JPH066611B2 - Hydrophilic-hydrophobic thermoreversible polymer compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel vinyl compound polymer. More specifically, the present invention provides a hydrophilic-hydrophobic thermoreversible high reversible type which can be used in a light shield, a temperature sensor, an adsorbent, a toy, an interior, a printing aid, a display, a separation functional film, and a mechanochemical material. The present invention relates to a molecular compound and a method for efficiently producing the same.

2. Description of the Related Art Some water-soluble polymer compounds show a special reversible dissolution behavior in which, in an aqueous solution state, when the temperature is higher than a certain temperature (transition temperature or cloud point), it becomes cloudy and precipitates, and below that temperature, it becomes transparent. This is called a hydrophilic-hydrophobic thermoreversible polymer compound, and in recent years, it has been attracting attention as a light-shielding body in a greenhouse, a chemical laboratory, a temperature sensor, or the like.

As such hydrophilic-hydrophobic thermoreversible polymer compounds, polyvinyl acetate partially saponified product, polyvinyl methyl ether, methyl cellulose, polyethylene oxide, polyvinyl methyl oxazolidinone, polyacrylamide derivative and the like have been known so far. There is.

Among these hydrophilic-hydrophobic thermoreversible polymer compounds, polyacrylamide derivatives are stable in water and can be produced at a relatively low cost, and thus are suitable for the above-mentioned applications,
Those having thermoreversibility include poly (N-ethyl (meth) acrylamide), poly (Nn-propyl (meth) acrylamide), poly (N-isopropyl (meth) acrylamide), poly (N-). Cyclopropyl (meth) acrylamide), poly (N, N-diethylacrylamide), poly (N-methyl-N-ethylacrylamide), poly (N-methyl-Nn-propylacrylamide), poly (N-methyl-) N-isopropylacrylamide), poly (N-acrylpiperidine), poly (N-tetrahydrofurfuryl (meth) acrylamide), poly (N-methoxypropyl (meth) acrylamide), poly (N-ethoxypropyl (meth) acrylamide) , Poly (N-isopropoxypropyl (meth)
Acrylamide), poly (N-ethoxyethyl (meth)
Acrylamide), poly (N- (2,2-dimethoxyethyl) -N-methylacrylamide) and the like are known.

However, such a compound has a limited transition temperature even if it is intended to be used as a temperature sensor or a light-shielding body, for example, and it cannot be arbitrarily selected according to the purpose. There wasn't.

Problems to be Solved by the Invention Under the circumstances, an object of the present invention is to provide a novel novel compound having a different transition temperature in order to expand the application range of the hydrophilic-hydrophobic thermoreversible polyacrylamide derivative. It was made for the purpose of providing a hydrophilic-hydrophobic thermoreversible polyacrylamide derivative and a method for producing the same.

Means for Solving the Problems The present inventors have conducted diligent research to develop new hydrophilic-hydrophobic thermoreversible polyacrylamide derivatives having different transition temperatures, and as a result, the general formula (II ) (Wherein R is a hydrogen atom or a methyl group), which is obtained by radical polymerization of a vinyl compound represented by the general formula (I) (R in the formula is a hydrogen atom or a methyl group) and has an intrinsic viscosity [η] of 0.01 at a temperature of 27 ° C. in a tetrahydrofuran solution.
A polymer compound having a molecular weight corresponding to ˜6.0 was found to be a hydrophilic-hydrophobic thermoreversible polymer compound which is insoluble in water by heating, and the present invention has been completed based on this finding. .

The polymer compound of the present invention is a novel compound described in the end of the literature. It can be easily produced by carrying out a vinyl compound radical polymerization represented by the general formula (II).

The vinyl compound represented by the general formula (II), that is, N-
1-methyl-2-methoxyethyl (meth) acrylamide, which is synthesized, for example, as shown by the following formula.

(A) (meth) acrylic acid chloride and 2-amino-1-
A method of reacting methoxypropane and triethylamine in a solvent, preferably at a temperature of 0 to 10 ° C.

