JP6999892B2 - Polymer compounds, their manufacturing methods, and optical materials - Google Patents

Description

The present invention relates to a polymer compound, a method for producing the same, and an optical material.

In recent years, in the field of functional polymers, the development of higher-performance materials has been required in order to respond to the diversification and sophistication of applications. In particular, from the viewpoint of the possibility of application to optical materials such as optical switching materials and organic lenses, mechanical properties such as strength and rapid responsiveness to external stimuli such as temperature and pH changes (hereinafter referred to as "stimulus responsiveness"). ), And the development of materials with excellent processability such as molding is required.

Patent Document 1 discloses a technique for increasing the mechanical strength of a film by using a polymer having a high molecular weight. Further, Patent Document 2 discloses a technique for lowering the glass transition point by using a polymer having a star-shaped structure. Further, Non-Patent Document 1 discloses a technique for constructing a three-dimensional gel structure having a mutual network structure for a stimulus-responsive polymer material to achieve both stimulus-responsiveness and mechanical properties.

However, the polymer disclosed in Patent Document 1 has a problem that it has high mechanical properties but is inferior in processability. Further, although the star-shaped polymer disclosed in Patent Document 2 has improved processability, it cannot maintain mechanical properties. Further, the stimulus-responsive polymer disclosed in Non-Patent Document 1 has a problem that secondary processing cannot be performed because the shape of the stimulus-responsive polymer is fixed when the three-dimensional network structure is constructed.

Therefore, conventional techniques cannot provide polymer compounds with mechanical properties, stimulus responsiveness, and processability.

An object of the present invention is to provide a polymer compound having mechanical properties, stimulus responsiveness, and processability.

The polymer compound of the present invention is characterized by having a structure in which a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are crosslinked.

（式（１）中、Ｒ１およびＲ２は水素または炭素数１または２のアルキル基から選択されるいずれかの基、Ｒ３は－Ｃ_２Ｈ_４－またはエーテル基から選択されるいずれかの基、Ｒ４は水素、Ａは下記式（ＡＡ）で示される繰り返し単位、Ｂは下記式（ＢＢ）で示される繰り返し単位、Ｘはハロゲン元素、水素、下記式（ＡＡ）の中から選択されるいずれかの基、但し、式（１）でＢを含まない場合は、下記式（ＡＡ）中のｎが１～５００の整数であり、式（１）でＢを含む場合は、下記式（ＡＡ）中のｎと下記式（ＢＢ）中のｍの和が１～５００の整数である）

(In formula (1), R1 and R2 are any group selected from hydrogen or an alkyl group having 1 or 2 carbon atoms, and R3 is any group selected from -C ₂ H _4- or an ether group. R4 is hydrogen , A is a repeating unit represented by the following formula (AA), B is a repeating unit represented by the following formula (BB), X is a halogen element, hydrogen, and any of the following formulas (AA) is selected. However, if B is not included in the formula (1), n in the following formula (AA) is an integer from 1 to 500, and if B is included in the formula (1), the following formula (AA) is included. ) And m in the following formula (BB) is an integer from 1 to 500 )

（式中、Ｒ５およびＲ６は水素または炭素数１または２のアルキル基から選択されるいずれかの基）

(In the formula, R5 and R6 are any group selected from hydrogen or an alkyl group having 1 or 2 carbon atoms ).

（式中、Ｒ８は水素、炭素数１～１２のアルキル基、メトキシポリエチレングリコール基、フェノキシポリエチレングリコール基、２－ヒドロキシエチル基、３－ヒドロキシプロピル基、または４－ヒドロキシブチル基、Ｒ９は水素またはメチル基）

(In the formula, R8 is hydrogen, alkyl having 1 to 12 carbon atoms.Basic, Methoxypolyethylene glycolBasic, Phenoxy Polyethylene GlycolBasic, 2-HydroxyethylBasic, 3-HydroxypropylBasic,or4-HydroxybutylGroup,R9 is hydrogen or methylBasic)

（式（２）中、Ｒ７は炭素数１または２のアルキレン基から選択されるいずれかの基）

(In formula (2), R7 has 1 or 2 carbon atoms.Alkylene groupOne of the groups selected from)

According to the present invention, it is possible to provide a polymer compound having mechanical properties, stimulus responsiveness, and processability.

