KR100798596B1 - Brush polyether-based polymer having chemical sensing capability, preparation thereof and chemical sensor comprising the polymer - Google Patents

Abstract

A brush polyether-based polymer compound, a method for preparing the brush polyether-based polymer compound, and a chemical sensor using the brush polyether-based polymer compound are provided to prevent the leaching of active component and to improve melting property. A brush polyether-based polymer compound is represented by the formula 1, wherein 9<x<=100; 0<=y<100; x+y=100; w is an integer of 0-10; m is an integer of 0-20; A is -S-, -OCO-, -COO-, -O-, -NH-, -CH2-, -OC6H4-, -OC6H4COO- or -OC6H4CONH-; D is -SR, -OR, -R, -OC6H4R, -OC6H4COOR, -OC6H4CONHR, -OCOR, -NHCOR, -COO or -NHCOOR; R is a C1-C20 alkyl group; E is H, a C1-C20 alkyl group, -CH2A(CH2)mGPh(R1, R2) or -CH2D; G is -OCO-, -COO- -O-, -NHCO- or -CO; R1 is a trifluoroacetyl group; and R2 is H, -ROH, -RCHO, -RCOOH, -RCOOR, -RNHCOR or -RCONHR.

Description

Chemical sensor functional brush polyether-based polymer compound, a manufacturing method thereof, and a chemical sensor device using the same {BRUSH POLYETHER-BASED POLYMER HAVING CHEMICAL SENSING CAPABILITY, PREPARATION THEREOF AND CHEMICAL SENSOR COMPRISING THE POLYMER}

1 is a cross-sectional view of a typical coated wire ion selective electrode,

Figure 2 shows the sensitivity to carbonate ions of the ion-selective electrode membrane using the functional brush polyether polymer compound of the present invention,

3 is a graph showing the electrochemical characteristics of the carbonate ion of the ion-selective electrode membrane using the functional brush polyether polymer compound of the present invention,

4 is an infrared spectroscopic spectrum result for the stability test of the functional brush polyether compound of the present invention.

The present invention relates to a chemical sensor functional brush polyether polymer compound, a preparation method thereof, and a chemical sensor device using the same.

For many years, research on ion selective electrodes has been actively conducted, and various ion selective electrode membranes including ion carriers have been proposed.

Ion-selective electrode membranes generally consist of about 33% of a polymeric binder, about 66% of a plasticizer, a small amount of ion carriers, and a lipophilic additive.

Poly (vinyl chloride) (PVC) is typically used as the polymer binder material for the ion-selective electrode membrane. In addition, polyurethane, polyacrylate, silicone rubber, epoxy acrylate, polystyrene, etc. Synthetic polymers are known (see Bakker, E . ; Buhlmann, P .; Pretch, E. Chem. Rev. 1997 , 97 , 3083-3132).

However, in these ion-selective electrode membranes based on the polymer binder, electrode performance is due to leaching of active components used for ion-selective electrodes, that is, ion carriers, lipophilic additives, and plasticizers. ) Has been a problem.

 Accordingly, it is an object of the present invention to provide a polymer compound having a chemical sensor function excellent in ion selectivity as well as no leaching of the active ingredient, and a method for producing the same.

Still another object of the present invention is to provide a chemical sensor device including the polyether polymer compound.

In accordance with the above object, the present invention provides a chemical sensor functional brush polyether-based high molecular compound of the general formula (1):

Where

x and y represent the content (mol%) of the polyether unit, where 0 <x ≦ 100, 0 ≦ y <100, and x + y = 100;

 w is an integer from 0 to 10, m is an integer from 0 to 20;

A is -S-, -OCO-, -COO-, -O-, -NH-, -CH _2- , -OC ₆ H _4- , -OC ₆ H ₄ COO- or -OC ₆ H ₄ CONH- ;

D is -SR, -OR, -R, -OC ₆ H ₄ R, -OC ₆ H ₄ COOR, -OC ₆ H ₄ CONHR, -OCOR, -NHCOR, -COO or -NHCOOR, where R is C _1-20 alkyl group;

E is H, a C _1-20 alkyl group, -CH ₂ A (CH ₂ ) _m GPh (R ₁ , R ₂ ) or -CH ₂ D;

G is -OCO-, -COO-, -O-, -NHCO- or -CO-;

R ₁ is a trifluoroacetyl group;

R ₂ is H, -ROH, -RCHO, -RCOOH, -RCOOR, -RNHCOR or -RCONHR.

