WO2018174297A1 - ポリマーの製造方法、ラジカル重合の開始基含有化合物及びポリマー - Google Patents
ポリマーの製造方法、ラジカル重合の開始基含有化合物及びポリマー Download PDFInfo
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- WO2018174297A1 WO2018174297A1 PCT/JP2018/012042 JP2018012042W WO2018174297A1 WO 2018174297 A1 WO2018174297 A1 WO 2018174297A1 JP 2018012042 W JP2018012042 W JP 2018012042W WO 2018174297 A1 WO2018174297 A1 WO 2018174297A1
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- 0 C*C(C(*)(*)Br)=O Chemical compound C*C(C(*)(*)Br)=O 0.000 description 1
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- C08F2/00—Processes of polymerisation
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F8/00—Chemical modification by after-treatment
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08F2438/00—Living radical polymerisation
Definitions
- the present invention relates to a method for producing a new polymer using a radically polymerizable monomer having an unsaturated bond, and more specifically, a novel polymer capable of initiating radical polymerization with a termination reaction by using a simple commercially available material. And a polymer obtained using the radical polymerization initiating group-containing compound. More specifically, it is advantageous in terms of cost, and it is mixed and heated using a simple commercially available material without using a radical polymerization initiator, a special material used for living radical polymerization, or a metal-based catalyst.
- the present invention relates to a technique capable of providing a polymer whose structure is controlled in various states desired.
- a polymer obtained by polymerizing a radical polymerizable monomer having an unsaturated bond such as a vinyl group, vinylidene group or vinylene group (hereinafter sometimes simply referred to as “monomer”) is obtained by radical polymerization or ionic polymerization. Obtained, highly versatile and used in various places.
- radical polymerization thermal polymerization using an azo radical polymerization initiator or peroxide polymerization initiator necessary for generating radicals, or photopolymerization using a photo radical polymerization initiator. To obtain the polymer.
- radical polymerization using a radical polymerization initiator for example, a polymer having a complicated structure such as a block copolymer, a graft copolymer, or a star polymer (star-shaped polymer) is used as a monomer. It cannot be obtained by the polymerization method.
- living radical polymerization although the above-described polymer having a complicated structure can be obtained, in that case, there are the following problems. That is, in living radical polymerization, a special compound is used, or a metal catalyst is used. Therefore, it is necessary to remove those compounds and catalysts, which is complicated industrially and requires a plurality of steps. In addition, the polymerization conditions have to be strict, such as requiring purification of the monomers used or in a nitrogen atmosphere.
- the object of the present invention is to use a general-purpose commercially available material as much as possible without using a radical polymerization initiator, a special material used for living radical polymerization, or a metal-based catalyst, and set strict polymerization conditions. Almost obtain polymers with controlled molecular weight and molecular weight distribution, and polymers with complex structures such as block copolymers, graft polymers, and star polymers as polymers controlled to the desired state by a simple method. It is an object of the present invention to provide an industrially useful method for producing a novel polymer, and a radical polymerization initiating group-containing compound that enables the production method. Moreover, the objective of this invention is to implement
- the present inventors have found that the radical polymerizable monomer (1) and the group (2) having a specific structure that functions as a polymerization initiating group defined in the present invention are obtained. These materials are mixed and added using the introduced organic compound and a compound having a chloride ion (chlorine ion) and a bromide ion (bromine ion) selected from the specific compound group of (3).
- a novel polymerization technique is found in which the polymerization of the radically polymerizable monomer (1) proceeds easily from the polymerization initiating group constituting the organic compound (2) simply by heating (heating), thereby obtaining a polymer.
- the present invention has been achieved.
- the present inventors further use the compound (4) having a group selected from the group consisting of an imide group, an N-bromoimide group, an N-iodoimide group and an organic base in addition to the above-described configuration. It has been found that the structure and molecular weight of the resulting polymer can be controlled very simply. According to the new polymerization method found by the present inventors, without using a radical polymerization initiator used in the conventional polymerization method, a special material used for living radical polymerization or a metal-based catalyst, By simply mixing and heating the above materials (1) to (3) or (1) to (4), a polymer can be easily obtained, and the shape and characteristics can be controlled as desired. It is realized to obtain a finished polymer.
- the “warming” defined in the present invention means that the temperature is set to room temperature or higher, for example, 40 ° C. or higher, and the temperature may be determined in consideration of the polymerization rate.
- the present invention introduces (1) a radically polymerizable monomer having an unsaturated bond and (2) one or more groups having a structure represented by the following general formula 1 that function as a polymerization initiating group of the monomer. And (3) a group consisting of a metal chloride salt, a metal bromide salt, a quaternary ammonium chloride salt, a quaternary ammonium bromide salt, a quaternary phosphonium chloride salt, and a quaternary phosphonium bromide salt.
- Polymerization in which radical polymerization accompanied by termination reaction of the monomer of (1) starts from the group of the structure by mixing and heating one or more selected compounds containing chloride ions and / or bromide ions.
- a process for producing a polymer characterized by comprising a step is provided.
- R 1 represents either H, an alkyl group, an acyl group, or an aryl group
- R 2 represents an alkyl group or an aryl group
- Y represents O or NH.
- Preferred forms of the polymer production method described above include the following. Do not use any of azo radical polymerization initiator, peroxide radical polymerization initiator and photo radical polymerization initiator in the polymerization step; and (4) imido group, N-bromoimide in the polymerization step.
- the group having a structure represented by the general formula 1 is a group having a structure represented by the following general formula 2.
- the present invention provides a radical polymerizable monomer having an unsaturated bond without using any of an azo radical polymerization initiator, a peroxide radical polymerization initiator, and a photo radical polymerization initiator.
- a radical polymerization initiating group-containing compound for causing radical polymerization with termination reaction which is a metal chloride salt, metal bromide salt, quaternary ammonium chloride salt, quaternary ammonium bromide salt, quaternary phosphonium
- the radical polymerizable monomer functions as a polymerization initiating group.
- Providing a starting group-containing compound radical polymerization of. (In General Formula 1, R 1 represents either H, an alkyl group, an acyl group, or an aryl group, R 2 represents an alkyl group or an aryl group, and Y represents O or NH.)