It is a schematic diagram which shows an example of the polymer compound of this invention. It is a schematic diagram which shows the crosslinked structure of an example (when X is bromine) of the polymer compound of this invention. It is a figure which shows the gel permeation chromatography (GPC) chart of the polymer represented by an example (Example 1) and the general formula (4) of the polymer compound of this invention. It is a figure which shows the infrared absorption spectrum of an example (Example 1) of the polymer compound of this invention. It is a figure which shows the nuclear magnetic resonance spectrum of an example (Example 1) of the polymer compound of this invention. It is a figure which shows the GPC chart of the polymer represented by another example (Example 2) and the general formula (4) of the polymer compound of this invention. It is a figure which shows the infrared absorption spectrum of another example (Example 2) of the polymer compound of this invention. It is a figure which shows the nuclear magnetic resonance spectrum of another example (Example 2) of the polymer compound of this invention. It is a figure which shows the GPC chart of the polymer represented by another example (Example 3) and the general formula (4) of the polymer compound of this invention. It is a figure which shows the infrared absorption spectrum of another example (Example 3) of the polymer compound of this invention. It is a figure which shows the nuclear magnetic resonance spectrum of another example (Example 3) of the polymer compound of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. FIG. 1 is a schematic diagram of a hyperbranched polymer which is an example of the polymer compound of the present invention. This hyperbranched polymer has a crosslinked structure in which the compound represented by the following general formula (1) is crosslinked by the compound represented by the following general formula (2).

一般式（１）中で、Ｒ１およびＲ２は水素または炭素数１または２のアルキル基から選択されるいずれかの基であり、Ｒ３は少なくとも炭素を２つ含むアルキレン基またはエーテル基から選択されるいずれかの基であり、Ｒ４は水素または炭素数１または２のアルキル基から選択されるいずれかの基である。また、Ａは下記式（ＡＡ）で示される繰り返し単位であり、Ｂは下記式（ＢＢ）で示される繰り返し単位である。さらに、Ｘはハロゲン元素または水素から選択されるいずれかの基である。

In the general formula (1), R1 and R2 are selected from hydrogen or an alkyl group having 1 or 2 carbon atoms, and R3 is selected from an alkylene group or an ether group containing at least 2 carbon atoms. Any group, R4 is any group selected from hydrogen or alkyl groups with 1 or 2 carbon atoms. Further, A is a repeating unit represented by the following formula (AA), and B is a repeating unit represented by the following formula (BB). Further, X is either a group selected from halogen elements or hydrogen.

In the general formula (1), by using R1 and R2 as any group selected from hydrogen or an alkyl group having 1 or 2 carbon atoms, the degree of polymerization can be easily controlled and a polymer having a high molecular weight can be obtained. can. When R1 and R2 are alkyl groups having 3 or more carbon atoms, the degree of polymerization is significantly reduced due to steric hindrance, and it is difficult to obtain a polymer having a high molecular weight.

Further, in the general formula (1), by using R3 as any group selected from an alkylene group containing at least two carbons or an ether group, a chemically stable and easy-to-handle polymer can be obtained. When R3 is hydrogen or an alkylene group having 1 carbon atom, the obtained polymer is often chemically unstable and difficult to handle.

Further, in the general formula (1), by using R4 as any group selected from hydrogen or an alkyl group having 1 or 2 carbon atoms, the degree of polymerization can be well controlled and a polymer having a high molecular weight can be obtained. can. When R4 is an alkyl group having 3 or more carbon atoms, it aggregates due to hydrophobic interaction and the degree of polymerization is significantly reduced, making it difficult to obtain a polymer having a high molecular weight.

Further, in the formula (AA), by using R5 and R6 as any group selected from hydrogen or an alkyl group having 1 or 2 carbon atoms, the polymerization reactivity is improved and a polymer having a high molecular weight can be obtained. can. When R5 and R6 are alkyl groups having 3 or more carbon atoms, the polymerization reactivity is lowered due to steric hindrance, and it is difficult to obtain a polymer having a high molecular weight.

Further, in the formula (BB), R8 is used as a group of hydrogen, an alkyl chain having 1 to 12 carbon atoms, methoxypolyethylene glycol, phenoxypolyethylene glycol, 2-hydroxyethyl, 3-hydroxypropyl, or 4-hydroxybutyl. This makes it possible to improve the flexibility and shapeability of the obtained polymer.

Further, in the formula (BB), by using R9 as a hydrogen or a methyl group, the polymerization reactivity becomes good and a polymer having a high molecular weight can be obtained. When R9 is an alkyl group having 2 or more carbon atoms, the polymerization reactivity is lowered due to steric hindrance, and it is difficult to obtain a polymer having a high molecular weight.

Further, in the general formula (1), the order of A and B is not particularly limited, and may be AB or BA. Further, the compound represented by the general formula (1) may be a block copolymer composed of A and B or a random copolymer, but a random copolymer is preferable from the viewpoint of ease of production.

Further, in the general formula (1), the halogen element that can constitute X is a halogen element such as chlorine, bromine, and iodine. When X is a halogen element, a polymer having a high refractive index derived from the halogen element can be obtained. Further, by polymerizing the compound of the general formula (1) and the compound of the general formula (2) and then performing a purification treatment, it is possible to replace each halogen element with hydrogen. Therefore, it can also be used in applications where materials containing halogen elements are not preferred.

