JPWO2014133117A1 - Temperature responsive polymer - Google Patents

Abstract

It has a repeating unit derived from a vinyl ether monomer containing a temperature-responsive group, and at least one terminal of the polymer chain is represented by the following formula (1) [wherein Y is an ether bond, a thioether bond, a group —NH -Or a group -OR1- * (R1 represents an alkylene group, * represents a position bonded to Ar1 in formula (1)), Ar1 is a substituted or unsubstituted divalent aromatic hydrocarbon group Ar2 represents a substituted or unsubstituted monovalent aromatic hydrocarbon group. ] The temperature-responsive polymer which has a structure represented by these. Even when it is supported on a fibrous base material, it can exhibit temperature responsiveness and can be easily manufactured. Provided are a hydrophilicity / hydrophobicity control agent containing the polymer, a method for controlling hydrophilicity / hydrophobicity using the polymer, and a temperature-responsive polymer-substrate composite on which the polymer is supported.

Description

  The present invention relates to a temperature-responsive polymer, a hydrophilicity / hydrophobicity control agent using the polymer, a method for controlling hydrophilicity / hydrophobicity, and a temperature-responsive polymer-substrate composite.

  Some polymer compounds exhibit a phase transition in response to external stimuli such as heat, pH, and light. Temperature sensors, separation membranes, adsorbents, drug release agents, water absorption using this phase transition phenomenon Materials, water retention agents, humidity control agents, indicator agents, etc. are being actively developed.

  Among the above-mentioned polymer compounds, those that exhibit a phase transition phenomenon in response to heat are called temperature-responsive polymers, and as such polymers, living polymers of vinyl ethers containing oxyethylene chains are known. Yes. This living polymer exhibits hydrophilicity at a specific temperature or lower, and exhibits hydrophobicity when the temperature is exceeded.However, since it is an oily compound, it does not have moldability and film-forming properties, and its use is greatly limited. It had been.

Therefore, a diblock copolymer of a vinyl ether containing an oxyethylene chain and an alicyclic vinyl ether has been developed as a polymer exhibiting temperature responsiveness and having film forming properties and moldability (Patent Document 1). ).
However, the block copolymer has a problem that the moldability is not yet sufficient, the formed film has a surface tack, and cracks are generated by contact with water.

  As means for solving such a problem, introduction of an azo group into a temperature-responsive polymer has been studied. For example, a diblock copolymer of a vinyl ether containing an oxyethylene chain and a vinyl ether containing an azobenzene structure is known (Patent Document 2). In addition, as a result of surface modification of various general-purpose resin films with the same diblock copolymer, polystyrene and polypropylene are particularly easily surface-modified, and the surface-modified polystyrene film is responsive to temperature and hydrophilicity. (Non-Patent Document 1).

JP 2006-131805 A JP 2005-154603 A

Yuya Tsuchida, “Development of polymer materials for collecting harmful substances”, Shiga Prefecture Tohoku Industrial Technology Center 2005 Report (http://www.hik.shiga-irc.go.jp/kenkyu/ken_kako/kenk_nag/ H17ken / report / H17_tsuchida.pdf)

However, the vinyl ether containing the azobenzene structure is difficult to obtain industrially, and the temperature-responsive polymers described in Patent Document 2 and Non-Patent Document 1 cannot be easily produced.
Further, the present inventors have investigated the temperature responsiveness of a diblock copolymer of a vinyl ether containing an oxyethylene chain and a vinyl ether containing an azobenzene structure as described in Patent Document 2 and Non-Patent Document 1. However, it has been found that such a temperature-responsive polymer has insufficient temperature responsiveness regarding hydrophilicity / hydrophobicity when supported on a fibrous base material.

  Accordingly, an object of the present invention is to provide a temperature-responsive polymer that can exhibit temperature responsiveness even when it is supported on a fibrous base material, and can be easily manufactured, and contains the temperature-responsive polymer. It is an object to provide a hydrophilicity / hydrophobicity control agent, a method for controlling hydrophilicity / hydrophobicity using the temperature-responsive polymer, and a temperature-responsive polymer-substrate composite carrying the temperature-responsive polymer.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors were completely surprised by introducing a specific terminal structure containing an azobenzene structure at the terminal of a vinyl ether-derived polymer containing a temperature-responsive group. In addition, the present inventors have found that a temperature-responsive polymer that can exhibit temperature responsiveness and can be easily produced even when it is supported on a fibrous base material has been completed.

  That is, the present invention has a repeating unit derived from a vinyl ether monomer, the repeating unit derived from the vinyl ether monomer contains a temperature-responsive group, and at least one end of the polymer chain has the following formula ( 1)

[In Formula (1), Y represents an ether bond, a thioether bond, a group —NH—, or a group —OR ¹ — * (R ¹ represents an alkylene group, and * represents a bond to Ar ^{1 in} Formula (1). Ar ¹ represents a substituted or unsubstituted divalent aromatic hydrocarbon group, and Ar ² represents a substituted or unsubstituted monovalent aromatic hydrocarbon group. ]
A temperature-responsive polymer having a structure represented by:

Moreover, this invention provides the hydrophilicity / hydrophobicity control agent containing the said temperature-responsive polymer.
Furthermore, the present invention provides a method for controlling hydrophilicity / hydrophobicity using the temperature-responsive polymer.
Furthermore, the present invention provides a temperature-responsive polymer-substrate composite in which the temperature-responsive polymer is supported on a substrate.

The temperature-responsive polymer of the present invention exhibits temperature responsiveness even when it is supported on a fibrous base material, and the hydrophilicity / hydrophobicity changes reversibly, so that temperature responsiveness is imparted to a wide range of base materials. In addition, it can be easily manufactured.
Therefore, according to the present invention, it is possible to provide a hydrophilicity / hydrophobicity control agent and a hydrophilicity / hydrophobicity control method capable of imparting temperature responsiveness to a wide range of substrates including a fibrous substrate. Moreover, the temperature-responsive polymer-substrate composite of the present invention has temperature responsiveness.

