JPWO2007007675A1 - Polyolefins with stimuli-responsive polymer chains - Google Patents

Abstract

A material that has a polymer chain with stimuli responsiveness and combines excellent physical properties and processability of polyolefin by using a block or graft polymer in which a polymer chain having stimuli responsiveness and a polyolefin chain are directly bonded by chemical bonding To provide. 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, and the polyolefin chain and the stimulus-responsive polymer chain are chemically bonded The polymer characterized by being made.

Description

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.

  So far, many polymers have been known as polymer materials whose affinity for liquid reversibly changes with the application of stimuli, so-called stimuli-responsive polymers, such as heat, light, pH, ionic strength. Adsorption of substances, change of solvent composition, application of electric current or electric field, etc. are used.

  Examples of temperature responsiveness include poly (N-isopropylacrylamide) and other acrylamide polymers, polyvinyl methyl ether, polymethacrylic acid, and examples of pH responsiveness include polyacrylic acid / PVA blends. It has been known to be used for actuators including artificial muscles, materials for energy conversion, controlled release of drugs, and cell culture.

  Such stimulus response is basically caused by repeated absorption of the liquid into the polymer material and elimination of the liquid from the polymer material.

  However, these stimuli-responsive polymers have high solubility in liquids and as such are poor in self-holding properties. Therefore, it is common to partially crosslink the molecular chain and use it as a gel.

  Polyolefins, on the other hand, have been used in various applications as structural materials because of their excellent physical properties and processability, but because they do not have functional groups, printability, paintability, adhesiveness, heat resistance, and impact resistance. It was difficult to impart high functionality such as hydrophilicity and stimulus responsiveness.

  In order to produce a material that has both the stimulus responsiveness of the stimulus responsive polymer and the excellent physical properties and processability of polyolefin, it is thought that the purpose can be basically achieved if each material is simply blended. In practice, many polymers are incompatible with each other and therefore usually do not mix with each other, and since they are not compatible with each other, it is difficult to produce a uniform molded product. In addition, even if molding is possible, each polymer is phase-separated, so the interaction between the polymers is weak, and when handling the molded body in a liquid, the affinity to the liquid is high and the stimulus response There is a disadvantage that only the polymer segment flows 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 bonding.

  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 excellent physical properties of polyolefin. It is to provide materials that have both workability and processability.

(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 are chemically A polymer characterized in that it is bonded together.
(2) Polymer obtained by polymerizing at least one α-olefin in which the polyolefin chain is represented by CH ₂ ═CH—R (R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). The polymer according to (1), which is a chain.
(3) The stimuli-responsive polymer chain is a poly-N-alkyl-substituted (meth) acrylamide such as poly (meth) acrylamide, poly-N-isopropyl (meth) acrylamide, poly (meth) acrylic acid or a metal salt thereof, poly It is at least one polymer chain selected from the group consisting of 2-hydroxyethyl (meth) acrylate, polyvinylbenzenesulfonic acid or its metal salt, poly (ethylene glycol monomethacrylate), and poly (ethylene glycol monoacrylate). The polymer as described in (1) or (2) characterized by these.

  The 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, having a polymer chain exhibiting stimulus-responsiveness, and a structural material It is possible to provide a polymer material excellent in self-holding property, which has both excellent physical properties and processability of polyolefin as a material.

  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.

  The stimuli-responsive polymer having the property of changing the affinity for the liquid used in the present invention includes the pH value, ionic strength, chemical adsorption / desorption, addition of solvent, heat, light of the liquid used. It is preferable that the affinity can be changed by applying an electric current or an electric field, and a state in which the affinity is incompatible with the liquid to be used can be easily formed. 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.

  In the present invention, the change in the absorbability of a liquid due to the application of a stimulus is defined as a change between a state in which the liquid is absorbed into the polymer compound by the application of a stimulus and a state in which the liquid is released from the polymer compound. be able to. These changes in the state can be distinguished by the state in which the polymer compound has swollen by absorbing the liquid and the state in which the liquid has shrunk by releasing the liquid. Specifically, a space such as length, area or volume can be distinguished. It can be observed as a change in quantity. Further, the change in solubility in a liquid due to the application of a stimulus in the present invention is a one-phase state in which a polymer compound is dissolved in a 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 the inhomogeneous two-phase state in which the liquid is insolubilized in the liquid. These changes in state can be distinguished by an optically almost transparent state and an opaque light scattering state. Among these states, in the state in which the polymer compound has contracted by releasing the liquid and the inhomogeneous state insolubilized in the liquid, even in the solid state in which the liquid is almost excluded from the polymer compound, A semi-solid state containing a liquid may be used.