Further, when B is not included in the general formula (1), a polymer having an appropriately high molecular weight can be obtained by setting n to an integer of 1 to 500. In addition, there is no compound in which n is less than 1, and when n is an integer exceeding 500, the molecular weight becomes too high and the processability tends to decrease.

When B is included in the general formula (1), a polymer having an appropriately high molecular weight can be obtained by setting the sum of n and m to an integer of 1 to 500. There is no compound in which the sum of n and m is less than 1, and when n or the sum of n and m is an integer exceeding 500, the molecular weight becomes too high and the processability tends to decrease.

Further, in the general formula (2), by using R7 as any group selected from the alkylene groups having 1 or 2 carbon atoms, the compound of the general formula (1) is crosslinked by the compound of the general formula (2). A hyperbranched polymer having a crosslinked structure can be produced. When R7 is an alkylene group having 3 or more carbon atoms, it aggregates due to hydrophobic interaction and the degree of polymerization is significantly lowered, making it difficult to obtain a polymer having a high molecular weight.

The hyperbranched polymer of this example has a structure represented by the following general formula (3). This structure is thought to constitute a site that exhibits stimulus responsiveness in the hyperbranched polymer of this example.

このように、本例のハイパーブランチポリマーは、刺激応答性部位を有し、高い分子量でありながら低いガラス転移点を有する。これにより、機械特性及び加工性に優れ、さらに刺激応答性を示すことができる。

As described above, the hyperbranched polymer of this example has a stimulus-responsive site and has a high molecular weight but a low glass transition point. As a result, it is possible to exhibit excellent mechanical properties and workability, and further exhibit stimulus responsiveness.

Examples of the stimulus responsiveness include lower critical solution temperature (LCST) characteristics and pH characteristics. The LCST characteristic is that in an environment where a polymer and water coexist, the polymer and water are incompatible at a predetermined temperature or higher, but are compatible at a temperature lower than a predetermined temperature. Further, the pH responsiveness is a characteristic that in an environment where a polymer and water coexist, the polymer and water are incompatible at a predetermined pH or higher, but are compatible at a pH lower than a predetermined pH.

The weight average molecular weight of the hyperbranched polymer of the present invention is preferably 60,000 or more and 150,000 or less, more preferably 80,000 or more and 150,000 or less, and further preferably 10,000 or more and 150,000 or less. Is.

When the weight average molecular weight is 60,000 or more and 150,000 or less, the temperature responsiveness is high and good mechanical properties and workability are exhibited. Further, when the weight average molecular weight is 80,000 or more and 150,000 or less, the temperature responsiveness is improved, and the mechanical properties and workability are also improved. Further, when the weight average molecular weight is 100,000 or more and 150,000 or less, the temperature responsiveness is extremely high, and extremely good mechanical properties and processability are exhibited. If the weight average molecular weight is less than 60,000, it is difficult to maintain the mechanical properties, and if the weight average molecular weight is 150,000 or more, it is often difficult to produce a hyperbranched polymer.

Next, a method for producing the hyperbranched polymer of this example will be described. The hyperbranched polymer of this example can be produced by cross-linking the compound represented by the following general formula (4) with the compound represented by the following general formula (5). The compound represented by the following general formula (4) can be produced, for example, by the following reaction (A). The results of infrared spectroscopic analysis of the compound represented by the general formula (4) are shown in FIG. Further, a commercially available cross-linking material can be used for the compound represented by the following general formula (5).

上記反応（Ａ）では、一般式（６）で表される２－ｈｙｄｒｏｘｙｅｔｈｙｌ－２－ｂｒｏｍｏｉｓｏｂｕｔｙｒａｔｅ（ＨＥＢｉＢ）を開始剤として、一般式（７）で表されるＮ－イソプロピルアクリルアミドに遷移金属触媒と触媒配位子を混合して、原子移動ラジカル重合反応させることにより、一般式（４）で表される化合物を製造することができる。これにより、一般式（４）で表される化合物は、一般式（６）で表される化合物と一般式（７）で表される化合物との共重合体を構成する。

In the above reaction (A), a transition metal catalyst and a catalyst are converted to N-isopropylacrylamide represented by the general formula (7) using 2-hydroxylytyl-2-bromoisobutyrate (HEBiB) represented by the general formula (6) as an initiator. By mixing the ligands and subjecting them to atom transfer radical polymerization reaction, the compound represented by the general formula (4) can be produced. As a result, the compound represented by the general formula (4) constitutes a copolymer of the compound represented by the general formula (6) and the compound represented by the general formula (7).