In addition, the present invention provides a method for producing a chemical sensor functional brush polyether polymer compound of the formula (1).

In addition, the present invention provides a chemical sensor device comprising an ion-selective electrode membrane derived from the chemical sensor functional brush polyether polymer compound of the formula (1).

Hereinafter, the present invention will be described in more detail.

The chemical sensor functional brush polyether polymer compound of Chemical Formula 1 according to the present invention is characterized in that it comprises a brush having a polyether as a main chain and a trifluoroacetophenyl group as a terminal group.

The functional brush polyether polymer compound of the present invention is not leached of the active ingredient, it is excellent in melting and solubility, and can be processed into various forms, and detects and detects the compound in the environment and the living body with only a lipophilic additive without adding a plasticizer. It can be usefully used for chemical sensor elements, such as an ion selective electrode, an optical sensor, and a gas sensor, as an analysis use.

In the functional brush polyether polymer compound of Chemical Formula 1 of the present invention, A in Formula 1 is -S-, -OCO-, -O-, or -OC ₆ H _4- ; D is -SR, -OR or -OC ₆ H ₄ R, wherein R is a C _1-20 alkyl group; E is H, a C _1-20 alkyl group, -CH ₂ A (CH ₂ ) _m GPh (R ₁ , R ₂ ) or -CH ₂ D; G is -OCO-, -COO-, -O- or -NHCO-; R ₁ is a trifluoroacetyl group; R ₂ is preferably H, -ROH, -RCHO, -RCOOH, -RCOOR -RNHCOR or -RCONHR.

As a functional brush polyether polymer of Formula 1 according to the present invention, poly (11- [4- (2,2,2-trifluoroacetyl) -benzoate] -undecyl having a structure of Formula 1a Sulfanyl) -propylene oxide) -co -poly (dodecylsulfanyl) -propylene oxide.

In the above formula, x and y are as defined in the formula (1).

In the chemical sensor functional brush polyether polymer compound of Chemical Formula 1, x representing the content (mol%) of the brush polyether unit is 10 to 100, preferably 50 to 100.

The weight average molecular weight of the functional brush polyether polymer compound is 5,000 to 5,000,000, preferably 5,000 to 500,000.

Chemical sensor functional brush polyether polymer compound of Chemical Formula 1 of the present invention, the preparation method thereof

1) preparing a polyether compound represented by the following Chemical Formula 3 through a cationic ring-opening polymerization reaction in the presence of a cationic initiator;

2) The compound of Formula 3 is prepared in an organic solvent with HA (CH ₂ ) _m Q and HAD, wherein H is hydrogen, Q = -COOH, -OH, -NH ₂ or halogen, and A and D are as defined in Reacting with) to introduce a functional group and an alkyl group into the alkyl group side chain to prepare a compound of Formula 4;

3) reacting the compound of formula 4 with the compound of formula 5 in an organic solvent.

[Formula 1]

Wherein x, y, w, m, A, D, E, G, R ₁ and R ₂ are as defined in Formula 1, n is 50 to 50000, X is F, Cl, Br or I and The same halogen, Q is COOH, -OH, -NH ₂ or halogen, and L is -OH, -COOH, -NH ₂ or halogen.

For example, the method of preparing the compound of Formula 1 may be represented by Scheme 1 below.

Where

x, y, w, m, n, A, D, E, G, Q, L, X, R ₁ and R ₂ are as defined above.

Hereinafter, the manufacturing method will be described in detail for each step.

Step 1) is a step of preparing a polyether (Formula 3) compound that is the main chain of the formula (1) of the present invention, the cyclic ether compound (Formula 2) without using a solvent or methylene chloride, chloroform, diethyl ether Cation ring-opening polymerization in the presence of a cationic initiator such as triphenylcarbenium hexafluorophosphate (TCHP) or triphenylcarbenium hexachloroantimoniate (TCHA), alkyl aluminum, etc. (Faust, R .; Shaffer, TD Cationic Polymerization; fundamentals and applications, Washington, DC: American Chemical Society, 1997).