- a preferred form of the radical polymerization initiating group-containing compound of the present invention is that the group having a structure represented by the general formula 1 is a group having a structure represented by the following general formula 2. (In General Formula 2, Y represents O or NH.)
- the organic substance is an organic substance formed by introducing two or more groups having a structure represented by the general formula 1 into the molecule; the organic substance represents a group having a structure represented by the general formula 1 or 2 in the molecule.
- the organic substance is a compound in which three or more groups having a structure represented by the general formula 1 or 2 are introduced into the molecule; the organic substance is generally It is a vinyl polymer formed by introducing three or more groups having a structure represented by Formula 1 or 2 into the molecule; the organic substance has introduced one or more groups having a structure represented by Formula 1 or 2 into the molecule.
- a copolymer of a monomer and a monomer having a reactive group bonded to the surface of the substrate are examples of the organic substance.
- the radically polymerizable monomer having an unsaturated bond of (1) and one or more groups having a structure represented by the following general formula 1 are introduced in the molecule (2 ) Radical polymerization-initiating group-containing compound, and metal chloride salt, metal bromide salt, quaternary ammonium chloride salt, quaternary ammonium bromide salt, quaternary phosphonium chloride salt, and quaternary phosphonium salt of (3) Radical polymerizability introduced into the initiating group-containing compound (2) by mixing and heating at least one chloride ion and / or bromide ion-containing compound selected from the group consisting of bromide salts
- a preferred form of the polymer of the present invention is that the radical polymerization initiating group-containing compound (2) is a polymer containing at least 2- (2-bromoisobutyryloxy) ethyl methacrylate as a constituent component. .
- the polymer of the present invention relates to a product invention.
- the invention of the product is specified.
- the polymer of the present invention functions as a polymerization initiating group based on the specific structure of the radical polymerization initiating group-containing compound (2) by the chloride ion and / or bromide ion-containing compound (3).
- a structure in which a polymer composed of the monomer (1) is grown starting from a specific group introduced into the organic compound (2) obtained by radical polymerization of the monomer (1) from the polymerization initiation group This is because it cannot be directly specified by its structure or characteristics, and can be specified for the first time by a process (production method) for obtaining a polymer. It is a well-known fact in the art that a polymer is an aggregate (mixture) of various polymer molecules having different molecular weights, and the structure and physical properties of individual polymer molecules contained in the aggregate (mixture) are specified. It's impossible and not nearly practical.
- a specific chloride ion (chlorine ion) and / or bromide ion (bromine ion) -containing compound selected from the specific compound group of (3) hereinafter referred to as “(3) Cl / Br ion-containing compound”
- (3) Cl / Br ion-containing compound a specific chloride ion
- the (3) Cl / Br ion-containing compound is not only easily available from commercially available general-purpose materials, but also has various structures and is not colored like iodine ions. This compound is stable to heat and light and is excellent as a material to be used industrially. Further, according to the production method of the present invention, the polymerization system using the materials (1) to (3) described above is further added with the compound (4) having an organic base or an imide group. Thus, a polymer having a molecular weight and a structure controlled to a desired state can be obtained more easily.
- the above-mentioned simple and excellent production method is skillfully utilized, for example, ABA block copolymer, star polymer, graft copolymer, surface graft polymer, heterogeneous graft / block / multi-branched polymer, etc. It is possible to industrially manufacture a polymer having a complicated structure, which is difficult, complicated and difficult to realize.
- the polymer production method of the present invention is environmentally useful and advantageous in terms of cost because the types of materials used for production are reduced. Furthermore, the polymer production method of the present invention does not require the use of explosive compounds such as the conventionally used azo polymerization initiators and peroxide polymerization initiators. And the material does not need to be frozen and refrigerated as in the case of those initiators.
- the production method of the present invention uses a compound in which a bromine atom is bonded to the polymerization initiating group, the bond is relatively stable and is used in living radical polymerization, although it is very useful, Since there is no need to use a polymerization initiating compound having an iodine atom that can be decomposed by light, there is a great merit in storing materials. These mean that the polymer production method has extremely high practical value.
- the above-described method for producing the polymer of the present invention capable of obtaining various excellent effects can be realized for the first time by the radical polymerization initiator-containing compound of the present invention.
- the radical polymerization initiation group-containing compound of the present invention is a general-purpose compound that is not limited as long as one or more groups having a simple structure defined by the present invention are introduced. Specifically, it can be used as a general-purpose low molecular weight compound, polymer or monomer by appropriately changing the number of groups to be introduced and the form of the organic compound into which the group has been introduced.
- radical polymerization initiating group-containing compound of the present invention ABA block copolymer, star polymer, bottle brush polymer, concentrated polymer brush, heterogeneous graft / block / multi-branched polymer, etc. designed to the desired structure Various polymers can be obtained easily and economically.
- the radical polymerization-initiating group-containing compound of the present invention is mixed with a Cl / Br ion-containing compound (3) selected from the general-purpose compound group defined in the present invention, and is heated in a simple operation. The point that it can function as a polymerization initiating group is extremely useful industrially.
- the present invention will be described in more detail with reference to preferred embodiments.
- the present inventors have used complicated materials using simple commercially available materials without using conventional materials with problems of safety and storage.
- the present invention has been accomplished by finding an unprecedented and completely new method for polymerizing a polymer, which makes it possible to easily obtain a polymer having a structure, which is extremely useful industrially.
- a radical polymerizable monomer (2) an organic compound into which a group having a specific structure that functions as a polymerization initiating group defined in the present invention is introduced, and (3) Of the above-mentioned Cl / Br ion-containing compound, and these components are mixed and heated (heated) with a very simple operation.
- the radical polymerization of the radical polymerizable monomer starts and proceeds to obtain a polymer.
- At least one radical polymerizable monomer having an unsaturated bond (1) and a group having a structure represented by the following general formula 1 functioning as a polymerization initiating group of the monomer are contained in the molecule. It consists of the organic compound (2) introduced and a metal chloride salt, metal bromide salt, quaternary ammonium chloride salt, quaternary ammonium bromide salt, quaternary phosphonium chloride salt, quaternary phosphonium bromide salt.
- R 1 represents either H, an alkyl group, an acyl group, or an aryl group
- R 2 represents an alkyl group or an aryl group
- Y represents O or NH.
