JPH0521102B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel vinyl compound. More specifically, the present invention is applicable to light shielding bodies, temperature sensors, adsorbents, toys, interior decorations,
The present invention relates to a vinyl compound suitable as a raw material monomer for a hydrophilic-hydrophobic thermoreversible polymer compound that can be used in printing agents, displays, separation membranes, and mechanochemical materials.

Prior Art Some water-soluble polymer compounds exhibit a special reversible dissolution behavior in which they precipitate and become cloudy above a certain temperature (transition temperature or cloud point) in an aqueous solution state, and dissolve and become transparent below that temperature. Yes, this compound is called a hydrophilic-hydrophobic thermoreversible polymer compound, and in recent years it has been used as a light-shielding material in greenhouses, chemical laboratories, etc.
It has started to attract attention as a temperature sensor, etc.

As such thermoreversible polymer compounds, partially saponified polyvinyl acetate, polyvinyl methyl ether, methylcellulose, polyethylene oquinde, polyvinylmethyloxazolidinone, polyacrylamide derivatives, etc. have been known so far.

Among these thermoreversible polymer compounds, polyacrylamide derivatives are particularly useful because they are stable in water and can be produced at relatively low cost. -n-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-N-n-propylacrylamide), poly(N-methyl-N-isopropylacrylamide), poly(N-acrylicpiperidine), 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), poly(N-1-methyl-2-methoxyethyl (meth)acrylamide), poly(N-1-methoxymethylpropyl(meth)acrylamide), poly(N-(1,3-
dioxolan-2-yl)-N-methylacrylamide), poly(N-8-acryloyl-1,4
-dioxa-8-aza-spiro[4,5]decane) and the like are known. However, even if these thermoreversible polymer compounds are used for temperature sensors, light shields, etc., their transition temperature is limited, and they cannot be arbitrarily selected depending on the purpose, limiting the range of application. I couldn't avoid being attacked.

Problems to be Solved by the Invention Under these circumstances, the present invention solves the problem of hydrophilic
In order to expand the scope of use of hydrophobic thermoreversible polymer compounds, the purpose of this invention was to provide raw material monomers for hydrophilic-hydrophobic thermoreversible polymer compounds having different transition temperatures.

Means for Solving the Problems The present inventors have conducted intensive research to develop hydrophilic-hydrophobic thermoreversible polymer compounds having different transition temperatures. The formula obtained by radical polymerization of the vinyl compound represented by A polymer compound consisting of repeating units represented by the formula and having a molecular weight corresponding to an intrinsic viscosity [η] of 0.01 to 6.0 in a tetrahydrofuran solution at a temperature of 27°C is a hydrophilic-hydrophobic thermoreversible type that becomes insolubilized in water by heating. discovered that it is a polymer compound,
Based on this knowledge, we have completed the present invention.

The vinyl compound of the present invention is a new compound that has not been described in any literature, that is, N,N-di(2-methoxyethyl)acrylamide, and for example, the reaction formula According to the above, acrylic acid chloride, bis(2-methoxyethyl)amine and triethylamine were
Either react in a solvent kept at 10℃ or use the reaction formula It can be obtained by reacting allylyl chloride and bis(2-methoxyethyl)amine in a solvent maintained at 0 to 10°C.

Regarding the solvents used in these methods,
There is no particular restriction as long as it is inert to acrylic acid chloride, and benzene, acetone, toluene, etc. are generally used. Regarding the reaction temperature, if it is too high, side reactions will occur, so it is preferable to carry out the reaction in the range of 0 to 10°C.

To isolate the target compound from the reaction mixture thus obtained, usually first, triethylamine hydrochloride or bis(2-methoxyethyl)amine hydrochloride is removed by filtration, etc., and then a rotary evaporator is used. The solvent is distilled off from the filtrate using a filtrate, followed by distillation under reduced pressure for purification. The distillate at this time can be further subjected to repeated distillation under reduced pressure as necessary to make it highly pure.

