JPH0481408A - Heat-sensitive high polymer compound capable of phase transfer in water or alcohol solvent and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject new heat-sensitive high polymer compound having specific intrinsic viscosity, capable of phase transfer in water or alcohol solvent and used for temperature sensor, etc., by subjecting a specific acrylic amide derivative having 1,3-dioxolane ring to radical polymerization. CONSTITUTION:N-Methyl-N-2-(1,3-dioxolane-2-yl)ethylacryl amide prepared by reacting N-methyl-2-aminoethyl-1,3-dioxolane with acrylic acid chloride in the presence of triethylamine in benzene and expressed by formula I is polymerized in the presence of a radical polymerization initiator such as azobisisobutyronitrile (AIMN) in a solvent such as benzene while heating to provide the aimed heat sensitive high polymer compound consisting of recurring units expressed by formula II and having molecular weight in which intrinsic viscosity [eta] at 27 deg.C in an aqueous solution corresponds to 0.01-6.0.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel heat-sensitive polymer compound that undergoes a phase transition in water and alfur solvents, and a method for producing the same. More specifically, the present invention is applicable to light shielding bodies, temperature sensors, adsorbents, and even toys. Some compounds exhibit a special reversible dissolution behavior in which they precipitate and become cloudy, but dissolve and become transparent below that temperature. These compounds are also called hydrophilic-hydrophobic thermoreversible polymer compounds or thermosensitive polymer compounds. In recent years, it has attracted attention as a material for light shields in greenhouses, temperature sensors, and water-soluble organic substance adsorbents.

Until now, such heat-sensitive polymer compounds include partially saponified polyvinyl acetate, polyvinyl methyl ether,
Methyl cellulose, polyethylene oxide, polyvinylmethyloxazoliteinone, and polyacrylamide derivatives are known. Among these heat-sensitive polymer compounds, polyacrylamide derivatives are stable in water and can be produced at relatively low cost. So far, poly(N-ethyl acrylamide), 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-furopylacrylamide), poly(N-methyl-N-isofuropylacrylamide), poly(N-acryloyl piperidine), poly(N-axoloylpyrrolidine)
, poly(N-tetrahydrofurfuryl(meth)acrylamide), poly(N-methquinfurfuryl(meth)acrylamide), poly(N-ethoxypropyl(meth)acrylamide), poly(N-isofurfururyl(meth)acrylamide), Poly(N-ethynethyl(meth)acrylamide), Poly(N-(2,2-dimethoxyethyl)N-methylacrylamide), Poly
(N-1 methyl-2-methoxyethyl (meth)acrylamide), poly (N-1-methoxymethylfurovir (
meth)acrylamide), poly(N-(1,3-dioxolan-2-ylmethyl)-N-methylacrylamide), poly(N-8-acryloyl 1,4-dioxa-8
-aza-spiro [4.5] decane) etc. are known.

However, all of these heat-sensitive polymer compounds show heat sensitivity in an aqueous solution, but do not show heat sensitivity in other solvents. Poly(N-(1°3-dioxolane-2-
ylmethyl)-N-methylacrylamide) and poly(
N-1,3-dioxolan-2-ylmethylacrylamide), which is different from the above-mentioned heat-sensitive polymers and is insoluble at temperatures below the transition temperature and soluble at temperatures above the transition temperature (as disclosed in the published patent publication No. 63-243112) and application (No. 72995 Hei 2-72)).

[Problem to be solved by the invention]

Under these circumstances, the purpose of the present invention is to develop a thermosensitive polymer compound that undergoes a phase transition upon thermal stimulation in water and alcohol solvents, and a method for producing the same, in order to expand the scope of use of thermosensitive polymer compounds. It was made for the purpose of providing.

CH2=CH C= ○ N -CH3 OCH2 [Means for solving the problem] The present inventors have conducted extensive research to develop a thermosensitive polymer compound that undergoes phase transition in water and alcohol solvents. It can be easily produced by radical polymerizing a vinyl compound represented by , ←-CH2-CH-→-- C=O.

conohinyl compound, i.e. N-methyl-N-2-(1
,3-dioxolan-2-yl)ethyl acrylamide is also a new compound, for example, it consists of repeating units represented by the reaction formula % formula %, and 27
It has been 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 °C is a heat-sensitive polymer compound that undergoes a phase transition in water and alcohol solvents, Based on this knowledge, we have completed the present invention.