  The temperature-responsive polymer of the present invention has a repeating unit derived from a vinyl ether monomer, the repeating unit derived from the vinyl ether monomer contains a temperature-responsive group, and at least one end of the polymer chain, Following formula (1)

[In formula (1), Y represents an ether bond (—O—), a thioether bond (—S—), a group —NH—, or a group —OR ¹ — * (R ¹ represents an alkylene group, * represents It indicates the position which binds to Ar ¹ in the formula (1)), Ar ¹ is a substituted or represents an unsubstituted divalent aromatic hydrocarbon group, Ar ² is a substituted or unsubstituted monovalent aromatic hydrocarbon Indicates a group. ]
It has the structure represented by these. Such a structure represented by the formula (1) has an effect of imparting permeability to a substrate such as a resin, and such a structure is difficult to obtain when an azobenzene structure is introduced into a polymer side chain. Temperature responsiveness when it is supported on the substrate can also be expressed. The temperature-responsive polymer of the present invention may not have an azobenzene structure in the side chain.
First, each symbol in the above formula (1) will be described.

  In said formula (1), as Y, an ether bond and a thioether bond are preferable, and an ether bond is more preferable.

The number of carbon atoms of the alkylene group represented by R ¹ is preferably 1 to 10, more preferably from 1 to 6, more preferably 1 to 4, particularly preferably 1 to 2. The alkylene group may be linear or branched. Specific examples include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

In the formula (1), Ar ¹ represents a substituted or unsubstituted divalent aromatic hydrocarbon group. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, and an anthracylene group. From the viewpoint of temperature responsiveness and permeation diffusibility to a substrate, a phenylene group and a naphthylene group are preferable. The group is particularly preferred. The binding site of the divalent aromatic hydrocarbon group may be on any carbon on the aromatic ring.

Moreover, as a substituent which the said bivalent aromatic hydrocarbon group may have, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, Examples thereof include an alkoxyalkyl group having 2 to 6 carbon atoms, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group, and an aminosulfonyl group, and an alkyl group having 1 to 4 carbon atoms is preferable.
In addition, the position and number of these substituents are arbitrary, and when they have two or more substituents, the substituents may be the same or different.

As carbon number of the said C1-C4 alkyl group, 1 or 2 is preferable. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and an isobutyl group.
The haloalkyl group having 1 to 4 carbon atoms means a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a halogen atom such as a chlorine atom, a bromine atom, or a fluorine atom, The number and position of the substituted halogen atoms are arbitrary. The carbon number of the haloalkyl group having 1 to 4 carbon atoms is preferably 1 or 2, and the halogen atom is preferably a fluorine atom. Examples of the haloalkyl group include a trifluoromethyl group, a pentafluoroethyl group, and a 2,2,2-trifluoroethyl group.
Moreover, as carbon number of the said C1-C4 alkoxy group, 1 or 2 is preferable. The alkoxy group may be linear or branched, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an isobutoxy group. Can be mentioned.
Moreover, as carbon number of the said C2-C6 alkoxyalkyl group, 2-4 are preferable. The alkoxyalkyl group may be linear or branched, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a 2-methoxyethyl group, and a 2-ethoxyethyl group.
Moreover, as said halogen atom, the thing similar to the halogen atom contained in the said haloalkyl group is mentioned.

Moreover, as a suitable specific example of Ar < ¹ >, following formula (1-2) or (1-3)

[In Formula (1-2), each R ² independently represents an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxyalkyl group, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group, or an aminosulfonyl group, ** represents a position bonded to Y in the formula (1), and *** represents a formula The position which couple | bonds with the nitrogen atom in (1) is shown, p-1 is an integer of 0-4. ]

[In Formula (1-3), p-2 is an integer of 0 to 6, and R ² , ** and *** are as defined above. ]
What is represented by these is mentioned, and what is represented by Formula (1-2) from a viewpoint of temperature responsiveness and the osmosis | permeation diffusivity to a base material is preferable.

In the above formulas (1-2) and (1-3), specific examples of each group represented by R ² are the same as the substituents that the divalent aromatic hydrocarbon group may have.
Further, p-1 in the formula (1-2) is preferably an integer of 0 to 2, and p-2 in the formula (1-3) is preferably an integer of 0 to 4.

In formula (1), Ar ² represents a substituted or unsubstituted monovalent aromatic hydrocarbon group. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group and a naphthyl group are preferable from the viewpoint of temperature responsiveness and permeation diffusibility to a substrate. Is particularly preferred. The binding site of the monovalent aromatic hydrocarbon group may be on any carbon on the aromatic ring.
The substituent that the monovalent aromatic hydrocarbon group may have is the same as the substituent that the divalent aromatic hydrocarbon group may have.

Moreover, as a suitable specific example of Ar < ² >, following formula (1-4) or (1-5)

[In Formula (1-4), R ³ is each independently an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxyalkyl group, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group or an aminosulfonyl group, and *** indicates a position bonded to the nitrogen atom in the formula (1), and p-3 Is an integer from 0 to 5. ]

[In formula (1-5), p-4 is an integer of 0 to 7, and R ³ and *** are as defined above. ]
What is represented by these is mentioned, and what is represented by Formula (1-4) from a viewpoint of temperature responsiveness and the osmosis | permeation diffusivity to a base material is preferable.

In the above formulas (1-4) and (1-5), specific examples of each group represented by R ³ are the same as the substituents that the divalent aromatic hydrocarbon group may have.
Moreover, as p-3 in Formula (1-4), the integer of 0-3 is preferable, and as p-4 in Formula (1-5), the integer of 0-5 is preferable.

  In addition, the temperature-responsive polymer of the present invention has the structure represented by the formula (1) at one end or both ends, but the other end when the structure has only one end is the start An agent residue, a hydrogen atom, etc. are mentioned.