ここで、遷移金属触媒は、特に限定するものではなく、原子移動ラジカル重合反応に用いられる触媒として一般に市販されているものを用いることができる。このような遷移金属触媒としては、例えば、チタン、鉄、コバルト、ニッケル、モリブデン、ルテニウム、ロジウム、パラジウム、レニウム、オスミウム、銅等の遷移金属またはこれらの遷移金属の化合物などが挙げられる。このうち、反応性の観点から、銅系の触媒が好ましく、中でも臭化銅がより好ましい。

Here, the transition metal catalyst is not particularly limited, and a commercially available catalyst can be used as a catalyst used in the atom transfer radical polymerization reaction. Examples of such a transition metal catalyst include transition metals such as titanium, iron, cobalt, nickel, molybdenum, ruthenium, rhodium, palladium, renium, osmium, and copper, or compounds of these transition metals. Of these, a copper-based catalyst is preferable from the viewpoint of reactivity, and copper bromide is more preferable.

Further, the catalytic ligand is not particularly limited, and a commercially available ligand can be used as a ligand used for atom transfer radical polymerization. Examples of such catalytic ligands include bipyridine, dimethylbipyridine, tris [2- (dimethylamino) ethyl] amine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, Examples thereof include amine-based ligands such as N'and N'-tetraethylenediamine. Of these, N, N, N', N ", N" -pentamethyldiethylenetriamine is preferable from the viewpoint of reactivity.

In the reaction (A), the compound represented by the following general formula (8) is further added to the reaction system of the compound represented by the general formula (6) and the compound represented by the general formula (7). Therefore, a copolymer can be formed. Also in this case, the transition metal catalyst used in the above reaction (A) and the catalytic ligand can be mixed to carry out an atom transfer radical polymerization reaction.

The obtained copolymer can constitute a copolymer of a compound represented by the general formula (6), a compound represented by the general formula (7), and a compound represented by the general formula (8). can. This copolymer can be used for producing a hyperbranched polymer having excellent stimulus responsiveness, mechanical properties, and processability, similar to the compound represented by the above general formula (4).

上記式（８）中で、Ｒ８はメトキシポリエチレングリコール、フェノキシポリエチレングリコール、２－ヒドロキシエチルのいずれかの基である。Ｒ９は水素またはメチル基である。

In the above formula (8), R8 is a group of any one of methoxypolyethylene glycol, phenoxypolyethylene glycol and 2-hydroxyethyl. R9 is a hydrogen or methyl group.

In the general formula (8), by using R8 as a group of any one of methoxypolyethylene glycol, phenoxypolyethylene glycol and 2-hydroxyethyl, the flexibility and formability of the obtained copolymer can be improved. Further, by using R9 as a hydrogen or a methyl group, the polymerization reactivity becomes good and a copolymer having a high molecular weight can be obtained.

Hereinafter, examples of the hyperbranched polymer of this example will be described. First, a method for producing a compound (compound represented by the general formula (4)) used for producing the hyperbranched polymer of this example will be specifically described. 1.1 g of N-isopropylacrylamide represented by the above general formula (7), 0.0196 g of 2-hydroxythyyl-2-bromoisobutyrate (HEBiB) represented by the above general formula (6), and copper (I) bromide 0. Weigh 017 g into a polymerization tube.

Oxygen is removed by degassing this polymerization tube, 0.025 g of N, N, N', N ", N" -pentamethyldiethylenetriamine and 1 ml of water are added to the polymerization tube under a nitrogen atmosphere, and 15 at 0 ° C. Stir for minutes. The compound of the general formula (4) is obtained by reprecipitating a diluted product obtained by adding 1 ml of chloroform to the polymerized tube after stirring with diethyl ether and drying the filtered solid.

Further, the hyperbranched polymer shown in FIG. 1 can be produced by the following reaction (B).

反応（Ｂ）は、反応（Ａ）における反応物に上記一般式（５）の架橋材を加えて再度攪拌することにより製造することができる。分離精製した上記一般式（４）で示される化合物を開始剤として用い、上記一般式（５）の架橋材、遷移金属触媒、及び触媒配位子を混合し、原子移動ラジカル重合反応により製造することもできる。

The reaction (B) can be produced by adding the cross-linking material of the above general formula (5) to the reaction product in the reaction (A) and stirring again. Using the separated and purified compound represented by the general formula (4) as an initiator, the cross-linking material of the general formula (5), the transition metal catalyst, and the catalytic ligand are mixed and produced by an atom transfer radical polymerization reaction. You can also do it.

The transition metal catalyst is not particularly limited, and commercially available catalysts that are generally used for the atom transfer radical polymerization reaction can be used. The transition metal constituting the transition metal catalyst also includes simple substances or compounds such as salts.

Examples of such a transition metal catalyst include titanium, iron, cobalt, nickel, molybdenum, ruthenium, rhodium, palladium, rhenium, osmium, and copper-based catalysts. In this example, a copper-based catalyst is preferable, and copper bromide can be used more preferably, from the viewpoint of reactivity.

The catalytic ligand is not particularly limited, and commercially available ligands that are generally used in the atom transfer radical polymerization reaction can be used. Examples of such catalytic ligands include bipyridine, dimethylbipyridine, tris [2- (dimethylamino) ethyl] amine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, Examples thereof include N', N'-tetraethylenediamine, and in this example, N, N, N', N ", N" -pentamethyldiethylenetriamine are preferable from the viewpoint of reactivity.

