JPH06306033A - Novel vinyl compound - Google Patents

Abstract

PURPOSE:To provide a novel vinyl compound suitable as a monomer for a heat-sensitive polymeric compound exhibiting phase-transition in water and utilizable as light-shielding material, temperature sensor, adsorbent, toy, interior goods, printing agent, display, separation membrane and mechanochemical material. CONSTITUTION:This is a vinyl compound of formula (R is H or CH3), e.g. N-2-isopropoxyethylacrylamide. The compound of formula I can be produced e.g. by reacting acryloyl chloride or methacryloyl chloride of formula II with 2-aminoethyl isopropyl ether and triethylamine in a solvent maintained at 0-10 deg.C. The polymeric compound derived from the novel vinyl compound is soluble in water at a low temperature and becomes water-insoluble at a high temperature.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel vinyl compound. More specifically, the present invention relates to a light-shielding body, a temperature sensor, an adsorbent, a toy, an interior, a textile printing agent, a display, a separation membrane, and a thermosensitive polymer compound having a phase transition in water which can be used for mechanochemical materials. The present invention relates to a vinyl compound suitable as a raw material monomer.

[0002]

2. Description of the Related Art Among water-soluble polymer compounds, they show a special reversible dissolution behavior in which, when they are in an aqueous solution state, they become cloudy at a certain temperature (transition temperature or cloud point) or more, and they become soluble and transparent below the temperature. These are also called hydrophilic-hydrophobic thermoreversible polymer compounds or heat-sensitive polymer compounds, and in recent years, such as greenhouses and other light-shielding substances, temperature sensors or nonionic surfactant adsorbents, etc. It has come to be noticed as a material.

As such a heat-sensitive polymer compound,
So far, 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) 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-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), 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-dioxolane-2-
Ilmethyl) -N-methylacrylamide), poly (N
-8-acryloyl-1,4-dioxa-8-aza-spiro [4.5] decane) and the like are known.

However, these heat-sensitive polymer compounds have a limited transition temperature even if they are used as temperature sensors or light-shielding bodies, and cannot be arbitrarily selected according to the purpose. Was not restricted.

[0006]

Under these circumstances, the object of the present invention is to provide a raw material monomer for a thermosensitive polymer compound that undergoes a phase transition in water in order to expand the range of use of the thermosensitive polymer compound. It was made for the purpose of providing.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to develop a heat-sensitive polymer compound that undergoes a phase transition in water, the general formula

A general formula obtained by radical polymerization of a vinyl compound represented by the formula

[Chemical 2] And has an intrinsic viscosity [η] of 0.07 at a temperature of 27 ° C. in a tetrahydrofuran solution.
The polymer compound having a molecular weight corresponding to 1 to 6.0 is
The present invention has been completed based on the finding that it is a thermosensitive polymer compound that undergoes a phase transition in water.

The vinyl compound of the present invention is a novel compound which has not been published in the literature, that is, N-2-isopropoxyethyl acrylamide and N-2-isopropoxyethyl methacrylamide.

[Chemical 3] According to the method, acrylic acid chloride or methacrylic acid chloride, 2-aminoethylisopropyl ether and triethylamine are reacted in a solvent kept at 0 to 10 ° C, or

[Chemical 4] According to the procedure, acrylic acid chloride or methacrylic acid chloride and 2-aminoethyl isopropyl ether were
It can be obtained by reacting in a solvent kept at -10 ° C.

The solvent used in these methods is not particularly limited as long as it is inert to acrylic acid chloride or methacrylic acid chloride, and generally benzene, acetone, toluene and the like are used. Regarding the reaction temperature, if it is too high, side reactions occur, so 0 to 10 ° C
It is preferable to react in the range of.

From the reaction mixture thus obtained,
To isolate the target compound, usually, first, triethylamine hydrochloride or 2-aminoethylisopropyl ether hydrochloride is removed by filtration or the like, the solvent is distilled off from the filtrate using a rotary evaporator, and then the pressure is reduced by a conventional method. Purify by distillation. At this time, if necessary, vacuum distillation may be further repeated to obtain a highly pure product.

The N-2-isopropoxyethylacrylamide thus obtained had a boiling point of 118 ° C./2 mm.
Hg) A colorless liquid, soluble in solvents such as water, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, chloroform, benzene, n-hexane, n
-Insoluble in heptane. In addition, N-2-isopropoxyethylmethacrylamide (boiling point 108 ° C / 1 mm
Hg) A colorless liquid, soluble in solvents such as water, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, chloroform, benzene, n-hexane, n
-Insoluble in heptane.