- a radical polymerizable monomer having an unsaturated bond (hereinafter referred to as “monomer of (1)”), which is a polymer forming component, is used as an essential component.
- the monomer (1) include conventionally known monomers having an unsaturated bond such as a monomer having a vinyl group, a vinylidene group, or a vinylene group. That is, any of conventionally known monomers capable of radical polymerization can be used and is not particularly limited.
- styrene vinyl toluene, vinyl hydroxybenzene, chloromethyl styrene, vinyl naphthalene, vinyl biphenyl, vinyl ethyl benzene, vinyl dimethyl benzene, ⁇ -methyl styrene, ethylene, propylene, isoprene, butene, butadiene, 1-hexene, cyclohexene, cyclodecene , Dichloroethylene, chloroethylene, fluoroethylene, tetrafluoroethylene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, isocyanatodimethylmethane isopropenylbenzene, phenylmaleimide, cyclohexylmaleimide, hydroxymethylstyrene, styrenesulfonic acid, vinylsulfone Acid, vinylamine, allylamine, aminostyrene, vinylmethylamine,
- (meth) acrylate type and (meth) acrylamide type monomers are mentioned. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-methylpropane (meth) acrylate, t-butyl (meth) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) Acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, behenyl
- the monomers containing hydroxyl groups are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl ( Examples thereof include mono (meth) acrylates of alkylene glycol such as (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and cyclohexanediol mono (meth) acrylate.
- a monomer having a glycol group, poly (n 2 or more, the same applies hereinafter) ethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, mono or polyethylene glycol mono or Examples include mono (meth) acrylates of polyalkylene glycols, such as mono (meth) acrylates of polypropylene glycol random copolymers, mono (meth) acrylates of mono or polyethylene glycol mono or polypropylene glycol block copolymers.
- ethylene glycol monomethyl ether (meth) acrylate (poly) ethylene glycol monooctyl ether (meth) acrylate, (poly) ethylene glycol monolauryl ether (meth) acrylate, (poly) ethylene glycol monostearyl ether ( (Meth) acrylate, (poly) ethylene glycol monooleyl ether (meth) acrylate, (poly) ethylene glycol monostearate (meth) acrylate, (poly) ethylene glycol monononylphenyl ether (meth) acrylate, (poly) propylene glycol Monomethyl ether (meth) acrylate, (poly) propylene glycol monoethyl ether (meth) acrylate, (poly) propylene glycol mono (Polyalkylene) glycol monoalkyl, alkylene, alkyne ether such as cutyl ether (meth) acrylate, (poly)
- the following monomers which are monomers having an acid group can also be used.
- the monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, acrylic acid dimer, itaconic acid, fumaric acid, crotonic acid, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth).
- examples thereof include monomers obtained by reacting hydroxyalkyl (meth) acrylate such as acrylate with maleic anhydride, succinic anhydride, phthalic anhydride, and the like, and monoester monomers of maleic acid and itaconic acid.
- Examples of the monomer having a sulfonic acid group include dimethylpropylsulfonic acid (meth) acrylamide, ethyl sulfonate (meth) acrylate, and ethyl (meth) acrylamide.
- Examples of the monomer having a phosphoric acid group include (di, tri) methacryloyloxyethyl phosphate.
- Oxygen atom-containing monomers such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, oxetanylmethyl (meth) acrylate, morpholino (meth) acrylate, methylmorpholino (meth) acrylate, methylmorpholinoethyl (meth) acrylate Etc.
- Examples of monomers having amino groups include the following. Examples of the monomer having a primary amino group include 2-aminoethyl (meth) acrylate and 2-aminopropyl (meth) acrylamide. Examples of the monomer having a secondary amino group include t-butylaminoethyl (meth). Examples thereof include acrylate, tetramethylpiperidyl (meth) acrylate, and t-butylaminopropyl (meth) acrylamide.
- Examples of the monomer having a tertiary amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, N-ethylmorpholino (meth) acrylate, dimethylpropyl (meth) acrylamide and the like. Can be mentioned.
- Examples of monomers having a quaternary amino group include trimethylaminoethyl (meth) acrylate chloride, diethylmethylaminoethyl chloride (meth) acrylate, benzyldimethylaminoethyl chloride (meth) acrylate, and trimethylaminoethyl (meth) acrylate methyl sulfate. Is mentioned.
- examples include monomers obtained by reacting primary and secondary amines with glycidyl group-containing monomers such as glycidyl (meth) acrylate.
- a nitrogen atom-containing monomer for example, (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, and blocked isocyanate-containing (meth) acrylates in which the isocyanate is blocked with caprolactone or the like, Ethyleneiminoethyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc.
- Amide monomers N-vinylpyrrolidone, N-vinylacetamide, N-vinylcaprolactam and the like.
- Other monomers that can be used in the present invention include the following. Obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone and ⁇ -butyrolactone using the (poly) alkylene glycol mono (meth) acrylic acid ester such as (meth) acryloyloxyethyl mono or polycaprolactone as an initiator. Polyester-based mono (meth) acrylic acid ester; 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl succinate, etc.
- ester-based (meth) acrylate obtained by reacting an alkylene glycol mono (meth) acrylic acid ester with a dibasic acid to form a half ester and then reacting the other carboxylic acid with an alcohol or an alkylene glycol;
- mono (meth) acrylates of polyfunctional hydroxyl compounds having two or more hydroxyl groups such as glycerol mono (meth) acrylate and dimethylolpropane mono (meth) acrylate; 3-chloro-2-hydroxypropyl (meth) acrylate
- Halogen atom-containing (meth) acrylates such as octafluorooctyl (meth) acrylate and tetrafluoroethyl (meth) acrylate
- 2- (4-benzoxy-3 UV-absorbing monomers such as -hydroxyphenoxy) ethyl (meth) acrylate, 2- (2'-hydroxy-5- (meth) acryloyloxyethylphenyl) -2H-benzotriazole
- ethyl- ⁇ -hydroxymethyl A ⁇ -position hydroxyl-substituted acrylates such
- a cyclic vinyl monomer can be used, and a monomer having two or more addition polymerizable groups can be used as necessary.