As described above, in this example, the compound of the general formula (5) is added to the reaction product by using the reaction product obtained in the reaction (A) as the compound represented by the general formula (4). By carrying out the above reaction (B), the polymer shown in FIG. 1 can be obtained. That is, since the hyperbranched polymer of this example can be produced using a commercially available compound, it is easy to produce.

The method for producing the hyperbranched polymer of this example will be described more specifically. 1.1 g of N-isopropylacrylamide represented by the above general formula (7), 0.0196 g of 2-hydroxythyyl-2-bromoisobutyrate (HEBiB) represented by the above general formula (6), and copper (I) bromide 0. Weigh 017 g into a polymerization tube.

Oxygen is removed by degassing this polymerization tube, 0.025 g of N, N, N', N ", N" -pentamethyldiethylenetriamine and 1 ml of water are added to the polymerization tube under a nitrogen atmosphere, and 15 at 0 ° C. Stir for minutes. After stirring, 0.0775 g of N, N'-methylenebisacrylamide (BIS), which is the cross-linking material of the general formula (5), is further added, and the mixture is further stirred at 0 ° C. for 30 minutes. The polymer of FIG. (1) is obtained by reprecipitating 1 ml of chloroform added to the polymerized tube after stirring and diluting it with diethyl ether, and drying the filtered solid.

In addition, the hyperbranched polymer of this example can be molded into any shape. The molding method is not particularly limited, but for example, in the case of plasticizing by applying heat or pressure, it is possible to mold into an arbitrary shape by using a predetermined mold. Since the hyperbranched polymer of this example can be dissolved in water or various solvents, it can also be molded by applying a known coating technique.

The hyperbranched polymer of this example has excellent stimulus responsiveness, mechanical properties, and processability as described above, and thus can be suitably used for various optical material applications. For example, by processing the hyperbranched polymer of this example into an arbitrary shape, it is possible to provide an optical material such as an optical switching material or a dimming material. Specific examples of the optical switching material include a switching element having a function of controlling the propagation of light by temperature. The optical switching element can form a temperature sensor device by combining with the exposure unit.

Further, the dimming material has a function of controlling the light transmittance by the temperature. That is, by processing the hyperbranched polymer of this example into a film, coexisting with water, sandwiching it with a transparent substrate or a transparent film and sealing it, the polymer becomes cloudy above a predetermined temperature and becomes transparent below a predetermined temperature. Special plates can be provided.

The structures of the compound represented by the general formula (1) and the hyperbranched polymer of this example can be confirmed by infrared spectroscopic analysis and nuclear magnetic resonance spectroscopic analysis. Further, the number average molecular weight, the weight average molecular weight, and the molecular weight distribution of the polymer can be calculated by size exclusion chromatography. In addition, the degree of cross-linking of the polymer (progress of the cross-linking reaction) can be confirmed from the cross-linking conversion rate. In addition, the refractive index of the polymer and the Abbe number of the polymer can be measured by spectroscopic ellipsometry.

Furthermore, the glass transition point of the polymer can be measured by differential scanning calorimetry. The specific analysis method, calculation method, and measurement method are as follows.

<Number average molecular weight, weight average molecular weight and molecular weight distribution>
The weight average molecular weight (Mw), the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were measured by the gel permeation chromatography (GPC) method. The measurement conditions are as follows.
・ Equipment: HLC-8220 (manufactured by Tosoh Corporation)
-Column: Shodex asahipak GF-510 HQ + GF-310 x 2 (manufactured by Showa Denko KK) TSK G2000HXL and G4000HXL (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Eluent: 20 mM lithium bromide, 20 mM phosphoric acid-containing dimethylformamide solution ・ Flow rate: 0.5 ml / min ・ Detector: HLC-8200 Built-in RI-UV-8220
A 1 ml sample having a concentration of 0.5% by mass was set in the apparatus, and the weight average molecular weight of the polymer product was measured using the molecular weight calibration curve prepared from the monodisperse polystyrene standard sample from the molecular weight distribution of the polymer product measured under the above conditions. (Mw), the number average molecular weight (Mn) was calculated. The molecular weight distribution (Mw / Mn) is shown as the polydispersity by dividing Mw by Mn.

<Calculation of cross-linking conversion rate>
The cross-linking conversion rate indicates the progress of the cross-linking reaction, and the peak area derived from the polymer after cross-linking (for example, the hyperbranched polymer of FIG. 2) is represented by the polymer before cross-linking (for example, the general formula (4)). It was calculated by dividing by the peak area derived from the polymer.