The vinyl compound of the present invention has CH ₂ = CR-
Group (R is H or CH _3), - CONH- group, -CH ₂
Since it has a —O— group, a —CH ₂ group, a —CH ₃ group and the like, it can be identified by an infrared absorption spectrum, a mass spectrum and the like.

The heat-sensitive polymer compound of the present invention which undergoes a phase transition in water can be produced by radical polymerization of the above-mentioned N-2-isopropoxyethylacrylamide or N-2-isopropoxyethylmethacrylamide. However, this polymerization is usually a solution polymerization method or a bulk polymerization method, using benzoyl peroxide, a peroxide such as peracetic acid or an azo compound such as azobisisobutyronitrile as a polymerization initiator, or an ultraviolet ray, Radiation, electron beam,
It can be performed by irradiation with actinic rays such as plasma. The amount of the polymerization initiator used at this time is 0.005 to 5% by weight, and particularly 0.001 to 5% by weight, based on the weight of the monomer.
A range of 2% by weight is suitable.

Particularly preferred is the solution polymerization method, N-2.
-Isopropoxyethyl acrylamide or N-2
-A method in which isopropoxyethyl methacrylamide 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-2-isopropoxyethyl acrylamide or N-2-isopropoxyethyl methacrylamide. 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.

Regarding the degree of polymerization of the polymer compound obtained by radically polymerizing the vinyl compound of the present invention, the intrinsic viscosity [η] at a temperature of 27 ° C. in a tetrahydrofuran solution is in the range of 0.01 to 6.0. The ones are practical. Regarding the solubility in various solvents, cold water,
It is soluble in methanol, acetone, benzene, tetrahydrofuran, methyl acetate, ethyl acetate, ethylene glycol, chloroform and the like, but insoluble in cyclohexane, n-hexane, n-heptane 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 has the property of being soluble in water below the transition temperature and insoluble above the transition temperature. For example, the transition temperature of a 1% aqueous solution of this polymer compound varies depending on the molecular weight and the solution concentration, but is 15 to 18 ° C. for poly (N-2-isopropoxyethylacrylamide) and poly (N-2-isopropoxyethylmethacrylate). In the case of amide), it is 21 to 23 ° C.

[0017]

INDUSTRIAL APPLICABILITY The polymer compound of the present invention is a polymer compound which has not been published in the literature, and has the property of being soluble in water at low temperatures and insoluble in water at high temperatures. These polymers can be used in, for example, light-shielding bodies such as greenhouses, temperature sensors, toys, interiors, textile printing agents, displays, separation membranes, cosmetic substrates, mechanochemical element materials, and the like.

[0018]

The present invention will be described in more detail with reference to Examples and Reference Examples.

Example 1 Triethylamine (39.27 g), 2
-Add aminoethyl isopropyl ether (46.11g) and toluene (1l), cool with ice, keep the content liquid at a temperature below 10 ° C, and dilute acrylic acid chloride (32.6ml) with toluene (100ml) while stirring. Then, the solution was slowly dropped from the dropping funnel over about 3 hours. After completion of dropping
The reaction solution was left in the refrigerator overnight to complete the reaction, then filtered, toluene was distilled off using a rotary evaporator, and crude N-2-isopropoxyethylacrylamide was concentrated. Then, it is distilled under reduced pressure by a conventional method to give a boiling point of 118.
27.54 g of a liquid substance having a temperature of / 2 mmHg was obtained.

The infrared absorption spectrum of this substance is shown in FIG.
The mass spectrum is shown in FIG. The results of infrared absorption spectrum and mass spectrum analysis of this substance are shown in Tables 1 and 2.

[Table 1]

[Table 2]

From the above analysis results, it was confirmed to be N-2-isopropoxyethylacrylamide.

Example 2 Triethylamine (30.71 g), 2
-Add aminoethyl isopropyl ether (31.00 g) and toluene (450 ml), cool with ice, keep the content liquid at a temperature of 10 ° C or less, and dilute methacrylic acid chloride (24.9 ml) with toluene (50 ml) while stirring. Then, the solution was slowly dropped from the dropping funnel over about 3 hours. After completion of dropping
The reaction solution was left in the refrigerator overnight to complete the reaction, then filtered, toluene was distilled off using a rotary evaporator, and crude N-2-isopropoxyethylmethacrylamide was concentrated. Then, it is distilled under reduced pressure by a conventional method to give a boiling point of 10
41.76 g of a liquid substance having a temperature of 8 ° C./1 mmHg was obtained.

The infrared absorption spectrum of this substance is shown in FIG.
The mass spectrum is shown in FIG. The results of infrared absorption spectrum and mass spectrum analysis of this substance are shown in Tables 3 and 4.

