JPH03275682A - New vinyl compound - Google Patents

Abstract

NEW MATERIAL:N-(1,3-Dioxolan-2-yl)acrylamide shown by formula I. USE:A raw material monomer for heat-sensitive polymer compound useful in light shielding material, temperature sensor, adsorbent, toy, interia, printing agent, display, separating membrane and mechanochemical material. PREPARATION:Acrylic acid chloride shown by formula II is reacted with 2- aminomethyl-1,3-dioxolane shown by formula III and triethylamine 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 a highly heat-sensitive material that undergoes a phase transition in a monohydric alcohol solvent that can be used in light shielding bodies, temperature sensors, adsorbents, toys, interior decoration, textile printing agents, displays, separation membranes, and mechanochemical materials. This invention relates to vinyl compounds suitable as raw material monomers for molecular compounds.

[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. This material is also called a woody-hydrophobic thermoreversible polymer compound or a heat-sensitive polymer compound, and has recently attracted attention as a material for light shields in greenhouses, temperature sensors, and water-soluble organic substance adsorbents. It's starting to happen.

So far, heat-sensitive polymer compounds such as these include partially saponified polyvinyl acetate, polyvinyl methyl ether,
Methylcellulose, polyethylene oxide, polyvinylmethyloxasilideinone, polyacrylamide derivatives, and the like are known.

Among these heat-sensitive true molecular compounds, polyacrylamide derivatives are particularly useful because they are stable in water and can be produced relatively easily, and so far poly(N-ethyl acrylamide) has been used. 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-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
-isopropoxyprobyl (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-methoxymethyl propyl(meth)acrylamide), poly(N-(1,3-dioxolan-2-yl)-N-methylacrylamide), poly(N-8-acryloyl-di).

4-dioxa-8-aza-spiro[4.5]decane) and the like are known.

However, although all of these thermosensitive polymer compounds exhibit thermosensitivity in aqueous solutions, they do not exhibit thermosensitivity in other solvents. Poly(N -1,3-dioxolane-2
-yl)-N-methylacrylamide), which omit the above-mentioned heat-sensitive polymer and G, is insoluble at temperatures below the transition temperature, and soluble at temperatures above the transition temperature (published patent publication (Sho 63-243112)).

[Problem to be solved by the invention]

Under these circumstances, an object of the present invention is to provide a raw material monomer for a heat-sensitive polymer compound that undergoes a phase transition in a -hydric alcohol solvent, in order to expand the scope of use of the heat-sensitive polymer compound. It was done for a purpose.

CH2=CH20H-CH2 [Means for Solving the Problems] The present inventors have conducted intensive research to develop a thermosensitive polymer compound that undergoes a phase transition in an alcohol solvent.

It consists of repeating units represented by the formula -→--C'H2CH-←- 1 C=O NHOCH2 H2 =CH11 NH2 -CH2 OCHe Ce OCR2 obtained by radical polymerization of the vinyl compound represented by 27 in
It was discovered that a polymer compound having a molecular weight corresponding to an intrinsic viscosity [η] of 0.01 to 6.0 at a temperature of ℃ is a heat-sensitive polymer compound that undergoes a phase transition in a -hydric alcohol solvent. The present invention was completed based on the findings.

The vinyl compound of the present invention is a new compound that has not been described in any literature, that is, N-(1,3-dioxolan-2-yl)acrylic acid, and for example, according to the reaction formula % formula %: Y> lylic acid chloride. 2-aminomethyl-1,
3-dioxolane and triethylamine at 0 to 10°C.
Either acrylic acid chloride and 2-amitsumethyl-1,
It can be obtained by reacting with 3-dioxolane in a solvent maintained at 0 to 10''C.

Regarding the solvents used in these methods, see □・1;
-1 There is no particular restriction as long as it is inert to acrylic Jl/"IN chloride. Generally, benzene, acetone, toluene, etc. are used. Regarding the reaction temperature, side reactions will occur if it is too high, so 0 to 10 It is preferable to carry out the reaction in the temperature range of °C.

To isolate the target compound from the reaction mixture thus obtained, usually first, triethylamine hydrochloride or 2-amitsumethyl-1,3-dioxolane hydrochloride is removed by filtration, etc., and then a rotary evaporator is used. The solvent was distilled off from the filtrate, and then recrystallized using cyclohexane. do. At this time, if necessary, recrystallization may be repeated to obtain a product with 100% purity.

The N-(1,3-dioxolane-
(2-yl)acrylamide is a colorless crystalline solid (melting point 70°8°C) that can be mixed with water, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, chloroform,
It is soluble in solvents such as benzene and insoluble in n-hexane and n-hebutane.

The vinyl compound of the present invention has a CH2=CH- group, -CON
Since it has H- group, CH20- group, -CH< group, etc., it can be identified by infrared absorption spectrum, mass spectrum, etc.

The thermosensitive polymer compound of the present invention that undergoes a phase transition in m alcohol solvents is the aforementioned N-(1,3-dioxolane-2-
By radical polymerizing acrylamide)
However, this polymerization is usually carried out by a solution polymerization method or a bulk polymerization method, using an azo compound such as benzoyl peroxide or peracetic acid as a polymerization initiator, or by using ultraviolet rays, radiation, electron beams, plasma, etc. This can be done by irradiation with actinic radiation. 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-(1゜3-dioxolan-2-yl)acrylamide is dissolved in an organic solvent at 1%.
This is a method of dissolving and polymerizing at a concentration of ~80% by weight.