- divinylbenzene ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, (meth) acrylic acid ester of polyalkylene glycol adduct of trimethylolpropane, (meth) acrylic acid of alkylene oxide adduct of bisphenol A
- esters include esters.
- one or more radical polymerizable monomers having an unsaturated bond described above can be used.
- the present invention aims to easily obtain a linear polymer, an AB block copolymer, an ABA block copolymer, a star polymer, a bottle brush polymer, a concentrated polymer brush, a heterogeneous graft / block / multi-branched polymer, etc. Is used in two or more.
- methacrylic acid monomers are particularly preferably used for the following reasons.
- “methacrylic acid monomer” refers to methacrylic acid and methacrylate which is a methacrylic ester.
- Many methacrylic acid monomers have a relatively high glass transition point, and have a tertiary ester group, and thus are highly resistant to water and hydrolysis.
- the carbon to which chlorine or bromine is bonded obtained in the polymerization process of the new polymerization technique realized in the present invention is tertiary, and the radical of the tertiary carbon is relatively stable, This is because bromine is easily eliminated as a radical and is optimal for the mechanism of the polymerization technique realized in the present invention.
- group of formula 1 a group having a structure represented by the following general formula 1 (hereinafter sometimes referred to as “group of formula 1” or “polymerization initiating group”)
- group of formula 1 a group having a structure represented by the following general formula 1
- the organic compound (2) used in the present invention and characterizing the present invention may have the following structure introduced into the molecule. However, it functions as a polymerization initiating group for the monomer (1).
- the organic compound (2) is safer than conventional azo polymerization initiators and peroxide polymerization initiators conventionally used for radical polymerization, and is made of a material similar to conventional initiators. There is no need to freeze or refrigerate.
- a compound having a bromine atom bonded in its structure is used, the bond is relatively stable, and it is decomposed by heat or light like a polymerization initiating compound bonded with an iodine atom used in living radical polymerization. There is no end to it.
- R 1 represents either H, an alkyl group, an acyl group, or an aryl group
- R 2 represents an alkyl group or an aryl group
- Y represents O or NH.
- the “group of formula 1” defined in the present invention has a bromine atom (also referred to as bromo) bonded in its structure, and this bromine atom is a group that can be removed or substituted reactively. Furthermore, at least one electron withdrawing group such as an ester group, an amide group, a cyano group, a carboxy group, or an aryl group is bonded to the carbon to which the bromine atom is bonded. is there.
- any organic compound having a structure in which one or more such groups are introduced into the molecule can be used.
- the organic compound (2) for example, any form such as a low molecular weight compound, a monomer, and a polymer can be used.
- the “group of formula 1” will be described below.
- the “group of formula 1” defined in the present invention is specifically exemplified, but is not limited to the following.
- Examples of the “group of formula 1” include those having an ester bond or an amide bond in the structure thereof as shown below.
- an organic compound in which one or more “group of formula 1” constituting the present invention is introduced into a molecule has a bromine atom (Br) bonded through an ester bond or an amide bond. ing.
- Examples thereof include groups having an ester bond or an amide bond of ⁇ -bromoalkanoic acid as described below.
- Examples thereof include groups having an ester bond or an amide bond of ⁇ -chloro or bromoaryl-substituted alkanoic acid as described below.
- Examples thereof include groups having an ester bond or an amide bond of bromo-substituted acetoalkanoic acid as described below.
- the introduction of the “group of formula 1” as exemplified above into the organic compound may be any method, and is not particularly limited.
- the “group of formula 1” when the “group of formula 1” is introduced, it can be obtained by esterifying or amidating the corresponding carboxylic acid group-containing compound. Further, it can be obtained by reacting a compound having an “epoxy group” with a compound having “group of formula 1”.
- a compound in which a hydroxyl group is bonded to a group to which bromine is bonded in the structure of “group of formula 1” is used, and phosphorus tribromide or hydrobromic acid is used to form a hydroxyl group moiety of the compound. May be introduced by substituting with bromine.
- a compound having an unsaturated bond at the C—Br portion in the structure of the “group of formula 1” may be used, and bromo may be introduced by adding hydrogen bromide to the unsaturated bond.
- bromo may be introduced by adding hydrogen bromide to the unsaturated bond.
- the organic compound (2) characterizing the present invention may be any organic compound in any form as long as at least one “group of formula 1” described above is introduced. According to the study by the present inventors, among the “groups of the formula 1,” the group having a structure represented by the following general formula 2 is particularly high because the speed of the initiation polymerization reaction is high and the synthesis can be easily performed with a commercially available compound. It is preferable to use an organic compound into which (hereinafter also referred to as “group of formula 2”) has been introduced. (In General Formula 2, Y represents O or NH.)
- the above-mentioned “group of formula 2” can be obtained by conventionally known materials and methods, and various forms of organic compounds corresponding to the organic compound of (2) into which “group of formula 2” has been introduced can be easily obtained.
- the method is not particularly limited.
- an example in which an organic compound having the “group of formula 2” introduced therein can be easily synthesized will be described.
- an organic compound having a group capable of reacting with its carboxy group and its derivative is used as the organic compound into which the “group of formula 2” is introduced, and these are reacted.
- the compound used in this case is not particularly limited, and examples of the 2-bromoisobutyric acid compound include 2-bromoisobutyric acid, 2-bromoisobutyric acid bromide, and 2-bromoisobutyric anhydride. And these compounds and organic compounds having a reactive group that can react with a carboxyl group-based compound such as a hydroxyl group, an amino group, an epoxy group, a carbodiimide group, an oxazoline group, an isocyanate group, and an ethyleneimine group By reacting, the “group of formula 2” can be introduced into the organic compound through an ester bond or an amide bond.
- a carboxyl group-based compound such as a hydroxyl group, an amino group, an epoxy group, a carbodiimide group, an oxazoline group, an isocyanate group, and an ethyleneimine group
- the organic compound of (2) that characterizes the present invention is the above-mentioned “group of formula 1”, which is more preferable as “group of formula 2” (these are In some cases, “groups of formulas 1 and 2” may be collectively referred to as an organic compound having one or more introduced in the molecule.
- the organic compound to be used may be in any form, and conventionally known organic compounds are used. There are many types of conventionally known organic compounds that cannot be exemplified.
