Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F12/06—Hydrocarbons
  • C08F12/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/06—Organic solvent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/40—Redox systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Definitions

• the present invention relates to a living radical polymerization method.
• a radical polymerization method has been well known as a method for obtaining a vinyl polymer by polymerizing vinyl monomers.
• the radical polymerization method has a drawback that it is difficult to control the molecular weight of the obtained vinyl polymer.
• the obtained vinyl polymer becomes a mixture of compounds having various molecular weights, and it is difficult to obtain a vinyl polymer having a narrow molecular weight distribution.
• the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) could only be reduced to about 2 to 3. .
• a living radical polymerization method has been developed since around 1990 as a method for solving such drawbacks. That is, according to the living radical polymerization method, it is possible to control the molecular weight and obtain a polymer having a narrow molecular weight distribution. Specifically, since it is possible to easily obtain Mw / Mn of 2 or less, it has been attracting attention as a method for producing a polymer used in the most advanced fields such as nanotechnology.
• oxygen is known as a substance that inhibits radical reaction (polymerization inhibitor). Therefore, in general, the reaction is performed in an atmosphere that does not contain oxygen. Also in the living radical polymerization, the polymerization reaction is generally performed by substituting the atmosphere in the reaction vessel with an inert gas such as nitrogen gas or argon. That is, in order to perform the living radical polymerization reaction, it has been considered preferable to exclude oxygen in the atmosphere as much as possible. Those skilled in the art did not think that oxygen could be actively used for living radical polymerization. Furthermore, it was completely impossible for those skilled in the art to control living radical polymerization by controlling the concentration or amount of oxygen.
• a transition metal complex catalyst As a catalyst currently used in the living radical polymerization method, a transition metal complex catalyst is known.
• transition metal complex catalyst for example, a complex in which a ligand is coordinated to a compound having Cu, Ni, Re, Rh, Ru or the like as a central metal is used.
• a complex in which a ligand is coordinated to a compound having Cu, Ni, Re, Rh, Ru or the like as a central metal is used.
• Such catalysts are described in the following documents, for example.
• Patent Document 1 Japanese Patent Laid-Open No. 2002-249505 discloses the use of a complex having Cu, Ru, Fe, Ni or the like as a central metal as a catalyst.
• Patent Document 2 Japanese Patent Laid-Open No. 11-322822 discloses the use of a hydrido rhenium complex as a catalyst.
• Non-Patent Document 1 Journal of The American Chemical Society 119,674-680 (1997)) coordinated 4,4'-di- (5-nonyl) -2,2'-bipyridine to copper bromide.
• the use of a compound as a catalyst is disclosed.
• transition metal complex catalyst when such a transition metal complex catalyst is used, a large amount of the transition metal complex catalyst is required as a use amount, and it is not easy to completely remove a large amount of the catalyst used after the reaction from the product. was there.
• environmental problems may occur when the catalyst that is no longer needed is discarded.
• transition metals are highly toxic, and the toxicity of the catalyst remaining in the product may be an environmental problem, making it difficult to use transition metals in food packaging materials, biological / medical materials, etc. there were. In some cases, the toxicity of the catalyst removed from the product after the reaction becomes an environmental problem.
• the conductive transition metal remains in the polymer, the polymer is imparted with conductivity, making it difficult to use in electronic materials such as resists, organic EL, fuel cells, solar cells, and lithium ion batteries.
• electronic materials such as resists, organic EL, fuel cells, solar cells, and lithium ion batteries.
• it since it does not melt
• the ligand is usually expensive or has a problem of requiring complicated synthesis.
• high temperature for example, 110 degreeC or more
• a living radical polymerization method that does not require the use of a catalyst is also known.
• nitroxyl type and dithioester type methods are known.
• these methods have the disadvantage that a special protecting group must be introduced into the polymer growth chain, and this protecting group is very expensive.
• high temperature for example, 110 degreeC or more
• the polymer produced tends to have undesirable performance. That is, there is a drawback that the polymer to be produced tends to be colored in a color different from the original color of the polymer, and the polymer to be produced tends to have an odor.
• Non-Patent Document 2 Polymer Preprints 2005, 46 (2), 245-246
• Patent Document 3 Japanese Patent Laid-Open No. 2007-92014
• Patent Document 4 International Publication WO2008 / 139980
• Non-Patent Document 3 Polymer Preprints 2007, 56 (2), 2452 The Society of Polymer Science, 56th Polymer Debate
• a compound having phosphorus as a central metal is used as a catalyst.
• Non-Patent Document 1 the cost of the catalyst required for polymerizing 1 kg of the polymer was about several thousand yen.
• the inventions of Non-Patent Document 2 and Patent Document 3 significantly reduce the cost of the catalyst.
• the inventions of Non-Patent Document 3 and Patent Document 4 further reduce the cost of the catalyst.
• Patent Documents 1-4 and Non-Patent Documents 1-3 do not describe a method for obtaining a polymer having a narrow molecular weight distribution by controlling living radical polymerization without using a catalyst.
• the present invention is intended to solve the above-mentioned problems, and its main object is to provide a living radical polymerization method that does not require the addition of a catalyst.
• the present inventors established the above transition by setting the oxygen amount in the reaction vessel in the monomer polymerization step within a specific range in the living radical polymerization method. It has been found that a polymer having an extremely small molecular weight distribution can be obtained without using a catalyst such as a metal complex or a special protective group.
• the present invention has been completed based on these findings and further studies. That is, according to the present invention, the following polymerization method and polymer production method are provided, thereby solving the above-mentioned problems.
• a living radical polymerization method Including a step of performing polymerization by putting a reaction liquid containing a radical reactive monomer, a radical initiator, and an organic halide having a carbon-halogen bond into a reaction vessel,
• the amount of oxygen in the gas phase in the reaction vessel per 1 ml of the volume of the liquid phase in the reaction vessel is 1 to 70 mmol.
• the organic halide having a carbon-halogen bond is a compound having the following general formula (II): CR 2 R 3 R 4 X 3 (II) Wherein R 2 and R 3 are independently halogen, hydrogen or alkyl, R 4 is halogen, hydrogen, alkyl, aryl, heteroaryl or cyano, X 3 is halogen,
• the monomer having the radical reactive unsaturated bond is selected from: (Meth) acrylic acid ester monomer, aromatic unsaturated monomer (styrene monomer), carbonyl group-containing unsaturated monomer, (meth) acrylonitrile, (meth) acrylamide monomer, diene monomer, vinyl ester monomer, N-vinyl monomer , (Meth) acrylic acid monomers, vinyl halide monomers, and 1-olefin monomers.
• the oxygen amount (typically, the oxygen amount (concentration / volume) of the reaction vessel) provided to the reaction solution is controlled within a specific range. This is based on a concept completely different from the conventionally known living radical polymerization method of controlling the polymerization reaction.
• a living radical polymerization method having high control ability is provided. That is, in the present invention, by setting the oxygen concentration in the reaction vessel to a specific range, it is not necessary to use a catalyst such as a transition metal complex in the monomer polymerization step, and the adverse effects due to the use of the catalyst are eliminated. It becomes possible to do. For example, adverse effects such as toxicity of the catalyst compound contained in the polymer production process and product polymer and low solubility of the catalyst compound in the reaction solution can be eliminated. Since the polymerization method of the present invention has high reactivity, a high temperature (for example, 110 ° C. or higher) is not required for the polymerization reaction. Also, expensive and special protecting groups are not required to protect the polymer growing chain during the reaction. Furthermore, the molded product obtained from the polymer obtained by the method of the present invention has an advantage that it is substantially free from coloring or smelling during molding.
• the present invention has the following advantages.
• Monomer versatility various types of monomers having radical polymerizability can be used as polymer raw materials.
