JPS63295613A - Thermally reversible hydrophilic/hydrophobic polymeric compound and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a thermally reversible hydrophilic/hydrophobic polymeric compound which has a prescribed mol.wt. and is suitable as a light shielding substance for a green house, by subjecting N-1-methyl-2-methoxyethyl(meth) acrylamide to radical polymerization. CONSTITUTION:The aimed thermally reversible hydrophilic/hydrophobic polymeric compound which comprises repeating units of formula II and has a mol.wt. corresponding to a limited viscosity number of 0.01-6 in a tetrahydrofuran solution at 27 deg.C is produced by subjecting a vinyl compound of formula I (wherein R is H or methyl) to radical polymerization. Although this compound is hydrophilic at ordinary temperatures, it becomes insoluble in water reversibly by heating. The compound of formula I can be produced by reacting, for example, (meth)acryloyl chloride with 2-amino-1-methoxypropane and triethylamine in a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel vinyl compound polymer. More specifically, the present invention provides conventional hydrophilic-hydrophobic thermal technology that can be used in light shielding bodies, temperature sensors, adsorbents, toys, interiors, printing aids, displays, separation functional membranes, and mechanochemical materials. 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 compound is called a hydrophilic-hydrophobic thermoreversible polymer compound, and has recently attracted attention as a light shield for greenhouses, chemical laboratories, temperature sensors, etc.

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

Among these hydrophilic-hydrophobic thermoreversible polymer compounds, polyacrylamide derivatives are suitable for the above uses because they are stable in water and can be produced at relatively low cost. Until now, poly (N
-ethyl (meth)acrylamide), poly(N-n
-propyl (meth)acrylamide), poly(N-
isopropyl (meth)acrylamide), poly(N
-cyclopropyl (meth)acrylamide), poly
(NSN-diethylacrylamide), poly (N-methyl-N-ethylacrylamide), poly (N-methyl-N-n-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. .

Even when attempts were made to use it for temperature sensors, light shields, etc., the transition temperature was limited and it was not possible to arbitrarily select it depending on the purpose, limiting the range of application.

Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to develop novel polyacrylamide derivatives having different transition temperatures in order to expand the scope of use of hydrophilic-hydrophobic thermoreversible polyacrylamide derivatives. The purpose of this invention is to provide a hydrophilic-hydrophobic thermoreversible polyacrylamide derivative and a method for producing the same.

Means for Solving the Problems The present inventors have conducted intensive research to develop new hydrophilic-hydrophobic thermoreversible polyacrylamide derivatives having different transition temperatures. ) CHt=CR C=O NHCH-CHt 0-CHs (II)
CHs (R in the formula is a hydrogen atom or a methyl group) obtained by radical polymerization of a vinyl compound, and has the general formula (I) (CHs-0R)- ■ C=O N HCH-CH* O -CHs (I)
It consists of a repeating unit represented by Hs (R in the formula is a hydrogen atom or a methyl group), and has an intrinsic viscosity [η] of 0.01 to 27°C in a tetrahydrofuran solution.
It was discovered that a polymer compound having a molecular weight equivalent to 6.0 is a hydrophilic-hydrophobic thermoreversible polymer compound that becomes insolubilized in water by heating, and based on this knowledge, the present invention was completed. Ta.

The polymer compound of the present invention is a novel compound that has not been described in any literature. By radically polymerizing the vinyl compound represented by the general formula (II), N-1
-Methyl-2-methoxyethyl (meth)acrylamide, which is synthesized, for example, as shown by the following formula.

(A) (meth)acrylic acid chloride and 2-amino-
A method of reacting 1-methoxypropane and triethylamine in a solvent, preferably at a temperature of 0 to 10°C.

(B) (meth)acrylic acid chloride and 2-amino-
1-methoxypropane in a solvent, preferably 0
A method of reacting at a temperature of ~10°C.

