WO2007007675A1

WO2007007675A1 - Polyolefin having polymer chain responsive to stimulus

Info

Publication number: WO2007007675A1
Application number: PCT/JP2006/313587
Authority: WO
Inventors: Hideyuki Kaneko; Shinichi Kojoh; Nobuo Kawahara; Shingo Matsuo; Tomoaki Matsugi; Norio Kashiwa
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2005-07-07
Filing date: 2006-07-07
Publication date: 2007-01-18
Also published as: TW200710106A; JPWO2007007675A1

Abstract

A block or graft polymer comprising a polymer chain responsive to stimuli and a polyolefin chain directly bonded thereto by chemical bonding is provided as a material which has a polymer chain responsive to stimuli and combines excellent properties of polyolefins with the excellent processability of polyolefins. The polymer is a block or graft copolymer composed of a polyolefin chain and a stimulus-responsive polymer chain whose affinity for a liquid changes upon reception of a stimulus, and is characterized in that the polyolefin chain has been chemically bonded to the stimulus-responsive polymer chain.

Description

Specification

Polyolefins with stimuli-responsive polymer chains

Technical field

[0001] The present invention relates to a polyolefin in which a stimulus-responsive polymer chain whose affinity to a liquid is changed by applying a stimulus is chemically bonded.

Background art

[0002] So far, many polymers have been known as polymer materials whose affinity for liquid reversibly changes by the application of a stimulus, so-called stimulus-responsive polymers. pH, ionic strength, adsorption of substances, changes in solvent composition, application of electric current or electric field are used.

[0003] Examples of temperature responsiveness include poly (N-isopropylacrylamide) and other acrylamide polymers, polybutyl methyl ether, and polymethacrylic acid. Examples of pH responsiveness include polyacrylic acid. ZPVA blends, etc. are known, and attempts have been made to use them in human muscle and other activators, energy conversion materials, drug control releases, and cell culture.

[0004] Such stimulus responsiveness is basically caused by repeated absorption of the liquid into the polymer material and elimination of the liquid from the polymer material.

[0005] However, these stimuli-responsive polymers have poor self-holding properties as they are as they are highly soluble in liquids. Therefore, it is common to partially cross-link molecular chains and use them as gels.

[0006] On the other hand, polyolefin has been used in various applications as a structural material because it has excellent physical properties and strength. However, since it does not have a functional group, it has printability, paintability, adhesion, and resistance. It was difficult to impart high functionality such as heat resistance, impact resistance, hydrophilicity, and stimulus response.

[0007] In order to produce a material that combines the stimuli-responsive properties of stimuli-responsive polymers with the excellent physical properties and processability of polyolefins, it is considered that the objectives can be basically achieved by simply blending the materials. In practice, many polymers are incompatible. Therefore, they are usually not mixed, and are incompatible with each other, so that it is difficult to produce a uniform molded body. However, even if molding is possible, each polymer is phase-separated, so the interaction between the polymers is weak. The disadvantage is that only highly stimuli-responsive polymer segments will flow out. Therefore, it is difficult to synergistically express the characteristics of each material simply by blending. The present inventors have found that these problems can be solved by directly bonding these basically incompatible polymers by chemical bonds.

Disclosure of the invention

Problems to be solved by the invention

[0008] An object of the present invention is to use a block or graft polymer in which a polymer chain having stimuli responsiveness and a polyolefin chain are directly bonded by chemical bonding, thereby having a polymer chain having stimuli responsiveness and The aim is to provide materials that have both excellent physical properties and strength.

Means for solving the problem

[0009] (1) A block or graft copolymer composed of a polyolefin chain and a stimulus-responsive polymer chain whose affinity to a liquid changes upon application of a stimulus, the polyolefin chain and the stimulus-responsive polymer A polymer characterized in that the chain is chemically bonded.

(2) Polyolefin chain strength CH = CH— R (R is a hydrogen atom or carbon having 1 to 20 carbon atoms.

2

The polymer according to (1), which is a polymer chain obtained by polymerizing at least one kind of a-year-old refin represented by a hydrogen fluoride group.

(3) Stimulus responsive polymer chain strength Poly-N-alkyl substituted (meth) acrylamide, poly (meth) acrylic acid or its metal salt, poly 2 such as poly (meth) acrylamide, poly-N-isopropyl (meth) acrylamide —Hydroxyethyl (meth) acrylate, polybutylbenzene sulfonic acid or its metal salt, poly (ethylene glycol monometa acrylate), poly (ethylene glycol mono acrylate) At least one kind of polymer that can be selected as a group force The polymer according to (1) or (2), wherein the polymer is a chain. The invention's effect

[0010] A polyolefin having a stimulus-responsive polymer chain according to the present invention is a block or graft copolymer composed of a polyolefin chain and a stimulus-responsive polymer chain, and has a polymer chain exhibiting stimulus response. In addition, it is possible to provide a polymer material with excellent self-holding properties that combines the excellent physical properties and processability of polyolefin as a structural material.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] Hereinafter, the polyolefin having the stimulus-responsive polymer chain of the present invention will be specifically described.

The polyolefin having a stimulus-responsive polymer chain according to the present invention is a polymer having both a stimulus-responsive polymer chain and a polyolefin chain in the molecule.

[0013] The stimulus-responsive polymer used in the present invention has the property of changing the affinity for a liquid by the application of a stimulus. The pH value, ionic strength, adsorption / desorption of a chemical substance, addition of a solvent, It is preferable that the affinity changes due to application of heat, light, electric current or electric field, and the state can be easily formed without being compatible with the state that is compatible with the liquid to be used. Examples of the index representing the change in affinity of the stimulus-responsive polymer with respect to the liquid include a change in the absorbability of the liquid into the polymer and a change in the solubility in the liquid. In general, these affinity changes may be unidirectional or reversible.

[0014] In the present invention, the change in the absorbability of liquid due to the application of a stimulus is between the state in which the liquid is absorbed into the polymer compound by the application of the stimulus and the state in which the liquid is released from the polymer compound. Can be defined as change. These changes in the state can be distinguished from the state in which the polymer compound has swollen by absorbing the liquid and the state in which the polymer has been discharged and contracted, and specifically, the length, area, volume, etc. It can be observed as a change in space. In the present invention, the change in solubility in a liquid due to the application of a stimulus refers to a one-phase state in which the polymer compound is dissolved in the liquid and the two components of the polymer compound and the liquid are almost uniform, and the polymer compound. Can be defined as the change between an inhomogeneous two-phase state insolubilized in a liquid. These changes in state can be distinguished by an optically almost transparent state and an opaque light scattering state. Out of these states In the state in which the polymer compound is contracted by releasing the liquid and the inhomogeneous state in which the polymer compound is insoluble in the liquid, the liquid is partially contained even in the solid state in which the liquid is almost excluded from the polymer compound. Semi-solid state.