• a monomer having a highly reactive functional group for example, a hydroxyl group
• the method of the present invention is advantageous because it is hardly affected by the functional group of the monomer.
• the present invention is advantageous when a solvent having a highly reactive functional group is used.
• a living radical polymerization method has been realized that is much more environmentally friendly and economical than conventional methods, and that can be used for various purposes.
• a polymer having a very narrow molecular weight distribution can be obtained. That is, the polymer obtained by the method of the present invention has the advantage of the polymer obtained by the conventional living radical polymerization method.
• a polymer having a narrow molecular weight distribution obtained by the method of the present invention is useful as a material for various applications including the most advanced fields such as nanotechnology.
• hydrocarbon refers to a molecule or group composed of carbon and hydrogen.
• the chain hydrocarbon can be linear or branched.
• the cyclic hydrocarbon may be composed of only a cyclic structure, or may be a structure in which a chain hydrocarbon is further bonded to the cyclic structure.
• the carbon number of the hydrocarbon can be any natural number. The number is preferably 1 to 30, and more preferably 1 to 20. More preferably, it is 1-10.
• the unsaturated bond may be a double bond or a triple bond.
• the hydrocarbon molecule or hydrocarbon group may have only one unsaturated group or may have two or more unsaturated groups.
• hydrocarbons include alkyl, alkenyl, alkynyl, aryl and the like.
• alkyl refers to a monovalent group formed by losing one hydrogen atom from a linear or cyclic aliphatic hydrocarbon (alkane). In the case of a chain, it is generally represented by C k H 2k + 1 ⁇ (where k is a positive integer).
• a chain alkyl may be a straight chain or branched chain.
• the cyclic alkyl may be composed only of a cyclic structure, or may be a structure in which a chain alkyl is further bonded to the cyclic structure.
• the carbon number of the alkyl can be any natural number. The number is preferably 1 to 30, and more preferably 1 to 20.
• alkylene refers to a divalent group formed by losing one more hydrogen atom from alkyl.
• lower alkyl means an alkyl group having a relatively small number of carbon atoms. Preferably a C 1 ⁇ 10 alkyl, more preferably a C 1 ⁇ 5 alkyl, more preferably C 1 ⁇ 3 alkyl. Specific examples include, for example, methyl, ethyl, propyl, isopropyl and the like.
• lower alkylene refers to a divalent group formed by further losing one hydrogen atom from lower alkyl.
• substituted alkyl means a group in which hydrogen of an alkyl group is substituted with a substituent.
• substituents include aryl, heteroaryl, and cyano.
• halogenated substituted alkyl means a group in which a hydrogen of an alkyl group is substituted with a halogen and another hydrogen of the alkyl group is substituted with another substituent.
• another substituent include aryl, heteroaryl, and cyano.
• aryl refers to a group formed by leaving one hydrogen atom bonded to an aromatic hydrocarbon ring.
• the number of aromatic hydrocarbon rings constituting the aryl may be one, or two or more. Preferably, it is 1 to 3.
• the plurality of rings may or may not be condensed. Specifically, for example, phenyl, naphthyl, anthracenyl, biphenyl and the like.
• heteroaryl refers to a group containing a hetero element other than carbon as an element constituting the ring skeleton of an aromatic ring of aryl.
• Specific examples of heteroatoms include oxygen, nitrogen, sulfur and the like.
• the number of heteroatoms in the aromatic ring is not particularly limited. For example, it may include only one heteroatom, and may include two, three, or four or more heteroatoms.
• substituted aryl refers to a group formed by bonding a substituent to aryl.
• substituted heteroaryl refers to a group formed by bonding a substituent to heteroaryl.
• halogen refers to a monovalent group of elements such as fluorine (F), chlorine (Cl), bromine (Br), iodine (I) belonging to Group 7B of the periodic table. Preferred is bromine or iodine, and more preferred is iodine.
• alkoxy refers to a group in which an oxygen atom is bonded to the alkyl group. That is, when the alkyl group is represented as R-, it refers to a group represented by RO-.
• a chain alkoxy can be straight or branched.
• the cyclic alkoxy may be composed of only a cyclic structure, or may be a structure in which a chain alkyl is further bonded to the cyclic structure.
• the number of carbon atoms of alkoxy can be any natural number. The number is preferably 1 to 30, and more preferably 1 to 20. More preferably, it is 1 to 10, more preferably 1 to 5 alkoxy, and particularly preferably 1 to 3. Specific examples include, for example, methoxy, ethoxy, propoxy, isopropoxy and the like.
• amine refers to a compound in which three organic groups are bonded to nitrogen. This organic group is preferably alkyl.
• living radical polymerization means a polymerization reaction in which chain transfer reaction and termination reaction do not substantially occur in radical polymerization reaction, and the chain growth terminal retains activity even after the monomer has reacted. Say. In this polymerization reaction, the polymerization activity is maintained at the end of the produced polymer even after the completion of the polymerization reaction, and when the monomer is added, the polymerization reaction can be started again.
• Living radical polymerization is characterized by the ability to synthesize polymers having an arbitrary average molecular weight by adjusting the concentration ratio of monomer and polymerization initiator, and the molecular weight distribution of the resulting polymer is extremely narrow. It can be applied to polymers.
• the living radical polymerization may be abbreviated as “LRP”.
• the catalyst refers to a catalyst for reversibly generating radicals from dormant species in the living radical polymerization method.
• oxygen present as gas molecules is not included in the catalyst referred to in this specification.
• a conventional catalyst for reversibly generating radicals from dormant species is not used.
• the polymerization method of the present invention is based on a mechanism that living radical polymerization is controlled by introducing oxygen present as gas molecules into a reaction solution.
• the polymerization reaction is performed based only on the mechanism that living radical polymerization is controlled by introducing oxygen present as gas molecules into the reaction solution.
• no compounds other than those composed of halogen and oxygen are used as catalysts.
• a known catalyst can be used as a catalyst for the living radical polymerization method, if necessary.
• the catalyst pulls out halogens from dormant species during living radical polymerization to generate radicals. Therefore, the catalyst removes the group that suppresses the growth reaction of the compound used as the dormant species and converts it into an active species to control the growth reaction.
• a complex having Cu, Ru, Fe, Ni or the like as a central metal described in Patent Document 1 a copper complex catalyst described in Non-Patent Document 1, Non-Patent Document 2 and Patent Document 3, known compounds such as compounds having Ge, Sn or the like as a central metal, phosphorous compounds described in Non-Patent Document 3, or compounds having nitrogen or phosphorus as a central metal described in Patent Document 4 can be used.
• a catalyst having an oxygen atom as a central element can also be used.
• a catalyst having a carbon atom as a central element can also be used.
• the living radical polymerization reaction is performed without adding a catalyst.
• the catalyst is used in combination with an organic halide having a carbon-halogen bond used as a low molecular weight dormant species.
• the catalyst pulls out halogen from the organic halide during living radical polymerization to generate radicals.
• it is not necessary to add such a catalyst compound to the reaction solution.
• the growth reaction of the compound used as the dormant species is suppressed by providing an appropriate amount of oxygen from the gas phase in the reaction vessel to the reaction solution without adding a catalyst compound. Remove the existing group and convert it to an active species to control the growth reaction.
• the low molecular weight dormant species is not limited to organic halides.
• the polymerization reaction is preferably carried out without adding a catalyst. However, if necessary, a small amount of catalyst may be added.
• the amount of catalyst used can be 10 mmol (mM) or less per liter of reaction solution. In a more preferred embodiment, the amount of catalyst used can be 5 mmol or less per 1 liter of reaction solution, or 2 mmol or less. Furthermore, it can be 1 mmol or less, and can also be 0.5 mmol or less. In particularly preferred embodiments, it is 0.2 mmol or less, can be 0.1 mmol or less, can be 0.05 mmol or less, is 0.02 mmol or less, It is also possible to make it less than millimolar. On a weight basis, the amount of catalyst used can be 1% by weight or less of the reaction solution.