The repeating unit derived from the vinyl ether monomer of the temperature-responsive polymer of the present invention (hereinafter also referred to as repeating unit (a)) exhibits an action of imparting hydrophilicity or hydrophobicity in response to thermal stimulation.
The repeating unit (a) is not particularly limited as long as it has a temperature-responsive group, but the following formula (2-1) or (2-2)

[In formula (2-1), R ^4-1 represents a methyl group, an ethyl group or a carboxyphenyl group, and k is an integer of 1 to 10. ]

[In Formula (2-2), R ^4-2 represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms. ]
From the viewpoint of temperature responsiveness and the viewpoint of improving hydrophilicity when the temperature is lower than or equal to a predetermined temperature, the one represented by Formula (2-1) is preferable. The critical temperature at which the hydrophilicity / hydrophobicity changes can be adjusted by appropriately changing the chain length in such a repeating unit, or by using two or more repeating units having different chain lengths.

In the above formula (2-1), R ^4-1 is preferably a methyl group or an ethyl group from the viewpoint of temperature responsiveness and from the viewpoint of improving hydrophilicity when the temperature becomes a predetermined temperature or lower.
Moreover, in formula (2-1), k is an integer of 1 to 10, but an integer of 1 to 6 is preferable, an integer of 1 to 4 is more preferable, and an integer of 1 to 3 is particularly preferable.

In the above formula (2-2), the alkyl chain of the alkyl group having 1 to 4 carbon atoms and the hydroxyalkyl group having 1 to 4 carbon atoms represented by R ^4-2 may be linear or branched. Specific examples of the alkyl chain are the same as those exemplified as the substituent that the divalent aromatic hydrocarbon group may have.

Further, the total content of the repeating unit (a) is preferably 50 to 100 mol%, more preferably 70, from the viewpoint of temperature responsiveness and from the viewpoint of improving hydrophilicity when the temperature becomes a predetermined temperature or lower. It is -100 mol%, More preferably, it is 85-100 mol%. In addition, when it has another repeating unit, the upper limit of the said total content is 99.9 mol% or less, for example.
The content of the repeating unit (a) can be measured by NMR or the like.
When the temperature-responsive polymer of the present invention is a homopolymer of the repeating unit (a), there is an advantage that it can be produced particularly easily.

  The temperature-responsive polymer of the present invention may have a repeating unit derived from an oxystyrene monomer (hereinafter also referred to as a repeating unit (b)) in addition to the repeating unit (a). By introducing a repeating unit derived from an oxystyrene monomer, this can be improved when the water repellency of the polymer at a temperature higher than the critical temperature is insufficient.

  Examples of the repeating unit (b) include the following formula (3):

In [formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 2 carbon atoms 6 represents an alkoxyalkyl group, an alkanoyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group or an alkylsilyl group, and m is an integer of 1 to 3. ]
The thing represented by is mentioned.

In Formula (3), as a carbon number of a C1-C4 alkyl group shown by R < ⁵ >, 1 or 2 is preferable. As the carbon number of the alkyl group having 1 to 6 carbon atoms represented by R ^6, 1 to 4 are preferred.
These alkyl groups may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group.

In addition, the alkoxyalkyl group having 2 to 6 carbon atoms represented by R ⁶ is linear, branched, or cyclic (the two alkyl chains together with the oxygen atom form an oxygen-containing heterocycle. For example, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group and the like.

Also, 2-6 is preferable as the number of carbon atoms of the alkanoyl group represented by R ^6. Such an alkanoyl group may be linear or branched, and examples thereof include an acetyl group, a propionyl group, and a tert-butylcarbonyl group.

Also, 2-6 is preferable as the carbon number of the alkoxycarbonyl group represented by R ^6. Such an alkoxycarbonyl group may be linear or branched, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a tert-butoxycarbonyl group.

Also, 2-6 is preferable as the carbon number of the alkoxycarbonyl group represented by R ^6. Such an alkoxycarbonylalkyl group may be linear or branched, and examples thereof include a tert-butoxycarbonylmethyl group.

Also, 2-6 is preferable as the carbon number of the alkylsilyl group represented by R ^6. Examples of such an alkylsilyl group include a trimethylsilyl group and a tert-butyldimethylsilyl group.

In Formula (3), m is preferably 1 or 2, and more preferably 1. When m is 2 or 3, m —OR ⁶ may be the same or different.

Moreover, when the temperature-responsive polymer of this invention has a repeating unit (b), the total content of a repeating unit (b) makes temperature-responsiveness and the outstanding water repellency when exceeding predetermined temperature compatible. From a viewpoint, Preferably it is 0.1-20 mol%, More preferably, it is 0.25-10 mol%, More preferably, it is 0.5-5 mol%.
When the temperature-responsive polymer of the present invention has a repeating unit (b), the molar ratio of the repeating unit (a) and the repeating unit (b) contained in the temperature-responsive polymer [(a) :( b)] Is preferably 99.9: 0.1 to 80:20, more preferably 99.75: 0.25 to 90:10, and still more preferably 99.5: 0.5 to 95: 5.
In addition, the said content and ratio can be measured by NMR etc.

  When the temperature-responsive polymer of the present invention has a repeating unit other than the repeating unit (a), the copolymer is any of a block copolymer, a graft copolymer, a random copolymer, and an alternating copolymer. However, a block copolymer is preferred. In particular, a block copolymer including the segment A composed of the repeating unit (a) and the segment B composed of the repeating unit (b) is more preferable, and a diblock copolymer or a triblock copolymer is particularly preferable.

Moreover, as a weight average molecular weight (Mw) of the temperature-responsive polymer of this invention, the range of 5000-100000 is preferable and the range of 10000-50000 is preferable. Temperature responsiveness is improved by setting the weight average molecular weight (Mw) to 5000 or more, while solubility in a solvent can be improved by setting the weight average molecular weight (Mw) to 100,000 or less.
The temperature-responsive polymer is preferably narrowly dispersed from the viewpoint of temperature responsiveness, and the molecular weight distribution (Mw / Mn) is preferably in the range of 1.0 to 2.0, and 1.0 to A range of 1.5 is more preferable.
The said weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be measured by the method as described in the Example mentioned later.