[Table 3]

[Table 4]

From the above analysis results, it was confirmed to be N-2-isopropoxyethylmethacrylamide.

Reference Example 1 The polymer compound of the vinyl monomer obtained in Example 1 was produced. N-2-isopropoxyethylacrylamide 1.
93 g, 20 ml of benzene and 0.02 g of AIBN were placed in an ampoule, which was connected to a vacuum line, frozen and thawed under reduced pressure to remove oxygen in the ampoule, and then the ampoule was sealed. The polymerization reaction was carried out by heating this ampoule at 50 ° C. for 9 hours. The resulting polymer was isolated by mixing in n-hexane with the reaction solvent. Then, it was dissolved in water and freeze-dried to obtain a polymer. Yield = 1.86g.

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 compound, 1627 cm ^-1
It was confirmed that the vinyl group disappeared and that a polymer compound was produced.
The obtained polymer compound was used as a tetrahydrofuran solution, and the viscosity was measured at 27 ° C. using an Ubbelohde viscometer to determine the intrinsic viscosity [η]. Intrinsic viscosity = 0.65.

Further, the heat-sensitive characteristics were examined by measuring the light transmittance of the aqueous solution by thermal stimulation. The light transmittance of a 1 wt% aqueous solution at a wavelength of 500 nm 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 obtained from the temperature ( _TL ) at which the light transmittance of the aqueous solution at the time of temperature rise was 0.5 of the initial transmittance. T _L
= 15.0 ° C.

Reference Example 2 N-2-isopropoxyethylacrylamide 1.93
g, 20 ml of methanol and 0.02 g of AIBN were placed in an ampoule, the ampoule was connected to a vacuum line, frozen and thawed under reduced pressure to repeatedly remove oxygen in the ampoule, and then the ampoule was sealed. The polymerization reaction was carried out by heating this ampoule at 50 ° C. for 24 hours. The resulting polymer is
After removing the solvent, an acetone solution was prepared and mixed in n-hexane for isolation. Then dissolve in water and freeze-dry.
A polymer was obtained. Yield = 1.77g.

The formation of a polymer compound was confirmed by the same method as in Reference Example 1, and the intrinsic viscosity [η] at 27 ° C. in a tetrahydrofuran solution was 0.26. And the transition temperature of the aqueous solution was determined in the same manner as in Reference Example 1. T _L = 17.6 ° C.

Reference Example 3 The polymer compound of the vinyl monomer obtained in Example 2 was produced. 1.93 g of N-2-isopropoxyethyl methacrylamide, 20 ml of benzene and 0.02 g of AIBN
Was placed in an ampoule, the ampoule was connected to a vacuum line, frozen and thawed repeatedly under reduced pressure to remove oxygen in the ampoule, and then the ampoule was sealed. The polymerization reaction was carried out by heating this ampoule at 50 ° C. for 24 hours. The resulting polymer was isolated by mixing in n-hexane with the reaction solvent. Then, it was dissolved in water and freeze-dried to obtain a polymer. Yield = 1.36g.

The production of a polymer compound was confirmed in the same manner as in Reference Example 1 below. 27 ° C in tetrahydrofuran solution
Intrinsic viscosity [η] = 0.12. The transition temperature of the aqueous solution was determined in the same manner as in Reference Example 1. T _L = 22.0 ° C.

Reference Example 4 N-2-isopropoxyethyl methacrylamide 1.9
2 g, 20 ml of methanol and 0.02 g of AIBN were placed in an ampoule, which was connected to a vacuum line and frozen and thawed repeatedly under reduced pressure to remove oxygen in the ampoule, and then the ampoule was sealed. The polymerization reaction was carried out by heating this ampoule at 50 ° C. for 24 hours. The resulting polymer is
After removing the solvent, an acetone solution was prepared and mixed in n-hexane for isolation. Then dissolve in water and freeze-dry.
A polymer was obtained. Yield = 1.77g.

The production of a polymer compound was confirmed by the same method as in Reference Example 1 below. 27 ° C in tetrahydrofuran solution
Intrinsic viscosity [η] = 0.07. The transition temperature of the aqueous solution was determined in the same manner as in Reference Example 1. T _L = 22.0 ° C.

[0034]

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the vinyl monomer of Example 1.

2 is an infrared absorption spectrum of the polymer compound of Reference Example 1. FIG.

FIG. 3 is a mass spectrum of the vinyl monomer of Example 1.

FIG. 4 is an infrared absorption spectrum of the vinyl monomer of Example 2.

5 is an infrared absorption spectrum of the polymer compound of Reference Example 3. FIG.

FIG. 6 is a mass spectrum of the vinyl monomer of Example 2.

Claims (1)

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