(A) Law; CH! = CR+ N Ht CHCH* −0−
CHsCH*=OR+ (CtHs)sN-HC1C
20 N HCH-CHt -OCHs--Kazuyuki → Hs ゛(B) method: CHt=CR+2NHt-CH-CHl-0-CHs solvent CHt=CR+CHs-OCHt CHNHeHCl
C=OCHs NH-CH-CHl-0-CH3 CH3 For the solvents used in these methods, (meth)
There is no particular restriction 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 o - to ''c.

To isolate the target compound from the reaction mixture thus obtained, the triethylamine hydrochloride or 2-amino-1-methoxypropane hydrochloride is usually first removed by filtration, and then filtered using a rotary evaporator. The solvent can be made from the liquid to a purity level.

The vinyl compound represented by the general formula (II) used in the present invention, N-1-methyl-2-methoxyethyl acrylamide (boiling point 92°C/1 amHg) and N-
1-Methyl-2-methoxyethyl methacrylamide (
It is a colorless liquid with a boiling point of 108℃/3.5mmHg) and is soluble in solvents such as water, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, chloroform, carbon tetrachloride, and benzene, and is soluble in n-hexane and n- Insoluble in butane.

The vinyl compound represented by the general formula (II) used in the present invention, N-1-methyl-2-methoxyethyl acrylamide and N-1-methyl-2-methoxyethyl methacrylamide, is subjected to radical polymerization, and water is hydrated by heating. As a specific method for producing a hydrophilic-hydrophobic thermoreversible polymer compound that is insolubilized, for example, a solution polymerization method and a bulk polymerization method can be employed. As a method for starting polymerization, (I
) Polymerization amount There is no particular restriction as long as it dissolves Ruamide and N-1-methyl-2-methoxyethylmethacrylamide. For example, water, alcohol, acetone,
Examples include tetrahydrofuran, chloroform, carbon tetrachloride, benzene, alkyl acetates, etc., and these may be used alone or in combination of two or more types depending on the case.

The polymer compound of the present invention is soluble in water at low temperatures and insoluble in water at high temperatures. The transition temperature of the aqueous solution of the polymer compound is
Although it varies depending on the polymerization conditions, poly(N-1-methyl-2
33 to 35°C for a 1% aqueous solution of poly (N-1-methyl-2-methoxyethylmethacrylamide) and 42 to
It is in the range of 45°C.

The transition temperature of the aqueous solution of the polymer compound tends to decrease as the molecular weight increases.
The transition temperature can be precisely controlled in the range of 45°C.

The polymer compound of the present invention, poly(N-1-methyl-2-
Methoxyethyl acrylamide) and borylamide) have a -CONH- group, -CH, -0- group, and -CH< group, so they can be identified by infrared absorption spectroscopy or the like. In addition, regarding the degree of polymerization, the intrinsic viscosity [η] at a temperature of 30°C in a tetrahydrofuran solution
A range of 0.01 to 6.0 is practical. Furthermore, regarding solubility in various solvents, it is soluble in cold water, tetrahydrofuran, chloroform, benzene, methanol, acetone, etc., and insoluble in ethyl acetate, n-amyl acetate, isobutyl acetate, hexane, etc.

Effects of the Invention The polymer compound of the present invention is a new compound that has not been published in any literature, and is a hydrophilic-hydrophobic thermoreversible polyacrylamide derivative that is reversibly soluble in water at low temperatures and insoluble at high temperatures. in,
It has a transition temperature different from that of conventionally known hydrophilic-hydrophobic thermoreversible polyacrylamide derivatives, and can be used, for example, in light-shielding materials such as greenhouses, temperature sensors, surfactant adsorbents, and even toys and interior decoration. , printing aids, displays, separation functional membranes, mechanochemical device materials, etc.

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

Reference example 1 101.7 g of triethylamine in a No. 11 Erlenmeyer flask.

