JPS63270674A - Novel vinyl compound - Google Patents

Abstract

NEW MATERIAL:N-methyl-N-(1,3-dioxolan-2-yl)acrylamide of formula. USE:A raw material monomer for a water and alcoholic solvent-dependent thermally reversible polymeric compound usable as a light-shielding material, temperature sensor, adsorbent, toy, interior goods, printing agent, display, separation membrane and mechanochemical material. PREPARATION:The compound of formula can be produced either by reacting acryloyl chloride with 2-methylaminomethyl-1,3-dioxolane and triethylamine in a solvent maintained at 0-10 deg.C or by reacting acryloyl chloride with 2- methylaminomethyl-1,3-dioxolane in a solvent maintained at 0-10 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel vinyl compound. More specifically, the present invention provides water and alcohol solvent dependent thermoreversible polymers that can be used in light shields, temperature sensors, adsorbents, toys, interiors, textile printing agents, displays, separation membranes, and mechanochemical materials. This invention relates to vinyl compounds suitable as raw material monomers for compounds.

Conventional technology Some water-soluble polymer compounds exhibit a special reversible dissolution behavior in which they precipitate and turn 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 to hydrophobic thermoreversible polymer compound, and has recently attracted attention as a light shielding material for greenhouses, chemical laboratories, etc., and as a temperature sensor.

As such hydrophilic-hydrophobic thermoreversible polymer compounds, partially saponified polyvinyl acetate, polyvinyl methyl ether, methylcellulose, polyethylene oxide, polyvinylmethylexazolidinone, and polyacrylamide derivatives have been known. There is.

Among these hydrophilic-hydrophobic thermoreversible polymer compounds, polyacrylamide derivatives are particularly popular because they are stable in water and can be produced at relatively low cost. (meth)acrylamide), poly (N-n-propyl (meth)acrylamide), poly (N-isopropyl (meth)acrylamide),
Poly (N-cyclopropyl (meth)acrylamide), Poly (N, N-diethylacrylamide), Poly (NSN-diethylacrylamide), Poly (N-methyl-Nn-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), etc. are known.

However, although all of these thermoreversible polymer compounds exhibit thermoreversible properties in aqueous solutions, they do not exhibit such properties in solutions of other solvents, such as alcohol, so their range of use is limited. I couldn't avoid it.

Problems to be Solved by the Invention Under these circumstances, the present invention aims to expand the scope of use of hydrophilic-hydrophobic thermoreversible polyacrylamide derivatives, even when dissolved in a solvent other than water. This was done with the aim of providing a polyacrylamide-based raw material monomer that exhibits thermoreversible properties.

Means for Solving the Problems The present inventors have conducted intensive research to develop a new polymer compound that exhibits thermoreversible properties even in solvents other than water, and as a result, we have found that the formula % is expressed by the formula %. A polymer compound obtained by radical polymerization of a vinyl compound and consisting of repeating units represented by the formula % formula %) and having a molecular type corresponding to an intrinsic viscosity [η) of 0.01 to 6.0 at 27°C is: It was discovered that it exhibits thermoreversible properties of becoming insolubilized due to temperature changes even when dissolved in alcohol as well as water, and based on this knowledge, the present invention was developed.

The vinyl compound of the present invention is a novel compound that has not been described in any literature, namely, N-methyl-N-(1,3-dioxolane-2-
For example, according to the reaction formula %, acrylic acid chloride, 2-methylaminomethyl-1,3-dioxolane, and triethylamine are
Either react in a solvent kept at 10°C, or react with acrylic acid chloride and 2-methylamizmedel according to the reaction formula %.
It can be obtained by reacting 1,3-dioxolane with 1,3-dioxolane in a solvent maintained at 0 to 10°C.

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 used.

Regarding the reaction temperature, side reactions will occur if it is too high, so
It is preferable to carry out the reaction in the range of -10°C.

To isolate the target compound from the reaction mixture thus obtained, usually first, triethylamine hydrochloride or 2-methylaminomethyl-1,3-dioxolane 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-methyl-N-(1°3-dioxolan-2-yl)acrylamide (boiling point 117
°C/Imlmm1 (It is a colorless liquid, soluble in solvents such as water, methyl alcohol, ethyl alcohol, atocene, tetrahydrofuran, chloroform, carbon tetrachloride, benzene, etc., and soluble in n-hexane, n-hebutane, etc.) Insoluble.