[0015] The stimulus-responsive polymer having the above-described properties used in the present invention will be described. A substance whose affinity for a liquid is changed by application of heat is usually a polymer compound that undergoes a phase transition and is insolubilized or solubilized when heated from 20 ° C to 100 ° C. Specifically, Poly (meth) acrylamide, poly-N-alkyl substituted (meth) acrylamide such as poly-N-isopropyl (meth) acrylamide, polyvinyl alkyl ether such as N-butylisobutyramide, polybutylmethyl ether, poly (oxyethyleneoxyvinyl ether) , Poly (meth) acrylic acid or metal salts thereof, poly 2-hydroxyethyl (meth) acrylate, poly N— (meth) acrylic piperidine, poly (2-ethyloxazoline), polybutyl alcohol or Its partially saponified product, polyethylene oxide, polyethylene oxide and polypropylene oxide Copolymers, poly (ethylene glycol monometa acrylate), poly (ethylene glycol mono acrylate), substituted cellulose derivatives such as methyl cellulose, ethinoresenolose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc. Or the copolymer which has these high molecular compounds as a main component is mentioned.

[0016] In addition, poly (( (Meth) acrylic acid or metal salts thereof, polybulusulfonic acid, polybulu benzenesulfonic acid, poly (meth) acrylamide alkylsulfonic acid, polymaleic acid or metal salts thereof, or monomer components constituting these polymer compounds Copolymer obtained by using as a main component, polyvinyl alcohol, polyacrylic acid complex or metal salt thereof, poly (ethylene glycol monomethacrylate), metal salt of carboxymethylcellulose, metal salt of carboxyethylcellulose, etc. Examples thereof include a copolymer mainly composed of a high molecular compound.

[0017] For the adsorption / desorption system of the above chemical substances, various surfactants, amines, quaternary amamine salt derivatives, ionic low molecular compounds such as acids, acid chloride derivatives, etc. By adding an electric field and current to control adsorption / desorption to a polymer compound, The affinity of the polymer compound can be changed. In addition, when the affinity is changed depending on the pH value, for example, poly (meth) acrylate is insoluble when the pH is 2 or less and dissolves at a pH higher than that. A preferred range for this pH change is a pH range of 1-12. Such a change can be performed by addition of an acid or alkali or an electrode reaction.

[0018] Examples of the compound whose affinity is changed by the application of light include a polymer compound having a group such as a photochromic group whose structure is changed by a photoreaction. Nylmethane derivatives, spiropyran derivatives, poly (meth) acrylamides having groups such as spiroxazine derivatives, poly N-alkyl substituted (meth) acrylamides such as poly-N-isopropyl (meth) acrylamide, N-butylisobutyramide, Various types such as polybulu alkyl ethers such as polybulumethyl ether and poly (oxyethyleneoxyvinyl ether) s can be used. This change in affinity due to light is caused by, for example, the above-mentioned trifluoromethane derivative being irradiated with ultraviolet rays having a wavelength of about 350 nm, causing a cleavage reaction and improving the solubility in water. Irradiation causes the opposite reaction and decreases the solubility in water. When applying light, the wavelength of irradiation light is preferably in the range of 250 to 830 nm.

[0019] As a substance whose affinity is changed by an oxidation-reduction reaction by electricity, there is a CT complex (charge transfer complex) of a cationic high molecular weight compound and an electron accepting compound, specifically, dimethylaminopropyl. Amino-substituted (meth) acrylamides such as acrylamide, (meth) acrylic acid amino-substituted alkyl esters such as dimethylaminoethyl acrylate, jetylaminoethyl acrylate, dimethylaminopropyl acrylate, polystyrene derivatives, polyvinyl pyridine derivatives, polybules Strength rubazole derivatives, polydimethylaminostyrene, etc., and electrons such as benzoquinone, 7, 7, 8, 8—tetracyanquinodimethane (TCNQ), tetracyanethylene, chlorael, tri-trobenzene, maleic anhydride and iodine Used in combination with receptive compounds. For the change in affinity due to adsorption / desorption of a chemical substance due to the oxidation / reduction reaction or the electric field due to the application of electric current, it is preferable to apply a voltage of about 1 to 200 V to the electrode.

[0020] As the liquid used in the polyolefin having the stimulus-responsive polymer chain of the present invention, Water, aqueous electrolyte, alcohols such as methanol, ethanol, propanol, butanol, ketones, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, propylene carbonate, other aromatic organic solvents, aliphatic An organic solvent or a mixture thereof may be mentioned. In addition, the liquid contains surfactants and response accelerators that can be used to control stimulus response characteristics, Pioguchi derivatives to promote pH changes in the solution, acids, alkalis, salts, dispersion stabilizers, and antioxidants. A stabilizer such as an agent or an ultraviolet absorber may be added.

[0021] In the present invention, it is preferable that the stimulus-responsive polymer contained in the polyolefin having a stimulus-responsive polymer chain and a liquid include poly N-isopropyl (meth) acrylamide or N-isopropyl (meth) acrylamide. A copolymer containing water or a solution containing water as a main component, a copolymer containing polyvinyl methyl ether or butyl methyl ether as a main component, and water or water as a main component. Consists of solution

, Poly (meth) acrylate or a copolymer mainly composed of (meth) acrylate and water, an electrolyte aqueous solution or a solution mainly composed of water, dimethylaminopropyl (meth) Each complex of acrylamide or a copolymer based on it, and ketone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, propylene carbonate or other aromatic organic solvent The thing which consists of etc. is mentioned.

Accordingly, the polyolefin having the stimulus-responsive polymer chain of the present invention can be combined with the liquid and applied with the appropriate stimulus as described above, so that the affinity of the polymer moiety having the stimulus-responsive property in the polyolefin to the liquid is increased. Sex is expected to change.

[0023] As the polyolefin used in the present invention, CH = CH-R (R is a hydrogen atom or

2

And a polymer obtained by superimposing X-year-old refin, such as α-olefin, specifically represented by a hydrocarbon group having 1 to 20 carbon atoms. , Ethylene, propylene, 1-butene, 1-pentene, 3-methinole-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, Examples include linear or branched a-olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-otatadecene, 1-eicosene, etc. Among these exemplified olefins, ethylene, It is preferable to use at least one or more olefins selected from lopyrene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

[0024] Monomers constituting the stimuli-responsive polymer chain used in the present invention include, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N —N-alkyl-substituted (meth) acrylamides such as isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N dimethyl (meth) acrylamide, (meth) acrylic acid, sodium (meth) acrylate, (meth) Examples thereof include metal salts of (meth) acrylic acid such as lithium acrylate, 2-hydroxyethyl (meth) acrylate, benzene sulfonic acid or metal salts thereof. Further, it may be copolymerized with other vinyl monomers within a range that does not affect the stimulus response ability. Specific examples include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, and buresters such as vinyl acetate and butyl propionate. , Styrene, acrylonitrile and the like can be used, and the content of the monomer used in the copolymerization in the stimulus-responsive polymer chain is preferably within 10 mol%.

[0025] The olefin-based polymer of the present invention is preferably in the range of 5 to 95% by weight of the total force of the stimuli-responsive polymer chain, more preferably 10 to 80% by weight, even more preferably 10 to 70% by weight. As a result, the olefin-based polymer of the present invention has both stimulus responsiveness and excellent physical properties and moldability as a polymer, and has a stimulus-responsive polymer chain that is highly soluble in liquid. The self-holding property as a polymer is not lost in the liquid.