• it can be 0.75 wt% or less, and can be 0.70 wt% or less, and in a more preferred embodiment, 0.5 wt% or less. It is possible to make it 0.2% by weight or less, further 0.1% by weight or less, and 0.05% by weight or less.
• it can be 0.75% by weight or less, can be 0.70% by weight or less, and in a more preferred embodiment, is 0.5% by weight or less. It is possible to make it 0.2% by weight or less, further 0.1% by weight or less, and 0.05% by weight or less. In particularly preferred embodiments, it can be 0.02% by weight or less, 0.01% by weight or less, or 0.005% by weight or less.
• the polymerization reaction is controlled even when the conventional catalyst is present in such a small amount that it cannot function as a catalyst. That is, it is possible to carry out the reaction substantially without adding a catalyst.
• a protecting group for protecting the growing chain during the living radical polymerization reaction is used.
• various known protecting groups can be used as protecting groups conventionally used in living radical polymerization.
• a special protecting group when used, there are disadvantages such as the fact that the protecting group is very expensive.
• organic halides (low molecular dormant species)
• an organic halide having a carbon-halogen bond is preferably added to the reaction material, and a halogen imparted from the organic halide to the growing chain is used as a protective group.
• Such organic halides are relatively inexpensive and are advantageous over other known compounds used for protecting groups used in living radical polymerization.
• the organic halide used as the dormant species is not particularly limited as long as it has at least one carbon-halogen bond in the molecule and acts as the dormant species. In general, however, those in which one or two halogen atoms are contained in one molecule of the organic halide are preferred.
• the organic halide used as the dormant species preferably has an unstable carbon radical when the halogen is eliminated and a carbon radical is generated. Therefore, as an organic halide used as a dormant species, when a halogen is eliminated and a carbon radical is generated, three substituents that stabilize the carbon radical are bonded to the carbon atom that becomes the carbon radical. Things are not suitable. However, those in which one or two substituents that stabilize the carbon radical are bonded to the carbon atom to be the carbon radical often show appropriate radical stability and can be used as a dormant species.
• the number of hydrogen atoms of the organic halide used as the dormant species to which the halogen is bonded is preferably 2 or less, and preferably 1 or less. More preferably, it is more preferable not to have hydrogen. Further, the number of halogens bonded to the 1-position carbon of the organic halide is preferably 3 or less, more preferably 2 or less, and even more preferably 1. In particular, when the halogen bonded to the 1st carbon of the organic halide is chlorine, the number of chlorine is very preferably 3 or less, and even more preferably 2 or less, One is particularly preferred.
• one or more carbon atoms are bonded to the 1-position carbon of the organic halide used as the dormant species, and it is particularly preferable that two or three carbon atoms are bonded.
• the halogen atom of the organic halide used as the dormant species is preferably chlorine, bromine or iodine. More preferred is bromine or iodine. From the viewpoint of reducing the molecular weight distribution, iodine is most preferable. In one embodiment, bromine can also be preferably used. Since bromine compounds are generally more stable than iodine compounds, there are advantages such as easy storage of low-molecular dormant species and a relatively low need for removing terminal halogens from the resulting polymer.
• many compounds having a plurality of bromines are commercially available or can be easily synthesized, and various branched polymers such as a star shape, a comb shape, and a surface grafted type can be easily synthesized.
• various branched polymers such as a star shape, a comb shape, and a surface grafted type can be easily synthesized.
• a block copolymer can be easily synthesized from a compound having a bromine terminal.
• the halogen atom of the organic halide used as the dormant species may be the same as or different from the halogen atom in the catalyst. This is because even when the halogen atoms are different, the halogen atoms can be exchanged with each other between the organic halide and the catalyst compound. However, if the halogen atom of the organic halide used as the dormant species and the halogen atom in the catalyst are the same, the exchange of the halogen atom between the organic halide used as the dormant species and the catalyst compound Is preferred because it is easier.
• the organic halide used as the dormant species has the following general formula (II):
• R 2 is halogen, hydrogen or alkyl. Preferably, it is hydrogen or lower alkyl. More preferably, it is hydrogen or methyl.
• R 3 may be the same as or different from R 2 and is halogen, hydrogen or alkyl. Preferably, it is hydrogen or lower alkyl. More preferably, it is hydrogen or methyl.
• R 4 is halogen, hydrogen, alkyl, aryl, heteroaryl or cyano. Preferably, it is aryl, heteroaryl or cyano. When R 4 is halogen, hydrogen or alkyl, R 4 may be the same as or different from R 2 or R 3 .
• X 3 is halogen. Preferably, it is chlorine, bromine or iodine. More preferred is bromine or iodine, and most preferred is iodine.
• X 3 may be the same as or different from the halogen of R 2 to R 4 .
• the halogen of X 3 may be the same halogen contained in the catalyst compound. However, it may be a halogen different from the halogen contained in the catalyst compound.
• R 2 to R 4 and X 3 are each selected independently from each other, but 0 or 1 halogen atom is present in R 2 to R 4 (that is, as an organic halide, In which 1 or 2 halogen atoms are present.
• the organic halide used as the dormant species is an alkyl halide or a halogenated substituted alkyl. More preferably, it is a halogenated substituted alkyl.
• the alkyl is preferably a secondary alkyl, more preferably a tertiary alkyl.
• the alkyl preferably has 2 or 3 carbon atoms. Therefore, the organic halide used as the dormant species is more preferably halogenated substituted ethyl or halogenated substituted isopropyl. Examples of the substituent in the halogenated substituted alkyl used as the dormant species include phenyl and cyano.
• organic halide used as the low molecular weight dormant species include, for example, CH (CH 3 ) (Ph) I and C (CH 3 ) 2 (CN) I described below.
• organic halides used as low molecular weight dormant species include, for example, methyl chloride, methylene chloride, chloroform, chloroethane, dichloroethane, trichloroethane, bromomethyl, dibromomethane, bromoform, bromoethane, dibromoethane, tribromoethane.
• Tetrabromoethane bromotrichloromethane, dichlorodibromomethane, chlorotribromomethane, iodotrichloromethane, dichlorodiiodomethane, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, iodoform, diiodomethane, methyl iodide, Isopropyl chloride, t-butyl chloride, isopropyl bromide, t-butyl bromide, triiodoethane, ethyl iodide, diiodopropane, isopropyl iodide, t-butyl iodide Bromodichloroethane, chlorodibromoethane, bromochloroethane, iododichloroethane, chlorodiiod
• the organic halide used as a low molecular weight dormant species is not used as a solvent, and therefore it is not necessary to use it in such a large amount as to exhibit an effect as a solvent. Therefore, the amount of the organic halide used as the low molecular weight dormant species can be smaller than the so-called “solvent amount” (that is, the amount necessary to achieve the effect as a solvent).
• the organic halide used as the low molecular weight dormant species is used to provide halogen as a protective group to the growing chain as described above, so that the amount sufficient for the growing chain in the reaction system. It is sufficient to be able to provide this halogen.
• the amount of the organic halide used as the low molecular weight dormant species in the method of the present invention is preferably 0.5 mol or less per mol of the vinyl monomer (monomer). More preferably, it is 0.4 mol or less, More preferably, it is 0.3 mol or less, Especially preferably, it is 0.2 mol or less, Most preferably, it is 0.1 mol or less. Furthermore, if necessary, the amount may be 0.07 mol or less, 0.05 mol or less, 0.03 mol or less, 0.02 mol or less, or 0.01 mol or less per mol of the vinyl monomer. It is.