Add 89.48 g of 2-amino-1-methoxypropane and 45 hl of toluene, cool with water, keep the content below 10°C, and add 89.48 g of acrylic acid chloride while stirring.
A mixed solution of 0.0 ml and 50 ml of toluene was added dropwise over about 3 hours using a dropping funnel. After completion of the dropwise addition, the reaction solution was kept in the refrigerator for one day and night to react. Then, 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 92
℃/io+a+Hg) 101.7g. The results of mass spectrum analysis and infrared absorption spectrum analysis are as follows.

Mass spectral analysis: IIl/e M+1 =
144M OCHs
=111M--CHt-OCHs
= 98CH, =CH= 55 C=O CH, =CH= 27 ■ Infrared absorption spectrum analysis knee NH- = 3270 C11-' CH* = CH= 1620011-'-0-=
1108 cta-'>cmo = 1655ca+''l>CH
-=2930.2875cm-'2978 es
-' -CONH-=1545 cm-weight or higher analysis results confirmed that this substance was N-1-methyl-2-methoxyethylacrylamide.

Reference Example 2 Except for using 99 ml of methacrylic acid chloride instead of acrylic acid chloride in Reference Example 1, all <Example 1>
A colorless and transparent fraction (boiling point 108"C/3.
5+a+Hg) 138.2g was obtained.

The infrared absorption spectrum of this material is shown in FIG. The results of mass spectrum analysis and infrared absorption spectrum analysis are as follows.

Mass spectrum analysis: m/e M+1
=158M--0-CHI
=142M -CHI OCHs
=126CH*=CCHs
= 69C=O ■ CH* = C-CH@= 41 Infrared absorption spectrum analysis knee NH- = 3320 cm-' CH! =C< = 1618 cm-'-0
-= 1108 cta-'>C=O= 1655 cti-'>CH-= 2930.2875 cta-'298
0, -1 -CONH-,, = 1530ca+-'13. I.
't Example 1 A radical polymer of the vinyl monomer obtained in Example 1 was produced.

Using azobisisobutyronitrile as a polymerization initiator,
A predetermined weight of N-1=methyl-2- is added to the solvent at a predetermined concentration.
Methoxyethyl acrylamide was added, the ampoule was put into an ampoule, the ampoule was degassed under reduced pressure using liquid nitrogen, the tube was sealed, and the ampoule was kept in a constant temperature bath at a temperature of 50° C. for 7 hours to react. After the reaction, the solvent was removed, and then n-hexane was added to separate and collect the polymer. The polymerization reaction results of Example 1 are shown in Table 1.

Initiator concentration: O, 1 g/100 1 Polymerization solvent Examples 2 to 4 A radical polymer of the vinyl monomer obtained in Reference Example 1 was produced.

Add a predetermined amount of N-1-methyl-2-methoxyethyl acrylamide to 2 hl of polymerization solvent, put this into an ampoule, degas it under reduced pressure using liquid nitrogen, seal the tube, and apply an irradiation dose rate of 4.9 x 10'. R/hr, temperature 24℃
γ-ray irradiation from cobalt-60 was performed for 2 hours to cause a reaction. After the reaction, the solvent was removed and hexane was added to separate and collect the polymer. The polymerization reaction results of Examples 2 to 4 are shown in Table 2.

4 n-amyl acetate 1.90 1.85
The infrared absorption spectra of the two polymers precipitated in n-amyl acetate are shown in FIG. 1620 from a comparison of the infrared absorption spectrum of vinyl monomer and that of polymer
It was confirmed that the vinyl group of cl' disappeared and a polymer compound was formed.

This polymer was dissolved in tetrahydrofuran and investigated.

