JPH0613500B2 - Novel vinyl compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a novel vinyl compound. More specifically, the present invention relates to a light-shielding material, a temperature sensor, an adsorbent, a toy, an interior, a printing agent, a display, a separation membrane, a thermosensitive material that undergoes a phase transition in a water or alcohol solvent that can be used for mechanochemical materials. The present invention relates to a vinyl compound suitable as a raw material monomer for a polymer compound.

[Conventional technology]

Some water-soluble polymer compounds show a special reversible dissolution behavior in which, when the temperature is higher than a certain temperature (transition temperature or cloud point) in an aqueous solution state, it becomes cloudy and precipitates, and below that temperature, it becomes transparent. It is also called a hydrophilic-hydrophobic thermoreversible polymer compound or a thermosensitive polymer compound, and in recent years, it has attracted attention as a material such as a light shield for a greenhouse, a temperature sensor, a water-soluble organic substance adsorbent, or the like. Has become.

Such heat-sensitive polymer compounds have hitherto been partially saponified polyvinyl acetate, polyvinyl methyl ether,
Methyl cellulose, polyethylene oxide, polyvinyl methyl oxazolidinone, polyacrylamide derivatives and the like are known.

Among these thermosensitive polymer compounds, polyacrylamide derivatives are particularly useful because they are stable in water and can be produced at a relatively low cost, and thus far poly (N-ethylacrylamide). Poly (N-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-Nn-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), polyCN- (2,2-dimethoxyethyl) -N-
Methyl acrylamide), poly (N-1-methyl-2-)
Methoxyethyl (meth) acrylamide), poly (N-
1-methoxymethylpropyl (meth) acrylamide), poly (N- (1,3-dioxolan-2-ylmethyl) -N-methylacrylamide), poly (N-8-
Acryloyl-1,4-dioxa-8-aza-spiro [4.5] decane) and the like are known.

However, all of these heat-sensitive polymer compounds are heat-sensitive in an aqueous solution, but are not heat-sensitive in other solvents. As a polymer exhibiting heat sensitivity in an alcohol solvent, poly (N- (1,3-dioxolane-2-
Ilmethyl) -N-methylacrylamide) and poly (N
-1,3-dioxolan-2-ylmethylacrylamide), which is insoluble at a temperature lower than the transition temperature and soluble at a temperature higher than the transition temperature, unlike the above-mentioned thermosensitive polymer. 63-243112) and application (Head 2-72995)}.

[Problems to be Solved by the Invention]

Under such circumstances, an object of the present invention is to provide a thermosensitive polymer compound raw material monomer that undergoes a phase transition in water and an alcohol solvent in order to expand the range of use of the thermosensitive polymer compound. It was done for the purpose.

[Means for Solving the Problems]

The present inventors have conducted extensive research to develop a thermosensitive polymer compound that undergoes a phase transition in water and an alcohol solvent, and as a result, the formula Formula obtained by radical polymerization of vinyl compound represented by Consisting of repeating units represented by
Based on this finding, we found that a polymer compound having an intrinsic viscosity [η] at a temperature of 0.01 to 6.0 has a molecular weight corresponding to 0.01 to 6.0 is a thermosensitive polymer compound that undergoes a phase transition in water and alcohol solvents. The invention was completed.

The vinyl compound of the present invention is a novel compound that has not been published in the literature, that is, N-methyl-N-2- (1,3-dioxolane-
2-yl) ethyl acrylamide, for example, the reaction formula According to the method described above, acrylic acid chloride, N-methyl-2-aminoethyl-1,3-dioxolane and triethylamine are reacted in a solvent kept at 0 to 10 ° C. Accordingly, acrylic acid chloride and N-methyl-2-aminoethyl-1,3-dioxolane can be obtained by reacting them 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 and the like are generally used.
Regarding the reaction temperature, if it is too high, side reactions will occur, so
It is preferable to react in the range of 0 to 10 ° C.