  The stimuli-responsive polymer having the above 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 ( Poly (N-alkyl-substituted) (meth) acrylamides such as (meth) acrylamide and poly-N-isopropyl (meth) acrylamide, polyvinyl alkyl ethers such as N-vinylisobutyramide and polyvinyl methyl ether, poly (oxyethyleneoxyvinyl ether), poly ( (Meth) acrylic acid or a metal salt thereof, poly-2-hydroxyethyl (meth) acrylate, poly-N- (meth) acrylic piperidine, poly (2-ethyloxazoline), polyvinyl alcohol or a partially saponified product thereof, polyethylene oxide, poly Ethylene oxide and polypro Copolymers with lenoxide, poly (ethylene glycol monomethacrylate), poly (ethylene glycol monoacrylate), substituted cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc. or a polymer compound thereof as a main component And a copolymer.

  Poly (meth) acrylic is one that changes its affinity for liquids due to changes in pH value or ionic strength due to electrode reactions based on the adsorption / desorption of chemical substances, changes in solvent composition, application of electric current and electric field, and ionic strength. It can be obtained by using as a main component an acid or a metal salt thereof, polyvinyl sulfonic acid, polyvinyl benzene sulfonic acid, poly (meth) acrylamide alkyl sulfonic acid, polymaleic acid or a metal salt thereof, or a monomer component constituting these polymer compounds. Copolymers, polyvinyl alcohol-polyacrylic acid composites or metal salts thereof, poly (ethylene glycol monomethacrylate), metal salts of carboxymethyl cellulose, metal salts of carboxyethyl cellulose, etc., or a polymer compound thereof. A copolymer is mentioned.

  In the adsorption / desorption system of the above chemical substances, various surfactants, amines, quaternary amine salt derivatives, acids, acid chloride derivatives and other ionic low molecular compounds are added to the above-described polymer compounds, By applying an electric field or current to control adsorption / desorption to / from the polymer compound, the affinity of the polymer compound can be changed. When the affinity is changed depending on the pH value, for example, poly (meth) acrylate is insolubilized at a pH of 2 or lower and dissolved 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.

  Examples of the compound whose affinity changes by the application of light include a polymer compound having a group such as a photochromic group whose structure changes by a photoreaction, and specifically, a triphenylmethane derivative that is ion-cleavable by light. , Poly (meth) acrylamides having groups such as spiropyran derivatives and spirooxazine derivatives, poly-N-alkyl-substituted (meth) acrylamides such as poly-N-isopropyl (meth) acrylamide, N-vinylisobutyramide, polyvinyl methyl ether Various types such as polyvinyl alkyl ether type such as poly (oxyethylene oxy vinyl ether) type and the like. The change in affinity due to light is, for example, that the above-mentioned triphenylmethane derivative undergoes a cleavage reaction when irradiated with ultraviolet rays having a wavelength of about 350 nm, and the solubility in water is improved. Irradiation causes the opposite reaction and decreases the solubility in water. The wavelength of the irradiation light when applying light is preferably in the range of 250 to 830 nm.

  A substance whose affinity is changed by an oxidation / reduction reaction by electricity is a CT complex (charge transfer complex) of a cationic polymer compound and an electron accepting compound. Specifically, amino such as dimethylaminopropylacrylamide is used. Substituted (meth) acrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate and other (meth) acrylic acid amino-substituted alkyl esters, polystyrene derivatives, polyvinylpyridine derivatives, polyvinylcarbazole derivatives, polydimethylaminostyrene, etc., and benzoquinone , 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoethylene, chloranil, trinitrobenzene, maleic anhydride, iodine and other electron accepting compounds It is. For this change in affinity due to the oxidation / reduction reaction by the application of electric current or the adsorption / desorption of a chemical substance by the application of an electric field, it is preferable to apply a voltage of about 1 to 200 V to the electrode.

  Examples of the liquid used in the polyolefin having the stimulus-responsive polymer chain of the present invention include water, aqueous electrolyte solution, alcohols such as methanol, ethanol, propanol, and butanol, ketone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, Examples include propylene carbonate, other aromatic organic solvents, aliphatic organic solvents, and mixtures thereof. In addition, the liquid includes surfactants and response accelerators that can be used to control stimulus response characteristics, viologen derivatives to promote pH change of the solution, acids, alkalis, salts, dispersion stabilizers, antioxidants, or A stabilizer such as an ultraviolet absorber may be added.

  In the present invention, as a preferable combination of the stimulus-responsive polymer and the liquid contained in the polyolefin having the stimulus-responsive polymer chain, poly N-isopropyl (meth) acrylamide or N-isopropyl (meth) acrylamide is a main component. A copolymer and water or a solution containing water as a main component, a polyvinyl methyl ether or a copolymer containing vinyl methyl ether as a main component, and a solution consisting of water or a solution containing water as a main component, 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) acrylamide or the like Each of the complexes of a copolymer mainly composed of ketone, dimethylformamide, dimethylacetamide, dimethyl Le sulfoxide, acetonitrile, and those consisting of propylene carbonate or other aromatic organic solvents.

  Therefore, when the polyolefin having the stimuli-responsive polymer chain of the present invention is combined with the liquid and the appropriate stimulus described above is applied, the affinity of the polymer part having the stimulus-responsive property in the olefin to the liquid is changed. Is expected to do.

