JPS6312611A - Heat-sensitive high polymer having copper chelating ability - Google Patents

Abstract

PURPOSE:The titled novel polymer suitable as light shading material, tempera ture sensor, etc., water-soluble in a low temperature range but becoming water- insoluble under heating, obtained by copolymerizing N-(meth)acry loylbenzhydrazide with a specific vinyl compound. CONSTITUTION:(A) An N-(meth)acryloylbenzhydrazide shown by formula I (R1 is H or CH3) is copolymerized with (B) a vinyl compound which has struc ture shown by formula II (R1 is H or CH3; R2 and R3 are H, alkyl, etc.) and provides a homopolymer whose aqueous solution shows heat reversible properties and, if necessary, (C) another copolymerizable vinyl compound preferably by solution polymerization method to give the aimed polymer consisting of a hydrophilic-hydrophobic thermally reversible copolymer which becomes water- insoluble under heating and has copper chelating ability. For example, N-ethyl (meth)acrylamide, etc., are used as the component A and acrylamide, etc., are used as the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel hydrophilic-hydrophobic thermoreversible copolymer having copper chelating ability. More specifically, the present invention provides copper that becomes insolubilized by heating, which can be used in light shields, temperature sensors, adsorbents, copper ion indicators, toys, interiors, printing agents, displays, separation membranes, and mechanochemical materials. This invention relates to a hydrophilic-hydrophobic thermoreversible copolymer having chelating ability.

Conventional technology One of the water-soluble polymer compounds exhibits a special reversible dissolution behavior in which in an aqueous solution state, it precipitates and becomes cloudy above a certain temperature (transition temperature or cloud point), and dissolves and becomes transparent below that temperature. This material is called a hydrophilic-hydrophobic thermoreversible polymer compound, and in recent years it has been used as a light shielding material for greenhouses, chemical laboratories, etc.

It has started to attract attention as a temperature sensor, etc.

As such thermoreversible polymer compounds, partially saponified polyvinyl acetate, polyvinyl methyl ether, methylcellulose, polyethylene oxide, polyvinylmethyloxacilidinone, polyacrylamide derivatives, and the like have been known.

Among these thermoreversible polymers, polyacrylamide derivatives are suitable for the above-mentioned uses because they are stable in water and can be produced at relatively low cost.

So far, materials with thermoreversibility include poly(N-ethyl(meth)acrylamide), poly(N-n-propyl(meth)acrylamide), poly(t)-isopropyl(meth)acrylamide), and poly(N-ethyl(meth)acrylamide). -cyclopropyl(meth)acrylamide), poly(N,N-diethylacrylamide), poly(N-methyl-N-ethylacrylamide), poly(N,N-diethylacrylamide), po'J (N-methyl-N -ethylacrylamide), poly(N-methyl-N-propylacrylamide), poly(N-methyl-N-isopropylacrylamide), poly(N-acrylpyrrolidine), poly(N-methyl-N-isopropylacrylamide), poly(N-methyl-N-isopropylacrylamide),
N-acrylicpiperidine), poly (N-tetrahydrofurfuryl (meth)acrylamide), poly (N-methoxypropyl (meth)acrylamide), poly (N
-ethoxypropyl (meth)acrylamide), poly
(N-isopropococyprobyl (meth)acrylamide), poly(N-ethoxyethyl (meth)acrylamide), poly(N-(2゜2-dimethoxyethyl)-N-
Methylacrylamide) etc. are known.

However, it is difficult to use such compounds in applications such as temperature sensors and light shields.

The transition temperature is limited, and since it does not have the ability to chelate gold-14 ions, the range of application is inevitably limited.

Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to expand the scope of use of hydrophilic-hydrophobic thermoreversible polyacrylamide derivatives, which have copper chelating ability and can be used by heating. The object of the present invention is to provide a novel hydrophilic-hydrophobic thermoreversible copolymer that is insoluble in water.

Means to solve problems This is the result of extensive research by the inventors.

General formula (I) σ City = CR1Co NH-NHCo Co H5
(However, + R1 is H or CH3) and the general formula (II) CH2= CRr O (However, e Rr is H or C) h , R2, Rs are hydrogen, alkyl group, cyclic alkyl group, tetrahydro furfuryl group, alkoxyalkyl group), and a copolymer with a vinyl compound whose homopolymer aqueous solution exhibits thermoreversibility;
Or by a hydrophilic-hydrophobic thermoreversible copolymer which is made of a copolymer of the above two types of vinyl compounds and another copolymerizable vinyl compound and has a copper chelating ability that becomes insoluble in water by heating.