Next, the manufacturing method of the temperature-responsive polymer of this invention is demonstrated.
The temperature-responsive polymer of the present invention can be produced according to a conventional method. For example, a vinyl ether monomer containing a temperature-responsive group is polymerized by living cationic polymerization, and at least one terminal of the polymer chain is represented by the formula (1). It can be manufactured by introducing the structure represented. Since living cationic polymerization does not involve a side reaction of chain transfer reaction, a desired functional group can be easily introduced at the end of the polymer chain. Further, according to living cationic polymerization, the molecular weight and composition ratio can be controlled, and a narrowly dispersed polymer can be obtained.

  Specifically, the temperature-responsive polymer of the present invention comprises a living ether containing a repeating unit (a) obtained by subjecting a vinyl ether monomer containing a temperature-responsive group to living cationic polymerization in the presence of a starting species, a Lewis acid and a solvent. Step of extending the polymer chain (Step 1); If necessary, an oxystyrene monomer is added to the reaction system, and this is subjected to living cationic polymerization, whereby a living polymer chain containing the repeating unit (b) is obtained. Step of introducing (Step 2); Next, a compound that induces the terminal structure (1) is added to the reaction system containing the living polymer chain obtained in Step 1 or Step 2, and the terminal structure ( 1) is introduced (step 3). In step 2, a Lewis acid or a solvent may be further added.

  As a vinyl ether monomer containing a temperature-responsive group used in Step 1, the following formula (4-1) or (4-2)

[In formulas (4-1) and (4-2), each symbol is as defined above. ]
The thing represented by is mentioned.

Specifically, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 2- (2-ethoxyethoxy) ethyl vinyl ether, 2- (2- (2-methoxyethoxy) Ethoxy) ethyl vinyl ether, 2- (2- (2-ethoxyethoxy) ethoxy) ethyl vinyl ether, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethyl vinyl ether, 4- [2- (vinyloxy) Ethoxy] benzoic acid, 4- (vinyloxy) -1-butanol, isobutyl vinyl ether and the like may be mentioned, and one kind may be used alone, or two or more kinds may be used in combination.
Among these, from the viewpoint of improving hydrophilicity when the temperature is lower than a predetermined temperature, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2- (2-ethoxyethoxy) ethyl vinyl ether, 2- (2- ( 2-Methoxyethoxy) ethoxy) ethyl vinyl ether is preferred.

  Moreover, as an oxystyrene-type monomer used at the process 2, following formula (5)

[In formula (5), each symbol is as defined above. ]
The thing represented by is mentioned.

Specifically, hydroxystyrenes such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol; p-methoxystyrene, m- Methoxy styrene, o-methoxy styrene, p-ethoxy styrene, m-ethoxy styrene, o-ethoxy styrene, p-propoxy styrene, m-propoxy styrene, o-propoxy styrene, p-isopropoxy styrene, m-isopropoxy styrene, o-isopropoxystyrene, pn-butoxystyrene, mn-butoxystyrene, on-butoxystyrene, p-isobutoxystyrene, m-isobutoxystyrene, o-isobutoxystyrene, p-tert-butoxys Alkoxy, styrene such as len, m-tert-butoxystyrene, o-tert-butoxystyrene; p-methoxymethoxystyrene, m-methoxymethoxystyrene, o-methoxymethoxystyrene, p- (1-ethoxyethoxy) styrene, m -(1-ethoxyethoxy) styrene, o- (1-ethoxyethoxy) styrene, p- (2-tetrahydropyranyl) oxystyrene, m- (2-tetrahydropyranyl) oxystyrene, o- (2-tetrahydropyrani) L) Alkoxyalkyloxystyrenes such as oxystyrene; p-acetoxystyrene, m-acetoxystyrene, o-acetoxystyrene, p-tert-butylcarbonyloxystyrene, m-tert-butylcarbonyloxystyrene, o-tert-butyl Alkanoyloxystyrenes such as rubonyloxystyrene; alkoxycarbonylalkyloxystyrenes such as p-tert-butoxycarbonylmethyloxystyrene, m-tert-butoxycarbonylmethyloxystyrene, o-tert-butoxycarbonylmethyloxystyrene; p- Alkylsilyloxy such as trimethylsilyloxystyrene, m-trimethylsilyloxystyrene, o-trimethylsilyloxystyrene, p-tert-butyldimethylsilyloxystyrene, m-tert-butyldimethylsilyloxystyrene, o-tert-butyldimethylsilyloxystyrene Styrenes etc. are mentioned, 1 type may be used independently and 2 or more types may be used together.
Among these, hydroxystyrenes and alkoxystyrenes are preferable, and p-hydroxystyrene, p-isopropenylphenol, and p-tert-butoxystyrene are particularly preferable.

  As the compound for deriving the terminal structure (1) used in Step 3, the following formula (6)

[In Formula (6), Z shows a hydrogen atom or an alkali metal atom, and other symbols are synonymous with the above. ]
The thing represented by is mentioned. Examples of the alkali metal atom include lithium and sodium.

Specifically, 4- (phenyldiazenyl) phenol, 2- (phenyldiazenyl) phenol, 1-((2,4-dimethylphenyl) diazenyl) naphthalen-2-ol, 4- (phenyldiazenyl) benzenethiol, 2 -(Phenyldiazenyl) benzenethiol, 1-((2,4-dimethylphenyl) diazenyl) naphthalene-2-thiol, 4- (phenyldiazenyl) aniline, 2- (phenyldiazenyl) aniline, 1-((2,4 -Dimethylphenyl) diazenyl) naphthalen-2-amine, (4- (phenyldiazenyl) phenyl) methanol, (2- (phenyldiazenyl) phenyl) methanol, (1-((2,4-dimethylphenyl) diazenyl) naphthalene- 2-yl) methanol and the like.
Among these, 4- (phenyldiazenyl) phenol is particularly preferable in terms of reactivity and easy industrial availability.

