S
_{O 2) -Y'-, -Y '-} (SO 2) -Y'-, -NH-
(C = O)-,-(C = O) -NH-,-(C = O)-
NR ² '-, -Y'-(C = Y) -Y'- or -O-
(C = O) - (CH 2) n - (C = O) represents -O-, Y represents the same or different O or S, Y 'represents the same or different O or NH, n represents an integer of 0 to 20, and R ² and R ² ′ are the same or different hydrogen, a linear alkyl group, a branched alkyl group, a cycloalkyl group, an unsaturated hydrocarbon group, an aryl group, a saturated or unsaturated group. Represents a saturated heterocycle or a substitution product thereof. However, R ¹ is not hydrogen, a linear alkyl group, or a branched alkyl group. ) 2. X represents H or CH ₃ , R ¹ represents a substituted or unsubstituted aryl group or —Z—R ² , and Z represents —O.
-, - (C = O) -O- or -O- (C = O) - represents and R ² is a linear alkyl group, branched alkyl group, cycloalkyl group, unsaturated hydrocarbon group, an aryl group The film for detecting a chemical substance according to claim 1, which represents a saturated or unsaturated heterocycle or a substitution product thereof. 3. The chemical substance detection film according to claim 1, wherein the polymer is crosslinked. 4. A chemical substance detector comprising a chemical substance detecting film made of the polymer according to claim 1. 5. The detector according to claim 4, wherein the chemical substance is detected by swelling of the film. 6. The detector according to claim 4, wherein the chemical substance is detected by a change in film thickness. 7. The detector according to claim 4, wherein the chemical substance is detected by a change in the refractive index of the film. 8. A chemical substance is detected by optical means,
The detector according to any one of claims 4 to 7. 9. Detector according to claim 8, wherein interference amplification reflection measuring means is used as optical means. 10. The detector according to claim 4, which detects gasoline and diesel oil separately.