(B) (meth) acrylic acid chloride and 2-amino-1-
Methoxypropane in a solvent is preferably 0-10
Method of reacting at a temperature of ℃.

Method (A): Method (B): Regarding the solvent used in these methods, (meth)
There is no particular limitation as long as it is inert to acrylic acid chloride, and benzene, acetone, toluene and the like are generally used. Regarding the reaction temperature, if it is too high, side reactions occur, so it is preferable to carry out the reaction in the range of 0 to 10 ° C.

In order to isolate the target compound from the reaction mixture thus obtained, usually, triethylamine hydrochloride or 2-amino-1-methoxypropane hydrochloride is first removed by filtration or the like, and then the residue is filtered using a rotary evaporator. The solvent is distilled off from the liquid, followed by vacuum distillation for purification. The distillate at this time can be highly purified by repeating vacuum distillation if necessary.

The vinyl compound represented by the general formula (II) used in the present invention, N-1-methyl-2-methoxyethyl acrylamide (boiling point 92 ° C./1 mmHg) and N-1-methyl-2-methoxyethyl methacrylamide (boiling point 108 ℃ / 3.5mmHg)
Is a colorless liquid, which is soluble in solvents such as water, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, chloroform, carbon tetrachloride, and benzene, and insoluble in n-hexane and n-heptane.

The vinyl compound used in the present invention, represented by the general formula (II), N-1-methyl-2-methoxyethyl acrylamide and N-1-methyl-2-methoxyethyl methacrylamide are radically polymerized to be insolubilized by heating. As a specific method for producing the hydrophilic-hydrophobic thermoreversible polymer compound, for example, a solution polymerization method and a bulk polymerization method can be adopted. As a method for initiating the polymerization, (1) a method using a polymerization initiator, (2) irradiation with light such as ultraviolet rays and visible light, (3) a method by heat, (4) radiation, electron beam, ionization of plasma, etc. Any known radical polymerization method such as a method of irradiating with energy rays can be used. The polymerization initiator has the ability to initiate radical polymerization, and examples thereof include organic peroxides and azo compounds. Specifically, benzoyl peroxide, acetyl peroxide, azobisisobutyronitrile, etc. can be used. It is also possible to use two or more of the above polymerization initiators in combination. In this case, the amount of the polymerization initiator added is in the range of 0.005 to 5% by weight, preferably 0.001 to 2% by weight, based on the vinyl compound. A radical which is usually known as a solution having a concentration of 1 to 80 wt% prepared by dissolving N-1-methyl-2-methoxyethylacrylamide and N-1-methyl-2-methoxyethylmethacrylamide of the present invention in an organic solvent. Polymerization methods can be used.

The solvent used in such a solution polymerization method is N-
1-methyl-2-methoxyethyl acrylamide and N
There is no particular limitation as long as it can dissolve -1-methyl-2-methoxyethyl methacrylamide. For example, water,
Examples thereof include alcohols, acetone, tetrahydrofuran, chloroform, carbon tetrachloride, benzene, and alkyl acetates. These may be used alone or in combination of two or more depending on the case. .

The polymer compound of the present invention is soluble in water in a low temperature region and insoluble in water in a high temperature region. The transition temperature of the aqueous polymer compound solution is
Poly (N-1-methyl-2) varies depending on the polymerization conditions.
-Methoxyethyl acrylamide) in a 1% by weight aqueous solution is 33 to 35 ° C, and poly (N-1-methyl-2-methoxyethylmethacrylamide) in a 1% by weight aqueous solution is in the range of 42 to 45 ° C. The transition temperature of the aqueous solution of the polymer compound tends to decrease as the molecular weight increases. Therefore, if the molecular weight is changed, the transition temperature can be precisely controlled within the range of 42 to 45 ° C.

The polymer compound, poly (N-1-methyl-2-methoxyethyl acrylamide) and poly (N-1-methyl-2-methoxyethyl methacrylamide) of the present invention are -CO.
NH- group, _-CH 2 -O- group, because it has a -CH <group can be identified by infrared absorption spectrum. Regarding the degree of polymerization, the extreme viscosity [η] at a temperature of 30 ° C in a tetrahydrofuran solution is 0.01 to
The range of 6.0 is practical. Further, regarding the solubility in various solvents, it is soluble in cold water, tetrahydrofuran, chloroform, benzene, methanol, acetone and the like, but insoluble in ethyl acetate, n-amyl acetate, isobutyl acetate, hexane and the like.