In addition, examples of the starting species used in Step 1 include compounds that generate protons such as water, alcohol, and protonic acids, compounds that generate carbocations such as alkyl halides, and vinyl ethers and compounds that generate protons. Cation supplying compounds such as adducts can be mentioned, and among these, compounds that generate carbocations are preferred.
Compounds that generate such carbocations are broadly classified into monofunctional initiating species and bifunctional initiating species. When a monofunctional initiating species is used, the terminal structure (1) is introduced at one end of the polymer chain in Step 3, while when a bifunctional initiating species is used, the terminal is terminated at both ends of the polymer chain in Step 3. Structure (1) is introduced. In addition, when a bifunctional initiating species is used and step 2 is performed, a triblock copolymer can be obtained.
Examples of the monofunctional starting species include 1-alkoxyethyl acetate such as 1-isobutoxyethyl acetate. Examples of the bifunctional starting species include 1,4-bis (1-acetoxyethoxy) butane. And bis (acetoxyalkoxy) alkanes.
What is necessary is just to determine suitably the addition amount of the said start seed | species according to the molecular weight of the target temperature-responsive polymer.

In addition, the Lewis acid used in Step 1 and, if necessary, Step 2 may be any material that is generally used for living cationic polymerization. Specifically, organometallic halides such as Et _1.5 AlCl _1.5 ; TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ .OEt ₂ , SnCl ₂ , SnCl ₄ , SbCl ₅ , SbF ₅ , WCl ₆ , TaCl ₅ , metal halides such as VCl ₅ , FeCl ₃ , ZnBr ₂ , ZnCl ₄ , AlCl ₃ , and AlBr ₃ can be preferably used. Note that the Lewis acid may be used alone or in combination.

  Among such Lewis acids, the Lewis acid used in Step 1 is represented by the following general formula (7).

[In the formula (7), R ⁷ represents a monovalent organic group, X represents a halogen atom, r and s are r + s = 3, and 0 ≦ r <3 and 0 <s ≦ 3. ]
The organic aluminum halide compound or aluminum halide compound represented by these is preferable.

In formula (7), the monovalent organic group represented by R ⁷ is not particularly limited, but an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 12 carbon atoms), an aralkyl group (preferably May have 7 to 13 carbon atoms, an alkenyl group (preferably 2 to 8 carbon atoms), and an alkoxy group (preferably 1 to 8 carbon atoms).
Moreover, as a halogen atom shown by X, a chlorine atom, a bromine atom, a fluorine atom, etc. are mentioned, r becomes like this. Preferably it is the range of 1-2, s becomes like this.
Specific examples of such Lewis acids include diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, isobutylaluminium sesquichloride, methylaluminum dichloride, ethyl. Examples include aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum difluoride, isobutyl aluminum dichloride, octyl aluminum dichloride, ethoxy aluminum dichloride, phenyl aluminum dichloride and the like.

On the other hand, the Lewis acid used in Step 2 as necessary is preferably a metal halogen compound or an organometallic halogen compound whose metal is other than Al. Such compounds include TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ .OEt ₂ , SnCl ₂ , SnCl ₄ , SbCl ₅ , SbF ₅ , WCl ₆ , TaCl ₅ , VCl ₅ , FeCl ₃ , ZnBr ₂ and ZnCl ₄ . Among this, SnCl _4, FeCl ₃ and the like are preferable.
The amount of Lewis acid used is not particularly limited and may be set in consideration of the polymerization characteristics or polymerization concentration of each monomer used. Usually, it is used in the range of 0.5 to 500 mol% with respect to each monomer.
In Steps 1 and 2, a Lewis base may be used as an inhibitor for side reactions such as termination reaction. Specific examples include ester compounds such as ethyl acetate and n-butyl acetate.

Moreover, as a solvent used in each said process, aromatic hydrocarbon solvents, such as benzene, toluene, xylene; propane, n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane , Isooctane, decane, hexadecane, isopentane and other aliphatic hydrocarbon solvents; methylene chloride, ethylene chloride, carbon tetrachloride and other halogenated hydrocarbon solvents; tetrahydrofuran (THF), dioxane, diethyl ether, dibutyl ether, ethylene glycol Examples include ether solvents such as diethyl ether. These solvents may be used alone or in combination of two or more.
Moreover, although reaction temperature of each process is the range of -80 degreeC-150 degreeC normally, the inside of the range of -78 degreeC-80 degreeC is preferable. The reaction time is usually in the range of 0.5 hours to 12 hours.

Then, a proton scavenger (basic compound) is added to the polymer solution obtained in the above step 3 to trap free protons generated, and after further removing catalyst residues, the polymer is purified and isolated from the polymer solution. Thus, the temperature-responsive polymer of the present invention can be obtained.
In addition, as a method of removing the catalyst residue, a method of treating with an aqueous solution containing water such as hydrochloric acid, nitric acid, sulfuric acid or water; a method of treating with an inorganic oxide such as silica gel, alumina, silica-alumina; an ion exchange resin And the like. Examples of the isolation method include a method of distilling off volatile components from a polymer solution; a method of adding a large amount of a poor solvent to precipitate a polymer; and a method of combining them.

The temperature-responsive polymer of the present invention obtained as described above exhibits temperature responsiveness and reversibly changes its hydrophilicity / hydrophobicity even when supported on a fibrous base material. Temperature responsiveness can be imparted to the material, and it can be easily produced. Further, it can be firmly supported on the surface of a substrate such as a resin, and the surface of a resin or the like on which a temperature-responsive polymer is immobilized is smooth and has little tack.
Here, in the present specification, the temperature responsiveness refers to showing hydrophilicity (water permeability) when the temperature is lower than a predetermined temperature, and showing hydrophobicity (water repellency) when the temperature exceeds a predetermined temperature.

  Therefore, by using the temperature-responsive polymer of the present invention, the hydrophilicity / hydrophobicity of the substrate to be applied can be controlled using the temperature-responsiveness, and the temperature-responsive polymer of the present invention is used as the substrate. By being supported on the substrate, a temperature-responsive polymer-base composite having temperature responsiveness can be provided. The hydrophilicity / hydrophobicity control agent and temperature-responsive polymer-base complex of the present invention include, for example, a temperature sensor, a separation membrane, an adsorbent, a drug release agent, a water absorbent, a water retention agent, a humidity control agent, an indicator agent, Can be used as material.