The thus obtained N,N-di(2-methoxyethyl)acrylamide (boiling point 119°C/2
mmHg) It is a colorless liquid, 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 of the present invention has a CH ₂ =CH- group, -
Since it has CON< group, _-CH2 -O- group, _-CH3 group, etc., it can be identified by infrared absorption spectrum, mass spectrum, NMR spectrum analysis, etc.

By radically polymerizing the N,N-di(2-methoxyethyl)acrylamide of the present invention, a hydrophilic-hydrophobic thermoreversible polymer compound that becomes insoluble in water by heating can be produced. is usually carried out by solution polymerization or bulk polymerization, using peroxides such as benzoyl peroxide or peracetic acid, or azo compounds such as azobisisobutyronitrile as polymerization initiators, or by using ultraviolet rays, radiation, or electron beams. This can be carried out by irradiation with actinic radiation such as plasma. The amount of polymerization initiator used in this case is 0.005 to 5% by weight, based on the weight of the monomer.
In particular, a range of 0.001 to 2% by weight is suitable.

Particularly preferred is a solution polymerization method in which N,N-di(2-methoxyethyl)acrylamide is dissolved in an organic solvent at a concentration of 1 to 80% by weight and polymerized.

The solvent used in such a solution polymerization method is not particularly limited as long as it dissolves N,N-di(2-methoxyethyl)acrylamide. Examples include water, alcohols, acetone, tetrahydrofuran, chloroform, carbon tetrachloride, benzene, alkyl acetates, etc., and these may be used alone or in combination of two or more. .

Furthermore, regarding the degree of polymerization of the polymer compound obtained by radical polymerization of the vinyl compound of the present invention,
Practical materials have a limiting viscosity [η] of 0.01 to 6.0 at a temperature of 27° C. in a tetrahydrofuran solution. Furthermore, regarding solubility in various solvents, cold water, tetrahydrofuran, chloroform,
It is soluble in benzene, methyl acetate, ethyl acetate, alkyl acetate such as n-butyl acetate, etc., but insoluble in hot water, diethyl ether, n-hexane, n-heptane, etc.

The polymer compound obtained by radical polymerization of the vinyl compound of the present invention is a high-temperature hydrophobized thermoreversible polymer compound that dissolves in water at low temperatures and becomes insoluble in water at high temperatures. The transition temperature of this material varies depending on the polymerization conditions, but is usually in the range of 41 to 45°C.

Effects of the Invention The vinyl compound of the present invention is a new vinyl compound that has not been described in any literature, and the polymer compound has a hydrophilic property that reversibly dissolves in water at low temperatures and becomes insoluble at high temperatures.
It is a hydrophobic thermoreversible polymer compound that has a transition temperature different from that of conventionally known thermoreversible polyacrylamide derivatives. It can be used in temperature sensors, surfactant adsorbents, toys, interiors, textile printing agents, displays, separation membranes, mechanochemical device materials, etc.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples and Reference Examples, but the present invention is not limited to these Examples in any way.

Triethylamine 19.8 in the Erlenmeyer flask of Example 1
Add 26.0 g of bis(2-methoxyethyl)amine and 450 ml of toluene, cool with ice and drain the contents.
A mixture of 16.0 ml of acrylic acid chloride and 50 ml of toluene was added dropwise using a dropping funnel over a period of about 3 hours while stirring while maintaining the temperature at less than 10°C. After completion of the dropwise addition, the reaction solution was kept in the refrigerator for one day and night to react. Next, the reaction solution was filtered, toluene was removed from the filtrate using a rotary evaporator, and vacuum distillation was performed to obtain a colorless and transparent fraction (boiling point 119°C/2mmHg).
29.9g was obtained.

The infrared absorption spectrum of this substance is shown in Figure 1.
The mass spectrum is shown in Figure 3, and the NMR spectrum is shown in Figure 4.

The results of these spectral analyzes are as follows.