The polyolefin used in the present invention is obtained by polymerizing at least one α-olefin represented by CH ₂ ═CH—R (R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). A polymer is mentioned. Specific examples of such α-olefins include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl- Examples thereof include linear or branched α-olefins such as 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene. Among these exemplified olefins, it is preferable to use at least one olefin selected from ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

  Examples of the monomer constituting the stimulus-responsive polymer chain used in the present invention include (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, Examples include (meth) acrylic acid metal salts such as potassium (meth) acrylate, 2-hydroxyethyl (meth) acrylate, vinylbenzenesulfonic acid or metal salts thereof. Moreover, you may copolymerize with another vinyl monomer in the range which does not affect irritation | stimulation response ability. Specific examples include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, vinyl esters such as vinyl acetate and vinyl propionate, styrene, Acrylonitrile and the like can be used, and the content of the monomers used for the copolymerization in the stimulus-responsive polymer chain is preferably within 10 mol%.

  In the olefin polymer of the present invention, the proportion of the stimulus-responsive polymer chain is preferably in the range of 5 to 95% by weight of the whole polymer, more preferably 10 to 80% by weight, and still more preferably 10 to 70% by weight. It is. As a result, the olefin polymer of the present invention has both stimulus responsiveness and excellent physical properties and moldability as a polymer, and even if it has a stimulus responsive polymer chain having high solubility in liquid, Among them, the self-holding property as a polymer is not lost.

  The block or graft copolymer, which is an olefin 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) using a functional group-containing polyolefin as an initiator to polymerize the monomer constituting the stimulus-responsive polymer chain, or (Method 2) using a functional group-containing polyolefin as a macromonomer Examples include a method of copolymerizing with the monomer constituting the stimulus-responsive polymer chain, and (Method 3) a method of coupling the functional group-containing polyolefin chain and the stimulus-responsive polymer chain.

  (Method 2) and (Method 3) are known, but the method for producing the above-mentioned block or graft copolymer will be described in more detail below, particularly (Method 1).

  (Method 1) is a method of polymerizing a 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 group having radical polymerization initiating ability or anionic polymerization 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, so-called nitroxide mediated. A group having a terminal halogen atom, such as those used in the radical polymerization method or disclosed in Chem. Rev., 101, 2921 (2001) or Chem. Rev., 101, 3689 (2001), Those used in so-called atom transfer radical polymerization, which generate radicals by adding a ruthenium or copper chloride or a complex having a transition metal atom thereof, or a group having an azo group or a group having an oxygen-oxygen bond Can be combined, and a radical can be generated by thermal cleavage. Examples of the group having an anionic polymerization initiating ability include a group having an alkoxide of an alkali metal such as lithium or potassium. A block or graft polymer in which a polyolefin chain and a stimuli-responsive polymer chain are chemically bonded is produced by polymerizing monomers constituting the stimulus-responsive polymer chain in the presence of a polyolefin having such a group introduced. be able to.

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) A step of producing a polyolefin having 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 / or side chain. .
(2) A step of converting to a macroinitiator by imparting a radical polymerization initiating ability or anion polymerization initiating ability to the functional group-containing polyolefin obtained in the above step.
(3) A step of polymerizing a monomer constituting the stimulus-responsive polymer chain in the presence of the macroinitiator obtained in the step to give the polyolefin chain a stimulus-responsive polymer chain.

Step (1) produces a polyolefin having 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 / or side chain. It is a process to do.

  A polyolefin having 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 / or side chain produced in this step, For example, a group containing a carbon-carbon unsaturated bond or a group 13 element of the periodic table in a polyolefin having a group containing a carbon-carbon unsaturated bond or a group 13 element of the periodic table at the main chain terminal and / or side chain It is manufactured by converting.

  The polyolefin having a carbon-carbon unsaturated bond at the main chain end and / or side chain used in this step has, for example, 2 to 20 carbon atoms in the presence of a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. A method of polymerizing or copolymerizing α-olefin, having a plurality of carbon-carbon unsaturated bonds in the molecule such as α-olefin and butadiene, 1,5-hexadiene, 1,7-octadiene, 5-vinyl-2-norbornene, etc. It can be produced by a method of copolymerizing with a compound. Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, -Octene and the like are preferably used. It can also be produced by thermally decomposing polyolefin.

  The polyolefin having a group containing a group 13 element of the periodic table at the main chain terminal and / or side chain used in this step is, for example, the above-mentioned by a known polymerization catalyst in the presence of a compound containing a group 13 element of the periodic table. A method of (co) polymerizing α-olefin, a method of copolymerizing the α-olefin and the group 13 element-containing olefin compound of the periodic table, a polyolefin having a carbon-carbon unsaturated bond at the terminal and / or side chain Can be produced by a method of reacting a compound containing a Group 13 element of the periodic table such as diisobutylaluminum hydride and 9-BBN.