The polymer compound of the present invention is a novel compound described in the end of the literature, and is a hydrophilic-hydrophobic thermoreversible polyacrylamide derivative that reversibly dissolves in water at low temperatures and becomes insoluble at high temperatures. ,
It has a transition temperature different from that of the conventionally known affinity-hydrophobic thermoreversible polyacrylamide derivative. For example, light-shielding bodies such as greenhouses, temperature sensors, surfactant adsorbents, toys and interiors. , A printing aid, a display, a separation functional film, a mechanochemical element material, etc.

EXAMPLES Next, the present invention will be described in more detail by reference examples and examples, but the present invention is not limited to these examples.

Reference Example 1 11 Erlenmeyer flask was charged with 101.7 g of triethylamine, 89.48 g of 2-amino-1-methoxypropane and 450 ml of toluene.
80.0 ml of acrylic acid chloride and 50 parts of toluene while stirring and keeping the content liquid at a temperature of less than 10 ° C by cooling with ice and stirring.
The mixed solution of ml was applied for about 3 hours using an appropriate funnel. After completion of the appropriate conditions, the reaction solution was kept in the refrigerator for one day to react. Then, the reaction solution was filtered, toluene was removed from the filtrate using a rotary evaporator, and further distilled under reduced pressure to obtain 101.7 g of a colorless transparent fraction (boiling point 92 ° C./1 mmHg).

The infrared absorption spectrum of this substance is shown in FIG. The results of mass spectrum analysis and infrared absorption spectrum analysis are as follows.

Mass spectral analysis: Infrared absorption spectrum analysis: -NH- = 3270 cm ^-1 CH ₂ = CH- = 1620 cm ^-1 -O- = 1108 cm ^-1 > C = O = 1655 cm ^-1 > CH- = 2930,2875 cm ^-1 2978 cm ^-1 -CONH -= 1545 cm ^{-1 From} the analysis results above, this substance is N-1-methyl-2
-Methoxyethyl acrylamide was confirmed.

Reference Example 2 A colorless and transparent fraction (boiling point 108 ° C./3.5 mmHg) 138.2 in exactly the same manner as in Example 1 except that 99 ml of methacrylic acid chloride was used instead of acrylic acid chloride in Reference Example 1.
g was obtained.

The infrared absorption spectrum of this substance is shown in FIG. The results of mass spectrum analysis and infrared absorption spectrum analysis are as follows.

Mass spectral analysis: Infrared absorption spectrum analysis: -NH- = 3320 cm ^-1 CH ₂ = C <= 1618 cm ^-1 -O- = 1108 cm ^-1 > C = O = 1655 cm ^-1 > CH- = 2930,2875 cm ^-1 2980 cm ^-1 -CONH From the analysis results of − = 1530 cm ⁻¹ or more, this substance is N-1-methyl-2
-Methoxyethyl acrylamide was confirmed.

Example 1 A radical polymer of the vinyl monomer obtained in Example 1 was produced.

Using azobisisobutyl nitrile as a polymerization initiator,
A predetermined weight of N-1-methyl-2- was added to the predetermined concentration of solvent.
Add methoxyethylacrylamide, put it in an ampoule, degas under reduced pressure using liquid nitrogen, seal the tube, and
The reaction was carried out at 50 ° C. for 7 hours in a constant temperature bath. After the reaction, the solvent was removed, and then n-hexane was added to separate and recover the polymer. The results of the polymerization reaction of Example 1 are shown in Table 1.

Examples 2 to 4 Radical polymers of the vinyl monomer obtained in Reference Example 1 were produced.