Step 2) is a polyether (Formula 3) in the organic solvent HA (CH ₂ ) _m Q and HAD (where Q = -COOH, -OH, -NH ₂ , halogen, A and D are as defined in Formula 1 And a brush to introduce a brush to prepare a compound of Formula 5, wherein the ratio of HA (CH ₂ ) _m Q and HAD containing a functional group is adjusted to the side chain of the brush-type polyether (Formula 4). The desired amount of brush can be introduced. Examples of the solvent used include dimethylacetamide, dimethylformamide, diethyl ether, methylene chloride, tetrahydrofuran or a mixed solution thereof. The reaction in this step is preferably carried out at a temperature of -100 to 100 ℃ and a pressure of 1 to 5 atm.

Step 3) is a step of preparing a brush-type polyether polymer comprising a 4-trifluoroacetophenyl group (ion carrier) and an alkyl chain by reacting the compound of Formula 4 with the compound of Formula 5 in an organic solvent. As the organic solvent used, methylene chloride, dimethylacetamide, dimethylformamide or a mixed solution thereof may be used.

The process of preparing a coated wire ion-selective electrode using the brush polyether polymer compound of Chemical Formula 1 according to the present invention may be performed according to methods known in the art.

As such, the brush-type polyether polymer compound including the trifluoroacetophenyl group and the alkyl chain according to the present invention can be processed into various forms because leaching of the active ingredient does not occur, and melting and solubility are excellent. It is applicable to chemical sensor elements, such as an ion selective electrode, an optical sensor, and a gas sensor, for the use of detecting and analyzing a compound in a living body.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1 Preparation of Polyether Polymer (PTPO100)

(1-1): Preparation of Polyepichlorohydrin Compound

40 mL (512 mmol) of epichlorohydrin was added to a 100 mL round bottom flask and cooled to 5 ° C. under a nitrogen atmosphere. A solution of 2.56 mmol of initiator (TCHP) dissolved in methylene chloride was added thereto, followed by stirring at room temperature for 4 days. The reaction product was dissolved in a small amount of methylene chloride and purified by reprecipitation in methanol, which was then dried under vacuum at 40 ° C. for 8 hours to prepare polyepichlorohydrin.

(1-2)

1,382 mg (5.4 mmol) of 11-hydroxyundecylthiolate in a solution of 500 mg (5.4 mmol) of the polyepichlorohydrin compound obtained in the above (1-1) in 2 mL of dimethylacetamide (DMAc). Was dissolved in 10 mL of DMAc. The mixture was stirred at room temperature for 2 hours, extracted with chloroform, washed with water to remove the solvent, and then precipitated in hexane. This precipitate was dried under vacuum at 40 ° C. for 8 hours to obtain the target compound (1.34 g, yield 95%).

(1-3)

= 2931, 2859, 1722, 1467, 1408, 1284, 1179.551 mg benzoic acid as the (1-2) The compound 500 mg (1.92 mmol), 4- trifluoromethyl obtained from, N - (3- dimethylaminopropyl) - N - ethylcarbodiimide hydrochloride (EDC) and 586 mg N , 187 mg of N -dimethylaminopyridine (DMAP) was dissolved in 20 mL of methylene chloride, stirred at room temperature for 24 hours, and then extracted with chloroform. The extract was depressurized to remove the solvent, precipitated with cold hexane, and the obtained product was dried under vacuum at 40 ° C. for 8 hours to obtain the target compound (PTPO100) (904 mg, 96% yield). ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.23-8.14 (m, 4H), δ 4.41-4.36 (t, 2H), δ 3.73-3.64 (m, 5H), δ 2.72-2.56 (m, 4H), δ 2.07-0.88 (m, 18 H); IR (membrane):

= 2931, 2859, 1722, 1467, 1408, 1284, 1179.

Example 2 Preparation of Polyether Polymer (PTPO75)

In Example 1 (1-2), 1037 mg (4.05 mmol) of 11-hydroxyundecylthiolate and 342 mg (1.35 mmol) of dodecylthiolate were substituted for 11-hydroxyundecylthiolate. Target compound (PTPO75) (1.25 mg, yield 90) in the same manner as in Example 1, except that the residue was purified using a flash column instead of being precipitated with cold hexane in (1-3). %) Was obtained.

Example 3 Preparation of Polyether Polymer (PTPO50)

In Example 1 (1-2), 691 mg (2.7 mmol) of 11-hydroxyundecylthiolate and 685 mg (2.7 mmol) of dodecylthiolate instead of 11-hydroxyundecylthiolate. Target compound (PTPO75) (894 mg, yield) in the same manner as in Example 1, except that the residue was purified using a flash column instead of being precipitated with cold hexane in (1-3). 92%).