The hydrophilicity / hydrophobicity control agent of the present invention may contain a solvent in addition to the temperature-responsive polymer. Examples of such a solvent include those listed above as solvents for use in the polymerization reaction, lower alcohols (preferably having 1 to 3 carbon atoms) such as methanol, ethanol, propanol, and isopropanol, and water. It may be included, and two or more kinds of combinations may be included.
Although content of a thermoresponsive polymer is not specifically limited, Preferably it is 1-50 mass% in a hydrophilicity / hydrophobicity control agent, More preferably, it is 5-25 mass%.

Examples of the base material to be controlled for hydrophilicity / hydrophobicity include resins, plant fibers, animal fibers, and inorganic fibers. Examples of the resin include a synthetic resin and a natural resin. The synthetic resin is preferably a synthetic resin fiber, and the natural resin is preferably a natural resin fiber.
Examples of the synthetic resin include polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; polystyrene resins such as polystyrene; vinyl chloride resins; low density polyethylene, high density Polyolefin resins such as polyethylene and polypropylene; Polyether resins such as polyether ketone and polyether ether ketone; Polyamide resins such as nylon and aramid; Polycarbonate resins such as polycarbonate; Polyimide resins such as polyimide; Polyurethane resins such as polyurethane Examples of the natural resin include latex and natural rubber. Note that it may be a composite material composed of a plurality of these resins, an alloy, a copolymer, or the like.
Examples of the plant fiber include cotton, hemp, and linen. Examples of the animal fiber include wool, silk, and cashmere. Examples of the inorganic fiber include glass fiber and the like. These fibers may be used alone or in combination, and may be used in combination with a synthetic resin or a natural resin.

  In addition, the form of the substrate is not particularly limited, and examples thereof include beads, films, fibrous substrates, sheets, tubes, pipes, and composites thereof. However, fibrous substrates are preferable, and fiber sheets are more preferable. .

  Examples of the form of the fiber sheet include woven fabrics, knitted fabrics, and non-woven fabrics, and non-woven fabrics are preferable in that the gap between fibers is small. Nonwoven fabrics and composite nonwoven fabrics manufactured by various nonwoven fabric production methods such as air-through method, heat roll method, spun lace method, needle punch method, chemical bond method, airlaid method, melt blown method, and spun bond method (for example, , Spunbond / meltblown nonwoven fabric, spunbond / meltblown / spunbond nonwoven fabric) and the like. The fiber sheet may be a single layer or a laminate of multiple layers.

  In addition, the temperature-responsive polymer of the present invention can control the hydrophilicity / hydrophobicity of the base material as described above, but it contains an azo group having permeability to the resin, and the temperature-responsive polymer can be immobilized on the resin surface. Therefore, it is particularly suitable for controlling the hydrophilicity / hydrophobicity of the resin surface.

Moreover, as the hydrophilicity / hydrophobicity control method of the present invention, a method of dissolving the temperature-responsive polymer of the present invention in the above solvent and coating or impregnating it on a substrate can be mentioned.
The method of application or impregnation is not particularly limited, and examples thereof include a method in which a solution in which the temperature-responsive polymer is dissolved is applied using a spray, a roll, a brush, a dipping method, and the like.

The temperature-responsive polymer-substrate composite of the present invention is one in which the temperature-responsive polymer of the present invention is supported on the substrate. The base material may be any base material as described above, but a temperature-responsive polymer-fiber composite using a fiber base material such as synthetic resin fiber, natural resin fiber, plant fiber, animal fiber, or inorganic fiber may be used. preferable. Moreover, what consists of resin fiber is preferable as said fibrous base material, As a kind and form of such resin, the thing similar to the base material described previously is mentioned. Among such resin fibers, polyester fibers, polyolefin fibers, polyamide fibers, and composite fibers thereof are preferable.
In addition, as said temperature-responsive polymer-fiber composite, what the temperature-responsive polymer was fixed to the surface of the fiber which comprises a fibrous base material is preferable.

Moreover, the temperature-responsive polymer-base material composite of the present invention may contain a drug or the like, and may be a fiber base material that has been processed. For example, it may be provided with functions such as flame retardancy, antibacterial properties, deodorant properties, insect repellent properties, antifungal properties, aromatic properties, etc., and integrated with a sheet or film having these functions. It may be.
In addition, what is necessary is just to perform manufacture of the temperature-responsive polymer-base-material composite_body | complex of this invention similarly to the said hydrophilicity / hydrophobicity control method. Moreover, it can also obtain by forming a woven fabric, a knitted fabric, a nonwoven fabric, etc. using the fiber which fixed the temperature-responsive polymer on the surface.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. The physical properties of each polymer were evaluated by the following methods.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)>
Using a RI detector, it was determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC) method (column: KF-804L × 3 manufactured by Shodex, eluent: tetrahydrofuran).

Example 1 Production of methoxyethyl vinyl ether polymer having 4- (phenyldiazenyl) phenoxy group at one end (hereinafter referred to as “temperature-responsive polymer a”) The following temperature-responsive polymer a was obtained by the procedure described below.

A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. In this container, 2-methoxyethyl vinyl ether (hereinafter referred to as “MOVE”) 1.52M (63.1 g), ethyl acetate 0.95M (33.9 g), 1-isobutoxyethyl acetate (hereinafter “IBEA”) referred to as) 3.8mM (0.25g), and placed in toluene 261ML, the reaction system was cooled, 14.2 mm When the temperature reached 0 ° C., as a toluene solution (Et _1.5 AlCl _1.5 of Et _1.5 AlCl _1.5 ) Was added for polymerization.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE polymer was a monodisperse polymer with Mw = 20200 and Mw / Mn = 1.38.
Subsequently, an ethyl acetate solution (11.4 mM (0.92 g) as PDP) of 4- (phenyldiazenyl) phenol (hereinafter referred to as “PDP”) was added to the reaction system to stop the polymerization reaction. Furthermore, methanol containing sodium methoxide (1M as sodium methoxide) was added to the reaction system to trap free protons.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter with celite and a pore size of 1 μm, and concentrated under reduced pressure with an evaporator to purify the temperature-responsive polymer a. The temperature-responsive polymer a after purification was Mw = 20700 and Mw / Mn = 1.39.