The vinyl compound of the present invention has CH, -CH- group, -CON
< group, -CI- (t -0- group, -CH< group, CtI
Since it has an s-group etc., it can be identified by infrared absorption spectrum, mass spectrum analysis, etc.

N-methyl-N-(1,3-dioxolane-2 of the present invention)
Water and alcohol solvent-dependent thermoreversible polymer compounds can be produced by radical polymerizing acrylamide, but this polymerization is usually carried out by solution polymerization or bulk polymerization using benzoyl peroxide, peracetic acid, etc. The polymerization can be carried out using a peroxide such as or an azo compound such as azobisisobutyronitrile as a polymerization initiator, or by irradiation with actinic rays such as ultraviolet rays, radiation, electron beams, and plasma. The amount of polymerization initiator used in this case is 0.005 to 5% by weight, particularly 0.005 to 5% by weight, based on the weight of the monomer.
A range of 0.001% to 2% double forgeries is appropriate.

Particularly preferred is the solution polymerization method, in which N-methyl-N-(
This is a method in which 1,3-dioxolan-2-yl)acrylamide is dissolved in an organic solvent at a concentration of 1 to 80% by weight and polymerized.

Regarding the solvent used in such solution polymerization method, N-
There are no particular limitations as long as it dissolves methyl-N-(1,3-dioxolan-2-yl)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. .

Regarding the polymerization degree of the polymer compound obtained by radical polymerization of the vinyl compound of the present invention, the intrinsic viscosity [η] at a temperature of 27°C in a tetrahydrofuran solution is 0.
A value in the range of 01 to 6.0 is practical. Furthermore, regarding solubility in various solvents, it is soluble in cold water, tetrahydrofuran, chloroform, benzene, etc., cold alcohol, ethyl acetate, n-amyl acetate, isobutyl acetate, etc.
It is insoluble in acetone etc.

The polymer compound obtained by radical polymerization of the vinyl compound of the present invention is soluble in water at a low temperature, and the high temperature is usually in the range of 53 to 65°C, although it varies depending on the temperature. '□-This polymer compound is also an alcohol solvent-dependent thermoreversible polymer compound that is solubilized in aliphatic primary alcohol by heating. For example, the transition temperature of a 1% alcohol solution of this polymer varies depending on the polymerization conditions, but it is 0 to 30°C for methanol and 30°C for ethanol.
~60℃, 30-50℃ for n-propatool, 5eC
The temperature is 35 to 50°C for -butyl alcohol, 35 to 50°C for n-amyl alcohol, and 50 to 65°C for isopropyl alcohol, and generally varies depending on the type of alcohol.

Effects of the Invention The vinyl compound of the present invention is a new vinyl compound that has not been published in any literature, and the polymer compound is reversibly soluble in water at low temperatures, insoluble in water at high temperatures, and soluble in alcohol at high temperatures. is a thermoreversible polyacrylamide derivative that is insoluble in alcohol at low temperatures, and has a different transition temperature from conventionally known thermoreversible polyacrylamide derivatives. For example,
Light shielding materials for greenhouses, chemical laboratories, radioisotope laboratories, etc., temperature sensors, surfactant adsorbents, and even toys,
It can be used for interior decoration, textile printing agents, displays, separation membranes, mechanochemical device materials, etc.

Example Add 39.1 g of triethylamine to Erlenmeyer flask 1a.

2-Methylaminomethyl-1,3-dioxolane39.
1 g of toluene and 450 ml of toluene were added thereto, and while the contents were kept at a temperature below 10° C. by cooling with water and stirring, a mixed solution of 27.6 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 further vacuum distillation was performed to obtain a colorless and transparent fraction (boiling point 117°C/I mm T-(g
) 42.6g was obtained.

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

The results of these spectral analyzes are as follows.

Mass spectrum analysis: m/e M+1 = 172M
=171-CH2 0- CI-12 CH, =CH-C0-=55 CI-f2=CI-(-=27 Infrared absorption spectrum analysis Knee N< = 3500 cm-'CH2=C
H= 1803 cm-'0-= 1120 cm
-'>C=O=1640cm-'>CH-=2940.2880cm'' From the analysis results, N-methyl-N-(1゜3-dioxolane-2
-yl) acrylamide.

Reference Examples 1 to 6 Radical polymers of the vinyl monomers obtained in Examples were produced.