- an azo radical polymerization initiator, a peroxide radical polymerization initiator, and a photopolymerization radical polymerization initiator that are used in conventional radical polymerization are used. It will be described that the monomer (1) can be polymerized without using any of the agents, and polymers having various structures can be formed.
- the resulting polymer is The structure is such that the polymerization starts in the form of two chains extending from the organic compound.
- the form of the organic compound (2) used is a polymer component, and there are “groups of formulas 1 and 2” at both ends of the polymer, the polymer is defined as B, If the polymer from the monomer is A, it can be an ABA block copolymer.
- the polymer form of the organic compound (2) to be used has two “groups of the formulas 1 and 2” hanging in the molecule, the resulting polymer is converted into two comb structures.
- the polymer can be
- a conventionally known polymer can be used and is not particularly limited.
- examples thereof include polymers such as polyether, polyester, polyamide, polyurethane, polyolefin, polyimide, polyacryl, polymethacryl, polystyrene, polycarbonate, polysilicone, polyhalogenated olefin, and polyvinyl alcohol. These may be polymers having any structure of homopolymers, copolymers, graft copolymers, and block copolymers.
- a branched structure type polymer Or a star polymer or a graft polymer can be obtained.
- a polymer (polymer) of a vinyl monomer in which three or more “groups of formulas 1 and 2” are introduced is used as the organic compound (2). That is, when a vinyl polymer in which a plurality of “groups of formulas 1 and 2” are introduced into the organic compound of (2) is used, the polymer obtained by polymerizing the monomer of (1) becomes the polymer of (2).
- the vinyl polymer in which the “group of formulas 1 and 2” is introduced may be obtained by polymerizing the monomer in which the “group of formulas 1 and 2” is introduced, or a monomer having a hydroxyl group or the like is previously polymerized. Then, “groups of formulas 1 and 2” may be introduced. Moreover, the monomer in which the “group of formulas 1 and 2” is introduced and the other monomer described above may be copolymerized to form a copolymer. In this case, the amount of the monomer into which the “group of formulas 1 and 2” is introduced is arbitrary and is not particularly limited.
- the polymer introduced with the “groups of formulas 1 and 2” used as the organic compound (2) is obtained by living radical polymerization because the molecular weight distribution becomes narrow.
- a living radical polymerization method a nitroxide method (NMP method) using a nitroxide radical using a monomer into which “groups of formulas 1 and 2” are introduced, a dithioester compound, etc.
- NMP method nitroxide method
- RAFT method reversible addition-fragmentation chain transfer polymerization
- RTCP method reversible transfer catalytic polymerization
- atom transfer radical polymerization utilizing redox is not preferred because it may cause gelation because of polymerization of monomers and initiation of polymerization from bromo groups.
- the organic compound of (2) a monomer in which the “group of formulas 1 and 2” is introduced and a reactive monomer as another monomer component are copolymerized, and this reactive group is copolymerized.
- the surface of the article is treated using a copolymer having the following formula, and then the monomer of (1) is polymerized using the “group of formulas 1 and 2” constituting the copolymer as a polymerization initiating group.
- the polymer can be introduced into the surface of the article by grafting. That is, the surface of the article can be modified by the polymer introduced by grafting.
- the copolymer of the specific monomer when the polymerization method using the monomer having the “group of formulas 1 and 2” and the vinyl monomer having an alkoxysilyl group is living radical polymerization, the copolymer of the specific monomer Therefore, it is possible to introduce a dense polymer brush structure in which the polymer is an extended chain and the molecular weight is uniform.
- the organic compound (2) is used as a polymer component as described below.
- a monomer having a “group of formulas 1 and 2” and a vinyl monomer having an alkoxysilyl group are copolymerized to form a polymer component having a “group of formulas 1 and 2” and having an alkoxysilyl group
- a substrate such as glass, metal or plastic
- the surface is modified so that the “groups of formulas 1 and 2” characterizing the present invention function as a polymerization initiating group, and the radical of (1)
- the organic compound of (2) an organic compound into which one or more “groups of formulas 1 and 2” are introduced is used. It is more preferable to use a structure in which at least one organic substance is used as the organic compound (2).
- the organic substance include, for example, a polymer in which two “groups of formulas 1 and 2” are introduced in the molecule, a compound in which three or more are introduced in the molecule, or 3 in the molecule. Examples thereof include a copolymer of a vinyl polymer introduced by one or more or a monomer introduced by one or more in a molecule and a monomer having a reactive group bonded to the substrate surface.
- the polymer of the useful structure which was not able to be obtained easily with the prior art can be obtained simply.
- the organic compound of (2) having one “group of formulas 1 and 2” is used, the polymer obtained by the novel polymerization technique defined in the present invention is linear as described above. Become a thing. Since a linear polymer can be obtained by ordinary radical polymerization or living radical polymerization, it is compared with the production method of the present invention using an organic compound into which two or more of “groups of formulas 1 and 2” are introduced. And the benefits are not so great.
- the molecular weight of the polymer obtained can be controlled by adjusting the amount of “groups of formulas 1 and 2” introduced into the organic compound (2).
- the novel polymerization technique defined in the present invention involves a termination reaction such as radical polymerization, and may be coupled to have a high molecular weight. In this case, the amount of the initiator group cannot be adjusted. In that case, it can be avoided by adding a “catalyst” described later.
- the organic compound (2) (the radical polymerization initiating group-containing compound of the present invention) is an organic substance having a “group of formula 2”, 2- (2-bromoiso A polymer having at least butyryloxy) ethyl methacrylate as a constituent component is preferred. That is, 2- (2-bromoisobutyryloxy) ethyl methacrylate is available as a monomer and is commercially available, and is obtained by reacting a general-purpose monomer such as 2-hydroxyethyl methacrylate with bromoisobutyric acid. Therefore, it is useful as an industrial material.
- the metal chloride salt, metal bromide salt, quaternary ammonium chloride salt, quaternary ammonium bromide salt, quaternary phosphonium chloride salt and quaternary phosphonium bromide salt of (3) One or more chloride ion and / or bromide ion-containing compounds selected from the group consisting of (Cl / Br ion-containing compounds of (3)) are used in combination with the organic compound of (2) described above.