[0026] The block or graft copolymer which is an olefin-based polymer used in the present invention is characterized in that the stimulus-responsive polymer chain and the polyolefin chain are bonded to each other by a chemical bond. The method for producing such a block or graft copolymer is not particularly limited, and examples thereof include a method using a functional group-containing polyolefin as a raw material. Specifically, (Method 1) a method of polymerizing monomers constituting the above-mentioned stimuli-responsive polymer chain using a functional group-containing polyolefin as an initiator, or (Method 2) a functional group-containing polyolefin as a macromonomer. (Method 3) Functional group-containing polyolefin chain and stimuli-responsive polymer chain Examples include a coupling method.

[Method] (Method 2) and (Method 3) are known forces. Hereinafter, the method for producing the block or graft copolymer described above, particularly (Method 1) will be described in more detail.

[0028] (Method 1) is a method of polymerizing the monomer constituting the stimulus-responsive polymer chain using a functional group-containing polyolefin as an initiator. Examples of the functional group-containing polyolefin used in this method include polyolefins in which a radical polymerization-initiating ability or a group having a cation-initiating ability is introduced at the end of the molecular chain or in the molecular chain. As the group having radical polymerization initiating ability, for example, as disclosed in Chem. Rev., 101, 3661 (2001), a group having a nitroxide is bonded and a radical is generated by thermal cleavage. -Used in troxide-mediated radical polymerization methods or have terminal halogen atoms as disclosed in Chem. Rev., 10 1, 2921 (2001) and Chem. Rev., 101, 3689 (2001) A group is bonded, and a radical is generated by adding a ruthenium or copper chloride or a complex having a transition metal atom thereof, V, used in a so-called atom transfer radical polymerization method, or having an azo group Examples thereof include those in which radicals and oxygen-bonded groups are bonded and radicals are generated by thermal cleavage. Examples of the group having an ability to initiate diion polymerization include a group having an alkoxide of an alkali metal such as lithium or potassium. By polymerizing the monomers that make up the stimulus-responsive polymer chain in the presence of polyolefin introduced with such a group, a block or draft polymer in which the polyolefin chain and the stimulus-responsive polymer chain are chemically bonded is formed. Can be manufactured.

[0029] The block or graft polymer according to the present invention can be obtained, for example, by sequentially performing the following steps (1) to (3).

(1) Hydroxyl group, amino group, epoxy group, carboxyl group at main chain end and Z or side chain

A process for producing a polyolefin having a functional group (A) in which an acid halogen group, an acid anhydride group, and an isocyanate group strength are also selected.

(2) A step of converting to a macroinitiator by imparting a radical polymerization initiating ability or a cation polymerization initiating ability to the functional group-containing polyolefin obtained in the above step.

(3) Construct a stimulus-responsive polymer chain in the presence of the macroinitiator obtained in the above step A step of polymerizing a monomer to give a stimulus-responsive polymer chain to a polyolefin chain. Step (1) has a functional group (A) selected from a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, an acid anhydride group, and an isocyanate group at the main chain end and Z or side chain. This is a process for producing polyolefin.

[0030] The functional group (A) selected from hydroxyl group, amino group, epoxy group, carboxyl group, acid halogen group, acid anhydride group, isocyanate group at the main chain end and Z or side chain produced in this step Polyolefins having, for example, carbon-carbon unsaturated bonds or groups in the periodic table in polyolefins having groups containing a carbon-carbon unsaturated bond or a group 13 element in the periodic table at the main chain end and Z or side chain. Manufactured by converting groups containing group elements.

[0031] Polyolefin having a carbon-carbon unsaturated bond at the main chain end and Z or side chain used in this step is a carbon in the presence of an olefin polymerization catalyst such as a known Ziegler-Natta catalyst or a metalocene catalyst. Polymerization or co-polymerization of ex-olefin with 2-20 atoms, α-olefin and butadiene, 1,5-hexagen, 1,7-octagen, 5 vinyl 2-norbornene, etc. It can be produced by a method of copolymerizing with a compound having a plurality of compounds. Examples of a-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 3-methinole-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-Otaten or the like is preferably used. It can also be produced by thermally decomposing polyolefin.

[0032] Polyolefin having a group containing a group 13 element of the periodic table at the main chain end and Z or side chain used in this step is, for example, known polymerization in the presence of a compound containing a group 13 element of the periodic table. A method of (co) polymerizing the α-olefin with the catalyst, a method of copolymerizing the α-olefin and the group 13 element-containing olefin-containing compound of the periodic table, the terminal and the side or side chain. It can be produced by a method in which a polyolefin containing a carbon-carbon unsaturated bond is reacted with a compound containing a group 13 element of the periodic table such as diisoptylluminumno, idride or 9-ΒΒΝ.

[0033] Polyolefin having a group containing a carbon-carbon unsaturated bond or a group 13 element in the periodic table at the end of the main chain and at the side or the side chain is a hydroxyl group, an amino group, an epoxy group, a carboxyl group. Examples of a method for converting to a polyolefin having a functional group (A) having a functional group (A) in which a group, an acid halogen group, an acid anhydride group, and an isocyanate group are also selected include, for example, carbon-carbon unsaturated bonds in polyolefin and organic compounds such as m-peroxybenzoic acid. A method for producing an epoxy group-containing polyolefin by reaction with a peroxyacid, a carbon-carbon unsaturated bond in hydrogen peroxide and hydrogen peroxide in the presence of monoaminomethylphosphonic acid, tungstic acid and a phase transfer catalyst. A method of making an epoxy group-containing polyolefin by reaction, a method of making a hydroxyl group-containing polyolefin by reacting a group containing a group 13 element in the periodic table with oxygen and hydrogen peroxide, etc., and a group 13 element in the polyolefin By reacting the containing group with an azide compound such as 1-butyl azide and hydrolyzing, And a method of the fins. Moreover, the method of converting the polyolefin which has the functional group obtained by said method into another functional group is also illustrated. That is, preferred examples include a method of oxidizing a hydroxyl group-containing polyolefin to a carboxyl group-containing polyolefin, a method of reacting an epoxy group-containing polyolefin with an amine compound such as ethylenediamine or ethanolamine to obtain an amino group-containing polyolefin. Is done.