  A polyolefin having a group containing a carbon-carbon unsaturated bond or a group 13 element of the periodic table at the main chain terminal and / or side chain is converted into a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, an acid anhydride group, As a method for converting to a polyolefin having a functional group (A) selected from an isocyanate group, for example, an epoxy group is contained by a reaction between a carbon-carbon unsaturated bond in the polyolefin and an organic peroxide such as m-chloroperbenzoic acid. Polyolefin method, α-aminomethylphosphonic acid, tungstic acid and phase transfer catalyst in the presence of a carbon-carbon unsaturated bond in polyolefin and reaction with hydrogen peroxide to form epoxy group-containing polyolefin, period in polyolefin The hydroxyl group is contained by the reaction of the group containing group 13 element with oxygen or hydrogen peroxide. How to polyolefins, such as methods of an amino group-containing polyolefin and the like by hydrolysis is reacted with an azide compound of the group containing a Group 13 element in the polyolefin 1 like Buchiruajido. Moreover, the method of converting the polyolefin which has a 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, and a method of reacting an epoxy group-containing polyolefin with an amine compound such as ethylenediamine and ethanolamine to obtain an amino group-containing polyolefin.

  Further, a polyolefin having 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 / or side chain produced in this step Can also be produced by copolymerizing the α-olefin and an olefin having a functional group using a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Examples of olefins having a functional group used for copolymerization include allyl alcohol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 8-nonen-1-ol, 10 -Unsaturated alcohols in which the hydrocarbon moiety is linear, such as undecen-1-ol, unsaturated compounds such as 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid In the exemplification of unsaturated amines such as carboxylic acids, allylamine, 5-hexeneamine, 6-hepteneamine, (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride and compounds in the above unsaturated carboxylic acids , Unsaturated acid anhydrides such as compounds in which a carboxylic acid group is replaced with a carboxylic acid anhydride group, and compounds of the above unsaturated carboxylic acids In the figure, unsaturated carboxylic acid halides such as compounds in which the carboxylic acid group is replaced with a carboxylic acid halide group, 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7- Unsaturated epoxy compounds such as epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy-1-undecene, 9-allyl-9 -Borabicyclo [3.3.1] nonane, 9-but-3-enyl-9-borabicyclo [3.3.1] nonane, 9-pent-4-enyl-9-borabicyclo [3.3.1] nonane 9-hex-5-enyl-9-borabicyclo [3.3.1] nonane, 9-hept-6-enyl-9-borabicyclo [3.3.1] nonane, 9-oct-7-e. Lu-9-borabicyclo [3.3.1] nonane, 9-non-8-enyl-9-borabicyclo [3.3.1] nonane, 9-dec-9-enyl-9-borabicyclo [3.3. 1] Unsaturated boron compounds such as nonane.

  In the step (2), a radical is added to the polyolefin having 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 / or side chain. It is a step of converting to a macroinitiator by providing a group having a polymerization initiating ability or an anionic polymerization initiating ability. Specifically, for example, the polyolefin having the functional group (A) at the main chain terminal and / or side chain produced in the step (1) can be chemically bonded to the functional group (A) contained in the polyolefin. A method of reacting a compound (R) having both a functional group (P) and a group (Q) having radical polymerization initiating ability, and a functional group (A) contained in the polyolefin produced in the step (1) The method etc. which convert to group (S) which has anion polymerization initiating ability are mentioned.

  Examples of the functional group (P) that can be chemically bonded to the functional group (A) contained in the polyolefin include a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, an acid anhydride group, and an isocyanate group. The 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, the functional group (P) is preferably an epoxy group, carboxyl group, acid halogen group, acid anhydride group, or isocyanate group. When the functional group (A) is an epoxy group, the functional group (P) is preferably a hydroxyl group, and the functional group (A). Is a carboxyl group or an acid halogen group, the functional group (P) is preferably a hydroxyl group or an amino group. When the functional group (A) is an amino group, the functional group (P) is a carboxyl group, an acid halogen group or an acid anhydride. Groups are preferred.

  Examples of the group (Q) having radical polymerization initiating ability include, for example, Trend Polym. Sci. , (1996), 4, 456, and those used in the so-called nitroxide-mediated radical polymerization method in which radicals are generated by bonding a group having a nitroxide and thermally cleaved, or Macromolecules, ( 1995), 28, 1721 and Science, (1996), 272, 866, and the like used in the so-called atom transfer radical polymerization method. Specifically, 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) group, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxy group, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy group, 3-amino-2,2,5,5-tetramethyl-1-pyrrolidinyloxy group, 2,2,5,5- A group having an N—O bond such as a tetramethyl-1-pyrrolidinyloxy group and a di-t-butylnitroxy group, and an unsaturated group selected from a carbonyl group, a cyano group, a sulfonyl group, and an aryl group In addition, a group having a structure in which these unsaturated groups are bonded to a halogen atom with one carbon atom interposed therebetween may be mentioned. Among these, 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) group or a group having a structure in which a carbonyl group is bonded to a chlorine atom or a bromine atom with one carbon atom in between. Is preferred.