The transition temperature was determined from the light transmittance associated with the temperature change of the aqueous solution. That is, an aqueous polymer solution with a concentration of 1% by weight was prepared, and a temperature increase rate of 1" was prepared using a spectrophotometer with a temperature controller.
The light transmittance at a wavelength of 500 nm is measured while increasing the temperature at a rate of C/min, and the transition temperature is determined when this light transmittance is 0 of the initial transmittance.
．． It was determined from the temperature (TL) at which the temperature was 5. These results are shown in Table 3.

4 n-amyl acetate 1.52
33.5 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.

Examples 5 to 9 Radical polymers of the vinyl monomer obtained in Reference Example 2 were produced. N-1-methyl-2 instead of N-1-methyl-°2-methoxyethyl acrylamide in Reference Example 1
The reaction was carried out in the same manner as in Example 1 except that -methoxyethylmethacrylamide was used and kept in a constant temperature bath for 24 hours at a temperature of 50°C. 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 Examples 5 to 9.

Initiator concentration: 0.01 g/100 ml Polymerization solvent The infrared absorption spectrum of the polymer of Example 8 is shown in FIG. Infrared absorption spectrum of vinyl monomer and that of polymer
(Fig. 3), it was confirmed that the vinyl group of 1618effi-' disappeared and a polymer compound was formed.

Example 1 shows the intrinsic viscosity and transition temperature of these polymers.
□ 9 Tetrahydrofuran 0.21
44.2 The transmittance-temperature curve of the aqueous polymer solution of Example 6 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.

[Brief explanation of drawings]

FIG. 1 shows the infrared absorption spectrum of the vinyl monomer of Reference Example 1, and FIG. 2 shows the infrared absorption spectrum of the polymer of Example 2. FIG. 3 shows the infrared absorption spectrum of the vinyl monomer of Reference Example 2, and FIG. 4 shows the infrared absorption spectrum of the polymer of Example 8. FIG. 5 shows a transmittance versus temperature curve for a 1% by weight aqueous solution of the polymer of Example 1, and FIG. 6 shows a transmittance versus temperature curve for a 1% by weight aqueous solution of the polymer of Example 6. Figure 1: 40003000200016001jlo0800 wave number (α - wave number (, -1) Figure 3: Wave @ (α) Figure 5: Temperature -C) Figure 6: Temperature (°C) Indication 1988 Patent Application No. 131cl15 2 Name of the invention Lignophilic-hydrophobic thermoreversible polymer compound and its manufacturing method 3 Relationship with the person making the amendment Case Patent applicant 1-3 Kasumigaseki, Chiyoda-ku, Tokyo No. 1 (I14) Director of the Agency of Industrial Science and Technology Kozo Iizuka 5, Date of amendment order Vol. 6 Number of inventions increased by amendment 0 & Contents of amendment (I) "Reference examples" in the 5th line from the top of page 13 of the specification "Reference examples and examples" has been corrected to "Reference examples and working examples." (2) Delete "," in the second line from the top of page 14. (3) Delete "tsu" from "Two Examples" in the fifth line from the bottom of page 17. (4) Insert "~4" next to "All Example 1" on the third line from the top of page 19. (5) Next to the 3rd line of the notes in Table 4 on page 19 of the same page, "Polymerization solvent capacity: Example 5, 100 m1. Examples 6~
Insert 9,2omJ.

Claims (1)

[Claims] 1 General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼---(I) From the repeating unit represented by (R in the formula is a hydrogen atom or a methyl group) The intrinsic viscosity [η] at a temperature of 27°C in a tetrahydrofuran solution is 0.01 to 6.
A hydrophilic-hydrophobic thermoreversible polymer compound having a molecular weight corresponding to 0. 2 General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼---(II) Characterized by radical polymerization of the vinyl compound represented by (R in the formula is a hydrogen atom or a methyl group) The general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼---(I) (R in the formula is a hydrogen atom or a methyl group). The intrinsic viscosity [η] at a temperature of 27°C is 0.01 to 6.
A method for producing a hydrophilic-hydrophobic thermoreversible polymer compound having a molecular weight corresponding to 0.