JPH02145553A - Novel vinyl compound - Google Patents

Abstract

NEW MATERIAL:N-(2-Methoxyethyl)-N-n-propylacrylamide expressed by the formula. USE:Useful as a raw material monomer for hydrophilic-hydrophobic heat reversible type high polymer compounds utilizable as a light shielding unit, temperature sensor, adsorbent, toy, interior, resist paste, display, separation membrane, mechanochemical material, etc. PREPARATION:Acryloyl chloride is reacted with N-(2-methoxyethyl)-n- propylamine and triethylamine in a solvent (e.g. benzene) kept at 0-10 deg.C to afford the compound expressed by the formula. The hydrophilic-hydrophobic heat reversible type high polymer compounds are reversibly soluble in water within a low temperature region, become insoluble within a high temperature region and have the transition temperature different from that of conventionally known heat reverisble type polyacrylamide derivatives.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel vinyl compound. Specifically, the present invention relates to a novel vinyl compound. Raw materials for reversible polymer compounds
This invention relates to a vinyl compound suitable as a vinyl compound.

Conventional technology 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. These compounds are called hydrophilic-hydrophobic thermoreversible polymer compounds, and have recently attracted attention as mechanochemical materials, dye resist pastes, separation materials, etc.

As such thermoreversible polymer compounds, partially saponified polyvinyl acetate, polyvinyl methyl ether, methylcellulose, polyethylene oxide, polyvinylmethyloxacilidinone, and polyacrylamide derivatives are known. Among reversible polymer compounds, polyacrylamide derivatives are particularly useful because they are stable in water and can be produced at relatively low cost. ) acrylamide, poly N-isopropyl (meth)acrylamide, poly N-cyclopropyl (meth)acrylamide,
Poly N.

N-diethylacrylamide, 7bolyN-methyl-N-
Ethylacrylamide, poly N-methyl-N-n-propylacrylamide, poly N-methyl-N-isopropylacrylamide, poly N-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, polyN-1-methyl-2-methodo, polyN-(1,3-dioxolan-2-yl)-N-methylacrylamide, polyN-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 in temperature sensors, light shields, etc., their transition temperature is limited, and they cannot be arbitrarily selected depending on the purpose, which limits the scope of their application. I couldn't avoid being attacked.

Problems to be Solved by the Invention Under these circumstances, the present invention aims to expand the scope of use of hydrophilic-hydrophobic thermoreversible polymer compounds. The purpose of this study was to provide raw material monomers for thermoreversible polymer compounds.

Means for Solving the Problems The present inventors further developed hydrophilic compounds having different transition temperatures.
As a result of intensive research to develop a hydrophobic thermoreversible polymer compound, it was found that it consists of repeating units represented by the formula % and has an intrinsic viscosity [η) of 0.
It was discovered that a polymer compound having a molecular weight corresponding to 01 to 6.0 is a hydrophilic-hydrophobic thermoreversible polymer compound that becomes insolubilized in water by heating, and based on this knowledge, the present invention was completed. reached.

The vinyl compound of the present invention is a new compound that has not been described in any literature, that is, N-(2-methoxyethyl)-N-n-propylacrylamide, and is obtained by radical polymerization of a vinyl compound represented by the reaction formula, for example. Formula % Formula % CH2CH20-CH3 / CH2= CH+ NH + (C2Hs )s N-> \ C=0 CHaCH2CH* CH2=CH+ (C2Ha)z N -HC1C
;ON CHt CHt 0-CHI\ CHaCHtCHa According to
Reacted in a solvent kept at ~10°C / CHa = CH+2 N H l \ C=OCH2CH2CHs CI CHs CHz 0-CHs
-> / CH2=CH+ NH-HC1 1\C=0 CH2CH2CHs N CHtCH* OCHi\CHaCH2CHx Acrylic acid chloride and N-(2-methoxyethyl)-n-propylamine in a solvent kept at 0 to 10°C It can be obtained by reacting in

The solvent used in these methods is not particularly limited as long as it is inert to acrylic acid chloride, and benzene, acetone, toluene, etc. are generally used6.
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)-n-propylamine hydrochloride is removed by filtration or the like. The solvent is distilled off from the filtrate using a rotary evaporator, 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.

N-(2-methoxyethyl)- thus obtained
N-n-propylacrylamide has a boiling point of 98℃/2
mdg) is a colorless liquid that can be mixed with water, methyl alcohol,
Ethyl alcohol, acetone, tetrahydrofuran, chloroform, carbon tetrachloride, ben-CON< group, -CH2
Since it has 0-group, CHs group, etc., it can be identified by infrared absorption spectrum, mass spectrometry, etc.

By radical polymerizing the N-(2-methoxyethyl)-N-n-propylacrylamide 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 using ultraviolet light.

This can be carried out by irradiation with active rays such as radiation, electron beams, and plasma. The amount of the polymerization initiator used in this case is suitably in the range of 0.005 to 5% by weight, particularly o,oot to 2% by weight, based on the weight of the monomer.

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

The solvent used in such solution polymerization method is N-
There is no particular restriction as long as it dissolves (2-methoxyethyl)-N-n-propylacrylamide. For example, water, alcohols, acetone, tetrahydrofuran,
Examples include chloroform, carbon tetrachloride, benzene, alkyl acetates, etc., and these may be used alone or 1. Depending on the case, two or more types may be used in combination.