• the amount of the organic halide used as the low molecular weight dormant species is preferably 0.001 mol or more, more preferably 0.005 mol or more, per mol of the vinyl monomer (monomer). is there.
• the amount of the organic halide used as the low molecular weight dormant species in the method of the present invention is preferably 1 mmol or more, more preferably 2 mmol or more, as a concentration in the polymerization reaction solution, per liter of the reaction solution. More preferably 5 mmol or more. As needed, it can also be 10 mmol or more, can also be 20 mmol or more, and can also be 30 mmol or more. Further, it is preferably 500 mmol or less per 1 liter of reaction solution, more preferably 200 mmol or less, further preferably 150 mmol or less, and can be 120 mmol or less. It is also possible.
• organic halides used as the low molecular weight dormant species are known compounds, and it is possible to use a reagent commercially available from a reagent sales company or the like as it is. Or you may synthesize
• Organic halides used as low molecular weight dormant species can be charged with their raw materials, and organic halides can be generated in situ during polymerization, ie in reaction solutions, which can be used as organic halides in this polymerization process.
• an azo radical initiator for example, azobis (isobutyronitrile)
• a halogen single molecule for example, iodine (I 2 )
• an organic halide for example, iodide
• the alkyl CP-I (chemical formula as described above) can be generated in situ during the polymerization and used as the dormant species for this polymerization process.
• an azo radical initiator for example, azobis (isobutyronitrile)
• a halogen single molecule for example, iodine (I 2 )
• their amounts are not particularly limited, but the organic halide to be formed It is preferable to adjust so that the amount of the above becomes the amount of the organic halide described above. That is, it is preferable to use a halogen single molecule and an azo radical initiator corresponding to the amount of the organic halide to be used.
• organic halide used as the low molecular weight dormant species those immobilized on an inorganic or organic solid surface or an inorganic or organic molecular surface can also be used.
• an organic halide immobilized on the surface of a silicon substrate, the surface of a polymer film, the surface of inorganic or organic fine particles, the surface of a pigment, or the like can be used.
• immobilization for example, chemical bonds or physical bonds can be used.
• a radical polymerizable monomer is used as a monomer.
• the radical polymerizable monomer refers to a monomer having an unsaturated bond capable of performing radical polymerization in the presence of an organic radical. Such an unsaturated bond may be a double bond or a triple bond. That is, in the polymerization method of the present invention, any monomer conventionally known to perform living radical polymerization can be used.
• the vinyl monomer is a general term for monomers represented by the general formula “CH 2 ⁇ CR 5 R 6 ”.
• a monomer in which R 5 is methyl and R 6 is carboxylate in this general formula is referred to as a methacrylate monomer and can be suitably used in the present invention.
• methacrylate monomer examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, benzyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate.
• N-octyl methacrylate 2-methoxyethyl methacrylate, butoxyethyl methacrylate, methoxytetraethylene glycol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, 2- Hydroxy 3-fu Noxypropyl methacrylate, diethylene glycol methacrylate, polyethylene glycol methacrylate, 2- (dimethylamino) ethyl methacrylate, 2-isocyanoethyl methacrylate, 2- (acetoacetoxy) ethyl methacrylate, 2- (phosphoric acid) ethyl methacrylate (2- (Methacryloyloxy)) ethyl phosphate), trialkoxysilylpropyl methacrylate, dialkoxymethylsilylpropyl methacrylate, and the
• methacrylic acid or an alkali metal salt, alkaline earth metal salt or amine salt thereof can also be used.
• 2- (N, N-diethyl-N-methylamino) ethyl methacrylate + / trifluorosulfonyliminium (N (CF 3 SO 2 ) 2 ⁇ ) salt 2- (N-ethyl-N-methyl-N —Hydrogenated amino) ethyl methacrylate + / trifluorosulfonyliminium (N (CF 3 SO 2 ) 2 ⁇ ) salt
• ionic liquid methacrylates such as N-ethyl-N-methylpyrrolidinium methacrylate + / fluorohydrogenation ((FH) n F ⁇ ) salt can be used.
• a monomer in which R 5 is hydrogen and R 6 is carboxylate in the general formula of the vinyl monomer is generally referred to as an acrylic monomer and can be suitably used in the present invention.
• acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, glycidyl acrylate, cyclohexyl acrylate, and lauryl acrylate.
• N-octyl acrylate 2-methoxyethyl acrylate, butoxyethyl acrylate, methoxytetraethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-chloro 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2- Hydroxy 3-phenoxypropyl acrylate, diethylene glycol Cole acrylate, polyethylene glycol acrylate, 2- (dimethylamino) ethyl acrylate, 2-isocyanoethyl acrylate, 2- (acetoacetoxy) ethyl acrylate, 2- (phosphorylo) ethyl acrylate, tri Examples include alkoxysilylpropyl acrylate and dialkoxymethylsilylpropyl acrylate.
• Acrylic acid or its alkali metal salt, alkaline earth metal salt or amine salt can also be used.
• 2- (N, N-diethyl-N-methylamino) ethyl acrylate + / trifluorosulfonyliminium (N (CF 3 SO 2 ) 2 ⁇ ) salt 2- (N-ethyl-N-methyl-N —Hydrogenated amino) ethyl acrylate + / trifluorosulfonyliminium (N (CF 3 SO 2 ) 2 ⁇ ) salt
• ionic liquid acrylates such as N-ethyl-N-methylpyrrolidinium acrylate + / fluorohydrogenation ((FH) n F ⁇ ) salt can be used.
• the monomer in which R 5 is hydrogen and R 6 is phenyl in the general formula of the vinyl monomer is styrene, and can be suitably used in the present invention.
• a monomer in which R 6 is phenyl or a phenyl derivative is referred to as a styrene derivative and can be suitably used in the present invention.
• examples thereof include styrene, o-, m-, p-hydroxystyrene, o-, m-, p-styrene sulfonic acid, o-, m-, p-aminostyrene.
• vinyl naphthalene etc. whose R ⁇ 6 > is aromatic are mentioned.
• the monomer in which R 5 is hydrogen and R 6 is alkyl is alkylene and can be suitably used in the present invention.
• a monomer having two or more vinyl groups can also be used.
• a diene compound eg, butadiene, isoprene, etc.
• a compound having two allyl groups eg, diallyl phthalate
• dimethacrylate eg, ethylene glycol dimethacrylate having two methacryls
• acrylic ethylene glycol diacrylate.
• vinyl monomers other than those described above can also be used.
• vinyl esters eg, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate
• vinyl pyridines eg, 2-, 3-, 4-vinyl pyridine
• styrene other than those described above
• Derivatives eg ⁇ -methylstyrene
• vinyl ketones eg vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone
• N-vinyl compounds eg N-vinyl pyrrolidone, N-vinyl pyrrole, N-vinyl carbazole) N-vinylindole
• (meth) acrylamide and derivatives thereof eg, N-isopropylacrylamide, N-isopropylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N- Methy
• the radical polymerizable monomer may be used alone or in combination of two or more.
• a radical initiator In the living radical polymerization method of the present invention, a small amount of a radical initiator may be used as necessary.
• a known initiator can be used as an initiator used for radical reaction.
• an azo-based radical initiator and a peroxide-based radical initiator can be used.
• Specific examples of the azo radical initiator include, for example, azobis (isobutyronitrile) (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V70), 2, 2'-azobis (2,4-dimethylvaleronitrile) (V65).
• peroxide-based radical initiator examples include, for example, benzoyl peroxide (BPO), dicumyl peroxide, t-butyl peroxybenzoate (BPB), di (4-tert-butylcyclohexyl) peroxydicarbonate (PDX), A potassium oxide disulfate is mentioned.