In addition, a functional group selected from a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, an acid anhydride group, an isocyanate group at the main chain end and Z or side chain produced in this step (A For example, can be produced by copolymerizing the above-mentioned α-olefin with a functional group of olefins using an olefin polymerization catalyst such as a known Ziegler-Natta catalyst or a metacene catalyst. It is. Examples of olefins having functional groups used for copolymerization include aryl alcohol, 4-pentene 1-ol, 5 hexene 1-ol, 6 heptene 1-ol, 8 nonen 1-ol, 10-undecene. 1 Unsaturated alcohols in which the hydrocarbon moiety is linear, such as all, unsaturated carboxylic acids such as 5-hexenoic acid, 6-heptenoic acid, 7-otatenic acid, 8-nonenoic acid, 9-decenoic acid, Examples of unsaturated amines such as arylamine, 5-hexeneamine, 6-hepteneamine, (2,7-octagel) succinic anhydride, pentapropyl succinic anhydride and the above unsaturated carboxylic acids In the examples of unsaturated acid anhydrides such as compounds in which a carboxylic acid group is replaced with a carboxylic acid anhydride group, and compounds in the above unsaturated carboxylic acids, Carboxylic groups Sanha Unsaturated carboxylic acid halides such as compounds substituted with a hydride group, 4 Epoxy 1 Butene, 5 Epoxy 1 Penten, 6 Epoxy 1 Hexene, 7 Epoxy 1 Heptene, 8 Epoxy 1 Otaten, 9 Epoxy 1 Nonene 10 unsaturated epoxy compounds such as 10 epoxy 1-decene, 11 epoxy 1undecene, 9 aryl 9 9 borabicyclo [3. 3.1] nonane, 9 but 1 3 ell 9 borabicyclo [3.3.1] nonane, 9 Pentoh 4 ell 9 Borabicyclo [3. 3.1] Nonane, 9 Hexane 5 ber 9 Borabicyclo [3. 3.1] Nonane, 9 Hepter 6 ell 9 Borabicyclo [3.3 1] Nonane, 9—oct 7 ell 9 Borabicyclo [3. 3. 1] Nonan, 9 Nona 8 ell 9 Borabicyclo [3. 3.1] Nonane, 9 Deca 9 ell — 9 Unsaturated boron compounds such as borabicyclo [3.3.1] nonane.

[0035] In step (2), a functional group (A) selected from a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, an acid anhydride group, and an isocyanate group at the main chain terminal and Z or side chain. ) Is converted to a macroinitiator by imparting a radical having a radical polymerization initiating ability or an anion polymerization initiating ability to the polyolefin. Specifically, for example, a polyolefin having a functional group (A) at the main chain end and Z or side chain produced in step (1) and a chemical bond with the functional group (A) contained in the polyolefin. A functional group (P) and a compound (R) having both radical polymerization initiating ability (Q) and a functional group contained in the polyolefin produced in step (1). For example, a method of converting (A) into a group (S) having an ability to initiate cation polymerization.

[0036] The functional group (P) that can be chemically bonded to the functional group (A) contained in the polyolefin includes a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, an acid anhydride group, and an isocyanate group. And the like. A preferred combination of the functional group (A) and the functional group (P) is not particularly limited as long as they are a combination that reacts to form a chemical bond, but when the functional group (A) is a hydroxyl group, Epoxy group, carboxyl group, acid halogen group, acid anhydride group and isocyanate group are preferred as the functional group (P). When the functional group (A) is an epoxy group, a hydroxyl group is preferred as the functional group (P). When the functional group (A) is a carboxyl group or an acid halogen group, the functional group (P) is a hydroxyl group, and the preferred amino group is an amino group. When the functional group (A) is an amino group, the functional group (P) is a carboxyl group, an acid. A halogen group and an acid anhydride group are preferred. [0037] As the group (Q) having radical polymerization initiating ability, as disclosed in, for example, Trend Polym. Sci., (1996), 4, 456, a group having a nitroxide is bonded to form a thermal group. Used in the so-called -Toroxide-mediated radical polymerization method that generates radicals by free cleavage, as disclosed in Macromolecules, (1995), 28, 1721 and Science, (199 6), 272, 866. Examples thereof include those used in the so-called atom transfer radical polymerization method. Specifically, 2, 2, 6, 6-tetramethylpiperidyl-luoxy 1 (TEMPO) group, 4-hydroxy 2, 2, 6, 6-tetramethylpibelidi-lulu 1-oxy group, 2, 2, 5, 5— Tetramethyl-1 pyrrolidi-loxy group, 3 —amino-1, 2, 2, 5, 5-tetramethyl-1- 1-pyrrolidi-loxy group, 2, 2, 5, 5-tetramethyl-1 pyrrolidyl-loxy group, di-t-butylnitroxy A group having an N—O bond such as a group, a carbo group, a cyano group, a sulfole group, and an aryl group, which includes an unsaturated group selected and these unsaturated groups sandwich one carbon atom. And a group having a structure bonded to a halogen atom. Among these, there are 2, 2, 6, 6-tetramethylbi-beli-l-oxy (TEMPO) groups and groups having a structure in which a carbo group is bonded to a chlorine atom or a bromine atom with one carbon atom in between. preferable.

[0038] Reaction of polyolefin having functional group (A) at the main chain end and Z or side chain with compound (R) having both functional group (P) and radical polymerization initiating group (Q) Generally, dehydrated organic solvents can be generally used as the conditions, but preferably 0 ° C in a hydrocarbon-based organic solvent having a high affinity with polyolefin such as toluene, benzene, hexane, heptane, etc. The reaction is carried out in the temperature range of ~ 120 ° C. The reaction may be either a homogeneous system or a heterogeneous system, but a homogeneous system is preferred. If the reaction does not proceed easily, a Bronsted acid such as sulfuric acid or formic acid para-toluenesulfonic acid or a Lewis acid such as aluminum chloride may be used as a catalyst. When water is generated by the reaction, the reaction may be allowed to proceed efficiently by adding anhydrous magnesium sulfate molecular sieves or removing water under reflux conditions using Dean Stark.

[0039] Reaction of polyolefin having functional group (A) at the main chain end and Z or side chain with compound (R) having both functional group (P) and radical polymerization initiating ability (Q) The amount of the compound (R) added to the polymer is such that the polyfunctional group (A) containing an oxygen atom or a nitrogen atom is contained. The functional group (A) present in the olefin is usually 0.1 to: LOOO times mol, preferably 1 to 500 times mol. The product obtained by the reaction is precipitated with methanol or acetone, filtered, and washed with a solvent in which compound (R) is dissolved, whereby unreacted compound (R) can be easily removed.

[0040] Further, as a method for converting the functional group (A) contained in the polyolefin produced in the above step (1) into a group (S) having a cation polymerization initiating ability, for example, an olefin having a hydroxyl group Polymers include alkali metals such as lithium metal and potassium, alkali metal hydrides such as lithium hydride and potassium hydride, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, etc. And a method of preparing a metal alkoxide-containing olefin polymer by reacting with an alkylaluminum compound.

[0041] By the above method, the polyolefin having the functional group (A) at the main chain end and Z or side chain can be converted into a macroinitiator.

[0042] In the step (3), the monomer constituting the stimulus-responsive polymer chain is polymerized in the presence of the macroinitiator obtained in the step (2), and the product obtained in the step (2) is obtained. This is a process of imparting a stimulus-responsive polymer chain (Z) to an object.