The polymer compound of the present invention is a novel compound, poly(N-methyl-N-2-(1,3-dioxolane-2-
yl)ethyl acrylamide), the above vinyl compound is radically polymerized to form acrylic acid chloride, N-methyl-2aminoethyl-1,3-dioxolane, and triethylamine according to C-H2=CH C=O CH2=CH. of,
In a solvent kept at 0 to 10°C, react with
Alternatively, it can be obtained by reacting acrylic acid chloride and N-methyl-2-aminoethyl-1,3-dioxolane in a solvent maintained at 0 to 10°C according to the reaction formula %.

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, 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, the target compound is usually first isolated by filtration or the like.
After removing 3-dioxolane hydrochloride, the solvent is distilled off from the filtration using a rotary evaporator, and then purified by vacuum distillation using a conventional method. At this time, if necessary, vacuum distillation can be repeated to achieve high purity.

N-methyl-N-2-(1,3
-dioxolan-2-yl)ethyl acrylamide is (
It is a colorless liquid (boiling point: 127°C, 71 mm Hg), and is soluble in solvents such as water, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, chloroform, and benzene, and insoluble in n-hexane and n-heptane.

The thermosensitive polymer compound of the present invention that undergoes a phase transition in water and alcohol solvent is the above-mentioned N-methyl-N-2-(1,3-
Dioxolan-2-yl)ethyl acrylamide can be produced by radical polymerization, but this polymerization is usually carried out by solution polymerization or bulk polymerization using peroxides such as benzoyl peroxide and peracetic acid, or azo The polymerization can be carried out using an azo compound such as bisisobutyronitrile as a polymerization initiator, or by irradiation with ultraviolet rays, radiation, electron beams, or plasma active rays.

The amount of the polymerization initiator to be used in this case is suitably in the range of 0.005 to 5% by weight, particularly 1 to 2% by weight, based on the amount of M of the monomer.

Particularly preferred is N-methyl-N-2 produced by solution polymerization.
- (1,3-dioxolan-2-yl)ethyl acrylamide is dissolved in an organic solvent at a concentration of 1 to 80% by weight,
This is a method of polymerization. The solvent used in such a solution polymerization method is not particularly limited as long as it dissolves in N-methyl-N-2-(1,3-dioxolan-2-yl)ethyl acrylamide. Examples include water, alcohols, acetone, tetrahydrofuran, chloroform, benzene, alkyl acetates, etc.
These may be used alone or in combination of two or more types depending on the case.

The polymer compound of the present invention has the property of being soluble in alcohol above the transition temperature and insoluble below the transition temperature, and soluble in water below the transition temperature and insoluble above the transition temperature. The transition temperature of this substance also differs depending on the type of alcohol.

The polymer compound of the present invention has a -CONH- group, -CH2-
Since it has a 0- group, a -CH< group, a -CH3 group, etc., it can be identified by an infrared absorption spectrum or the like.

In addition, regarding the degree of polymerization, 27°C in aqueous solution
The intrinsic viscosity [η] at the temperature is 0. A range of O1 to 60 is practical. Furthermore, regarding solubility in various solvents, it is soluble in water, methanol, acetone, benzene, tetrahydrofuran, methyl acetate, ethyl acetate, hot alcohols, ethylene glycol, chloroform, etc., cold alcohols (excluding methanol), It is insoluble in cyclohegyusan, n-hegyusan, n-heflin, hot water, etc.

The polymer compound of the present invention has the property of being soluble in alcohol above the transition temperature and insoluble below the transition temperature, and soluble in water below the transition temperature and insoluble above the transition temperature. For example, the transition temperature of a 1% alcohol solution of this polymer compound is 24 to 26 degrees Celsius for ethanol, 16 to 17 degrees Celsius for n-furopanol, although it varies depending on the molecular weight.
The temperature is 23 to 27°C for isopropanol, 40 to 41°C for tert-amyl alcohol, and 20 to 22°C for isoamyl alcohol, and generally varies depending on the type of alcohol. Further, the transition temperature of a 1% aqueous solution is 65 to 78°C, although it varies depending on the molecular weight.

〔Effect of the invention〕

The polymer compound of the present invention is a polymer compound that has not yet been described in literature, and is soluble in alfur at high temperatures, insoluble in alcohol at low temperatures, soluble in water at temperatures below the transition temperature, and at temperatures above the transition temperature. It has the property of being insoluble. These polymers are used, for example, in light shielding materials such as greenhouses, temperature sensors, toys, interior decorations, printing agents, displays, separation membranes,
It can be used as mechanochemical element material, etc.

Next, the present invention will be explained in more detail with reference to Reference Examples and Examples, but the present invention is not limited to these Examples in any way.