• BPO benzoyl peroxide
• BPB t-butyl peroxybenzoate
• PDX di (4-tert-butylcyclohexyl) peroxydicarbonate
• a potassium oxide disulfate is mentioned.
• the amount of the radical initiator used is not particularly limited, but is preferably 1 mmol or more, more preferably 5 mmol or more, and further preferably 10 mmol or more with respect to 1 liter of the reaction solution. In one embodiment, it is 20 millimoles or more. Preferably, it is 500 mmol or less per liter of the reaction solution, 200 mmol or less in one embodiment, 150 mmol or less in another embodiment, and 120 mmol or less. Is possible. More preferably, it is 100 mmol or less, can be 90 mmol or less, can be 80 mmol or less, can be 70 mmol or less, and can be 60 mmol or less. Is possible. More preferably, it is 50 mmol or less.
• solvent If the reaction mixture such as monomer is liquid at the reaction temperature, it is not always necessary to use a solvent.
• a solvent may be used as necessary.
• the solvent it is possible to use a solvent that has been conventionally used for living radical polymerization as it is.
• the amount used is not particularly limited as long as the polymerization reaction is appropriately performed, but it is preferably used in an amount of 1 part by weight or more, more preferably in an amount of 10 parts by weight or more, It is more preferable to use 50 parts by weight or more. If the amount of solvent used is too small, the viscosity of the reaction solution may become too high.
• Emulsion polymerization, dispersion polymerization, and suspension polymerization can also be performed by using a solvent that does not mix with the monomer.
• a solvent that does not mix with the monomer.
• emulsion polymerization, dispersion polymerization, or suspension polymerization can be performed by using water as a solvent.
• additives The various materials for the living radical polymerization described above may be added with necessary amounts of known additives as required. Examples of such additives include polymerization inhibitors.
• the feed composition comprises a monomer having a radical reactive unsaturated bond, a radical initiator, and an organic halide (or organic halide) having a carbon-halogen bond used as a low molecular weight dormant species.
• Raw material for example, azo radical initiator and halogen molecule
• the raw material composition does not include raw materials other than the various raw materials described above.
• the raw material composition preferably does not substantially contain a raw material containing a transition metal.
• the feed composition comprises a monomer having a radical reactive unsaturated bond, a radical initiator, a solvent, and an organic halide (or organic halogen) having a carbon-halogen bond used as a low molecular weight dormant species. It is substantially free of raw materials other than chemical raw materials, such as azo radical initiators and halogen molecules.
• the raw material composition is substantially composed of a monomer having a radical reactive unsaturated bond, a radical initiator, and an organic halide (or organic halide) having a carbon-halogen bond used as a dormant species.
• a composition comprising a halide raw material (for example, an azo radical initiator and a halogen molecule) and a solvent.
• the solvent may not be included.
• the raw material composition does not substantially contain a material unrelated to living radical polymerization (for example, an episulfide compound).
• the raw material composition does not contain a catalyst.
• the raw material composition may include a catalyst as necessary.
• the raw material composition includes, for example, a catalyst, a monomer having a radical-reactive unsaturated bond, and an organic halide (or organic halide) having a carbon-halogen bond used as a dormant species.
• Raw materials for example, azo radical initiator and halogen molecule) and a radical initiator, and may further contain a solvent as necessary.
• a catalyst a monomer having a radical-reactive unsaturated bond, and an organic halide having a carbon-halogen bond used as a dormant species (or an organic halide raw material such as an azo-based radical initiator and a halogen molecule) ), Radical initiator, and raw materials other than the solvent.
• an organic halide raw material such as an azo-based radical initiator and a halogen molecule
• reaction temperature The reaction temperature in the method of the present invention is not particularly limited.
• the temperature is preferably 10 ° C or higher, more preferably 20 ° C or higher, still more preferably 30 ° C or higher, still more preferably 40 ° C or higher, and particularly preferably 50 ° C or higher. Further, it is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower, still more preferably 105 ° C. or lower, and particularly preferably 100 ° C. or lower. .
• reaction temperature is too high, there is a disadvantage that the heating equipment is costly.
• reaction temperature is not more than room temperature, there is a disadvantage that costs are required for equipment for cooling.
• the above-described temperature range slightly higher than room temperature and not excessively high is very suitable in a practical sense.
• reaction time The reaction time in the method of the present invention is not particularly limited. Preferably, it is 15 minutes or more, More preferably, it is 30 minutes or more, More preferably, it is 1 hour or more. Moreover, Preferably it is 3 days or less, More preferably, it is 2 days or less, More preferably, it is 1 day (24 hours) or less.
• reaction time is too short, it is difficult to obtain a sufficient molecular weight (or polymerization rate (monomer conversion rate)). If the reaction time is too long, the overall efficiency of the process is poor. By setting an appropriate reaction time, excellent performance (moderate polymerization rate and reduction of side reactions) can be achieved.
• the amount of oxygen in the gas phase in the reaction vessel is controlled. Thereby providing an appropriate amount of oxygen in the reaction solution. That is, during the polymerization step, a desired amount of oxygen (preferably 1 to 70 mM oxygen molecules per 1 ml of the liquid phase volume in the reaction vessel) is provided to the reaction solution.
• the amount of oxygen is preferably 1 mmol or more, more preferably 1.5 mmol or more per ml of liquid phase volume in the reaction vessel, and in one embodiment may be 2 mmol or more. Yes, in one embodiment it can be 2.5 mmol or more, in one embodiment it can be 3 mmol or more, and in one embodiment 3.5 mmol It is also possible to set it above, and in one embodiment, it can be set to 4 mmol or more. Further, the amount of oxygen is preferably 70 mmol or less, more preferably 60 mmol or less, still more preferably 50 mmol or less, and even more preferably, per 1 ml of the liquid phase in the reaction vessel. 40 mmol or less, particularly preferably 30 mmol or less. In one embodiment, it can be 25 mmol or less, and in one embodiment, it can be 20 mmol or less.
• oxygen concentration is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, and further preferably 1% by volume or more. In one embodiment, it may be 2% by volume or more. In one embodiment, it may be 3% by volume or more. In one embodiment, 4% by volume or more. In one embodiment, it may be 5% by volume or more. Moreover, 15 volume% or less is preferable, 12 volume% or less is more preferable, and 10 volume% or less is further more preferable. In one embodiment, it may be 9% by volume or less, in one embodiment, 8% by volume or less, and in one embodiment, 7% by volume or less. In one embodiment, it may be 6% by volume or less.
• the amount of oxygen can be adjusted by adjusting the volume of the gas phase in the reaction vessel.
• Any method can be used as a method for providing oxygen to the reaction solution. Specifically, for example, after putting a reaction solution into a reaction vessel, a mixed gas obtained by mixing a desired amount of oxygen and an inert gas (eg, argon or nitrogen) is introduced into the vessel. By conducting the polymerization reaction after replacing the gas phase in the container with the mixed gas, an appropriate amount of oxygen is provided to the polymerization reaction.
• an inert gas eg, argon or nitrogen
• a mixed gas composed of oxygen and an inert gas having a specific concentration into the reaction vessel, all the air initially present in the reaction vessel is eliminated. That is, the air in the reaction vessel is replaced with a mixed gas having a composition different from that of air.
• some or all of the air initially present in the reaction vessel may be used to provide oxygen to the reaction solution.
• only air present from the beginning in the reaction vessel may be used to provide oxygen to the reaction solution without introducing a mixed gas.
• the atmospheric pressure of the gas phase in the reaction vessel is preferably atmospheric pressure from the viewpoint of ease of operation, etc., but if necessary, the atmospheric pressure may exceed atmospheric pressure, May be a low pressure.