To isolate the desired compound from the reaction mixture thus obtained, usually, for example, by filtration, triethylamine hydrochloride or N-methyl-2-aminoethyl-1,
After removing 3-dioxolane hydrochloride, the solvent is distilled off from the filtrate using a rotary evaporator, and then the residue is distilled under reduced pressure by a conventional method for purification. At this time, if necessary, vacuum distillation may be further repeated to obtain a highly pure product.

The N-methyl-N-2- (1,3 thus obtained
-Dioxolan-2-yl) ethylacrylamide (boiling point 127 ° C / 1 mmHg) is a colorless liquid, water,
It is soluble in solvents such as methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, chloroform and benzene, but insoluble in n-hexane and n-heptane.

The vinyl compound of the present invention includes a CH ₂ ═CH— group, —CON
H- group, _-CH 2 -O- group, -CH <group, because it has a -CH ₃ group or the like, can be identified by infrared absorption spectrum, and mass spectrum.

The heat-sensitive polymer compound of the present invention which undergoes a phase transition in water and an alcohol solvent is the above-mentioned N-methyl-N-2- (1,3-
It can be produced by radically polymerizing dioxolan-2-yl) ethyl acrylamide, but this polymerization usually initiates polymerization of azo compounds such as benzoyl peroxide and peracetic acid by a solution polymerization method or a bulk polymerization method. It can be used as an agent or by irradiation with actinic rays such as ultraviolet rays, radiation, electron beams and plasma. The amount of the polymerization initiator used in this case is preferably 0.005 to 5% by weight, particularly 0.001 to 2% by weight, based on the weight of the monomer.

Particularly preferred is N-methyl-N-2 by the solution polymerization method.
In this method,-(1,3-dioxolan-2-yl) 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 is soluble in N-methyl-N-2- (1,3-dioxolan-2-yl) ethylacrylamide. For example, water, alcohols, acetone, tetrahydrofuran, chloroform, benzene, alkyl acetates and the like can be mentioned, and these may be used alone or in combination of two or more depending on the case.

The degree of polymerization of the polymer compound obtained by radically polymerizing the vinyl compound of the present invention is
It is practical that the intrinsic viscosity [η] at a temperature of 27 ° C is in the range of 0.01 to 6.0. Regarding the solubility in various solvents, it is soluble in cold water, methanol, acetone, benzene, tetrahydrofuran, methyl acetate, ethyl acetate, hot alcohols, ethylene glycol, chloroform, etc.
It is insoluble in cold monohydric alcohols (excluding methanol), cyclohexane, n-hexane, n-heptane hot water and the like.

The vinyl compound of the present invention is a novel vinyl compound that has not been published in the literature, and its polymer compound is soluble in alcohol at a transition temperature or higher, insoluble at a transition temperature or lower, and in water at a transition temperature or lower, It also has the property of becoming insoluble above the transition temperature. For example, the transition temperature of a 1% alcohol solution of this polymer compound varies depending on the molecular weight, but is 24 to 26 ° C. for ethanol and 16 to 1 for n-propanol.
7 ° C., 23 to 27 ° C. for isopropanol, 40 to 41 ° C. for tert-amyl alcohol, and 20 to 22 ° C. for isoamyl alcohol, which generally differ depending on the type of alcohol. Further, the transition temperature of the 1% aqueous solution is 65 to 78 ° C, although it depends on the molecular weight.

〔The invention's effect〕

The vinyl compound of the present invention is a novel vinyl compound that has not been published in the literature. The polymer compound is a polymer compound that has not been published in the literature, and is soluble in alcohol at high temperatures, insoluble in alcohol at low temperatures, soluble in water at temperatures below the transition temperature, and insoluble at temperatures above the transition temperature. It has the property that These polymers include, for example, light-shielding bodies such as greenhouses, temperature sensors,
Further, it can be used for toys, interiors, textile printing agents, displays, separation membranes, mechanochemical element materials and the like.