<Nuclear magnetic resonance spectroscopy>
Nuclear magnetic resonance spectroscopy was performed on the hyperbranched polymer of this example using a nuclear magnetic resonance spectroscope (JOEL-ECS-400K, manufactured by JEOL Ltd.). Degree of polymerization: n is calculated by measuring the number of hydrogens at each site by nuclear magnetic resonance spectroscopy (= ¹ H-NMR). Specifically, it is calculated from the ratio of the total integrated value of ¹ H derived from the initiator (the number of hydrogens) and the total integrated value of ¹ H derived from the repeating unit.

<Infrared spectroscopy>
The obtained polymer was identified using a Fourier transform infrared spectrophotometer (FT-IR) (FT / IR 4200, manufactured by Nippon Spectroscopy Co., Ltd.).

<Visible spectroscopic ellipsometry>
The refractive index of the obtained polymer was measured using a spectroscopic ellipsometer (1H3LNWWP manufactured by HORIBA, Ltd.). Specifically, the polymer was dissolved in PGME, a thin film was formed on a silicon wafer by spin coating, and the measurement was performed using a light source having a wavelength of 632.8 nm. Further, the refractive indexes measured by changing the light sources to those having wavelengths of 587.56 nm, 486.13 nm, and 656.27 nm, respectively, were set to nd, nF, and nC, and the Abbe number of the polymer was calculated by the following formula (C). Calculated.
Abbe number = (nd-1) / (nF-nC) ... (C)

<Pyrolysis temperature>
The thermal decomposition temperature of the obtained polymer was measured. A thermogravimetric measuring device (TGA-50 / 50H, manufactured by Shimadzu Corporation) was used for measuring the thermal decomposition temperature. The measuring method was carried out by weighing about 3 mg of the polymer on an aluminum pan, under a nitrogen atmosphere, and under the condition of a temperature rise temperature of 10 ° C./min. For the analysis of the thermal decomposition temperature, the thermal decomposition start temperature, the temperature at the weight retention rate of 95%, and the temperature at the weight retention rate of 80% were analyzed according to JIS-7120K.

<Evaluation of temperature response speed>
The temperature response rate was evaluated using an ultraviolet-visible spectrophotometer (V-660DS, manufactured by JASCO Corporation). 2.0 mg of the obtained polymer was dissolved in 20 ml of distilled water, heated to 40 ° C., and the absorbance at 400 nm was measured every second. The measurement time when the change in the measured value was within 5% from the start of the measurement was defined as the saturation time. The evaluation points were 0 points for a saturation time of 10 seconds or more, 1 point for 8 seconds or more and less than 10 seconds, 3 points for 7 seconds, 5 points for 6 seconds, and 7 points for 5 seconds.

<Evaluation of mechanical properties and workability>
Mechanical properties and workability were evaluated by impact test. In the impact test, 200 mg of the obtained polymer was compression-molded into a disk shape of 20 mmφ, and then freely dropped onto a glass plate from a height of 30 cm. Among the landed polymer molded products, the weight of the largest one was measured, and the weight change rate was measured according to the following formula (D).
(Weight before falling g-Weight g of the largest one) / Weight before falling g x 100 ... (D)
The evaluation of mechanical properties and workability was 1 point for those with a weight change rate of 80% or more, 2 points for those with a weight change rate of 75% or more and less than 80%, 3 points for those with a weight change rate of 65% or more and less than 75%, and less than 65%. I gave it 4 points. In addition, 0 points were given to those that could not be compression-molded into a predetermined disk shape.

<Comprehensive evaluation>
Comprehensive evaluation is the sum of the evaluation points of temperature response speed and the evaluation points of mechanical properties and workability. If one of them has 0 points, it is E, if the total points are 4 points or less, it is D, and 5 points or more and less than 7 points. Was C, 7 points or more and less than 10 points was B, and 10 points or more was A.

Hereinafter, the conditions of Examples and Comparative Examples will be specifically described.
(Example 1)
1.1 g of N-isopropylacrylamide represented by the above general formula (7), 0.0196 g of 2-hydroxythyyl-2-bromoisobutyrate (HEBiB) represented by the above general formula (6), and copper (I) bromide 0. Weigh 017 g into a polymerization tube. Oxygen is removed by degassing this polymerization tube, 0.025 g of N, N, N', N ", N" -pentamethyldiethylenetriamine and 1 ml of water are added to the polymerization tube under a nitrogen atmosphere, and 15 at 0 ° C. Stir for minutes. After stirring, 0.0775 g of N, N'-methylenebisacrylamide (BIS), which is the cross-linking material of the general formula (5), is further added, and the mixture is further stirred at 0 ° C. for 30 minutes. After stirring, 1 ml of chloroform was added to the polymerization tube to dilute it, and the mixture was reprecipitated with diethyl ether. This was filtered, and then the filtered solid was dried to obtain a polymer. The ratio (molar ratio) of BIS and HEBiB is 5. The obtained polymer was evaluated according to the above procedure. The polymer obtained in Example 1 showed good temperature response and mechanical properties.