Add 2.2 g of N-methyl-N-(1,3-dioxolan-2-yl)acrylamide to 20 mρ of the polymerization solvent, put it into an ampoule, degas it under reduced pressure using liquid nitrogen, and then seal the tube. Rate 3.9X10'R/hr, temperature 24
The reaction was carried out by irradiating gamma rays from cobalt 60 at ℃ for 1 hour. After the reaction, the solvent was removed, and then n-hexane was added to separate and collect the polymer. The polymerization reaction results of Reference Examples 1 to 6 are
Shown in the table.

Table 1 MDA PMDA Reference example at 30℃
Solvent Amount used (g) Yield (g) Solubility of PMDA 1 Benzene 2.23 2.
23 PMDA dissolved in benzene: MDA polymer The infrared absorption spectrum of the polymer of Reference Example 2 is shown in Figure 3'. By comparing the infrared absorption spectrum of the vinyl monomer with that of the polymer, it was confirmed that the vinyl group at 1603 cM −' disappeared and a polymer compound was formed.

The obtained polymer was made into a tetrahydrofuran solution, and the viscosity was measured at 27° C. using an Ubbelohde viscometer to determine the intrinsic viscosity [η]. 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. That is, an aqueous polymer solution with a concentration of 1% by weight was prepared, and the light transmittance at a wavelength of 500 nm was measured using a spectrophotometer with a temperature controller while raising the temperature at a rate of 1'C/min. The temperature was determined from the temperature (TL) at which the light transmittance was 0.5 of the initial transmittance. These results are shown in Table 2.

Table 2 6 Chloroform ---54,5 The transmittance-temperature curve of the aqueous polymer solution of Reference Example 3 is shown in FIG.

Among these, the solid line is the data when the temperature was increased.

The thermoreversibility of the polymer of Reference Example 3 in various alcohols was investigated. The transition temperature was determined from the light transmittance associated with the temperature change of the alcohol solution. That is, a polymer alcohol solution with a concentration of 1% by weight was prepared, and using a spectrophotometer with a temperature controller, the light transmittance at a wavelength of 500 nm was measured while lowering the temperature at a cooling rate of 1'C/min, and the transition temperature was determined. , the light transmittance was determined from the temperature (TL) at which the light transmittance was 0.5 of the initial transmittance. These results are shown in Table 3.

Table 3 Isopropyl alcohol 65.0 High temperature soluble Low temperature insolubilization The transmittance versus temperature curve of the polymer alcohol solution of Reference Example 3 is shown in FIG. Among these, the solid line is the data when the temperature was increased.

Reference Example 7 to IO A radical polymer of the vinyl monomer obtained in the example was produced.

Using azobisisobutyronitrile as a polymerization initiator,
A predetermined weight of N-methyl-N-(1,3-dioxolane-
2-yl) acrylamide was added, this was put into an ampoule, the tube was degassed under reduced pressure using liquid nitrogen, the tube was sealed, and the temperature was increased to 5.
The mixture was kept in a constant temperature bath at 0°C for 2 hours to react. 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 Reference Examples 7 to 10.

Table 4 10 Tetrahydrofuran 2,22 2.21
The intrinsic viscosity and transition temperature of these polymers dissolved in tetrahydrofuran were determined in the same manner as in Reference Examples 1-6. The results are shown in Table 5 Table 5 1G Tetrahydrofuran 0.06
65.0 Furthermore, the transition temperature of the polymer of Reference Example 8 in various alcohols was measured in the same manner as in Example 3. The results are shown in Table 6.

Table 6 Isopropyl alcohol 65.5 High temperature soluble Low temperature insolubilization

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the vinyl monomer of Example, FIG. 2 shows the total spectrum of the vinyl monomer of Example, and FIG. 3 shows the infrared absorption spectrum of the polymer of Reference Example 2. FIG. 4 shows Reference Example 3 according to the method of the present invention.
The transmittance-yM degree curve of the polymer in a 1% by weight aqueous solution is shown. FIG. 5 shows the permeability versus temperature curve of the polymer of Reference Example 3 in a 1% by weight alcohol solution according to the method of the present invention. Patent applicant: Director of the Agency of Industrial Science and Technology Kozo Iizuka Designated agent: Director of the Agency of Industrial Science and Technology ■Sword 2 swords powerful 8I) α9 wave number
(CM-“) Fig. 2 (-/e) Fig. 3 Wave number (OM-1) Fig. 4 Fig. 5 Temperature (°C)

Claims (1)

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