• the reaction vessel used is not particularly limited. However, in a preferred embodiment, the polymerization reaction is performed in a sealed container. In the case of a reaction vessel that is not sealed, the polymerization reaction is carried out while controlling the amount of oxygen transferred between the inside and outside of the reaction vessel.
• the reaction is carried out with the container sealed until the polymerization reaction is completed.
• the vessel is sealed and the polymerization reaction is performed.
• the container may be opened and closed during the polymerization reaction. In that case, it is necessary to control the amount of oxygen entering the container not to exceed an appropriate amount.
• the desired amount of oxygen described above is preferably provided to the reaction vessel at the time when the polymerization reaction is started. However, if necessary, a part thereof may be provided to the reaction container when the reaction starts, and the rest may be provided to the reaction container after the reaction starts.
• the reaction is preferably carried out while stirring the reaction solution.
• oxygen in the gas phase of the container is promoted to enter the reaction solution.
• Stirring can be performed by a conventionally known method.
• the stirring means which can be remotely operated from the outside, for example, a magnetic stirrer.
• a mixed gas of inert gas and oxygen for example, nitrogen gas containing 1% oxygen
• the stirring shaft provided with the stirring blade is preferably rotated by a motor or rotated by using a magnet and stirred.
• the shaft drive (rotation) part where the stirring shaft is attached to the reactor can prevent outside air from entering the interior by using a method of electromagnetically sealing or a method of sealing with water or oil. Also, if the inside of the reactor is pressurized (for example, a pressure 1 to 5% higher than the pressure outside the reaction vessel), even if there is a gap in the shaft drive unit, outside air can be prevented from entering. This is preferable.
• a method for introducing oxygen a method of flowing an oxygen-containing gas having a predetermined concentration continuously or intermittently into the space of the reactor or bubbling into the reaction solution is used.
• the living radical polymerization method of the present invention can be applied to homopolymerization, that is, production of a homopolymer, but it is also possible to produce a copolymer using the method of the present invention for copolymerization.
• the copolymerization may be random copolymerization or block copolymerization.
• the block copolymer may be a copolymer in which two or more types of blocks are bonded, or may be a copolymer in which three or more types of blocks are bonded.
• a block copolymer can be obtained by a method including a step of polymerizing the first block and a step of polymerizing the second block.
• the method of the present invention may be used for the step of polymerizing the first block
• the method of the present invention may be used for the step of polymerizing the second block. It is preferable to use the method of the present invention for both the step of polymerizing the first block and the step of polymerizing the second block.
• a block copolymer can be obtained by polymerizing the first block and then polymerizing the second block in the presence of the obtained first polymer.
• the first polymer can be subjected to polymerization of the second block after being isolated and purified, or the first polymer is not isolated and purified, and the first polymer can be subjected to the first polymerization during or after the polymerization of the first polymer.
• the block can be polymerized by adding a second monomer to the polymerization.
• a step of polymerizing each block is performed to obtain a desired copolymer weight. Coalescence can be obtained. And it is preferable to use the method of this invention in superposition
• the basic concept of the living radical polymerization method is a reversible activation reaction of a dormant species (polymer-X) to a growth radical (polymer.), Using a halogen as a protecting group X and a transition metal complex as an activation catalyst.
• the system is one of the useful living radical polymerization methods.
• the halogen of the organic halide can be extracted with high reactivity without using a catalyst, and a radical can be generated reversibly.
• transition metals are excellent in the action of catalyzing various chemical reactions because their electrons can be in various transition states. For this reason, it has been considered that transition metals are excellent as a catalyst for living radical polymerization.
• the polymerization reaction proceeds very efficiently without the addition of a catalyst compound.
• Scheme 1 shows a reaction formula when a catalyst is used in living radical polymerization.
• A is a catalyst, and when A pulls out a halogen atom (X) of a dormant species, a growth radical can be obtained reversibly.
• the resulting polymer obtained by the method of the present invention has a halogen (for example, iodine) at the terminal.
• a halogen for example, iodine
• the terminal halogen can be removed and used.
• the reactivity of the terminal halogen is generally high and can be removed or converted by a wide variety of reactions.
• the following scheme shows an example of a method for treating a polymer terminal when the halogen is iodine.
• the polymer terminal can be utilized by the reactions shown in these schemes.
• the halogen is other than iodine, the polymer terminal can be similarly converted to a functional group.
• a polymer having a narrow molecular weight distribution can be obtained.
• a polymer having a ratio Mw / Mn of a polymerization average molecular weight Mw to a number average molecular weight Mn of 1.5 or less by appropriately selecting the composition of reaction materials and reaction conditions.
• Mw / Mn of 1.4 or less, 1.3 or less, 1.2 or less, or even 1.1 or less.
• the living radical polymerization method of the present invention even when the halogen atom of the organic halide used as the dormant species is bromine, it is possible to obtain a polymer having Mw / Mn of less than 2.0. Compared with this radical polymerization method, a polymer having a narrow molecular weight distribution can be obtained. As described above, since the bromine compound is more stable than the iodine compound, the necessity for removing the terminal halogen from the produced polymer is relatively low, and the usefulness of the resulting polymer is extremely high.
• the polymer obtained by the living radical polymerization method of the present invention can be used for various applications.
• resists, adhesives, lubricants, paints, inks, dispersants, packaging materials, drugs, personal care products (hairdressing products, cosmetics, etc.), elastomers (automobile materials, industrial products, sports equipment, wire clothing materials, building materials) Etc.) and coating (powder coating etc.) can be used for production. It can also be used to create new electronics, optics, mechanics, crystals, separation, lubrication, and medical materials.
• the resulting polymer when a catalyst is not used, the resulting polymer can be used for a wide range of applications in that a compound derived from the catalyst (catalyst residue) is not contained. That is, the present invention can be suitably used for applications in which the obtained resin (polymer) has a high purity and a high-purity resin is required.
• the catalyst residue may or may not be removed from the produced polymer depending on the application.
• the polymer may be molded or dissolved or dispersed in a solvent or dispersion medium. However, the polymer after molding, or the polymer after dissolution or dispersion, etc. It retains the advantages of the invention and still falls within the range of polymers obtained with the polymerization process of the present invention.
• the polymer synthesized by using the polymerization method of the present invention has a narrow molecular weight distribution and can be used for various applications by taking advantage of the fact that the polymer does not contain any compound derived from the catalyst at all or is low in cost. is there.
• a homopolymer having a narrow molecular weight distribution, a random copolymer, and a block copolymer made of benzyl methacrylate can be used as a high-performance resist.
• polymers such as methacrylate (for example, dimethylamino methacrylate, 2-hydroxyethyl methacrylate), methacrylic acid, acrylate, and acrylic acid can be used for applications such as adhesives, paints, inks, and pigment dispersants. .
• a multi-branched polymer is synthesized by the method of the present invention, it is useful as a lubricant.
• the polymer obtained by the method of the present invention (for example, hydroxyethyl methacrylate, polyethylene glycol methacrylate, etc.) is also useful as a drug release material / medical material.
• polymers obtained by the method of the present invention are also useful for personal care products (eg, hairdressing products and cosmetics). is there.
• the polymer obtained by the method of the present invention (for example, (acrylate, methacrylate, styrene, diene, etc.) is also useful for applications such as elastomers and coatings.
• the polymer obtained by the method of the present invention is also useful for the creation and production of new electronic materials, optical materials, mechanical materials, crystal materials, separation materials, lubricating materials, medical materials, etc., which have not been conventionally used.
• the method of the present invention can be applied to, for example, surface graft polymerization, and a high-density polymer brush can be produced and used for various applications.
• a polymer that can be suitably used can be obtained in applications (for example, resist and organic EL) in which conductive impurities are required not to remain in the polymer.