[0043] Examples of the radical polymerization method used in the present invention include the above-described -troxide-mediated radical polymerization method and atom transfer radical polymerization method. The atom transfer radical polymerization in the present invention is one of living radical polymerizations, and is a radical polymerizable monomer using an organic halide or halogenated sulfonyl compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. This is a method of radical polymerization of a monomer. Specifically, for example, Matyja szewski et al., Chem. Rev., 101, 2921 (2001), WO96 / 30421 publication, W097 / 18247 publication, WO98Z01480 publication, WO98Z40415 publication, WOOO / 156795 publication, Alternatively, Sawamoto et al., Chem. Rev., 101, 3689 (2001), JP-A-8-41117, JP-A-9-208616, JP-A-2000-264914, JP-A-2001-316410, JP No. 2002-80523, JP-A No. 2004-307872, etc. Examples of the initiator to be used include organic halogen compounds, nonogeny sulfonyl compounds, and in particular, the _α- position of a carbon-carbon double bond or a carbon-oxygen double bond. As the initiator structure, a structure in which a carbon-halogen bond existing in or a plurality of halogens on one carbon atom is attached is suitable.

[0044] The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a metal complex having a central metal of a Group 7, 8, 9, 10, or 11 element of the periodic table. is there. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, copper and iron complexes are preferred. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. It is. In the case of using a copper compound, 2, 2′-bibilidyl or a derivative thereof, 1, 10-phenanthoxylin or a derivative thereof, or tetramethylethylenediamine, pentamethyljetylenetriamine or hexane is used to increase the catalytic activity. Polyamines such as methyltris (2-aminoethyl) amine are added as ligands. A tristriphenyl-phosphine complex of divalent ruthenium chloride (RuCl (PPh)) is also suitable as a catalyst. When using ruthenium compounds as catalysts

2 3 3

In this case, aluminum alkoxides are added as activators. In addition, divalent iron piston phosphine phosphine complex (FeCl (PPh)), divalent nickel bistriphenyl phosphite.

2 3 2

Complex (NiCl (PPh)) and divalent nickel bistributylphosphine complex (NiBr

2 3 2

(PBu)) is also suitable as a catalyst.

2 3 2

[0045] In the production method of the present invention, the polymerization method is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk 'suspension polymerization, and the like can be applied. As the solvent that can be used in the radical polymerization of the present invention, any solvent that does not inhibit the reaction can be used. For example, as specific examples, aromatics such as benzene, toluene, and xylene are used. Hydrocarbon solvents, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorine mouth, dichlorobenzene, trichloroethane port benzene, methylene chloride, black hole Holm, four chlorinated hydrocarbon solvents such as carbon tetrachloride and tetrachlorethylene E Chile down, methanol, ethanol, _n _ propanol. —Alcohol solvents such as propanol, n-butanol, sec-butanol and tert-butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; acetic acid Examples thereof include ester solvents such as ethyl and dimethyl phthalate, and ether solvents such as dimethyl ether, jetyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole. Further, suspension polymerization and emulsion polymerization can be carried out using water as a solvent. These solvents may be used alone or in combination of two or more. Moreover, it is preferable that the reaction solution becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

[0046] The reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and it is not uniform depending on the degree of polymerization of the desired polymer, the type and amount of the radical polymerization initiator and the solvent to be used. 100 ° C to 250 ° C. Preferably, it is −50 ° C. to 180 ° C., more preferably 0 ° C. to 160 ° C. In some cases, the reaction can be carried out under reduced pressure, normal pressure or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

[0047] In the radical polymerization used in the present invention, examples of the solvent that can be used include aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, benzene, and toluene. Aetherole solvents such as aromatic hydrocarbons, jetyl ether, dioxane, tetrahydrofuran (THF), monoglyme and diglyme are used. These solvents can be used alone or in combination of two or more. Of these, aromatic hydrocarbons and ether solvents are preferably used. The polymerization is usually 100 ° C to 100 ° C, preferably 80 ° C to 80 ° C, more preferably — at a polymerization temperature of 70 ° C to 70 ° C, for 1 minute to 500 hours, preferably 10 minutes to 300 It is carried out over a period of time, more preferably 15 minutes to 150 hours.

[0048] In addition, (Method 1) can also produce the block or graft polymer which is the polyolefin according to the present invention by sequentially performing the following steps (4) and (5). .

(4) A process for producing halogen-modified polyolefin by reaction of polyolefin with a halogenating agent.

(5) A step of polymerizing monomers constituting the stimulus-responsive polymer chain in the presence of the halogen-modified polyolefin obtained in the above step to give the stimulus-responsive polymer chain to the polyolefin chain. [0049] Step (4) is a step of producing a halogen-modified polyolefin by reaction of polyolefin with a halogenating agent.

[0050] Examples of the polyolefin used in this step include those represented by the following (A1) to (A5).

(Al) CH = CH-C H (where x is 0 or a positive integer)

2 2χ + 1

Homopolymer or copolymer.

(A2) an α-olefin compound represented by CH = CH-C H (x is 0 or a positive integer) and

2 2χ + 1

A copolymer with a monoolefin-containing compound having an aromatic ring.

(A3) an α-olefin compound represented by CH = CH-C H (x is 0 or a positive integer) and

2 2χ + 1

A copolymer with a cyclic monoolefin compound represented by the following general formula (1).

(A4) an α-olefin compound represented by CH = CH-C H (x is 0 or a positive integer) and

2 2χ + 1

Random copolymers with unsaturated carboxylic acids or their derivatives.

(Α5) A polyolefin obtained by modifying the polymer represented by (A1) to (Α4) with an unsaturated carboxylic acid or a derivative thereof.

[0051] [Chemical 1]

(In the formula (1), η is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ¹ to 1 ^ and R ^a and R ^b are independently (A group force consisting of a hydrogen atom, a halogen atom and a hydrocarbon group also represents an atom or group selected, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring.)

The halogen-modified polyolefin produced in this step (4) is a polyolefin as described above. And a halogenating agent. Halogen content of the thus modification by halogen polio Refuin obtained is from 0.01 to 70 weight ^_0/0, preferably from 0.02 to 50 weight ^_0/0, preferably a further 0.05 to 30 wt% It is. In the present invention, such halogen is selected from fluorine, chlorine, bromine or iodine, and may be a combination thereof.

[0053] The halogenating agent used in this step (4) is not particularly limited as long as it can produce a halogen-modified polyolefin by halogenating the above-mentioned polyolefin. Specifically, chlorine, bromine, iodine Phosphorus trichloride, Phosphorus tribromide, Phosphorus triiodide, Phosphorus pentachloride, Phosphorus pentabromide, Phosphorus pentaiodide, Chloride thiol, Sulfuryl chloride, Thiol bromide, N Chlorosuccinimide, N —Bromosuccinimide, N-bromocaprolatatam, N-bromophthalimide, 1,3 dib-mouthed Mo 5,5 Dimethylhydantoin, N-chloroglutarimide, N-bromoglutarimide, N, Ν '--Dib mouthed moisocyanuric acid, Ν Bromoacetamide, ブロ Bromocarbamic acid ester, Dioxanedibuguchimide, Phenoltrimethylammomutribu Mouthamide, Pyridihum hydrobromide Perpromide, pyrrolidone hydrotrib mouthamide, t-butyl hypochlorite, t-butyl hypobromite, copper (II) chloride, copper (II) bromide, salt iron (III), oxalyl chloride, IBr, etc. Is mentioned. Of these, chlorine, bromine, N-chlorosuccinimide, N bromosuccinimide, N bromocaprolatatam, N bromophthalanolimide, 1,3 dib-mouthed 5,5 dimethylhydantoin, N-chloroglutarimide, N Bromoglutarimide, N, Ν '—Dibu-mouthed moisocyanuric acid, more preferably bromine and Ν-bromosuccinimide, ブロモ bromocaprolatatam, Ν bromophthalimide, 1,3 dibromo-5,5-dimethylhydantoin It is a compound having a Br-Br bond such as bromoglutarimide, Ν, N'-dib mouth moisocyanuric acid.