[Reference example]

2! Triethylamine (39.27g) in an Erlenmeyer flask
), N-methyl-2-aminoethyl-1,3-dioxolane (50.84g) and benzene (431ml) were added, cooled with water, and kept the content at a temperature of 10"C or less,
While stirring, acrylic acid chloride (31 ml) was diluted with benzene (69 ml) and slowly added dropwise from the dropping funnel over about 3 hours. After the addition was completed, the reaction solution was left in the refrigerator overnight to complete the reaction, and then filtered. Then, using a rotary evaporator, benzene was distilled off and crude N-methyl-N-2-(1°3-dioxolan-2-yl)ethyl acrylamide was concentrated.Next, it was distilled under reduced pressure by a conventional method to obtain a boiling point of 127 °C/1 mm Hg liquid substance 57
．． 24 g was obtained.

The results of infrared absorption spectrum and quality spectrum analysis of this substance are as follows.

Infrared spectrum analysis: -f1 block- CH2=CH- >C=○>CH- 5゜Ocm-' cc1 0cm-' 2C "1 8 80 cm-' OCH2 Mass spectrum analysis: m/e M+1 = 186 -CH2 CH2 =CH O- = 130 CH2 OCR2 CH2 CH2=CH-C○ - =55 CH2=CH- =27 From the above analysis results, N-methyl-N-2-(1,3-
It was confirmed to be dioxolan-2-yl)ethyl acrylamide.

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

27.82 g of N-methyl-N-2-(1°3-dioxolan-2-yl)ethyl acrylamide was placed in a 500 ml Erlenmeyer flask with a U-tube equipped with a capillary stopper.
200 ml (175°27 g) of benzene and 15 g of AIBNo were added, and nitrogen gas was vigorously bubbled through for 30 minutes. Then, it was heated at 60°C for 3 minutes with stirring under a nitrogen stream.
This was done by heating for a period of time.

The resulting polymer was isolated by mixing it 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 compound, it was confirmed that the vinyl group of 1607CM-' 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 calculated.

Intrinsic viscosity [η] = 0.73°.Thermal sensitivity characteristics were also investigated by measuring the light transmittance of an aqueous solution or an alcoholic solution under thermal stimulation.

The light transmittance at a wavelength of 500 nm of a 1% concentration polymer compound aqueous solution or alcohol solution was measured using a spectrophotometer with a temperature controller at a heating rate of 1'C/min and a cooling rate of 1°C/min. . The transmittance-temperature curve of the aqueous polymer solution of Example 1 is shown in FIG.

Among these, the solid line is the data when the temperature is rising, and the dotted line is the data when the temperature is falling.

Further, the transmittance-temperature curve of the alcohol solution of the polymer of Example 1 is shown in FIG. Among these, the solid line is the data when the temperature is rising, and the dotted line is the data when the temperature is falling. The transition temperature was determined from the temperature (TL) at which the light transmittance when the temperature rises for an aqueous solution or the light transmittance when the temperature falls for an alcohol solution becomes 0.5 of the initial transmittance.

The transition temperature for the water τ solution is 78°C0. Among these, the transition temperature for the alcohol solution is shown in Table 1.

Table 1 [Example 2] In a 500 ml Erlenmeyer flask equipped with a U-tube equipped with a capillary stopper, 11.04 g of N-methyl-N-2-(1°3-dioxolan-2-yl)ethyl acrylamide was added.
150.36 g of water was added and nitrogen gas was vigorously bubbled through for 30 minutes. Then, 15.0 mg of ammonium persulfate was added at 60° C. while stirring under a nitrogen stream to initiate polymerization, which was heated for 4 hours. The resulting polymer was isolated by mixing it with the reaction solvent in n-hemisan.

Yield = 11.03g.

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

Transition temperature of aqueous solution: 65.5°C0 Among these, the transition temperature of alcoholic solution is shown in Table 2.

Table 2

[Brief explanation of drawings]

FIG. 1 shows the infrared absorption spectrum of the vinyl monomer of Reference Example, and FIG. 2 shows the infrared absorption spectrum of the polymer compound of Example 1. Figure 3 shows the transmittance of a 1% by weight aqueous solution of the polymer compound of Example 1 according to the method of the present invention.
FIG. 4 shows a transmittance-temperature curve in a 1% by weight alcohol solution of the polymer compound of Example 1 according to the method of the present invention. Patent applicant Ken Sugiura, Director of the Agency of Industrial Science and Technology

Claims (2)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ It consists of repeating units represented by 27
A heat-sensitive polymer compound having a molecular weight corresponding to an intrinsic viscosity [η] of 0.01 to 6.0 at a temperature of °C. (2) Formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Characterized by radical polymerization of the vinyl compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Consisting of repeating units represented by the aqueous solution 27 in
A method for producing a heat-sensitive polymer compound having a molecular weight corresponding to an intrinsic viscosity [η] of 0.01 to 6.0 at a temperature of °C.