• Example 1 [Methyl methacrylate (MMA) polymerization] (Entry 1) As an alkyl halide to be a low molecular dormant species, 80 mM 2-iodo-2-cyanopropyl (CP-I; the chemical structural formula is as described above) was used. No catalyst was used. 20 mM AIBN was used as a radical initiator. These materials were dissolved in methyl methacrylate (MMA) to obtain a reaction solution having the above concentration. The monomer concentration was about 8M. The solubility of these materials was good and a uniform solution was formed. This solution was placed in a container having an internal volume of 33 ml. The amount of reaction solution in the container is shown in the table below.
• the air in the container was replaced with an oxygen / argon mixed gas containing 1% oxygen (that is, a mixture of 1 vol% oxygen and 99 vol% argon), and the container was sealed.
• the solution was stirred using a magnetic stirrer. While controlling the rotation of the rotor of the stirrer by remote control from the outside of the container, stirring was continued while the container was sealed, and the reaction solution was heated to 80 ° C. to carry out the polymerization reaction.
• Table 1A shows the composition of the experiment and the amount of the reaction solution. The reaction temperature, time and results are shown in Table 1B.
• the concentration “mM” indicates the number of millimoles based on 1 liter of monomer. For example, 80 mM means that 1 milliliter of monomer contains 80 mmol.
• the concentration “M” indicates the number of moles based on 1 liter of monomer. For example, 8M means that 8 mol is contained in 1 liter of monomer. In the case of MMA, 1 liter of monomer (bulk) is 8 mol at room temperature.
• the ratio of the oxygen in the gaseous phase of a container is shown by volume%.
• the oxygen concentration the volume of the liquid phase in the initial number of moles (mM) before starting the reaction of O 2 in the gas phase in the reaction vessel per 1 ml of the volume of the liquid phase in the reaction vessel is described.
• PDI indicates the ratio of Mw / Mn .
• M n is the number average molecular weight of the obtained polymer.
• M n, theo is
• [M] 0 and [RI] 0 represent the initial concentrations (charge concentrations) of the monomer and the alkyl iodide serving as the dormant species, respectively. Further, conv is a monomer conversion rate (polymerization rate).
• MMA Methyl methacrylate
• RI 2-iodo-2-cyanopropyl
• CP-I 2-iodo-2-cyanopropyl
• I radical initiator
• AIBN azobisisobutyronitrile
• Mn and PDI Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• GPC gel permeation chromatography
• THF tetrahydrofuran
• Example 2 and Comparative Example 2 [Methyl methacrylate (MMA) polymerization] As shown in Table 2A and Table 2B below, methyl methacrylate (MMA) was polymerized in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed. The results are shown in Table 2A and Table 2B.
• the entries 1 to 3 are the experiments of Example 2, and the entries C-1 and C-5 are the experiments of Comparative Example 2.
• the oxygen concentration was 80 mM, and the polymerization was not controlled.
• MMA Methyl methacrylate
• RI 2-iodo-2-cyanopropyl
• CP-I Catalyst: not used radical initiator
• In azobisisobutyronitrile
• Mn and PDI Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• Example 3 [Methyl methacrylate (MMA) polymerization]
• MMA methyl methacrylate
• Entry 1 to 4 are the experiment of Example 3, and entry C-1 is the experiment of Comparative Example 3.
• MMA Methyl methacrylate
• RI 2-iodo-2-cyanopropyl
• CP-I 2-iodo-2-cyanopropyl
• I radical initiator
• AIBN azobisisobutyronitrile
• Mn and PDI Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• GPC gel permeation chromatography
• THF tetrahydrofuran
• Example 4 [Methyl methacrylate (MMA) polymerization]
• a container having an internal volume of 33 ml was used as a reaction container.
• the experiment was performed in the same manner as the experiment in Example 1 except that the reaction materials and conditions were changed as shown in the following table.
• the experimental results are shown in the following table.
• MMA Methyl methacrylate
• RI 2-iodo-2-cyanopropyl
• CP-I 2-iodo-2-cyanopropyl
• I radical initiator
• AIBN azobisisobutyronitrile
• Mn and PDI Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• GPC gel permeation chromatography
• THF tetrahydrofuran
• Example 5 methyl methacrylate (MMA) was polymerized in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed.
• the experimental results are shown in the following table.
• Entry 1 to 4 are the experiments of Example 5, and entries C-1, C-3, and C-4 are the experiments of Comparative Example 4.
• Polymerization was also controlled in solution polymerization using a highly polar solvent such as MFDG and 1-butanol.
• MMA Methyl methacrylate
• Solvent Dipropylene glycol monomethyl ether (MFDG) or butanol monomer concentration: 8M (bulk)
• Catalyst not used radical initiator (In): azobisisobutyronitrile (AIBN).
• Mn and PDI Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• GPC gel permeation chromatography
• Example 6 methyl methacrylate (MMA) was polymerized in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed. The experimental results are shown in the following table.
• Polymerization was controlled regardless of the type of initiator and polymerization temperature. It was controlled by both azo compounds (AIBN, V70, V65) and peroxides (BPO, PDX).
• MMA Methyl methacrylate
• RI 2-iodo-2-cyanopropyl
• CP-I Catalyst: not used radical initiator
• In azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V70), 2,2′-azobis (2,4-dimethylvaleronitrile) (V65), Benzoyl peroxide (BPO), Di (4-t-butylcyclohexyl) peroxydicarbonate (PDX) Mn
• PDI Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• GPC gel permeation chromatography
• THF tetrahydrofuran
• Example 7 As shown in the table below, methyl methacrylate (MMA) was polymerized in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed. The experimental results are shown in the following table.
• MMA methyl methacrylate
• a method of generating low-molecular dormant species (alkyl iodide) in a reaction solution during polymerization was also applicable. It did not depend on the type of radical initiator and the polymerization temperature.
• MMA Methyl methacrylate
• RI Alkyl halide
• I 2 radical initiator
• Catalyst not used radical initiator
• AIBN azobisisobutyronitrile
• V70 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile
• V65 2,2'-azobis (2,4-dimethylvaleronitrile
• PDI Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• GPC gel permeation chromatography
• THF tetrahydrofuran
• entries 1 to 5 are the experiments of Example 8, and entries C-1 and C-5 are the experiments of Comparative Example 5. Polymerization was controlled in the oxygen concentration range of 1.8 mM to 26 mM.
• Styrene All bulk polymerization (monomer concentration is 8M (8000 mM)) Radical initiator: benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN) Alkyl halide (RI) to be dormant species: 2-iodo-2-cyanopropyl (CP-I) Mn and PDI: Polystyrene (PSt) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• GPC gel permeation chromatography
• THF tetrahydrofuran
• Example 9 Polymerization of benzyl methacrylate (BzMA)] As shown in the table below, polymerization was carried out in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed. The experimental results are shown in the following table.
• Monomer benzyl methacrylate (BzMA) Radical initiator: Azobisisobutyronitrile (AIBN) Bulk polymerization (monomer concentration is 8M (8000 mM)) Alkyl halide (RI) to be dormant species: 2-iodo-2-cyanopropyl (CP-I) Mn and PDI: Molecular weight and molecular weight distribution index determined by a multi-angle light scattering (MALLS) detector using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• MALLS multi-angle light scattering
• Example 10 [Polymerization of GMA] As shown in the table below, polymerization was carried out in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed. The experimental results are shown in the following table.
• MALLS multi-angle light scattering
• Example 11 [Polymerization of PEGMA] Polymerization was carried out in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed as shown in the following table. The results are shown in the table below.
• PEGMA Polyethylene glycol methacrylate
• BPO bulk polymerization, monomer concentration 8M (8000 mM)
• PDI molecular weight and molecular weight distribution index determined by a multi-angle light scattering (MALLS) detector using gel permeation chromatography (GPC) using dimethylformamide (DMF) as an eluent.