[0054] The reaction between the polyolefin and the halogenating agent is preferably carried out in an inert gas atmosphere. Examples of the inert gas include inert gases such as nitrogen, anoregon, and helium. Moreover, a solvent can be used for reaction of this invention as needed. Any solvent can be used as long as it does not inhibit the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane, heptane, octane, Aliphatic hydrocarbon solvents such as nonane and decane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene Motokei solvent, black hole, dichlorobenzene, trichloroethane port benzene, methylene chloride, black hole Holm, Yonshioi匕炭arsenide and tetrachlorethylene, chlorinated hydrocarbon solvents such as tetrachloro E Tan, methanol, ethanol, _n _ propanol , _iso _ propanol, _n _ butanol one Le, alcohol solvents such as sec- butanol and tert- butanol, acetone, Mechirue ethyl ketone and ketone solvents such as methyl isobutyl ketone; ester solvents such as acetic Echiru and dimethylcarbamoyl Rufutareto, dimethyl ether And ether solvents such as jetyl ether, di-n-amyl ether, tetrahydrofuran and dioxy-sol. Preferably, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorine Examples thereof include chlorinated hydrocarbon solvents such as benzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, tetrachlorocarbon, tetrachloroethylene, and tetrachloroethane. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

In the reaction with the halogenating agent, a radical initiator may be added as necessary to accelerate the reaction. Radical initiators include, for example, azobisisoptyl-tolyl, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane hydrochloride, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride Azo initiators such as 4,4'-azobis-4-cyananovaleric acid, benzoyl peroxide, 2,4-dichloroperoxybenzoic acid, di-tert-butyl peroxide, lauroyl peroxide, acetylyl peroxide , Diisopropyl peroxide, tamen hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinan hydroperoxide, methyl ethyl ketone peroxide Xoxide, cyclohexanone peroxide, diisopropylperoxydicarbonate, tert-butyl Peroxide initiators such as oxylaurate, di-tert-butylperoxyphthalate, dibenzyloxide or 2,5-dimethylhexane-2,5-dihydroperoxide, or benzoyl peroxide Redox systems such as -Ν, Ν -dimethylaline or peroxodisulfuric acid-sodium hydrogen sulfite An initiator etc. are mentioned. Of these, azo initiators or peroxide initiators are preferable, and benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, acetyl acetyl peroxide, peroxides are more preferable. Diisopropyl dicarbonate, tamen hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, azobisisobutyoxy-tolyl, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitryl, dimethyl azobisisobutyrate It is. These radical initiators can be used alone or in combination of two or more at the same time.

[0056] As the method of reacting the polyolefin and the halogenating agent, various conventionally known methods can be employed. For example, polyolefin is suspended or dissolved in a solvent, usually at a temperature of 80 ° C to 250 ° C, preferably at a temperature not lower than room temperature and not higher than the boiling point of the solvent. A method in which an initiator is added and mixed, or the polyolefin is melted and kneaded at a temperature not lower than its melting point, for example, 180 to 300 ° C, with a rogenizing agent and, if necessary, a radical initiator. The method of making it contact is mentioned.

[0057] A halogen-modified polyolefin is produced by the above method.

[0058] Step (5) is a step of polymerizing the monomer constituting the stimulus-responsive polymer chain in the presence of the halogen-modified polyolefin obtained in the above step to give the stimulus-responsive polymer chain to the polyolefin chain.

[0059] In this step (5), there is no particular limitation on the method for polymerizing the monomer constituting the stimulus-responsive polymer chain in the presence of the neuron-modified polyolefin obtained in the above step. The atom transfer radical polymerization method exemplified in the above step (3) is preferably used. In the halogen-modified polyolefins of this kind, it is possible to use a carbon halogen bond existing at the _α- position of a carbon-carbon double bond or a structure in which multiple halogens are added on one carbon atom as an initiator structure. it can.

(Method 2) is a method in which a functional group-containing polyolefin is used as a macromonomer and copolymerized with the monomer constituting the stimulus-responsive polymer chain. In this method, the functional group-containing polyolefin used in this method has a carbon-carbon double bond such as a polymerizable functional group at the end of the molecular chain or in the molecular chain, for example, a (meth) atalyloyl group or a styryl group. Examples include polyolefins into which groups have been introduced. Specific examples include, for example, JP-A-2004-143403. The structure and the manufacturing method disclosed in Japanese Patent Laid-Open No. 2004-269642 can be exemplified. By copolymerizing such a group-introduced polyolefin and the monomer constituting the stimulus-responsive polymer chain, a graft polymer in which the polyolefin chain and the stimulus-responsive polymer chain are chemically bonded can be produced. . As a method for copolymerizing the functional group-containing polyolefin and the monomer constituting the stimulus-responsive polymer chain, for example, a known polymerization method such as radical polymerization, ion polymerization, or coordination polymerization can be used.

[0060] In the radical polymerization, any initiator used in ordinary radical polymerization can be used as the initiator, such as azobisisobutyoxy-tolyl, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbox. Nitril, azobis 2 amidinopropane hydrochloride, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride or 4,4'-azobis-4 cyanovaleric acid, azo initiators, benzoyl peroxide, 2, 4 dichloro Benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, tamen hydroperoxide, t ert-butyl hydroperoxide, dicumyl peroxide, p- Menthane hydroperoxide, pinane hydroperoxide, methylethyl Tonperoxide, cyclohexanone peroxide, diisopropylperoxydicarbonate, tert-butylperoxylaurate, di-tert-butylperoxyphthalate, dibenzyloxide or 2,5-dimethylhexane 2,5-dihydroperoxide Examples thereof include peroxyacid-based initiators such as xoxide, or redox-based initiators such as peroxybenzoic acid N, N dimethylaline or peroxodisulfuric acid sodium hydrogen sulfite.

Of these, azo initiators or peroxyacid initiators are preferred, and more preferred are azobisisobutyronitrile, azobis 2,4 dimethylvaleronitrile, azobiscyclohexanecarbo-tolyl. Dimethyl azobisisobutyrate, benzoyl peroxide, benzoyl 2,4 dichloroperoxide, di-tert-butyl peroxide, lauroyl peroxide, disodium peroxide pyrrole dicarbonate or peroxyacetyl peroxide. These radical polymerization initiators can be used alone or in combination of two or more thereof simultaneously or sequentially.