  The reaction conditions of the polyolefin having the functional group (A) at the main chain terminal and / or the side chain and the compound (R) having both the functional group (P) and the group (Q) having radical polymerization initiating ability are: Generally, dehydrated organic solvents can be generally used, but preferably in a hydrocarbon-based organic solvent having a high affinity with polyolefins such as toluene, benzene, hexane, heptane, etc., in a temperature range of 0 ° C. to 120 ° C. Perform the reaction. The reaction may be either a homogeneous system or a heterogeneous system, but a homogeneous system is preferred. If the reaction is difficult to proceed, a Bronsted acid such as sulfuric acid, formic acid or paratoluenesulfonic 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 or molecular sieves or by removing water under reflux conditions using Dean Stark.

  Compound in reaction of polyolefin having functional group (A) at main chain terminal and / or side chain and compound (R) having both functional group (P) and group (Q) having radical polymerization initiating ability ( The addition amount of R) is usually 0.1 to 1000 times mol, preferably 1 to 500 times the functional group (A) present in the polyolefin having the functional group (A) containing an oxygen atom or a nitrogen atom. Double mole. The product obtained by the reaction is precipitated with methanol or acetone, filtered, and washed with a solvent in which the compound (R) is dissolved, whereby the unreacted compound (R) can be easily removed.

  Moreover, as a method for converting the functional group (A) contained in the polyolefin produced in the above step (1) into a group (S) having an anionic polymerization initiating ability, for example, an olefin polymer having a hydroxyl group is converted to metallic lithium. And alkali metal such as potassium metal, alkali metal hydride such as lithium hydride and potassium hydride, and alkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and trihexylaluminum. The method of using a metal alkoxide containing olefin polymer is mentioned.

  By the above method, the polyolefin having the functional group (A) at the main chain terminal and / or side chain can be converted into a macroinitiator.

  In step (3), the monomer constituting the stimulus-responsive polymer chain is polymerized in the presence of the macroinitiator obtained in step (2), and the product obtained in step (2) is stimulated. This is a step of imparting a responsive polymer chain (Z).

  Examples of the radical polymerization method used in the present invention include the aforementioned nitroxide-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, in which a radical polymerizable monomer is formed using a metal complex having an organic halide or a sulfonyl halide compound as an initiator and a transition metal as a central metal as a catalyst. This is a method of radical polymerization. Specifically, for example, Matyjaszewski et al., Chem. Rev., 101, 2921 (2001), WO96 / 30421, WO97 / 18247, WO98 / 01480, WO98 / 40415, WO00 / 15695. Or 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-A-2002-80523, JP-A-2004-307872, and the like can be mentioned. Examples of the initiator used include organic halides and sulfonyl halide compounds, and in particular, a carbon-halogen bond present at the α-position of a carbon-carbon double bond or a carbon-oxygen double bond, or a single carbon. A structure in which a plurality of halogen atoms are added on an atom is suitable as the initiator structure.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. 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. is there. When a copper compound is used, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, or tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltris (2-aminoethyl) amine is used to increase the catalytic activity. Polyamines such as are added as ligands. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  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, specific examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, pentane, and the like. , Aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform , Chlorinated hydrocarbon solvents such as carbon tetrachloride and tetrachloroethylene, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone, And ketone solvents such as methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole. . Further, suspension polymerization and emulsion polymerization can be performed 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 liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

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

  In the radical polymerization used in the present invention, usable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, Ether solvents such as diethyl ether, dioxane, tetrahydrofuran (THF), monoglyme and diglyme are used. These solvents can be used singly or in combination of two or more. Of these, aromatic hydrocarbons and ether solvents are preferably used. The polymerization is usually performed at a polymerization temperature of −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 300 hours, more preferably. Is carried out over 15 minutes to 150 hours.

Further, in (Method 1), the block or graft polymer which is the polyolefin according to the present invention can also be produced by sequentially performing the following steps (4) and (5).
(4) A step of producing a halogen-modified polyolefin by a reaction between a polyolefin and a halogenating agent.
(5) A step of polymerizing a monomer constituting the stimulus-responsive polymer chain in the presence of the halogen-modified polyolefin obtained in the above step to impart a stimulus-responsive polymer chain to the polyolefin chain.

  Step (4) is a step of producing a halogen-modified polyolefin by a reaction between a polyolefin and a halogenating agent.

As polyolefin used at this process, what is shown by the following (A1)-(A5) is mentioned, for example.
(A1) A homopolymer or copolymer of an α-olefin compound represented by CH ₂ = CH-C _x H _{2x + 1} (x is 0 or a positive integer).
(A2) A copolymer of an α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3) Copolymer of α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and cyclic monoolefin compound represented by the following general formula (1) .
(A4) A random copolymer of an α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and an unsaturated carboxylic acid or derivative thereof.
(A5) A polyolefin obtained by modifying the polymer represented by (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.

(In the formula (1), n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently, Represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, 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 produced by the reaction of the polyolefin and the halogenating agent as described above. The halogen content of the halogen-modified polyolefin thus obtained is 0.01 to 70% by weight, preferably 0.02 to 50% by weight, and more preferably 0.05 to 30% by weight. In the present invention, such a halogen is selected from fluorine, chlorine, bromine or iodine, and may be a combination thereof.