A predetermined amount of N-1-methyl-2-methoxyethylacrylamide was added to 20 ml of a polymerization solvent, which was placed in an ampoule,
Irradiation dose rate 4.Deaerated under reduced pressure with liquid nitrogen and sealed.
9 × 10 ⁴ R / hr, temperature 24 ° C for 2 hours γ from cobalt 60
The rays were irradiated to react. After the reaction, the solvent was removed and then n-
Hexane was added and the polymer was separated and collected. Examples 2 to
The results of the polymerization reaction of No. 4 are shown in Table 2.

The infrared absorption spectrum of the polymer of Example 2 is shown in FIG. By comparing the infrared absorption spectrum of the vinyl monomer with that of the polymer, it was confirmed that the vinyl group at 1620 cm ^-1 disappeared and a polymer compound was produced.

This polymer was used as a tetrahydrofuran solution, and the viscosity was measured at 27 ° C. using an Ubbelohde viscometer.

The thermal reversibility of this polymer in water was examined.
The transition temperature was determined from the light transmittance of the aqueous solution with temperature change. That is, a polymer aqueous solution having a concentration of 1% by weight was prepared, and a spectrophotometer with a temperature controller was used.
The light transmittance at a wavelength of 500 nm was measured while the temperature was raised at a rate of / min, and the transition temperature was determined from the temperature (T _L ) at which the light transmittance was 0.5 of the initial transmittance. The results are shown in Table 3.

The transmittance-temperature curve of the aqueous polymer solution of Example 1 is shown in FIG. Among them, the solid line is the data when the temperature is raised and the dotted line is the data when the temperature is lowered.

Examples 5 to 9 Radical polymers of the vinyl monomer obtained in Reference Example 2 were produced. Instead of N-1-methyl-2-methoxyethylacrylamide in Reference Example 1, N-1-methyl-2-
Except for using methoxyethylmethacrylamide, the reaction was carried out in the same manner as in Examples 1 to 4 by keeping the temperature at 50 ° C for 24 hours in a constant temperature bath. After the reaction, the solvent was removed, and then n-hexane was added to separate and collect the polymer. Table 4 shows the polymerization reaction results of Examples 1 to 9.

The infrared absorption spectrum of the polymer of Example 8 is shown in FIG. By comparing the infrared absorption spectrum of the vinyl monomer with that of the polymer (Fig. 3), it was confirmed that the vinyl group at 1618 cm ^-1 disappeared and a polymer compound was produced.

The intrinsic viscosity and transition temperature of these polymers were determined in the same manner as in Examples 1 to 4. The results are shown in Table 5.

The transmittance-temperature curve of the aqueous polymer solution of Example 6 is shown in FIG. Among these, the solid line is the data at the time of temperature rise and fall, and the dotted line is the data at the time of fall.

[Brief description of drawings]

FIG. 1 shows the infrared absorption spectrum of the vinyl monomer of Reference Example 1, and FIG. 2 shows the infrared absorption spectrum of the polymer of Example 2. FIG. 3 shows the infrared absorption spectrum of the vinyl monomer of Reference Example 2, and FIG. 4 shows the infrared absorption spectrum of the polymer of Example 8. FIG. 5 shows the transmittance-temperature curve of the polymer of Example 1 in a 1 wt% aqueous solution, and FIG. 6 shows the transmittance-temperature curve of the polymer of Example 6 in a 1 wt% aqueous solution.

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Claims (2)

[Claims] 1. A general formula (I) (R in the formula is a hydrogen atom or a methyl group) and has an intrinsic viscosity [η] of 0.01 to 6.0 at a temperature of 27 ° C. in a tetrahydrofuran solution.
A hydrophilic-hydrophobic thermoreversible polymer compound having a molecular weight corresponding to. 2. General formula (II) (In the formula, R is a hydrogen atom or a methyl group.) The vinyl compound represented by the formula (I) is characterized by being radically polymerized. (R in the formula is a hydrogen atom or a methyl group) and has an intrinsic viscosity [η] of 0.01 to 6.0 at a temperature of 27 ° C. in a tetrahydrofuran solution.
A method for producing a hydrophilic-hydrophobic thermoreversible polymer compound having a molecular weight corresponding to.