Example 2 Production of methoxyethyl vinyl ether-bp-paraisopropenylphenol having 4- (phenyldiazenyl) phenoxy group at one end (hereinafter referred to as “temperature-responsive polymer b”) Polymer b was obtained.

A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. In this vessel, MOVE 1.49M (63.1 g), ethyl acetate 0.93M (33.9 g), IBEA 3.7 mM (0.25 g), and 261 mL of toluene were cooled, and the reaction system was cooled to a temperature of 0 ° C. Upon reaching and (as Et _1.5 AlCl _1.5 13.9mM) in toluene Et _1.5 AlCl _1.5 was polymerized by adding.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE polymer was a monodisperse polymer with Mw = 20200 and Mw / Mn = 1.38.
Then, p- isopropenylphenol (hereinafter, referred to as "PIPP") was added an ethyl acetate solution of (7.5 mM as PIPP (0.42 g)) to the reaction system of the further SnCl ₄ toluene solution (SnCl ₄ As the reaction was continued.
When the conversion of PIPP was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE-b-PIPP polymer was a monodisperse polymer having Mw = 22700 and Mw / Mn = 1.43.
Next, an ethyl acetate solution of PDP (11.1 mM (0.92 g) as PDP) was added to the reaction system to stop the polymerization reaction. Furthermore, methanol containing sodium methoxide (1M as sodium methoxide) was added to the reaction system to trap free protons.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter with celite and a pore size of 1 μm, and concentrated under reduced pressure with an evaporator to purify the temperature-responsive polymer b. The temperature-responsive polymer b after purification was Mw = 22700 and Mw / Mn = 1.44.

Example 3 Production of methoxyethyl vinyl ether polymer having 4- (phenyldiazenyl) phenoxy groups at both ends (hereinafter referred to as “temperature-responsive polymer c”) The following temperature-responsive polymer c was obtained by the procedure described below.

A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. In this container, MOVE 1.52M (63.1 g), ethyl acetate 0.94M (33.9 g), 1,4-bis (1-acetoxyethoxy) butane 3.8 mM (0.42 g), and 261 mL of toluene were placed. , the reaction system was cooled, and when the temperature reached 0 ° C., was (as Et _1.5 AlCl _1.5 14.2mM) in toluene Et _1.5 AlCl _1.5 was polymerized by adding.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE polymer was a monodisperse polymer with Mw = 23500 and Mw / Mn = 1.36.
Next, an ethyl acetate solution of PDP (22.8 mM (1.84 g) as PDP) was added to the reaction system to stop the polymerization reaction. Furthermore, methanol containing sodium methoxide (1M as sodium methoxide) was added to the reaction system to trap free protons.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter with celite and a pore size of 1 μm, and concentrated under reduced pressure with an evaporator to purify the temperature-responsive polymer c. The temperature-responsive polymer c after purification was Mw = 22800 and Mw / Mn = 1.39.

Comparative Example 1 Production of methoxyethyl vinyl ether-b-phenyl (4- (2-vinyloxyethoxy) phenyl) diazene (hereinafter referred to as “diblock polymer d”) The following diblock polymer d was obtained by the procedure described later. .

A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. In this vessel, MOVE 1.20M (63.2g), ethyl acetate 0.78M (35.2g), IBEA 3.1mM (0.25g), and 270mL of toluene were cooled, and the reaction system was cooled to a temperature of 0 ° C. the Upon reaching, polymerization was initiated by the addition of (11.6 as Et _1.5 AlCl _1.5) toluene solution of Et _1.5 AlCl _1.5.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained MOVE polymer was a monodisperse polymer with Mw = 23600 and Mw / Mn = 1.37.
Next, a toluene solution of phenyl (4- (2-vinyloxyethoxy) phenyl) diazene (hereinafter referred to as “PVEPD”) (0.062M (8.56 g) as PVEPD) was added to the reaction system, and Et _1.5 AlCl _1.5 in toluene (58.3 mM as Et _1.5 AlCl _1.5 ) was added to continue the reaction.
When the conversion of PVEPD was completed, methanol containing sodium methoxide (1M as sodium methoxide) was added to the reaction system to stop the reaction, and diblock polymer d was obtained. The obtained MOVE-b-PVEPD polymer (diblock polymer d) was a monodispersed polymer having Mw = 25000 and Mw / Mn = 1.47.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter with celite and a pore size of 1 μm, and concentrated under reduced pressure with an evaporator to purify the diblock polymer d. The diblock polymer d after purification had Mw = 24300 and Mw / Mn = 1.53.

Comparative Example 2: Production of phenyl (4- (2-vinyloxyethoxy) phenyl) diazene-b-methoxyethyl vinyl ether-b-paraisopropenylphenol (hereinafter referred to as “triblock polymer e”) Triblock polymer e was obtained.

A glass container with a three-way stopcock was prepared, the inside of the container was purged with argon, and then heated to remove the adsorbed water in the glass container. PVEPD0.065M (8.57g), ethyl acetate 0.82M (35.3g), IBEA 3.25mM (0.25g), and toluene 350mL are put in this container, the inside of a reaction system is cooled, and temperature is 0 degreeC. the Upon reaching, polymerization was initiated by the addition of (30.4 mm as Et _1.5 AlCl _1.5) toluene solution of Et _1.5 AlCl _1.5.
A small amount of the reaction solution was collected when the conversion of PVEPD was completed, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained PVEPD polymer was a monodisperse polymer with Mw = 2800 and Mw / Mn = 1.09.
Then, MOVE1.25M (63.2 g) was added to the reaction system to continue the reaction.
When the conversion of MOVE was completed, a small amount of the reaction solution was collected, and methanol containing sodium methoxide was added thereto to stop the reaction. The obtained PVEPD-b-MOVE polymer was a monodisperse polymer with Mw = 29800 and Mw / Mn = 1.24. Further, it was confirmed from the GPC chart of this polymer that the peak derived from the PVEPD polymer completely disappeared.
Then, ethyl acetate was added a solution of PIPP (6.5 mM as PIPP (0.43 g)) to the reaction system described above, the reaction was continued by adding further toluene solution of SnCl ₄ (30.4 mm as SnCl _4).
When the conversion of PIPP was completed, methanol containing sodium methoxide (5M as sodium methoxide) was added to the reaction system to stop the reaction, and triblock polymer e was obtained. The obtained triblock polymer e (PVEPD-b-MOVE-b-PIPP polymer) was a monodispersed polymer having Mw = 33500 and Mw / Mn = 1.30.
Subsequently, 5 mass% of aluminum oxide was added to the solution which stopped the said reaction, and it stirred for 2 hours. This solution was passed through a filter with celite and a pore size of 1 μm and concentrated under reduced pressure with an evaporator to purify the triblock polymer e. Triblock polymer e after purification had Mw = 34700 and Mw / Mn = 1.30.