  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 polyolefin. Specifically, chlorine, bromine, iodine, phosphorus trichloride Phosphorus tribromide, phosphorus triiodide, phosphorus pentachloride, phosphorus pentabromide, phosphorus pentaiodide, thionyl chloride, sulfuryl chloride, thionyl bromide, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N-bromoglutarimide, N, N′-dibromoisocyanuric acid, N-bromoacetamide, N-bromocarbamic acid ester , Dioxane dibromide, phenyltrimethylammonium tribromide, pyridini Muhydrobromide perbromide, pyrrolidone hydrotribromide, t-butyl hypochlorite, t-butyl hypobromite, copper (II) chloride, copper (II) bromide, iron (III) chloride, oxalyl chloride, IBr Etc. Of these, chlorine, bromine, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N -Bromoglutarimide, N, N'-dibromoisocyanuric acid, more preferably bromine and N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, It is a compound having an N-Br bond such as N-bromoglutarimide and N, N′-dibromoisocyanuric acid.

  The reaction between the polyolefin and the halogenating agent is preferably performed in an inert gas atmosphere. Examples of the inert gas include inert gases such as nitrogen, argon, 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, as specific examples, aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane, heptane, octane, nonane and Aliphatic hydrocarbon solvents such as decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, tetrachloroethane Chlorinated hydrocarbon solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl isobutyl Ketone solvents such as tons; ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, diethyl ether, di -n- amyl ether, tetrahydrofuran and ether solvents such as dioxy anisole and the like. Preferably, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, Examples include chlorinated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene, and tetrachloroethane. These solvents may be used alone or in combination 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. Examples of the radical initiator include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane hydrochloride, dimethyl azobisisobutyrate, and azobisisobutylamidine hydrochloride. Or azo initiators such as 4,4'-azobis-4-cyanovaleric acid, benzoyl peroxide, 2,4-dichlorobenzoic peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, Diisopropyl oxide dicarbonate, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxide Peroxide initiators such as urate, di-tert-butylperoxyphthalate, dibenzyl oxide or 2,5-dimethylhexane-2,5-dihydroperoxide, or benzoyl peroxide-N, N-dimethylaniline or peroxodi Examples thereof include redox initiators such as sulfuric acid-sodium hydrogen sulfite. Of these, azo initiators or peroxide initiators are preferred, and more preferred are benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, cumene hydro Peroxide, tert-butyl hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, dimethyl azobisisobutyrate. These radical initiators can be used alone or in combination of two or more simultaneously or sequentially.

  Moreover, conventionally well-known various methods are employable about the method of making polyolefin and a halogenating agent react. For example, a polyolefin is suspended or dissolved in a solvent, and a halogenating agent and a radical initiator, if necessary, are usually added at a temperature of −80 ° C. to 250 ° C., preferably at a temperature of room temperature to the boiling point of the solvent. Examples thereof include a method in which the mixture is added and reacted, or a method in which a halogenating agent and, if necessary, a radical initiator are brought into contact with each other while melting and kneading the polyolefin at a temperature equal to or higher than its melting point, for example, 180 to 300 ° C.

  The halogen-modified polyolefin is produced by the above method.

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

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 halogen-modified polyolefin obtained in the above step, but for example, exemplified in the above step (3) An atom transfer radical polymerization method is preferably used. In the halogen-modified polyolefin of this step, a carbon-halogen bond existing at the α-position of the carbon-carbon double bond, or a structure in which a plurality of halogens are added on one carbon atom can be used as an initiator structure. .

(Method 2) is a method in which a functional group-containing polyolefin is used as a macromonomer and copolymerized with a monomer constituting the stimulus-responsive polymer chain. As the functional group-containing polyolefin used in this method, a polymerizable functional group, for example, a group having a carbon-carbon double bond such as a (meth) acryloyl group or a styryl group is introduced at the end of the molecular chain or in the molecular chain. Specific examples include the structures and production methods disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2004-143403 and 2004-269642. By copolymerizing such a group-introduced polyolefin and a 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, anionic polymerization, or coordination polymerization can be used.

  In radical polymerization, any initiator used in ordinary radical polymerization can be used as the initiator, and examples thereof include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarboxyl. Azo initiators such as nitrile, azobis-2-amidinopropane hydrochloride, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride or 4,4′-azobis-4-cyanovaleric acid, benzoyl peroxide, 2,4-dichloro Benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide Peroxidation of sid, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxylaurate, di-tert-butyl peroxyphthalate, dibenzyl oxide or 2,5-dimethylhexane-2,5-dihydroperoxide Or a redox initiator such as benzoyl peroxide-N, N-dimethylaniline or peroxodisulfuric acid-sodium hydrogen sulfite.

  Of these, azo initiators or peroxide initiators are preferable, and azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, dimethyl azobisisobutyrate, Benzoyl oxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, diisopropyl dicarbonate peroxide or acetyl peroxide. These radical polymerization initiators can be used alone or in combination of two or more simultaneously or sequentially.