= 2931, 2859, 1722, 1467, 1408, 1284, 1179. ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.23-8.14 (m, 4H), δ 4.41-4.36 (t, 2H), δ 3.73-3.64 (m, 10H), δ 2.72-2.56 (m, 8H), δ 2.07-0.88 (m, 38H); IR (membrane):

= 2931, 2859, 1722, 1467, 1408, 1284, 1179.

Example 4 Preparation of Polyether Polymer (PTPO25)

In Example 1 (1-2), 346 mg (1.35 mmol) of 11-hydroxyundecylthiolate and 1028 mg (4.05 mmol) of dodecylthiolate were used instead of 11-hydroxyundecylthiolate. In the same manner as in Example 1, except that the precipitate was purified using a flash column instead of the precipitate using the cold hexane in (1-3), the target compound (PTPO25) (899 mg, yield 97% )

Example 5 Preparation of Polyether Polymer (PTPO10)

In Example 1 (1-2), 138 mg (0.54 mmol) of 11-hydroxyundecylthiolate and 1233 mg (4.86 mmol) of dodecylthiolate were used instead of 11-hydroxyundecylthiolate. In the same manner as in Example 1, except that the precipitate was purified using a flash column instead of the precipitate using the cold hexane in (1-3) (PTPO10) (911 mg, 99% yield). )

Examples 6 to 10 Preparation of Ion Selective Sensors

An ion selective sensor having a structure as shown in FIG. 1 was prepared as follows.

Ag was treated with 0.1M FeCl ₃ solution to make Ag / AgCl electrode. The electrode was coated with 6 wt% polyvinyl alcohol containing 0.1 M KCl solution to form a hydrogel layer. Herein, a mixture of 60 wt% of the compounds obtained in Examples 1 to 5 and 40 wt% of tridodecylmethylammonium chloride (TDMACl) as a lipophilic additive was dissolved in THF, respectively, to make a 10 wt% solution, and then the solution was Dropped onto the prepared hydrogel layer and dried for one day at room temperature to produce a coated wire ion selective electrode according to the present invention.

Test Example 1 Test of Sensitivity to Carbonate Ion of Ion-Selective Electrode Membrane

The coated wire ion selective electrodes prepared in Examples 6 to 10 were used to investigate the sensitivity to carbonate ions.

The response curves for the dissolved total carbon dioxide (T _CO2 ) of the carbonate selective membrane were shown in Example 6, the electrode coated with the ion selective membrane, the external reference electrode, and the double junction Ag / AgCl electrode (model 90-02-00). , Orion) is connected to a 16-channel analog-to-digital converter to change the concentration of T _{CO2 in} the buffer solution (0.1 M Tris-HCl (pH 8.6)) every 100 seconds. Confirmed by.

As can be seen in Figure 2, it can be seen that the more the content of the brush having a trifluoroacetophenyl group terminal group as an ion carrier, the sensitivity to carbonate ions is improved.

Test Example 2: Electrochemical Characteristic Test

In addition, the electrochemical characteristics (tilt, detection limit) for the carbonate ions of the ion selective electrode membranes of Examples 6 to 10 of the present invention were measured and the results are shown in FIG. 3. 3 is a calibration curve showing the change in potential according to the conversion of the response curve obtained in Test Example 1 with the concentration of NaHCO ₃ injected differently with time.

The slope was obtained by obtaining a calibration curve (Fig. 3), which is a graph of concentration and potential difference, on the sensitivity curve of FIG. 2 to draw a straight line for the concentration range having linearity. The intersection of the straight line at the concentration and the straight line at the concentration not detected was found.

As can be seen in Figure 3, the electrode membrane (Examples 6 to 8) in which the trifluoroacetophenyl group, which is an ion carrier, is immobilized at least 50% (Examples 6 to 8) has a Nernst slope, and the conventional PVC Electrochemical properties that are comparable to or better than those of the electrode film based on

Test Example 3: Stability test of ion selective electrode membrane

The ion-selective membrane-coated wafers prepared in Examples 6 to 10 in a buffer solution (0.1 M Tris-HCl, pH 8.6) were sufficiently dried at room temperature, followed by infrared spectroscopy (ATI Mattson FTIR spectrometer Model Research Series 2). The leaching of the activator capable of selectively detecting ions was analyzed. The stability of the electrode membrane in which the ion carrier is immobilized on the membrane support by covalent bonding was tested over time, and the results are shown in FIG. 4.