• MALLS multi-angle light scattering
• Example 12 [HEMA polymerization] Polymerization was carried out in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed as shown in the following table. The results are shown in the table below.
• HEMA 2-hydroxyethyl methacrylate
• V70 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)
• V70 Bulk polymerization (monomer concentration 8M (8000mM))
• PDI molecular weight and molecular weight distribution index determined by a multi-angle light scattering (MALLS) detector using gel permeation chromatography (GPC) with dimethylformamide (DMF) as an eluent.
• MALLS multi-angle light scattering
• Entry 1 to 7 are the experiments of Example 13, and entries C-1 and C-2 are the experiments of Comparative Example 6.
• Polymerization was controlled in the oxygen concentration range of 1.8 mM to 26 mM.
• Monomer 2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA)
• Solvent Dipropylene glycol monomethyl ether (MFDG) Radical initiator: azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V70) entry C-1, C-2, 1-5: Bulk polymerization (monomer concentration 8M (8000 mM)) entry 6, 7: solution polymerization (monomer concentration 4M (4000 mM))
• MFDG Dipropylene glycol monomethyl ether
• AIBN
• Example 14 [MAA-MMA random copolymerization] Polymerization was carried out in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed as shown in the following table. The results are shown in the table below.
• Monomer Methacrylic acid (MAA), Methyl methacrylate (MMA) Monomer concentration: 8M (bulk polymerization) Alkyl halide which becomes a dormant species (R-I): produced in the container by reaction with I 2 and V70.
• Radical initiator 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V70) Mn and PDI: Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using dimethylformamide (DMF) as an eluent.
• GPC gel permeation chromatography
• DMF dimethylformamide
• Example 15 [Copolymerization of ICEMA-MMA] Polymerization was carried out in the same manner as in Example 14 except that the reaction materials and reaction conditions were changed as shown in the following table. The results are shown in the table below.
• Entry 1 is the experiment of Example 15, and entry C-1 is the experiment of Comparative Example 7.
• Monomer 2-isocyanoethyl methacrylate (ICEMA), methyl methacrylate (MMA) Radical initiator: 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V70) Bulk polymerization (monomer concentration is 8M (8000 mM)) Alkyl halide (RI) to be dormant species: 2-iodo-2-cyanopropyl (CP-I) Mn and PDI: Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using dimethylformamide (DMF) as an eluent.
• ICEMA 2-isocyanoethyl methacrylate
• MMA methyl methacrylate
• Radical initiator 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)
• V70 Bulk polymerization (monomer concentration is 8M (8000 mM)
• Example 16 Polymerization of acrylonitrile (AN)] Polymerization was carried out in the same manner as in Example 1 except that the reaction materials and reaction conditions were changed as shown in the following table. The results are shown in the table below.
• Monomer Acrylonitrile (AN) Bulk polymerization (monomer concentration is 8M (8000 mM)) Radical initiator: Benzoyl peroxide (BPO) Solution polymerization (monomer concentration is 4M (4000 mM)) Solvent: Alkyl halide to be ethylene carbonate dormant species (RI): 2-iodo-2-cyanopropyl (CP-I) Mn and PDI: molecular weight and molecular weight distribution index determined by a multi-angle light scattering (MALLS) detector using gel permeation chromatography (GPC) with dimethylformamide (DMF) as an eluent.
• MALLS multi-angle light scattering
• MMA Methyl methacrylate
• AIBN Azobisisobutyronitrile
• RI Alkyl halide
• CP-I 2-iodo-2-cyanopropyl
• PDI Polymethylmethacrylate (PMMA) equivalent molecular weight and molecular weight distribution index using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• the catalyst concentration (CuBr complex concentration) in this experiment is 5 mM.
• peroxide was not used. This is because, in the case of a copper complex catalyst, it was a technical common knowledge of those skilled in the art that no peroxide is used. The reason for this is that (1) in the case of a copper complex catalyst, a radical reaction is initiated without using a peroxide, and (2) when a peroxide is added to the copper complex catalyst, The deactivation reaction occurs and the molecular weight distribution becomes wider.
• the non-patent document 1 also describes that a reaction raw material not containing a peroxide is used.
• PEB 1-phenylethyl bromide dHbipy: A ligand for dissolving CuBr in a monomer (styrene).
• the polymerization rate was considerably lower than the polymerization rate of styrene in Example 8. Further, Mn after the reaction was 1200 to 1400, which was extremely low, and high molecular weight polystyrene could not be obtained.
• the method of the present invention is highly capable of living radical polymerization regardless of whether the transition metal complex catalyst in the prior art is not used. Is controlled.
• reaction temperature can be lowered by 10 to 40 ° C.
• the method of the present invention is a method of performing living radical polymerization by controlling the oxygen concentration in the container without adding a catalyst.
• the oxygen concentration in the container has never been considered to be controlled because it has not been considered important for living radical polymerization.
• the present invention is a new technique that enables living radical polymerization only by controlling the oxygen concentration, and is a new concept method that has never been conceived.
• oxygen has been widely known to those skilled in the art as a polymerization inhibitor for radical polymerization. Therefore, in radical polymerization, it has been common knowledge for those skilled in the art to remove oxygen. However, in the present invention, it has been discovered that living radical polymerization is possible by setting the oxygen concentration to an appropriate concentration. It is a revolutionary method that is extremely advantageous from an industrial point of view because it does not require addition of a catalyst, is new, is low in cost, and has high safety to human bodies and the environment.
• the key to the present invention is to appropriately control the oxygen concentration and to combine these two points of using an alkyl halide as a dormant species for living radical polymerization. That is, in the presence of alkyl halides, oxygen was found to act as a living radical polymerization controller rather than a polymerization inhibitor in the appropriate concentration range, creating a new concept of living radical polymerization.
• the present inventors have invented a new type of living radical polymerization method (precisely controlled radical polymerization) in which it is not necessary to substantially add a catalyst.
• a catalyst since it is not necessary to use a catalyst, problems with conventional catalysts (catalyst toxicity, solubility, extreme reaction conditions, coloring / odor, etc.) are solved. Therefore, the method of the present invention is much more environmentally friendly and economical than conventional living radical polymerization.
• living radical polymerization can be applied to the production of various high-value-added materials.
• thermoplastic elastomers autonomous materials, industrial products, medical materials, footwear, sports equipment, toys, wire covering materials, construction / civil engineering materials, resin modification, etc.
• resists organic EL
• adhesives polymers Alloys, various filler additives, lubricants, surfactants, paints, inks, packaging materials, drugs (for example, pharmaceutical release materials), personal care products (cosmetics, hairdressing agents, etc.), sealing agents, plasticizers, tackifiers
• the market scale is extremely large.
• the living radical polymerization of the present invention can be widely used as an excellent process for producing new electronic materials, optical materials, separation materials, or biomaterials.
• the present inventors have discovered that living radical polymerization can be controlled by controlling the concentration and amount of oxygen in a reaction vessel without using a compound that has been used as a catalyst in conventional living radical polymerization.
• the living radical polymerization was realized at a much lower cost.
• the cost of the catalyst required to synthesize 1 kg of polymer is calculated based on the price described in the catalog of Aldrich, for example, in the case of the copper complex catalyst most commonly used in conventional catalysts
• the cost of the catalyst is about several thousand yen.
• using a germanium catalyst costs about 1,000 yen, but the present invention eliminates the cost of the catalyst. That is, according to the present invention, the cost can be reduced by orders of magnitude compared to the conventional method using a catalyst.
• the present invention has both high environmental safety not found in the conventional method, excellent economic efficiency far superior to the conventional method, and high simplicity, and is extremely practical.

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