[0062] Any solvent that does not inhibit the reaction may be used. For example, specific examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane, cyclohexane, and methylcyclohexane. Cycloaliphatic hydrocarbon solvents such as xanthane and decahydronaphthalene, chlorine such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, tetrachlorocarbon and tetrachloroethylene Hydrocarbon solvents, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Esters such as ethyl acetate and dimethyl phthalate And ether-based solvents such as sole, etc. - solvent, dimethyl ether, Jefferies chill ether, di -n- Amirueteru, tetrahydrofuran and Jiokishia. In addition, suspension polymerization or emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in combination of two or more. In addition, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but it may be a heterogeneous plural phase.

[0063] The reaction temperature may be any temperature as long as the polymerization reaction proceeds, and is not uniform depending on the degree of polymerization of the desired polymer and the type and amount of the radical polymerization initiator and solvent used. 100 ° C to 250 ° C. Preferably, it is −50 ° C. to 180 ° C., more preferably 0 ° C. to 160 ° C. In some cases, the reaction can be carried out under reduced pressure, normal pressure or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

[0064] In addition to the above-described method using a radical polymerization initiator, for example, a living radical polymerization method described in the following literature can be used as the radical polymerization.

1) Chem. Rev., 101 2921 (2001)

2) Chem. Rev., 101 3689 (2001)

3) Chem. Rev., 101 3661 (2001)

In the cation polymerization, any of the initiators used in the usual cation polymerization can be used as the cation polymerization initiator, for example, butyl lithium, propylene. Organic lithium compounds such as rulithium, ethyllithium, and methyllithium, Grignard reagents, and the like can be used.

Examples of the solvent that can be used include aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, jetyl ether, dioxane, Ether solvents such as tetrahydrofuran (THF), monoglyme and diglyme are used. These solvents can be used alone or in combination of two or more. Of these, aromatic hydrocarbons and ether solvents are preferably used. The polymerization is usually −100 ° C. to 100 ° C., preferably 80 ° C. to 80 ° C., more preferably —70 ° C. to 70 ° C. for 1 minute to 500 hours, preferably 10 minutes to It is carried out for 300 hours, more preferably 15 minutes to 150 hours.

(Method 3) is a method of coupling a functional group-containing polyolefin chain and a stimulus-responsive polymer chain. As functional group-containing polyolefin used in this method, reactive groups such as hydroxyl group amino group, carboxyl group, acid halogen group, acid anhydride group, epoxy group, isocyanate group are introduced at the end of the molecular chain or in the molecular chain. Polyolefins. The stimuli-responsive polymer chain to be coupled with the polyolefin having such a reactive group must have a functional group capable of reacting with these reactive groups at the end of the molecular chain or in the molecular chain. is there. By reacting polymer chains having these reactive groups, a block or graft polymer in which a polyolefin chain and a stimulus-responsive polymer chain are chemically bonded can be produced.

In (Method 3), the block or graft polymer which is the polyolefin according to the present invention can be produced by sequentially performing the following steps (6) to (8).

Step (6) Polyolefin having functional group (A) selected from hydroxyl group, amino group, epoxy group, carboxyl group, acid halogen group, acid anhydride group and isocyanate group at the main chain end and Z or side chain Manufacturing process.

Step (7) A step of producing a stimulus-responsive polymer chain having a functional group at the terminal.

Step (8) Polyolefin having the functional group (A) produced in the step (6), and the step (8)

A step of binding the stimulus-responsive polymer chain having a functional group at the terminal produced in 7). [0066]

Hereinafter, the method for producing the block or graft polymer of the present invention will be described in detail for each step.

[0067] In step (6), for example, the same method as in step (1) can be used.

[0068] Step (7) is a step of producing a stimulus-responsive polymer chain having a functional group at the terminal.

As a method for producing such a polymer chain, for example, the functional group (P) capable of chemically bonding with the functional group (A) contained in the polyolefin used in the step (2) and radical polymerization initiating ability are used. It is produced by polymerizing a monomer constituting a stimulus-responsive polymer chain using a compound (R) having both of the group (Q) having a diol as an initiator. The stimulation-responsive polymer chain obtained in this step has a functional group (P) derived from an initiator at its end.

[0069] In the step (8), the main chain terminal and Z or side chain obtained in the step (6) have a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, an acid anhydride group, and an isocyanate group. This is a step of performing a coupling reaction between the polyolefin having the selected functional group (A) and the stimulus-responsive polymer chain having a functional group at the terminal obtained in the step (7). A preferred combination of the functional group (A) contained in the polyolefin and the terminal functional group (P) contained in the stimulus-responsive polymer chain when performing this step is described in the step (2). A combination similar to the combination of is mentioned.

[0070] Polyolefin having a functional group (A) having a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, an acid anhydride group, and an isocyanate group at the main chain terminal and Z or side chain, and a terminal. The reaction conditions for the reaction with the stimulus-responsive polymer chain having a functional group are the same as the conditions described in the above step (2), such as the solvent, the reaction temperature, the reaction time, the condensing agent and the basic catalyst used Conditions can be applied.

Hereinafter, the power for further specifically explaining the present invention based on examples, the present invention is not limited to these examples.

Example 1

[0072] [Synthesis of terminal aryl alcohol-modified PE]

To a 1 L glass polymerization vessel purged with nitrogen, 900 mL of toluene was added, and 6.6 ml (48 mmol) of triethyl aluminum and 2.72 ml (40 mmol) of aryl alcohol were added. 5 minutes at C Stir. Into another nitrogen-substituted 20 mL Schlenk flask, 17.6 mg of methacene represented by the following formula (I) is added, and 1.12 ml of a toluene solution of methylalumoxane (MAO) (Al = l.28M) is added, After stirring for about 10 seconds, the solution was added to the polymerization solution. At the same time, ethylene gas was passed at 3 L / h and stirred at 50 ° C for 105 minutes. The reaction was stopped with isobutyl alcohol (30 ml) and concentrated hydrochloric acid (6 ml), and poured into 2 L of methanol to precipitate the polymer. After stirring overnight, the mixture was filtered through a glass filter, and the obtained polymer was dried under reduced pressure conditions of 50 ° C. and lOTorr for 10 hours to obtain 8.63 g of terminal aryl alcohol-modified PE. As a result of analysis by gel permeation chromatography (GPC), the polymer had a weight average molecular weight (Mw) of 26500 and a molecular weight distribution (MwZMn) of 2.26. From the result of iH-NMR measurement, a peak of terminal hydroxymethylene (—CH 2 —OH) derived from introduction of allylic alcohol was observed at δ = 3.3-3.4 ppm.