The polymer compound obtained by radical polymerization of the vinyl compound of the present invention has -CON< group, CH2-〇- group, -
Since it has CH< group and CH3 group, it can be identified by infrared absorption spectrum, etc. Regarding the degree of polymerization of the polymer compound, the intrinsic viscosity [η] at a temperature of 27°C in a tetrahydrofuran solution is 0.01 to 6.
．． A range of 0 is practical. Furthermore, regarding solubility in various solvents, cold water, alcohols such as methanol, ethanol, and isopropanol, acetone, tetrahydrofuran, dioxa, chloroform, benzene, methyl acetate, ethyl acetate, n-propyl acetate, and other alkyl acetates, etc. is soluble, hot water, cyclohexane, n-
It is insoluble in hexane, n-hebutane, etc.

The polymer compound obtained by radical polymerization of the vinyl compound of the present invention is a hydrophilic-hydrophobic thermoreversible polymer compound that is reversibly soluble in water at low temperatures and insoluble at high temperatures. The transition temperature of this material varies depending on the polymerization conditions, but is usually in the range of 11 to 14°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-hydrophobic thermoreversible property that is reversibly soluble in water at low temperatures and insoluble at high temperatures. It is a type polymer compound with a transition temperature different from that of conventionally known thermoreversible polyacrylamide derivatives, and is useful, for example, as a light shield for greenhouses, chemical laboratories, radioisotope laboratories, temperature sensors, surfactants, etc. It can also be used as an adsorbent for toys, interior decoration, dye-resistant gates, 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 in any way by these Examples.

Triethylamine 87.549N was added to the Erlenmeyer flask of Example 11.
-(2-methoxyethyl)-n-propylamine 101
．． 31 g of toluene and 450 ml of toluene were added, cooled with water, and kept at a temperature of less than 10°C. While stirring, a mixed solution of 70 ml of acrylic acid chloride and 50 ml of toluene was added using a dropping funnel over a period of about 3 hours. 1 drop completed. The post-reaction solution was kept in the refrigerator for one day and night to react.

Then, the reaction solution was filtered, toluene was removed from the filtrate using a rotary evaporator, and further vacuum distillation was performed to obtain a colorless and transparent fraction (boiling point 98°C/2mmHg) 117.4
I got g.

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

The results of these spectral analyzes are as follows.

Mass spectrum: M+L M -CH2-○-CH3 -CH2N-CH2CH20- CH2= CHC0- CH2=CH- m/e =172 =171 =126 =72 =55 =27 Infrared absorption Subek-N< CH2=CH- > C+SO > CH- Tor analysis: =34950Il-1 =1612 cm-' =1115 cm-' = 1648 ca+-' = 2975.2940co+-From the surprising analysis results, N-(2-methoxyethyl)-N
-n-propylacrylamide was confirmed.

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

Benzene 100ml, N-(2-methoxyethyl)-
19.41 g of N-n-propylacrylamide and 0.5 g of azobisisobutyronitrile were added to a 150 m sealed tube and dissolved.Next, after repeated cooling and degassing operations using liquid nitrogen, the tube was sealed. After 0 reaction, which was kept in a constant temperature bath at a polymerization temperature of 50° C. for 3 hours, 200 ml of methanol was added to stop the polymerization reaction. After drying the reaction solution, the generated polymer compound was made into an ethanol solution at 30°C.
It was isolated by precipitation in a large amount of water. Yield 19.05
g.

The infrared absorption spectrum of this polymer compound is shown in Figure 2. By comparing the infrared absorption spectrum of the vinyl monomer with that of the polymer compound, 1612 was obtained. The viscosity was measured at 27°C, and the intrinsic viscosity [η
] was sought. Intrinsic viscosity [η) = 1.46 Also, by adjusting the aqueous solution of a polymer compound with a concentration of 1% by weight,
Using a spectrophotometer with a temperature controller, the heating rate was 1℃.
The light transmittance at a wavelength of 500 nm was measured while increasing the temperature at a rate of 0.5 min.
It was determined from the temperature (T L ) that gives a value of 5.

Transition temperature TL = 12.4°C Reference example 2 Methanol 20ml. N-(2-methoxyethyl)
Add and dissolve 4.82 g of -N-n-propylacrylamide and 4 mg of azobisisobutyronitrile in a 30 ml sealed tube.Then, after repeating the cooling and degassing operation using liquid nitrogen, the tube was sealed. After the reaction, the reaction solution was kept in a constant temperature bath for 5 hours at a polymerization temperature of 50'C, and the produced polymer compound was isolated by drying the reaction solution, making it an ethanol solution, and precipitating it in a large amount of water at a temperature of 30°C or higher. . Yield: 1.91g.

By comparing the infrared absorption spectrum of this polymer compound and the infrared absorption spectrum of vinyl monomer, it was found that 1612
The spectrum based on the vinyl group of CM-1 disappeared, confirming the formation of a polymer compound.

The intrinsic viscosity in a tetrahydrofuran solution at 27°C was determined by the same method as in Reference Example 1.

Intrinsic viscosity [η)=0.51 Further, the transition temperature of a 1% by weight aqueous solution of a polymer compound was determined by the same method as in Reference Example 1.

Transition temperature TL=12.0℃ No. figure

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the tonyl 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 tonyl monomer of the example. Wave number (value -') Figure 1, Display of the case Patent Application No. 302096 of 1988 2, Title of the invention New vinyl compound 3, Relationship with the person making the amendment case

Claims (1)

[Claims] formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A vinyl compound represented by