(Example 2)
A polymer was obtained in the same manner as in Example 1 except that the ratio (molar ratio) of BIS and HEBiB was set to 5 to 7.5. The obtained polymer was evaluated in the same manner as in Example 1. The polymer obtained in Example 2 showed good temperature response and mechanical properties.

(Example 3)
A polymer was obtained in the same manner as in Example 1 except that the ratio (molar ratio) of BIS and HEBiB was set to 5 to 10. The obtained polymer was evaluated in the same manner as in Example 1. The polymer obtained in Example 3 showed good temperature response and mechanical properties.

(Example 4)
0.55 g of N-isopropylacrylamide represented by the general formula (7), 0.0196 g of 2-hydroxyethyl-2-bromoisobutyrate (HEBiB) represented by the general formula (6), and 0.0196 g represented by the general formula (9) below. The same procedure as in Example 1 was carried out except that 0.60 g of hydroxyethyl acrylate and 0.017 g of copper (I) bromide were weighed in a polymerization tube to obtain a polymer. The obtained polymer was evaluated according to the above procedure. The polymer obtained in Example 4 showed good temperature response and mechanical properties.

(Example 5)
0.55 g of N-isopropylacrylamide represented by the above general formula (7), 0.0196 g of 2-hydroxyethyl-2-bromoisobutyrate (HEBiB) represented by the above general formula (6), and the following general formula (10). A polymer was obtained in the same manner as in Example 1 except that 0.50 g of methyl methacrylate and 0.017 g of copper (I) bromide were weighed in a polymerization tube. The ratio (molar ratio) of BIS and HEBiB is 5. The obtained polymer was evaluated according to the above procedure. The polymer obtained in Example 5 showed good temperature response and mechanical properties.

(Comparative Examples 1 and 2)
Commercially available poly N-isopropylacrylamide (PIPAAm manufactured by Aldrich) was evaluated in the same manner as in Example 1.

(Comparative Example 3)
Commercially available isopropylacrylamide (NIPAM (registered trademark) manufactured by KJ Chemicals Co., Ltd.) (3.0 mmol, 0.34 g) and azobisisobutyronitrile (AIBN) (0.090 mmol, 0.014 g) were added to the polymerization tube. In addition, it was dissolved in 3 ml of DMF. After freeze-deaeration, the tube was sealed and reacted at 60 ° C. for 20 hours. After completion of the reaction, the reaction solution was added dropwise to diethyl ether to precipitate a solid. The polymer was obtained by drying under reduced pressure at 60 ° C. The obtained polymer was evaluated in the same manner as in Example 1.

(Comparative Example 4)
After mixing 1.0 g each of N-isopropylacrylamide and 2-hydroxyethyl methacrylate, 2 g of water was added and the mixture was stirred at 5 ° C. After stirring, 0.1 g of ammonium peroxodisulfate was added and the mixture was stirred quickly, and then allowed to stand at 5 ° C. for 20 hours to obtain a polymer. The obtained polymer was evaluated in the same manner as in Example 1.

3 to 5 show a gel permeation chromatography (GPC) chart, an infrared absorption spectrum, and a nuclear magnetic resonance spectrum for Example 1, respectively. 6 to 8 show a GPC chart, an infrared absorption spectrum, and a nuclear magnetic resonance spectrum for Example 2, respectively. Further, FIGS. 9 to 11 show a GPC chart, an infrared absorption spectrum, and a nuclear magnetic resonance spectrum for Example 3, respectively.

From the GPC charts of FIGS. 3, 6 and 9, the weight average molecular weight, the number average molecular weight and the molecular weight distribution (multidispersity) of the polymers obtained in Examples 1 to 3 can be seen. Further, the polymers obtained in Examples 1 to 3 from the infrared absorption spectra of FIGS. 4, 7, 10 and the nuclear magnetic resonance spectra of FIGS. 5, 8 and 11 are hyperbranches shown in FIGS. 1 and 2. It can be seen that it indicates a polymer.

The evaluation results of Examples 1 to 5 are shown in Table 1.

表１より、実施例１～５で得られたポリマーは、いずれも高い架橋転化率を示しており、架橋の度合いが高いといえる。また、実施例１～５で得られたポリマーは、いずれも低いガラス転移点を示しており、加工性が良好であるといえる。

From Table 1, it can be said that the polymers obtained in Examples 1 to 5 all show a high cross-linking conversion rate and have a high degree of cross-linking. In addition, the polymers obtained in Examples 1 to 5 all show a low glass transition point, and it can be said that the processability is good.

Further, in Table 1, the comprehensive evaluations of Comparative Examples 1 to 5 were all D or less, whereas in Examples 1 to 5, the comprehensive evaluations were all C or more. Further, in Examples 2 to 5, the overall evaluation was B or higher. Further, in Example 3, the overall evaluation was A.

As described above, the polymer of this example has a high molecular weight and a low glass transition point at the same time, and has both excellent temperature responsiveness, mechanical properties and processability. Therefore, it can be applied to optical materials such as optical switching elements.