The inventors have found a way to achieve the above object, and have completed the present invention based on this knowledge.

That is, the present invention has the general formula (I) CRr Co NH-NHCo C6H
5 (however, + Rs is H or σ) and the general formula (II) C) h = CR1 O (however, Rs is H or CHI, R2, Rs is H,
alkyl group, cyclic alkyl group, tetrahydrofurfuryl group, alphukidialkyl group), and the homopolymer aqueous solution thereof shows thermoreversibility, or a copolymer of the above two types of vinyl compounds and other vinyl compounds. The present invention provides a hydrophilic-hydrophobic thermoreversible copolymer which is made of a copolymer with a copolymerizable vinyl compound and has a copper chelating ability that becomes insolubilized in water by heating.

General formula (I) used in the present invention CH2=CRI Co NHNHCo C5H5
(When R+ = H, N-acryloylbenzhydrazide, hereinafter abbreviated as ABH; when R+ = CH3, N-methacryloylbenzhydrazide, hereinafter abbreviated as MABH), a homopolymer of a vinyl compound has copper ions and This is known to selectively chelate.

For example, [Di macromolecular chemistry (Di
e Macromolculare Chemie)
J, Vol. 85, pp. 92-105 (published in 1965).

In the present invention, one or more vinyl compounds represented by the general formula (II) whose homopolymers are hydrophilic-hydrophobic thermoreversible polymers can be used. Specifically, these include N-ethyl (meth)acrylamide,
N n-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-cyclopropyl (
meth)acrylamide, N,N-diethylacrylamide.

N-methyl-N-ethylacrylamide, N-methyl-
N-n-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acrylpyrrolidine,
N-acrylicpiperidine, N-tetrahydrofurfuryl (meth)acrylamide, N-methoxypropyl (meth)acrylamide, N-ethoxypropyl (meth)acrylamide, N-impropococypropyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide ) acrylamide, N-(2,2-dimethoxyethyl)-N-methylacrylamide, and the like.

In the present invention, other copolymerizable vinyl compounds that can be used as the third component include hydrophilic vinyl compounds (excluding the above-mentioned thermoreversible vinyl compounds).

One or more of ionic vinyl compounds and lipophilic vinyl compounds can be used. As a hydrophilic vinyl compound, 2
For example, N-methylolacrylamide, acrylamide, methacrylamide, N-methylacrylamide, NI
N-dimethylacrylamide, acryloylmorpholine, diacetone acrylamide, hydroxyethyl methacrylate.

Hydroxymethyl methacrylate, hydroxymethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, N-methoxypropylacrylamide, N-methoxypropylmethacrylamide, 2-methyl-5-vinylpyridine, N-vinyl-2-
Pyrolidone etc. can be given. As an ionic monomer.

For example, acid supports such as acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propanesulfonic acid, styrenesulfonic acid, and their salts N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate-1- , N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminopropylacrylamide, and salts thereof. As the lipophilic vinyl compound, for example, Nn-butylacrylamide + Nn-butylmethacrylamide.

N-5ea-butylacrylamide 5N-sec butyl methacrylamide, N-tert-butylacrylamide, N-tert-butyl methacrylamide, N
-n-hexyl acrylamide l N-alkyl such as N-n-hexylmethacrylamide, (meth)acrylamide derivatives, (meth)acrylate derivatives such as ethyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, acrylonitrile, vinyl acetate , vinyl chloride, styrene, α-methylstyrene% wo, j) l”!'

A specific method for producing a hydrophilic-hydrophobic thermoreversible copolymer by copolymerizing the vinyl compound represented by the above general formulas (I) and (II) and the vinyl compound serving as the third component is 2. For example, (1) a method in which monomers are directly copolymerized without diluting them with a solvent, (2) a method in which solution copolymerization is performed by diluting monomers in a solvent, (3) a method in which suspension copolymerization is carried out, (4) A method such as emulsion copolymerization can be adopted. The polymerization mode at that time is radical polymerization. As a method to initiate polymerization,
(1) Method using a polymerization initiator, (2) Light irradiation such as ultraviolet rays and visible light, (3) Method using heat, (4) Irradiation with ionizing energy rays such as radiation, electron r-rays, and plasma. A method such as that can be adopted. The polymerization initiator is not limited as long as it has the ability to initiate radical polymerization; examples thereof include inorganic peroxides, organic peroxides, combinations of these peroxides and reducing agents, and azo compounds. Specifically, ammonium persulfate, potassium persulfate, hydrogen peroxide,
Examples include tert-butyl peroxide, benzoyl peroxide, and cumene hydroperoxide, and reducing agents used in combination with these include sulfites and hydrogen sulfites. Examples of azo compounds include azobisisobutyronitrile, 2,2'-azobis-2-aminodipropane dihydrochloride 42g2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4- Ciatsuvaleic acid and the like can be used. or.