- the Cl / Br ion-containing compound (3) will be described.
- bromine in the structure of the “group of formulas 1 and 2” introduced into the organic compound of (2) is It is considered that a Cl / Br ion-containing compound and bromine-bromine exchange or bromine-chlorine exchange generate radicals, and the monomer (1) is inserted therein, and polymerization occurs therefrom.
- the Cl / Br ion-containing compound (3) may act as a redox catalyst to cause polymerization of the monomer (1).
- the Cl / Br ion-containing compound (3) may be referred to as “(3) halogenating agent”.
- the Cl / Br ion-containing compound (3) comprises a metal chloride salt, a metal bromide salt, a quaternary ammonium chloride salt, a quaternary ammonium bromide salt, a quaternary phosphonium chloride salt, and a quaternary phosphonium bromide salt.
- Any compound can be used as long as it is a compound selected from the group and has a conventionally known chlorine ion or bromine ion, and is not particularly limited. Specific examples include the following.
- the metal chloride salt include lithium chloride, sodium chloride, potassium chloride, calcium chloride, magnesium chloride and the like.
- Examples of the metal bromide salt include lithium bromide, sodium bromide, potassium bromide, magnesium bromide and the like.
- Examples of the quaternary ammonium chloride salt include tetramethylammonium chloride, tetraethylammonium chloride, and tetrabutylammonium chloride.
- Examples of the quaternary ammonium bromide salt include tetramethylammonium bromide, tetraethylammonium bromide, and tetrabutylammonium bromide.
- Examples of the quaternary phosphonium chloride include tetrabutylphosphonium chloride, tributylmethylphosphonium chloride, and triphenylmethylphosphonium chloride.
- Examples of the quaternary phosphonium bromide include tetrabutylphosphonium bromide, tributylmethylphosphonium bromide, and triphenylmethylphosphonium bromide.
- the amount of the halogenating agent (3) used is preferably about equimolar to the “group of formulas 1 and 2” constituting the organic compound (2) to be used in combination, depending on the polymer to be produced. What is necessary is just to determine the usage-amount and it does not specifically limit.
- the amount of the halogenating agent of (3) is not equivalent to the number of moles of “groups of formulas 1 and 2”, but a part of the number of moles of “groups of formulas 1 and 2” is It is also a preferred form to add the halogenating agent (3) in an amount that substitutes the chlorine ion or bromine ion of the halogenating agent).
- the present inventors by adding these materials further, it is possible to prevent the termination reaction of the radical polymerization that occurs in the polymerization process of the present invention as described above, and prevent high molecular weight and gelation. can do. Although the action is unknown, the present inventors do not contribute to prevention of coupling of growth radicals by, for example, bromine and amino groups becoming radicals by further using the compound of (4). I think. Hereinafter, the component (4) may be simply referred to as “catalyst” or “catalyst (4)”.
- the catalyst of (4) may be any compound having any group selected from the group of (4) imide group, N-bromoimide group, N-iodoimide group and organic base, and conventionally known compounds are used. They are not particularly limited. Specifically, examples of the compound having an imide group include cyclic imide compounds such as succinimide, maleic acid imide, and phthalic acid imide, and examples of the compound having an N-bromoimide group include N-bromosuccinimide, N— Examples of the compound having an N-iodoimide group include N-iodosuccinimide, N-iodophthalimide, and N-iodocyclohexanilimide.
- organic base conventionally known ones such as triethylamine, tributylamine, pyridine, morpholine, diazabicycloundecene (DBU), diazabicyclooctane (DABCO), and phosphazene base can be used.
- DBU diazabicycloundecene
- DABCO diazabicyclooctane
- phosphazene base phosphazene base
- the amount of the catalyst (4) is arbitrary and is not particularly limited. Preferably, it is used in the range of 0.001 to 0.1 mol times the “group of formulas 1 and 2” of (2) which functions as a polymerization initiating group to be used together. If the amount used is too large, the function as a catalyst is not sufficiently exhibited and a side reaction may occur, which is not preferable.
- the polymerization step of the method for producing a polymer of the present invention is preferably solution polymerization in which polymerization is performed using an organic solvent.
- the halogenating agent (3) can exert its effect even if it is not dissolved in the reaction system.
- the halogenating agent (3) is dissolved and homogenized in the reaction system.
- an ionic material such as the halogenating agent of (3) that is a Cl / Br ion-containing compound may not be dissolved in the monomer of (1), and the organic compound of (2)
- the exchange of bromine in the structure of the “group of formulas 1 and 2” introduced in 1 and the halogen ion of the halogenating agent of (3) must be performed by dissolving the halogenating agent as described above.
- the organic solvent having a high polarity as described below is preferably used in part or in whole.
- an organic solvent that is an alcohol, glycol, amide, sulfoxide, or ionic liquid.
- these organic solvents are not always necessary.
- organic solvents include conventionally known nonpolar solvents such as hydrocarbons, halogens, ketones, esters, glycols, etc., in combination with these solvents, A high solvent may be used. In that case, the ratio of the solvent having high polarity is arbitrary, and the solvent is selected so as to dissolve the polymer of the present invention obtained by polymerizing the monomer (1).
- preferable solvents include alcohols, glycols, amides, ureas, sulfoxides, and ionic liquids as listed below.
- alcohol solvents such as methanol, ethanol and isopropanol
- glycol solvents such as ethylene glycol, propylene glycol, glycerin, diethylene glycol and propylene glycol monomethyl ether
- dimethylformamide, dimethylacetamide, N-methylpyrrolidone 3- Amide solvents such as methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide
- urea solvents such as tetramethylurea and dimethylimidazolidinone
- sulfoxide solvents such as dimethylsulfoxide
- imidazo Examples include ionic liquids such as a lithium salt and a quaternary ammonium salt. These can be used alone or in combination of two or more.
- the amount of these organic solvents used during polymerization is not particularly limited as long as the halogenating agent (3) is dissolved. Preferably, it is 30% to 80% by mass. If it is less than 30%, the solid content may be too high, resulting in a high viscosity. If it is more than 80%, the monomer concentration may be too low to increase the polymerization rate. More preferably, it is 40% to 70%.