Further, the polymers obtained in Examples 1 to 5 all show a high refractive index and an Abbe number, and are suitable for applications of optical materials.

Although the embodiments of the present invention have been described in detail above, the present invention is not limited to these embodiments, and various modifications and modifications are made within the scope of the invention described in the claims. Is possible.

Japanese Patent No. 5614746 Special Table 2013-542305 Gazette

Yuta Sakaguchi, 2012, Research on improvement and evaluation of mechanical properties of PNIPAAm-based hydrogel, Master's program, Graduate School of Engineering, Mie University, Department of Mechanical Engineering, Biosystem Engineering Laboratory

Claims (10)

A polymer compound characterized by having a structure in which a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are crosslinked.

( In formula (1), R1 and R2 are any group selected from hydrogen or an alkyl group having 1 or 2 carbon atoms, and R3 is any group selected from -C ₂ H _4- or an ether group. R4 is hydrogen , A is a repeating unit represented by the following formula (AA), B is a repeating unit represented by the following formula (BB), X is a halogen element, hydrogen, and any of the following formulas (AA) is selected. However, if B is not included in the formula (1), n in the following formula (AA) is an integer from 1 to 500, and if B is included in the formula (1), the following formula (AA) is included. ) And m in the following formula (BB) is an integer from 1 to 500 )

( In the formula, R5 and R6 are either hydrogen or an alkyl group having 1 or 2 carbon atoms ).

( In the formula, R8 is hydrogen, an alkyl group having 1 to 12 carbon atoms, a methoxypolyethylene glycol group , a phenoxypolyethylene glycol group , a 2-hydroxyethyl group , a 3-hydroxypropyl group , or a 4-hydroxybutyl group, and R9 is hydrogen or Methyl group)

( In formula (2), R7 is any group selected from alkylene groups having 1 or 2 carbon atoms). The polymer compound according to claim 1, wherein the weight average molecular weight is 60,000 or more and 150,000 or less. The polymer compound according to claim 1 or 2, wherein X in the general formula (1) is a halogen element. Any of claims 1 to 3, wherein the compound represented by the general formula (1) is a copolymer of a compound represented by the following general formula (6) and a compound represented by the following general formula (7). The polymer compound according to item 1.

The compound represented by the general formula (1) is a compound represented by the following general formula (6), a compound represented by the following general formula (7), and a compound represented by the following general formula (8). The polymer compound according to any one of claims 1 to 3, which is a copolymer.

(In the formula, R8 is hydrogen, an alkyl group having 1 to 12 carbon atoms, a methoxypolyethylene glycol group , a phenoxypolyethylene glycol group , a 2-hydroxyethyl group , a 3-hydroxypropyl group , or a 4-hydroxybutyl group, and R9 is hydrogen or Methyl group) An optical material using the polymer compound according to any one of claims 1 to 5. A method for producing a polymer compound, which comprises polymerizing a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

(In formula (1), R1 and R2 are any group selected from hydrogen or an alkyl group having 1 or 2 carbon atoms, and R3 is any group selected from -C ₂ H _4- or an ether group. R4 is hydrogen , A is a repeating unit represented by the following formula (AA), B is a repeating unit represented by the following formula (BB), X is a halogen element, hydrogen, and the following formula ( AA ) is selected. Any group , however, if B is not included in the formula (1), n in the following formula (AA) is an integer from 1 to 500, and if B is included in the formula (1), the following formula ( The sum of n in AA) and m in the following equation (BB) is an integer from 1 to 500 )

( In the formula, R5 and R6 are either hydrogen or an alkyl group having 1 or 2 carbon atoms ).

( In the formula, R8 is hydrogen, an alkyl group having 1 to 12 carbon atoms, a methoxypolyethylene glycol group , a phenoxypolyethylene glycol group , a 2-hydroxyethyl group , a 3-hydroxypropyl group , or a 4-hydroxybutyl group, and R9 is hydrogen or Methyl group)

( In formula (2), R7 is any group selected from alkylene groups having 1 or 2 carbon atoms). The method for producing a polymer compound according to claim 7, wherein X in the general formula (1) is a halogen element. The compound represented by the general formula (1) is a compound represented by the following general formula (6), a compound represented by the following general formula (7), and a compound represented by the following general formula (8). The method for producing a polymer compound according to claim 7 or 8, which is obtained by subjecting to a polymerization reaction.

(In the formula, R8 is hydrogen, an alkyl group having 1 to 12 carbon atoms, a methoxypolyethylene glycol group , a phenoxypolyethylene glycol group , a 2-hydroxyethyl group , a 3-hydroxypropyl group , or a 4-hydroxybutyl group, and R9 is hydrogen or Methyl group) The method for producing a polymer compound according to claim 7 or 8, wherein the polymerization reaction is carried out in the presence of a transition metal catalyst and an amine-based ligand.

Images