Mass spectrum: m/e M = 187 M- -CH ₂ OCH ₃ = 142 CH ₂ ＝CH−CO− ＝55 CH ₂ ＝CH− ＝27 Infrared absorption spectrum analysis: −N＜ ＝3500cm ⁻¹ CH ₂ ＝CH− ＝1618cm ⁻¹ −O− ＝1122cm ⁻¹ ＞C＝O ＝1655cm ^-1 ＞CH− =2950, 2900cm ^-1 NMR spectrum analysis: H _A : 6.60~6.70PPM H _B : 6.32~6.37PPM H _C : 5.65~5.70PPM H _D : 3.60~3.65PPM H _E : 3.48~3.58PPM H _F : 3.34PPM From the above analysis results, N, N- It was confirmed to be di(2-methoxyethyl)acrylamide.

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

Using azobisisobutyronitrile as a polymerization initiator, add 20ml of benzene at a concentration of 0.05g/100ml.
After adding 5.12 g of N,N-(2-methoxyethyl)acrylamide into an ampoule containing the ampoule, the tube was repeatedly degassed under reduced pressure using liquid nitrogen, the tube was sealed, and the ampoule was kept in a constant temperature bath at a temperature of 50°C for 1 hour. Made it react. After the reaction, hydroquinone was added to stop the polymerization reaction. The produced polymer compound was mixed with the reaction solvent in n-hexane, precipitated, and isolated. Yield 1.31
g.

The infrared absorption spectrum of this polymer compound is shown in FIG. By comparing the infrared absorption spectrum of vinyl monomer with that of polymer compounds,
It was confirmed that the vinyl group of 1618CM ^-1 disappeared and a polymer compound was formed.

The obtained polymer compound was dissolved in tetrahydrofuran and measured at 27% using an Ubbelohde viscometer.
The viscosity was measured at °C to determine the intrinsic viscosity [η]. Intrinsic viscosity [η] = 1.37.

In addition, the transition temperature was determined from the light transmittance associated with the temperature change of the aqueous solution, and the thermoreversibility in water was investigated. FIG. 5 shows the transmittance-temperature curve of the aqueous solution of the polymer compound of the reference example. Among these, the solid line is the data when the temperature is increased, and the broken line is the data when the temperature is decreased. That is,
Prepare an aqueous solution of a polymer compound with a concentration of 1% by weight,
Using a spectrophotometer with a temperature controller, measure the light transmittance at a wavelength of 500 nm while increasing the temperature at a rate of 1°C/min. The transition temperature is the temperature at which this light transmittance becomes 0.5 of the initial transmittance. (T _L ).
Transition temperature T _L =41.5°C Reference Example 2 A polymer compound of the vinyl monomer obtained in Example was produced.

Using azobisisobutyronitrile as a polymerization initiator, methanol at a concentration of 0.02g/100ml
After adding 10.30 g of N,N-di(2-methoxyethyl)acrylamide into a 300 ml Erlenmeyer flask containing 50 ml, dry nitrogen was passed for about 1 hour. Temperature 50℃
The mixture was kept in a constant temperature bath for 6 hours and reacted under a nitrogen stream.
After the reaction, hydroquinone was added to stop the polymerization reaction. After once removing methanol, which is a polymerization solvent, the mixture was mixed in hot water of 60° C. or higher to precipitate it and isolated. Yield 7.40g.

The formation of a polymer compound was confirmed in exactly the same manner as in Reference Example 1, and the intrinsic viscosity [η] = 0.50 at 27°C in tetrahydrofuran solvent and the transition temperature T _L =42.6°C were obtained.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of the vinyl monomer of Example, Figure 2 shows the infrared absorption spectrum of the polymer compound of Reference Example 1, and Figure 3 shows the mass spectrum of the vinyl monomer of Example. Figure 4 shows the mass spectrum of the vinyl monomer of the example. Figure 5 shows the transmittance of a 1% by weight aqueous solution of the polymer compound of Reference Example 1 by the method of the present invention.
The temperature curve is shown.

Claims (1)

[Claims] 1 formula A vinyl compound represented by