As can be seen in Figure 4, even after soaking in the buffer solution for more than 40 days it was confirmed that the membrane according to the present invention to maintain a stable covalent bond.

As described above, the chemical sensor brush polyether-based polymer compound of Chemical Formula 1 of the present invention does not leach out of the active ingredient, has excellent melting and solubility, and can be processed into various forms, and detects and detects compounds in the environment and in vivo. As an analysis use, it can use for chemical sensor elements, such as an ion selective electrode, an optical sensor, and a gas sensor.

Claims (11)

Chemical sensor functional brush polyether polymer compound of Formula 1 <Formula 1>

Where x and y represent the content (mol%) of the polyether unit, where 0 <x ≦ 100, 0 ≦ y <100, and x + y = 100; w is an integer from 0 to 10, m is an integer from 0 to 20; A is -S-, -OCO-, -COO-, -O-, -NH-, -CH _2- , -OC ₆ H _4- , -OC ₆ H ₄ COO- or -OC ₆ H ₄ CONH- ; D is -SR, -OR, -R, -OC ₆ H ₄ R, -OC ₆ H ₄ COOR, -OC ₆ H ₄ CONHR, -OCOR, -NHCOR, -COO or -NHCOOR, where R is C _1-20 alkyl group; E is H, a C _1-20 alkyl group, -CH ₂ A (CH ₂ ) _m GPh (R ₁ , R ₂ ) or -CH ₂ D; G is -OCO-, -COO-, -O-, -NHCO- or -CO-; R ₁ is a trifluoroacetyl group; R ₂ is H, -ROH, -RCHO, -RCOOH, -RCOOR, -RNHCOR or -RCONHR. The method of claim 1, In Formula 1, A is -S-, -OCO-, -O- or -OC ₆ H _4- ; D is -SR, -OR or -OC ₆ H ₄ R, wherein R is a C _1-20 alkyl group; E is H, a C _1-20 alkyl group, -CH ₂ A (CH ₂ ) _m GPh (R ₁ , R ₂ ) or -CH ₂ D; G is -OCO-, -COO-, -O- or -NHCO-; R ₁ is a trifluoroacetyl group; R ₂ is H, -ROH, -RCHO, -RCOOH, -RCOOR -RNHCOR or -RCONHR. Chemical sensor functional brush polyether polymer compound. The method of claim 1, Chemical sensor functional brush polyether polymer compound having a weight average molecular weight of 5,000 to 5,000,000. The method of claim 1, The chemical sensor functional brush polyether polymer compound whose x is 10-100. The method of claim 1, Chemical sensor, which is poly (11- [4- (2,2,2-trifluoroacetyl) -benzoate] -undecylsulfanyl) -propylene oxide) -co -poly (dodecylsulfanyl) -propylene oxide Functional brush polyether polymer compound. 1) preparing a polyether compound represented by the following Chemical Formula 3 through a cationic ring-opening polymerization reaction in the presence of a cationic initiator; 2) A compound of formula 3 is prepared in an organic solvent with HA (CH ₂ ) _m Q and HAD wherein H is hydrogen and Q = -COOH, -OH, -NH ₂ or halogen, and A and D Reacting with the same to form a functional group and an alkyl group in the alkyl group side chain to prepare a compound of Formula 4; And 3) A process for preparing a chemical sensor functional brush polyether polymer compound comprising reacting a compound of Formula 4 with a compound of Formula 5 in an organic solvent: <Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

Wherein x, y, w, m, A, D, E, G, Q, R ₁ and R ₂ are as defined in claim 1, n is 50 to 50000, X is halogen, Q is COOH , -OH, -NH ₂ or halogen, and L is -OH, -COOH, -NH ₂ or halogen. The method of claim 6, In step 1), the cationic initiator is triphenylcarbenium hexafluorophosphate (TCHP), triphenylcarbenium hexachloroantimoniate (TCHA) or alkyl aluminum. The method of claim 6, In step 2), the organic solvent is dimethylacetamide, dimethylformamide, diethyl ether, methylene chloride, tetrahydrofuran phosphorus or a mixture thereof. The method of claim 6, In step 2), the reaction takes place at a temperature of -100 to 100 ° C. and a pressure of 1 to 5 atm. The method of claim 6, In step 3), the organic solvent is methylene chloride, dimethylacetamide, dimethylformamide or a mixture thereof. A chemical sensor element comprising a film of the chemical sensor functional brush polyether polymer compound according to any one of claims 1 to 5.

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