The solvent used in such a solution polymerization method is not particularly limited as long as it dissolves per-1 (or N=-1, a-dioxolan-2-yl)acrylamide. Examples include water, -hydric alcohols, acetone, tetrahydrofuran, chloroform, benzene, alkyl acetates, etc., and these may be used alone or in combination of two or more types depending on the case.

In addition, regarding the degree of polymerization of the polymer compound obtained by radical polymerization of the vinyl compound of the present invention, those having an intrinsic viscosity [η] of 0.01 to 6.0 at a temperature of 27°C in an aqueous solution are practically used. It is true. Furthermore, regarding solubility in various solvents, it is soluble in water, hot alcohols, chloroform, etc., alkyl acetates such as acetone, benzene, methyl acetate, ethyl acetate, n-butyl acetate, diethyl ether, n-hexane, n-hexane, etc. -Insoluble in hebutane etc.

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 the property of being soluble in m alcohols when heated above the transition temperature, and becoming insoluble when cooled. The transition temperature of a 1%-hydric alcohol solution of a polymer compound is 18-20℃ for methanol and 44-46℃ for ethanol, although it varies depending on the molecular weight.
℃, 32-34℃ for n-propanol, 48-52℃ for isopropanol, 32℃ for n-butyl alcohol.
~35°C, and 31~35°C for isoamyl alcohol, and generally varies depending on the type of m alcohol.

〔Effect 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 is a polymer compound that has not been described in any literature, and is reversibly dissolved in m alcohols in a high temperature range. It is a heat-sensitive polymer compound that undergoes a phase transition in an alcohol solvent and becomes insoluble in m alcohols, which is different from the conventionally known heat-sensitive polymers that undergo a phase transition in an aqueous solution. These polymers can be used, for example, in light shielding bodies for greenhouses, temperature sensors, toys, textile printing agents, displays, separation membranes, mechanochemical device materials, and the like.

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.

〔Example〕

2I? Add triethylamine (100°8) to a Erlenmeyer flask.
0g), 2-methyl-1,3-dioxolane (102,60g) and benzene (980mN) in 1. %, cool on ice, keep the content at a temperature below 10°C, and while stirring, dilute acrylic Muri Loli F (80m#) with benzene (20m/) and slowly drop it from the dropping funnel over about 3 hours. did. After completing the dropwise addition, the reaction solution was left in the refrigerator for a day and night to complete the reaction, and then filtered, and benzene was distilled off using a rotary evaporator to obtain crude N-(
The 1,3-dioxolan-2-yl)acrylate was concentrated. Then, it was recrystallized by a conventional method to obtain 113.58 g of a crystalline substance having a melting point of 70.8°C.

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.

Infrared spectrum NH- CH2=C 0- >C=O ) CH- Tor analysis: Mass spectrum analysis: M+1 3293cm-'1628cm-'1146cm-'1661cm-' 2955, 2918ca+-' m/e = 158 OCH2 CH2=CH -G O- = 55 CH2=CH- = 27 From the above analysis results, N-(1,3-dioxolane-2
-yl) acrylamide.

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

In a 500 mf Erlenmeyer flask with a U-tube fitted with a capillary stopper, 5.02 g of N-1,3-dioxolan-2-yl)acrylic acid, 80 m# of benzene, and 0.0 m of azobisisobutyronitrile were placed. 0419 g was added thereto, and the mixture was kept at 60° C. for 1 hour while stirring under a nitrogen stream to polymerize. Polymer precipitated as the polymerization progressed. After the reaction, the produced polymer compound was mixed with the reaction solvent in acetone, precipitated, and isolated. Yield: 2.61g.

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 compound, it was confirmed that the vinyl group of 1628CM-1 disappeared and a polymer compound was formed.

The obtained polymer compound was made into an aqueous solution, and the viscosity was measured at 27°C using an Ubbelohde viscometer, and the intrinsic viscosity [η
] was sought. Intrinsic viscosity [η) = 0.59°.Thermal sensitivity characteristics were also investigated by measuring the light transmittance of m alcohol solutions under thermal stimulation. The light transmittance of a polymer compound-hydric alcohol solution having a concentration of 1% by weight at a wavelength of 500 nm was measured using a spectrophotometric needle with a temperature controller at a cooling rate of 1° C./min. The transition temperature is determined when this light transmittance is 0.0% of the initial transmittance.
It was determined from the temperature (TL) at which the temperature was 5. These results are the first
Shown in the table.

In the Erlenmeyer flask shown in Table 1, N-1,3-dioxolane-2-
il) acrylamide 4.07g, water 100.69g,
0.0512 g of ammonium persulfate was added, and the mixture was kept at 60° C. for 5 hours while stirring under a nitrogen stream for polymerization. As the polymerization progressed, the polymer grew and became a highly viscous aqueous solution. After the reaction, the mixture was dehydrated, mixed in acetone, precipitated, and isolated.

Yield: 4.04g.

The formation of a polymer compound was confirmed in exactly the same manner as in Example 1, the intrinsic viscosity [η] = 1.23 at 27°C in an aqueous solution, and the transition temperature of a monohydric alcohol solution was determined in the same manner as in Reference Example 1. . These results are shown in Table 2.

[Reference example 2] 500mf table 2 with U-shaped tube with capillary stopper

[Brief explanation of drawings]

I! 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.

Claims (1)

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