It is also possible to use two or more of the above polymerization initiators in combination. In this case, the amount of the polymerization initiator added is 0.01 to 5% by weight, preferably 0.05% by weight, based on the vinyl compound of the structural unit.
% to 2% by weight.

In the present invention, a method of ordinary solution copolymerization is preferably used. In this solution copolymerization.

Dissolve two or more of the above vinyl compounds in a solvent and
A commonly known radical polymerization method can be used as an 80% strength solution. There are no particular restrictions on the solvent used in such solution copolymerization, but examples include water, alcohols, and N.

N-dimethylformamide, N,N-dimethylacetamide, acetone, dioxane, tetrahydrofuran, benzene, chloroform, carbon tetrachloride, etc. may be used alone or in combination of two or more.

The thus obtained copolymer of the present invention is as follows.

It has a part of 1ζ polymer unit of general formula (1) and forms a chelate with Cu2+ ion according to the following formula.

Furthermore, the copolymer of the present invention has a polymer unit of the general formula (II), and has a high-temperature hydrophobic property that is soluble in water in a low temperature range and insoluble in a high temperature range, regardless of copper chelate formation. It has thermoreversibility of oxidation type.

Generally, the transition temperature of an aqueous solution of a thermoreversible copolymer is
It can be controlled by a combination of types of vinyl compounds serving as structural units and their composition ratios. In this case, in the case of a copolymer in which the homopolymer is formed of two or more thermoreversible vinyl compounds, additivity often exists between the transition temperature of each homopolymer and its composition. Further, the homopolymer may copolymerize one or more thermoreversible vinyl compounds with one or more other copolymerizable non-thermoreversible vinyl compounds. As other copolymerizable non-thermoreversible vinyl compounds, one or more of hydrophilic vinyl compounds, ionic vinyl compounds, and lipophilic vinyl compounds can be employed. In that case, the introduction of these vinyl compounds changes the transition temperature of the aqueous copolymer solution, but in general, introduction of a hydrophilic vinyl compound increases the transition temperature, while introduction of a small amount of lipophilic vinyl compound lowers the transition temperature. It tends to go down. The introduction of large amounts of lipophilic vinyl compounds.

Makes the copolymer water-insoluble.

Regarding the copolymer of the present invention, the general formula (
Since the vinyl compound homopolymer represented by I) is a water-insoluble polymer, the (ABH) component and (MABH) component in the copolymer must be 10% or less in order to have thermoreversibility. It is desirable to do so.

The transition temperature of the copolymer aqueous solution of the present invention is determined by the vinyl compounds represented by general formula (I) and general formula (II), which are the constituent units in the copolymer, and other copolymerizable non-thermoreversible vinyls. It can be estimated from the type and composition of the compound and its composition ratio. Also, what is the transition temperature of the copolymer aqueous solution after copper chelation?

Depending on the degree of chelation, it generally lowers the transition temperature compared to that of the unchelated copolymer.

The unchelated copolymer of the present invention described above has a suitable high molecular weight. For example, the intrinsic viscosity at 30 °C in methanol solution (7:l = 0.01 to 6.0 It is practical, and particularly preferred is [7]; 0.1 to 3.0.

Effect of the invention The acrylamide thermoreversible copolymer of the present invention is.

It has high-temperature hydrophobization type thermoreversibility that dissolves in water at low temperatures and becomes insoluble in water at high temperatures, and unlike conventionally known thermoreversible acrylamide polymers, it has copper chelating ability. It is possible to change the transition temperature over a wide range by combining vinyl compounds, and it is useful for light shields, temperature sensors, adsorbents, copper ion indicators,
Even toys.

It can be used for interiors, textile printing agents, displays, separation membranes, and mechanochemical materials. For example, if the copolymer of the present invention is laminated on a transparent plate in the form of an aqueous solution or in the form of a hydrogel or microcapsule, it automatically prevents the indoor temperature from rising more than necessary due to direct sunlight. It is suitable as a light shielding body for

The present invention will be explained in more detail with reference to Examples below.

Examples 1 to 5 Using azobisisobutyronitrile as a polymerization initiator,
Add a predetermined weight of two or more of the above vinyl compounds to 2Qml of a methanol solution with a concentration of 50μ/1p, put this into an ampoule, degas it under reduced pressure using liquid nitrogen, seal the tube, and store at a temperature of 60°C. The reaction was allowed to proceed for 20 hours. After the reaction, methanol was evaporated, the solution was made into an acetone solution, and the copolymer was recovered by precipitation in diethyl ether.