  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, and octane can be used as specific examples. , Aliphatic hydrocarbon solvents such as nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride And chlorinated hydrocarbon solvents such as tetrachloroethylene, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl isobutyl ketone Ketone solvents; ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, diethyl ether, di -n- amyl ether, tetrahydrofuran and ether solvents such as dioxy anisole and the like. Further, suspension polymerization and emulsion polymerization can be performed 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 liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

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

In addition to the method using the above 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 anionic polymerization, as the anionic polymerization initiator, any initiator used in ordinary anionic polymerization can be used, for example, organolithium compounds such as butyl lithium, propyl lithium, ethyl lithium, methyl lithium, Grignard A reagent etc. can be used.

Solvents that can be used include, for example, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, diethyl ether, dioxane, tetrahydrofuran (THF), Ether-based solvents such as monoglyme and diglyme are used. These solvents can be used singly or in combination of two or more. Of these, aromatic hydrocarbons and ether solvents are preferably used. The polymerization is usually performed at a polymerization temperature of −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 300 hours, more preferably. Is carried out over 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 polyolefins used in this method, reactive groups such as hydroxyl groups, amino groups, carboxyl groups, acid halogen groups, acid anhydride groups, epoxy groups, and isocyanate groups 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 needs to have a functional group capable of reacting with these reactive groups at the end of the molecular chain or in the molecular chain. 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.
(Method 3) can produce the block or graft polymer which is polyolefin which concerns on this invention by implementing step (6)-(8) shown next sequentially.

Step (6) A step of producing a polyolefin having 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 / or side chain. .
Step (7) A step of producing a stimulus-responsive polymer chain having a functional group at the terminal.
Step (8) A step of bonding the polyolefin having the functional group (A) produced in the step (6) and the stimulus-responsive polymer chain having a functional group at the terminal produced in the step (7).

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

  For the step (6), for example, the same method as in the step (1) can be used.

  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 to the functional group (A) contained in the polyolefin used in the step (2) has radical polymerization initiating ability. The compound (R) having both of the groups (Q) is used as an initiator to polymerize monomers constituting the stimulus-responsive polymer chain. The stimulus-responsive polymer chain obtained in this step has a functional group (P) derived from the initiator at its end.

  Step (8) is 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, and an isocyanate group on the main chain terminal and / or side chain obtained in the step (6). This is a step of performing a coupling reaction between a polyolefin having a group (A) and a stimulus-responsive polymer chain having a functional group at the terminal obtained in the step (7). The 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 this step is performed is described in the step (2). The combination similar to a combination is mentioned.

  A polyolefin having a functional group (A) selected from a hydroxyl group, amino group, epoxy group, carboxyl group, acid halogen group, acid anhydride group and isocyanate group at the main chain terminal and / or side chain, and a functional group at the terminal The same conditions as described in the step (2) can be applied to the reaction conditions such as the reaction solvent, reaction temperature, reaction time, condensing agent and basic catalyst used in the reaction with the stimulus-responsive polymer chain.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

[Synthesis of terminal allyl alcohol-modified PE]
To a 1 L glass polymerization vessel purged with nitrogen, 900 mL of toluene was added, 6.6 ml (48 mmol) of triethylaluminum and 2.72 ml (40 mmol) of allyl alcohol were added, and the mixture was stirred at 50 ° C. for 5 minutes. Into another nitrogen-substituted 20 mL Schlenk flask, 17.6 mg of metallocene represented by the following formula (I) was put, and 1.12 ml of a toluene solution of methylalumoxane (MAO) (Al = 1.28 M) was added, and about After stirring for 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 a polymer. After stirring overnight, the mixture was filtered through a glass filter, and the obtained polymer was dried at 50 ° C. under a reduced pressure of 10 Torr for 10 hours to obtain 8.63 g of terminal allyl alcohol-modified PE. As a result of analysis by gel permeation chromatography (GPC), the molecular weight of the polymer was 26500 in terms of weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) was 2.26. ^From the result of ¹ H-NMR measurement, a peak of terminal hydroxymethylene (—CH ₂ —OH) derived from introduction of allyl alcohol was observed at δ = 3.3-3.4 ppm.