Examples 4 to 6 and Comparative Examples 3 and 4: Fabrication of Fiber Sheets 10% by mass ion exchange aqueous solutions of the polymers a to e obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were prepared, respectively, and the pore diameter was 1 μm. The solution was passed through the filter. A polyethylene terephthalate non-woven fabric (3 × 10 cm) was immersed in this aqueous solution for 1 hour, allowed to permeate, and thoroughly washed to obtain a fiber sheet carrying each polymer. In any of the obtained fiber sheets, no stickiness or unevenness derived from the polymer was observed on the surface, and the same form as the nonwoven fabric before impregnation was maintained. Table 1 shows the polymers supported on each fiber sheet.

Test Example: Water Permeability Evaluation Test On the surface of the fiber sheet obtained in Examples 4 to 6 and Comparative Examples 3 and 4, 100 μL of water droplets were arranged at 15 points at equal intervals, and the humidity was 43% and the temperature was 25 ° C. and 75 ° C. By counting the number of water droplets after 3 minutes under the temperature condition of ° C., the water permeability and the change of the water permeability due to the temperature were confirmed.
Table 1 shows the results of water permeability evaluation of each fiber sheet. For comparison, Table 1 also shows the results of a similar evaluation performed on a non-impregnated nonwoven fabric.

As shown in Table 1, a fiber sheet (comparative example) in which a diblock polymer (polymer d) obtained by copolymerizing vinyl ether (PVEPD) having a structure similar to the terminal structure (1) of the present invention together with MOVE is supported on a nonwoven fabric (Comparative Example) In 3), although the sheet surface was hydrophilized, it did not show responsiveness by heating. Further, when the triblock polymer (polymer e) further added with the oxystyrene monomer PIPP (Comparative Example 4) was used, although the water repellency at a high temperature was slightly improved, the temperature responsiveness was insufficient. there were.
On the other hand, the temperature-responsive polymer (polymers a to c) having the terminal structure (1) of the present invention at one end or both ends has a smaller number of azobenzene structures than the polymers d and e. Even when it was carried on a sheet (Examples 4 to 6), sufficient responsiveness was shown by heating.
From this result, it can be seen that the composite of the present invention has temperature responsiveness and can reversibly achieve hydrophilicity (water permeability) and hydrophobicity (water repellency) in response to thermal stimulation.

Claims (10)

It has a repeating unit derived from a vinyl ether monomer, the repeating unit derived from the vinyl ether monomer contains a temperature responsive group, and at least one terminal of the polymer chain has the following formula (1)

[In Formula (1), Y represents an ether bond, a thioether bond, a group —NH—, or a group —OR ¹ — * (R ¹ represents an alkylene group, and * represents Ar ^{1 in} Formula (1). Ar ¹ represents a substituted or unsubstituted divalent aromatic hydrocarbon group, and Ar ² represents a substituted or unsubstituted monovalent aromatic hydrocarbon group. ]
A temperature-responsive polymer having a structure represented by: Ar ¹ represents the following formula (1-2) or (1-3)

[In Formula (1-2), each R ² independently represents an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxyalkyl group, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group, or an aminosulfonyl group, ** represents a position bonded to Y in the formula (1), and *** represents a formula The position which couple | bonds with the nitrogen atom in (1) is shown, p-1 is an integer of 0-4. ]

[In Formula (1-3), p-2 is an integer of 0 to 6, and R ² , ** and *** are as defined above. ]
Ar ² is represented by the following formula (1-4) or (1-5)

[In Formula (1-4), R ³ is each independently an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxyalkyl group, a halogen atom, a carboxyl group, a nitro group, a sulfo group, a sulfooxy group or an aminosulfonyl group, and *** indicates a position bonded to the nitrogen atom in the formula (1), and p-3 Is an integer from 0 to 5. ]

[In formula (1-5), p-4 is an integer of 0 to 7, and R ³ and *** are as defined above. ]
The temperature-responsive polymer according to claim 1, which is represented by: The repeating unit derived from the vinyl ether monomer is represented by the following formula (2-1) or (2-2):

[In formula (2-1), R ^4-1 represents a methyl group, an ethyl group or a carboxyphenyl group, and k is an integer of 1 to 10. ]

[In Formula (2-2), R ^4-2 represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms. ]
The temperature-responsive polymer according to claim 1, which is represented by Further, the following formula (3)

In [formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 2 carbon atoms 6 represents an alkoxyalkyl group, an alkanoyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group or an alkylsilyl group, and m is an integer of 1 to 3. ]
The temperature-responsive polymer according to any one of claims 1 to 3, which has a repeating unit represented by formula (1).   The temperature-responsive polymer according to claim 4, which is a block copolymer comprising a segment A composed of repeating units derived from the vinyl ether monomer and a segment B composed of repeating units represented by the formula (3).   A hydrophilicity / hydrophobicity control agent containing the temperature-responsive polymer according to claim 1.   A method for controlling hydrophilicity / hydrophobicity using the temperature-responsive polymer according to claim 1.   A temperature-responsive polymer-base material composite in which the temperature-responsive polymer according to claim 1 is supported on a base material.   The temperature-responsive polymer-substrate composite according to claim 8, wherein the substrate is a fibrous substrate.   The temperature-responsive polymer-substrate composite according to claim 9, wherein the fibrous substrate is made of polyester fiber.