The thermoreversibility of this copolymer in water was investigated. The transition temperature was determined from the light transmittance associated with the temperature change of the aqueous solution. That is, an aqueous copolymer solution having a concentration of 1% by weight was prepared, and the light transmittance at a wavelength of 500 nm was measured using a spectrophotometer with a temperature controller while raising the temperature at a rate of 1°C/min.

The transition temperature was determined from the temperature (TL) at which the light transmittance was 0.5 of the initial transmittance.

Table 1 Example N I PAM (gl ABH(g) MA
M (g) T,, ('C)1 10.01 0.0
01.0036.52 10.02 0.601.00
28.03 10.02 1.201.0023.04
10.02 1.801.0020.55 1
0.01 2.40 1.00 Insoluble NI
PAM: N-isopropylacrylamide ABH: N-
Acryloylbenzhydrazide MAM: N-methylolacrylamide These results are shown in Table 1. In addition, Example 1 and Example 2. Example 4 The transmittance-temperature curve of the aqueous copolymer solution is shown in FIG. Among these, the solid line is when the temperature rises.

The dotted line is data when the temperature is decreasing. Example 2. Examples 3 and 4 When sulfuric acid was added to the copolymer aqueous solution, the color of the aqueous solution changed from blue to olive green, confirming the formation of copper chelate. The aqueous solution of the copper chelated copolymer produced showed thermoreversible dissolution properties.

Examples 6 to 10 Two or more of the above vinyl compounds containing a predetermined heavy metal were added to 20 ml of methanol solution, which was put into an ampoule, degassed under reduced pressure using liquid nitrogen, and then sealed, and the irradiation dose rate was 3.9X.
The reaction was carried out by irradiating gamma rays from cobalt 60 for 10 hours under the conditions of 10 R/hr and a temperature of 24°C. After the reaction,
After evaporating methanol, it was made into an acetone solution and precipitated in diethyl ether to recover the copolymer.

Table 2 Examples N I PAM (g) ABHIg)
T, (''C)6 3.36 0.00 31.0 7 3.21 0.31 24.0 8 3.05 0.57 1B, 5 9 2.88 0.85 Insoluble 10
2,74 1.18 Insoluble NIP
AM: N-isopropylacrylamide ABH: N-acryloylbenzhydrazide The thermoreversibility of aqueous solutions of these copolymers was investigated using the method described above. These results are shown in Table 2.

Example 7. Example 8 When copper ions were added to an aqueous copolymer solution, the color of the aqueous solution changed from blue to olive green, confirming the formation of copper chelate. Also.

The aqueous solution of the copper chelated copolymer produced showed thermoreversible dissolution properties.

FIG. 2 shows the transmittance-temperature curves of the Example 7 copolymer and the copper-chelated Example 7 copolymer aqueous solution.

Examples 11 to 24 Using azobisisobutyronitrile as a polymerization initiator,
Add a predetermined weight of two or more of the above vinyl compounds to 20 volumes of methanol solution with a concentration of 5n@/1ml, put this into an ampoule, degas it under reduced pressure using liquid nitrogen, seal the tube, and heat it at a temperature of 60'C. The reaction was allowed to take place for a predetermined period of time. Then, after the reaction,
After evaporating methanol, it was made into an acetone solution and precipitated in n-hexane to recover the copolymer.

The thermoreversibility of these copolymer aqueous solutions was investigated using the method described above. These results are shown in Table 3.

When j14(on) was added to the aqueous solution of Examples 11 to 22 copolymers, the color of the aqueous solution changed from blue to olive green, confirming the formation of copper chelate. , showed thermoreversible dissolution properties.

Table 3 2.04

[Brief explanation of drawings]

Figures 1 and 2 show transmittance versus temperature curves for a 1% by weight aqueous solution of the copolymer of the present invention.

Claims (1)

[Claims] General formula (I) CH_2=CR_1-CO-NH-NH-CO-C_6
Vinyl compounds represented by H_5 (where R_1 is H or CH_3) and general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 is H or CH_3, R_2, R_3 are H
, alkyl group, cyclic alkyl group, tetrahydrofurfuryl group, alkoxyalkyl group), and a copolymer with a vinyl compound whose homopolymer aqueous solution exhibits thermoreversibility;
Alternatively, a hydrophilic-hydrophobic thermoreversible copolymer comprising a copolymer of the above two types of vinyl compounds and another copolymerizable vinyl compound and having a steel chelating ability that becomes insolubilized in water by heating.