[Synthesis of 2-bromoisobutyryl group-modified PE]
5.6 g of terminal allyl alcohol-modified PE (Mw = 26500, Mw / Mn = 2.26) was placed in a 500 mL two-necked eggplant flask purged with nitrogen and 200 ml of dry toluene, 0.55 ml of triethylamine, 2-bromoisobutyrate. Rilbromide (0.99 ml) 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 through a glass filter. At this time, the polymer on the glass filter was washed successively with 100 ml of methanol three times, once with 100 ml of 1N hydrochloric acid, and twice with 100 ml of methanol. The polymer was dried at 50 ° C. under a reduced pressure of 10 Torr for 10 hours. From the results of ^{1 H-NMR, δ = 3.8-4.1} ppm in the terminal methylene _{(-CH 2 -OCOCBr (CH 3)} 2) is, [delta] = 1.8 ppm to terminal methyl _{(-CH 2 -OCOCBr (CH 3)} 2) Since the group was observed and the raw material hydroxymethylene peak was not observed, it was identified that 2-hydroxyisobutyryl group-modified PE in which all hydroxyl groups were modified was obtained.
[Synthesis of PE-b-poly (N-isopropylacrylamide) block polymer]
6.9 g of 2-bromoisobutyryl group-modified PE was placed in a 100 ml Schlenk flask purged with nitrogen, and deaeration with a vacuum pump and nitrogen substitution were repeated 5 times. Under a nitrogen stream, 96 mg of RuCl ₂ (PPh ₃ ) ₃ , 10 ml of o-xylene, 82 mg of aluminum isopropoxide, and 9.1 g of N-isopropylacrylamide (NIPAAm) were sequentially added, and a septum cap was attached. The temperature was raised to 120 ° C. and reacted for 9 hours with stirring. After cooling the reaction Schlenk flask with ice water, about 5 ml of methanol was added to stop the reaction, and the mixture was further poured into 600 ml 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 9.7 g of polymer. ^{From 1} H-NMR measurement, a PE-b-PNIPAAm block polymer of PE / PNIPAAm = 69/31 (wt%) was obtained. The polymer was moldable and could be a sheet. Moreover, even if it was immersed in water at normal temperature for 3.5 days, the sheet shape was maintained.

[Synthesis of propylene / 11-undecen-1-ol copolymer]
800 ml of toluene was introduced into a 1 L glass polymerizer equipped with a stirrer and sufficiently purged with nitrogen, and the temperature was maintained at 60 ° C. while supplying propylene gas (100 L / h). After adding 22 mmol of triisobutylaluminum and 44 mmol of 11-undecen-1-ol and stirring for 10 minutes, 0.003 mmol of dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride activated with 1.5 mmol of MAO was added. Polymerization was carried out for 15 minutes while keeping the temperature at 60 ° C. in the polymerization vessel. Methanol was introduced into the polymerization vessel to complete the polymerization, 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 ([η]) of the obtained polymer was 1.12. From the ¹ H-NMR measurement, the OH group content in the polymer was 2.34 mol%.
[Synthesis of 2-bromoisobutyryl group-modified PP]
7.0 g of the propylene / 11-undecen-1-ol copolymer obtained above was put into a 500 mL glass reactor substituted with degassed nitrogen, and 250 ml of dry toluene, 7.6 ml of triethylamine, 2-bromoisobutyrate. 6.3 ml of rilbromide was added, and the temperature was raised 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. From the results of ^{1 H-NMR, δ = 3.8-4.1} ppm in the terminal methylene _{(-CH 2 -OCOCBr (CH 3)} 2) is, [delta] = 1.8 ppm to terminal methyl _{(-CH 2 -OCOCBr (CH 3)} 2) Since the group was observed and the hydroxymethylene peak of the starting material was not observed, it was identified that a polymer in which all hydroxyl groups were 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 / 11-undecen-1-ol copolymer obtained above was put, and deaerated with a vacuum pump, and purged with nitrogen Was repeated 5 times. Under a nitrogen stream, RuCl ₂ (PPh ₃ ) ₃ 959 mg, o-xylene 100 ml, aluminum isopropoxide 820 mg, and NIPAAm 45 g were sequentially added, and a septum cap was attached. The temperature was raised to 120 ° C., and the reaction was carried out for 3 hours with stirring. After cooling the reaction Schlenk flask with ice water, about 5 ml of methanol was added to stop the reaction, and the mixture was 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. ^{From 1} H-NMR measurement, a PP-g-PNIPAAm graft polymer of PP / PNIPAAm = 18/82 (wt%) was obtained. The polymer was moldable and could be a sheet. Moreover, even if it was immersed in water at normal temperature for 3.5 days, the sheet shape was maintained.

  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 imparts stimulation. Because it has a stimulus-responsive polymer chain that changes its affinity for liquid, the adsorption and release of these substrates can be controlled according to each stimulus. It can be used as a release material. Moreover, since a volume change is shown with respect to each stimulus, it is also suitable as an actuator or a chemical valve. And since it has a polyolefin chain | strand, it is thought that it can be used for various uses as a structural material which has both stimulus responsiveness and self-holding property.

Claims (3)

  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, and the polyolefin chain and the stimulus-responsive polymer chain are chemically bonded The polymer characterized by being made. The polyolefin chain is a polymer chain obtained by polymerizing at least one α-olefin represented by CH ₂ ═CH—R (R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). The polymer according to claim 1. The stimuli-responsive polymer chain is a poly-N-alkyl-substituted (meth) acrylamide such as poly (meth) acrylamide, poly-N-isopropyl (meth) acrylamide, poly (meth) acrylic acid or a metal salt thereof, poly-2- It is at least one polymer chain selected from the group consisting of hydroxyethyl (meth) acrylate, polyvinylbenzenesulfonic acid or a metal salt thereof, poly (ethylene glycol monomethacrylate), and poly (ethylene glycol monoacrylate). The polymer according to claim 1 or 2.