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

〔Example〕

Triethylamine (39.27 g), N- in a 2-volume Erlenmeyer flask.
Methyl-2-aminoethyl-1,3-dioxolane (50.
Add 84 g) and benzene (431 ml), cool with ice, and add 1 part to the contents.
Acrylic chloride (31 ml) was diluted with benzene (69 ml) while stirring at a temperature of 0 ° C. or lower, and the mixture was slowly added dropwise from a dropping funnel over about 3 hours. After completion of the dropping, the reaction solution was left in the refrigerator all day and night to complete the reaction, and then filtered,
Benzene was distilled off using a rotary evaporator,
Crude N-methyl-N-2- (1,3-dioxolane-2-
Ill) ethyl acrylamide was concentrated. Then, a liquid substance having a boiling point of 127 ° C./1 mmHg is obtained by vacuum distillation according to a conventional method.
Got 57.24g.

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

The results of these spectral analyzes are as follows.

Infrared spectrum analysis: -NH- = 3480 cm ^-1 CH ₂ = CH- = 1607 cm ^-1 -O- = 1140 cm ^-1 > C = O = 1642 cm ^-1 > CH- = 2935,2880 cm ^-1 Mass spectrum analysis: m / _{e M + 1 = 186 M -} CH 2 = CH-CO- = 130 From _{CH 2 = CH-CO- = 55} CH 2 = CH- = 27 or more analysis results, N- methyl -N-2- (1,3-
It was confirmed to be dioxolan-2-yl) ethyl acrylamide.

[Reference Example 1] The polymer compound of the vinyl monomer obtained in Example was produced.

27.82 g of N-methyl-N-2- (1,3-dioxolan-2-yl) ethylacrylamide in a 500 ml Erlenmeyer flask with a U-shaped tube equipped with a capillary stopper,
200 ml of benzene (175.27 g) and AIBN
O. 15 g was added and nitrogen gas was vigorously bubbled through for 30 minutes. Then, heating was carried out at 60 ° C. for 3 hours while stirring under a nitrogen stream. The resulting polymer was isolated by mixing in n-hexane with the reaction solvent.

Yield = 25.72g.

The infrared absorption spectrum of this polymer compound 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 of 1607CM ^-1 disappeared and the polymer was produced.

The obtained polymer compound was made into an aqueous solution and the viscosity was measured at 27 ° C. using an Ubbelohde viscometer to obtain an intrinsic viscosity [η].
I asked.

Intrinsic viscosity [η] = 0.73.

In addition, the heat-sensitive characteristics were investigated by measuring the light transmittance of the aqueous solution or alcohol solution by thermal stimulation. Wavelength of 1% by weight polymer compound aqueous solution or alcohol solution 500n
The light transmittance at m was measured using a spectrophotometer with a temperature controller at a rate of temperature increase of 1 ° C./min and a rate of temperature decrease of 1 ° C./min. The transition temperature was determined from the temperature (T _L ) at which the light transmittance of the aqueous solution when the temperature was raised and the light transmittance of the alcohol solution when the temperature was lowered were 0.5, which is the desired transmittance.

Aqueous solution transition temperature 78 ° C.

Table 1 shows the transition temperatures of the alcohol solutions.

[Reference Example 2] 11.04 g of N-methyl-N-2- (1,3-dioxolan-2-yl) ethylacrylamide in a 500 ml Erlenmeyer flask with a U-shaped tube equipped with a capillary stopper,
150.36 g of water was added and nitrogen gas was vigorously passed for 30 minutes. Then, 15.0 mg of ammonium persulfate was added at 60 ° C. with stirring under a nitrogen stream to start polymerization, and heating was carried out for 4 hours. The produced polymer is n with the reaction solvent.
Isolated by mixing in hexane.

Yield = 11.03g.

The production of a polymer compound was confirmed by the same method as in Reference Example 1 below, and the intrinsic viscosity [η] at 27 ° C in an aqueous solution of 0.58 and the transition temperature of the aqueous solution and the alcohol solution were determined in the same manner as in Reference Example 1. .

Aqueous solution transition temperature 65.5 ° C.

Table 2 shows the transition temperatures of the alcohol solutions.

[Brief description of drawings]

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 Reference Example 1, and FIG. 3 shows the mass spectrum of the vinyl monomer of the Example.

Claims (1)

[Claims] 1. A formula A vinyl compound represented by.