- the polymer production method of the present invention is basically characterized in that it is not necessary to use a radical polymerization initiator that generates radicals.
- a radical polymerization initiator that generates radicals.
- the polymerization is performed using a compound that generates a radical such as azo, peroxide, or thiol.
- the above-described materials (1) to (3) are mixed and polymerization proceeds easily by heat. In some cases, it is expected that a polymer by the polymerization method of the present invention can be obtained even if a radical polymerization initiator is used in combination.
- radical polymerization starts from the structure of “groups of formulas 1 and 2” introduced into the organic compound of (2), as described above, the organic compound into which “groups of formulas 1 and 2” are introduced.
- the amount of the halogenating agent (3) for conversion to function as a polymerization initiating group the molecular weight can be controlled, and a polymer derived from a radical initiator cannot be produced. Only polymers that are controlled and use the “groups of formulas 1 and 2” as polymerization initiators can be obtained.
- Polymerization process The above are the materials necessary for the production method of the polymer of the present invention. In the present invention, these materials are mixed and heated (heated), so that the radicals of the monomer can be converted from “groups of formulas 1 and 2”. Polymerization starts and proceeds to obtain a polymer.
- the polymerization conditions are not particularly limited, and conventionally known methods are used. When more preferable specific conditions are listed, in a nitrogen or argon atmosphere or bubbling, there is no influence of oxygen and the polymerization proceeds well.
- the temperature may be room temperature or higher, and may be 40 ° C. or higher, but if it is room temperature or so, it takes a lot of polymerization time, so that polymerization is preferably performed at 60 ° C.
- the stirring speed does not particularly affect the polymerization, and light shielding is not always necessary.
- the polymerization rate is also arbitrary, and the monomer may not be completely consumed.
- the respective materials described above are prepared, mixed, and heated under the above conditions, whereby the polymer can be easily produced. Furthermore, by appropriately designing the form of the organic compound (2) that characterizes the present invention (the radical polymerization initiating group-containing compound of the present invention), the catalyst (4) is used as necessary. By doing so, the polymer of the desired peculiar (complex) structure can be obtained industrially more easily. That is, by using the polymerization technique of the present invention, a desired polymer controlled in various forms as described below can be easily provided.
- Polymers provided by the present invention include linear polymers, AB block copolymers, ABA block copolymers, branched polymers, graft polymers, star polymers (star polymers), dense polymer brushes, bottle brush polymers, and the like. .
- the polymer polymerization method using the organic compound (2) characterizing the present invention makes it possible to synthesize polymers in various forms as described above in a simpler manner than ever.
- a bottle brush polymer which is a kind of graft polymer
- 2- (2-bromoisobutyryloxy) ethyl methacrylate which is a monomer containing the above-mentioned “group of formula 2”, alone or other monomers
- radical polymerization or living radical polymerization is performed to obtain a polymer having a plurality of “groups of formula 2” introduced therein.
- tetrabutylammonium chloride and the monomer of (1) to be grafted to the obtained polymer are added, and if necessary, the catalyst of (4) is added.
- the polymerization step specified in the present invention which is mixed and heated, a graft type copolymer in which polymerization starts from “group of formula 2” and a polymer chain is generated can be obtained in one pot.
- the polymer of the present invention obtained as described above may be used as it is, or may be added to a poor solvent, precipitated, purified and used as a polymer component.
- the use of the polymer obtained in the present invention can be used for conventionally known applications and is not particularly limited.
- the present invention can be applied to various fields such as inks, paints, coatings, plastics, inkjet inks, color filter materials, energy-related materials, mechanical component-related materials, medical devices, medical materials, and pharmaceuticals.
- Example 1 Preparation of graft copolymer using a polymer having a plurality of polymerization initiating groups
- A Preparation of polymerization-initiating group-containing polymer 3-Methoxy-N, N-dimethylpropanamide (hereinafter abbreviated as MDPA) was used as a solvent in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube.
- MDPA polymerization-initiating group-containing polymer 3-Methoxy-N, N-dimethylpropanamide
- V-70 manufactured by Wako Pure Chemical Industries, Ltd.
- the polymer was separated, added to a large amount of water while stirring with a disper, washed, filtered, washed with water, dried in a blow dryer at 50 ° C. until the volatile matter disappeared, and purified. As a result, a white powdery solid was obtained.
- the white powdery solid obtained above becomes a polymer in which a plurality of “groups of Formula 2” defined in the present invention are bonded to the side chain as shown in Scheme I below.
- a powdered solid can be confirmed by identification with an infrared spectrophotometer (IR) or a nuclear magnetic resonance apparatus (NMR) to be a polymer having a plurality of “groups of formula 2” introduced in its side chain. It was. This is referred to as KP-1. Further, the molecular weight of KP-1 was measured by GPC as a solvent of tetrahydrofuran (abbreviated as THF), Mn was 26000 and PDI was 1.41.
- THF tetrahydrofuran
- Table 2 shows the physical property values of the graft copolymers obtained in Synthesis Examples 1 to 10, respectively.
- Example 2 Synthesis of hyperbranched polymer
- 100 parts of MDPA, pentaerythritol tetrakis (2-bromoisobutyrate) corresponding to the organic compound of (2) and having four “groups of formula 2” ) Is 1.83 parts
- MMA is 100.0 parts
- bromide ion-containing compound is 3.8 parts TBAB, and is heated to 75 ° C. while bubbling nitrogen. did.
- 0.74 parts of triethylamine (hereinafter referred to as TEA) as an organic base was added as a catalyst of (4), and polymerization was performed for 7 hours.
- the polymerization rate of the obtained polymer was 94.7%
- Mn was 25600
- PDI was 1.48. From this, it was confirmed that a 4-chain multi-branched polymer was obtained.
- Example 3 Synthesis of star polymer
- the same reactor as used in Synthesis Example 1 was charged with the following, and a core polymer was synthesized as described below.
- 400 parts of MDPA, a radical polymerizable monomer having a “group of formula 2” corresponding to the organic compound of (2), 2- (2-bromoisobutyryloxy) ethyl methacrylate (manufactured by Godo Resources Co., Ltd., hereinafter) 40 parts as a monomer of BEMA), 160 parts of MMA as a monomer of (1), and 41.6 parts of lauryltrimethylammonium chloride (hereinafter abbreviated as LTMAC) as a chloride ion-containing compound of (3).
