JPH0549661B2 - - 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 for dye resist pastes, 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. This compound is called a hydrophilic-hydrophobic thermoreversible polymer compound, and has recently attracted attention as a mechanochemical material, dye resist paste, separation material, etc.

As such thermoreversible polymer compounds, partially saponified polyvinyl acetate, polyvinyl methyl ether, methylcellulose, polyethylene oxide, 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, polyN
- Acryloylpiperidine, poly N-acryloylpyrrolidine, 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-otherspiro[4.5]decane and the like are known. However, even if these thermoreversible polymer compounds are used in temperature sensors, light shields, etc.,
Since the transition temperature is limited, it cannot be arbitrarily selected depending on the purpose, and the range of application is inevitably limited.

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 As a result of intensive research to develop hydrophilic-hydrophobic thermoreversible polymer compounds having different transition temperatures, the present inventors found that the formula 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 novel compound that has not been described in any literature, namely, N-(2-methoxyethyl)-N-
Ethylacrylamide, for example, reaction formula According to the reaction formula, acrylic acid chloride, N-(2-methoxyethyl)ethylamine, and triethylamine are reacted in a solvent kept at 0 to 10°C, or according to the reaction formula It can be obtained by reacting acrylic acid chloride and N-(2-methoxyethyl)ethylamine 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 N-(2-methoxyethyl)ethylamine 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-(2-methoxyethyl)-N-ethyl acrylamide (boiling point 86.5
°C/1.5mmHg) It is a colorless liquid, soluble in solvents such as water, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, chloroform, carbon tetrachloride, and benzene, but insoluble in n-hexane and n-heptane. . The vinyl compound of the present invention is
_CH2 =CH- group, -CON< group, _-CH2 -O- group, -
It has CH ₃ groups, etc., and can be identified by infrared absorption spectroscopy, mass spectrometry, etc.

By radically polymerizing the N-(2-methoxyethyl)-N-ethylacrylamide of the present invention, a hydrophilic-hydrophobic thermoreversible polymer compound that becomes insoluble in water by heating can be produced.
This polymerization is usually carried out by solution polymerization or bulk polymerization, using an azo compound such as benzoyl peroxide or peracetic acid as a polymerization initiator, or by irradiation with actinic radiation such as ultraviolet rays, radiation, electron beams, or perasma. It can be carried out. The amount of polymerization initiator used at this time is 0.005 to
A range of 5% by weight, especially from 0.001 to 2% by weight, is suitable.

Particularly preferred is the solution polymerization method, in which N-(2-
This is a method in which methoxyethyl)-N-ethylacrylamide 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-(2-methoxyethyl)-N-ethyl acrylamide. For example, water, alcohols, acetone, tetrahydrofuran, chloroform, carbon tetrachloride,
Examples include benzene and alkyl acetates, and these may be used alone or in combination of two or more types depending on the case.

The polymer compound obtained by radical polymerization of the vinyl compound of the present invention has -CON< group, -CH ₂ -O
Since it has - group, -CH< group, and _-CH3 group, it can be identified by infrared absorption spectrum. Furthermore, for polymerization of high molecular compounds, it is practical to use a tetrahydrofuran solution having an intrinsic viscosity [η] of 0.01 to 6.0 at a temperature of 27°C. Furthermore, regarding solubility in various solvents,
Cold water, alcohols such as methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, chloroform, benzene, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, n-acetate It is soluble in -amyl, alkyl acetate such as n-hexyl 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 hydrophilic-hydrophobic thermoreversible polymer compound that reversibly dissolves in water at low temperatures and becomes insoluble at high temperatures. The transition temperature of this substance varies depending on the polymerization conditions, but is usually in the range of 38 to 42°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 with a transition temperature different from that of conventionally known thermoreversible polyacrylamide derivatives. It can be used in sensors, surfactant adsorbents, toys, interiors, dye resisting pastes, 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 98.32 in the Erlenmeyer flask of Example 1
gN-(2-methoxyethyl)ethylamine
100.46 g and 450 ml of toluene were added, and while stirring and keeping the contents at a temperature below 10° C., a mixed solution of 80 ml of acrylic acid chloride and 50 ml of toluene was added dropwise using a dropping funnel over about 3 hours. 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 86.5℃/1.5mm
Hg) 122.5g was obtained.

The infrared absorption spectrum of this substance is shown in Figure 1.
The mass spectrum is shown in FIG.

The results of these spectral analyzes are as follows.

Mass spectrum: m/e M+1 = 158 M = 157 M- -CH ₂ -O-CH ₃ = 112 -N-CH ₂ CH ₂ -O- = 58 CH ₂ = CH-CO- = 55 CH ₂ = CH- =27 Infrared absorption spectrum analysis: -N< =3480cm ^-1 _CH2 =CH- =1604cm ^-1 -O- =1115cm ^-1 >C=O =1642cm ^-1 >CH- =2950, analysis of 2930cm ^-1 or more From the results, it was confirmed that it was N-(2-methoxyethyl)-N-ethylacrylamide.

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

12.67 g of N-(2-methoxyethyl)-N-ethylacrylamide and 200 g of water were added to a 500 ml Erlenmeyer flask equipped with a capillary and condenser, and nitrogen gas was vigorously bubbled through the flask. Add 10 ml of water containing 30.0 mg of ammonium persulfate as a polymerization initiator, and adjust the polymerization temperature.
The mixture was kept in a constant temperature bath at 40°C for 1 hour to react. After the reaction,
The polymerization reaction was stopped by adding 30 ml of methanol.
The produced polymer compound was isolated by heating the reaction solution to 60°C to precipitate it. Yield: 8.75g.

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, 1604
The spectrum based on the vinyl group at cm ^-1 disappeared, confirming the formation of a polymer compound.

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] = 3.15 In addition, an aqueous solution of a polymer compound with a concentration of 1% by weight was adjusted, and while being heated at a rate of 1°C/min using a spectrophotometer with a temperature controller,
The light transmittance at 500 nm is measured, and the transition temperature is the temperature at which this light transmittance becomes 0.5 of the initial transmittance (T _L ).
I asked for it from.

Transition temperature T _L =40.5°C.

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the vinyl monomer of the example, FIG. 2 shows the infrared absorption spectrum of the polymer compound of the reference example, and FIG. 3 shows the mass spectrum of the vinyl monomer of the example.

Claims (1)

[Claims] 1 formula A vinyl compound represented by