2

[0073] [Chemical 2]

[0074] [Synthesis of 2-bromoisobutyryl group-modified PE]

Terminal aryl alcohol-modified PE (Mw = 26500, Mw / Mn = 2. 26) 5.6 g was placed in a 500 mL 2-neck eggplant flask purged with nitrogen and purged with 200 ml of dry toluene, 0.55 ml of triethylamine, 2-bromo 0.999 ml of isobutyryl bromide was added thereto, the temperature was raised to 80 ° C., and the mixture was heated and stirred for 3 hours. The reaction solution was poured into 2 L of methanol, and the precipitated polymer was filtered with a glass filter. At this time, the polymer on the glass filter was sequentially washed three times with 100 ml of methanol, once with 100 ml of 1N hydrochloric acid, and twice with 100 ml of methanol. The polymer was dried for 10 hours under reduced pressure at 50 ° C. and 10 Torr. NMR results show that terminal methylene (-CH-OCOCBr (CH)) at δ = 3.8-4.1 ppm and terminal methyl (-CH-OCO at δ = 1.8 ppm

2 3 2 2

CBr (CH;)) group is observed and the raw material hydroxymethylene peak is not observed.

3 2

A 2-bromoisobutyryl group-modified PE with all hydroxyl groups modified was obtained. Identified.

[Synthesis of PE-b-poly (N-isopropylacrylamide) block polymer]

In a 100 ml Schlenk flask purged with nitrogen, 6.9 g of 2 bromoisobutyryl group-modified PE was added, and deaeration with a vacuum pump and nitrogen substitution were repeated 5 times. RuCl (under nitrogen flow

2

PPh) 96mg, o Xylene 10ml, Aluminum isopropoxide 82mg, N-Isopro

3 3

Pyracrylamide (NIPAAm) 9. lg was sequentially added and a septum cap was attached. The temperature was raised to 120 ° C., and the mixture was reacted for 9 hours with stirring. After cooling the reaction Schlenk flask with ice water, about 5 ml of methanol was used to stop the reaction, and the mixture was poured into 600 ml of acetone and stirred. The precipitated polymer was separated by filtration with a glass filter, and the polymer was vacuum-dried at 120 ° C for 10 hours to obtain 9.7 g of polymer. From the NMR measurement, PE-b-PNIPAAm block polymer of PE / PNIPAAm = 69Z31 (wt%) was obtained. The polymer could be molded into a sheet. In addition, the sheet shape was maintained even after being immersed in water at room temperature for 3.5 days.

Example 2

[Synthesis of propylene Zl 1 undecene 1-ol copolymer]

800 ml of toluene was introduced into a 1 L glass polymerization vessel equipped with a stirrer and sufficiently purged with nitrogen, and the temperature was maintained at 60 ° C. while propylene gas (lOOLZh) was supplied. After adding 22 mmol of triisobutylaluminum and 44 mmol of 11 undecene-1ol and stirring for 10 minutes, dimethylsilylbis (2-methyl-4-phenylindulyl) zirconium dichloride activated with 1.5 mmol of MAO was added to 0.003 mmol. In addition to the polymerization vessel, the polymerization was carried out for 15 minutes while maintaining the temperature at 60 ° C. Methanol was introduced into the polymerization vessel to terminate the polymerization, and the polymerization solution was poured into 2 L of hydrochloric acid-containing methanol, and the polymer was recovered by filtration. The polymer was vacuum-dried at 80 ° C. for 10 hours, and the obtained polymer was 17.4 g. The intrinsic viscosity ([7?]) Of the obtained polymer was 1.12. From the NMR measurement, the OH group content in the polymer was 2.34 mol%.

[2 Synthesis of PP modified with bromoisobutyryl group]

7.0 g of the propylene Z11-undecene-1-ol copolymer obtained above was put into a 500 mL glass reactor deaerated and purged with nitrogen, 250 ml of dry toluene, 7.6 ml and 2 bromoisobutyryl bromide 6.3 ml were added, heated to 80 ° C. and stirred for 3 hours. The reaction solution was poured into 2 L of methanol and the precipitated polymer was filtered through a glass filter. The obtained polymer was vacuum-dried at 80 ° C. for 10 hours to obtain 7.6 g of a powdery polymer. NMR results show that δ = 3.8-4.1 ppm at terminal methylene (-CH-OCOC

2

Br (CH)) is observed to have a terminal methyl (-CH -OCOCBr (CH)) group at δ = 1.8 ppm.

3 2 2 3 2

Since no hydroxymethylene peak of the sample was observed, it was identified that a polymer with all hydroxyl groups modified was obtained.

[Synthesis of PP-g-PNIPAAm graft polymer]

Into a 100 ml Schlenk flask purged with degassed nitrogen, 3.9 g of the 2-bromoisobutyryl group-modified propylene Z11-undecene 1-ol copolymer obtained above was added, and degassed with a vacuum pump and nitrogen purged 5 times. . RuCl (PPh) 959mg, o under nitrogen flow

2 3 3

—100 ml of xylene, 820 mg of aluminum isopropoxide, and 45 g of NIPAAm were sequentially added, and a septum cap was attached. The temperature was raised to 120 ° C, and the mixture was reacted for 3 hours with stirring. After the reaction Schlenk flask was cooled with ice water, about 5 ml of methanol was quenched and poured into 1 L of acetone and stirred overnight. The precipitated polymer was filtered off with a glass filter, and the polymer was vacuum-dried at 120 ° C. for 10 hours to obtain 27.4 g of polymer. A PP-g-PNIPAAm graph polymer of PPZPNIPAAm = 18Z82 (wt%) was obtained from ¾-NMR measurement. The polymer was moldable and could be a sheet. In addition, the sheet shape was maintained even after being immersed in water at room temperature for 3.5 days.

Industrial applicability

The polymer material comprising the block or graft copolymer of the present invention as a main component has affinity with biological components such as proteins, polysaccharides, lipids, and cell components, and drugs, and thus stimulates. Since it has a stimulus-responsive polymer chain that changes its affinity for liquid when applied, it is possible to control the adsorption and release of these substrates according to each stimulus. And can be used as a control release material. In addition, the actuator is suitable as a chemical valve or the like because it shows a volume change with respect to each stimulus. Shishikushi also has a polyolefin chain, so it can be used for various applications as a structural material having both stimulus response and self-holding properties.

Claims

The scope of the claims

[1] A block or graft copolymer composed of a polyolefin chain and a stimulus-responsive polymer chain whose affinity to a liquid changes upon application of a stimulus, wherein the polyolefin chain and the stimulus-responsive polymer chain A polymer characterized by being chemically bonded.

[2] The polyolefin chain is CH = CH—R (where R is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms.

2

2. The polymer according to claim 1, which is a polymer chain obtained by polymerizing at least one kind of a-olefin represented by (hydrogen group).

[3] Stimulus-responsive polymer chain strength Poly-N-alkyl-substituted (meth) acrylamides such as poly (meth) acrylamide, poly-N-isopropyl (meth) acrylamide, poly (meth) acrylic acid or metal salts thereof , Poly-2-hydroxyethyl (meth) acrylate, polybutylbenzene sulfonic acid or its metal salt, poly (ethylene glycol monomethacrylate), poly (ethylene glycol monoacrylate) group forces that can be selected at least 1 The polymer according to claim 1 or 2, wherein the polymer chain is of a kind.