- LTMAC lauryltrimethylammonium chloride
- the obtained polymer in the dry state is a core polymer having a plurality of “groups of formula 3” inside, and this is referred to as CP-1.
- Example 4 Preparation of crosslinked acrylic fine particles using polymer fine particles having a polymerization initiating group
- a 2-liter 3-neck round flask reactor equipped with a thermometer, 670 g of ethyl acetate as a solvent, 65 parts of diethylene glycol dimethacrylate (hereinafter abbreviated as DEGDMA) as a monomer of (1), an organic compound of (2) 5.7 parts of BEMA, which is a radical polymerizable monomer having the “group of formula 2” corresponding to the above, was added, loosely stoppered, and immersed in a 70 ° C. hot water bath.
- DEGDMA diethylene glycol dimethacrylate
- BEMA which is a radical polymerizable monomer having the “group of formula 2” corresponding to the above
- the obtained fine particles were measured with a Coulter counter (manufactured by Beckman Coulter, Inc.), and the weight average particle diameter was 1.84 ⁇ m. Hereinafter, unless otherwise indicated, the weight average particle diameter was measured by this method.
- the obtained white powder was pulverized by a pulverizer and passed through 100 meshes. This is referred to as fine particle B-1.
- NMP N-methyl-2-pyrrolidone
- TBAB a bromide ion-containing compound of (3)
- MMA a monomer of (1)
- TEA a catalyst of (4)
- the polymerization solution obtained above was diluted with methyl ethyl ketone (hereinafter abbreviated as MEK) and filtered with a 10 ⁇ m pressure filter to take out a solid matter.
- MEK methyl ethyl ketone
- 1500 g of methanol was charged into a 3000 ml flask, attached to a stirrer, and stirred.
- the above filtrated product was added to the methanol with stirring and stirred, and this was filtered, washed thoroughly with methanol, dried at 25 ° C. (room temperature) for 12 hours, and at 80 ° C. for 24 hours, and then a white lump (fine particles) )
- the weight average particle diameter of the obtained fine particles was 2.65 ⁇ m. This is referred to as microparticle A-1.
- Example 5 Preparation of multiple polymers
- the monomer of (1), 30 parts of MMA, and the “group of formula 2” corresponding to the organic compound of (2) 5.5 parts of the prepared KP-1 as a chloride ion-containing compound (3), 0.38 parts of lithium chloride (LiCl), and a catalyst having an imide group as a catalyst (4) 0.1 parts of acid imide was added and polymerized at 75 ° C. for 8 hours. Since the polymerization progressed to become a highly viscous liquid, it was sampled and the polymerization rate was measured and found to be 81%.
- Mn was 261000 and PDI was 1.41.
- the obtained polymer was put into methanol to precipitate the polymer.
- the precipitated polymer was filtered and washed with water, and then sufficiently dried in a dryer at 70 ° C. for purification.
- the obtained polymer in a dry state is a bottle brush composed of one kind of monomer, which is called PBR-1.
- PBR-1 showed almost no peak with the UV detector, but this polymer shows a large UV absorption, so the polymerization started from the initiation group where the second monomer (BzMA) remained. Thus, it is considered that a Janus bottle brush composed of two types of monomers was obtained.
- the termination reaction can be carried out by using a simple commercially available material without using a conventional radical polymerization initiator, a special material used for living radical polymerization, or a metal-based catalyst. Since a new polymerization method that can easily and industrially produce polymers having various structures by starting and proceeding with the accompanying radical polymerization is provided, by using this new polymerization method, innovative technology development can be expected by providing materials for fields that could not be used in the future.
- polymer materials having specific properties such as adhesion, friction properties (wear resistance), wettability, barrier properties, adsorption / separation / transport properties of specific substances, and polymers with such specific properties
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Abstract
Description
(一般式1中、R1は、H又はアルキル基又はアシル基又はアリール基のいずれかを表し、R2は、アルキル基又はアリール基を表し、Yは、O又はNHを表す。)
(一般式1中、R1は、H又はアルキル基又はアシル基又はアリール基のいずれかを表し、R2は、アルキル基又はアリール基を表し、Yは、O又はNHを表す。)
(一般式1中、R1は、H又はアルキル基又はアシル基又はアリール基のいずれかを表し、R2は、アルキル基又はアリール基を表し、Yは、O又はNHを表す。)
[(1)不飽和結合を有するラジカル重合性モノマー]
本発明のポリマーの製造方法では、ポリマーの形成成分である、(1)不飽和結合を有するラジカル重合性モノマー(以下、「(1)のモノマー」と記載する)を必須成分として使用する。(1)のモノマーとしては、例えば、ビニル基、ビニリデン基、ビニレン基を有するモノマー等の、従来公知の不飽和結合を有するモノマーが挙げられる。すなわち、下記に挙げるような、従来公知のラジカル重合しうるモノマーであればいずれも使用でき、特に限定されない。
次に、本発明を特徴づける、(2)の、上記(1)のモノマーの重合開始基として機能する、下記一般式1で表せる構造の基が、分子内に1個以上導入されている有機化合物(以下、単に「(2)の有機化合物」と記載する場合がある)について説明する。本発明者らの検討によれば、下記一般式1で表せる構造を有する基(以下、「式1の基」或いは「重合開始基」と記載する場合がある)の存在下、(1)のモノマーと、後述する(3)のCl/Brイオン含有化合物とを混合して加温すると、本発明を特徴づける上記特有の「式1の基」から(1)のモノマーの、停止反応を伴うラジカル重合が開始して、結果として、構造が制御された種々のポリマーを得ることができる。
(一般式2中、Yは、O又はNHを表す。)
本発明のポリマーの製造方法では、(3)の、金属塩化物塩、金属臭化物塩、第四級アンモニウムクロライド塩、第四級アンモニウムブロマイド塩、第四級ホスホニウムクロライド塩及び第四級ホスホニウムブロマイド塩からなる群から選ばれる1種以上の、塩化物イオン及び/又は臭化物イオン含有化合物((3)のCl/Brイオン含有化合物)を、前記した(2)の有機化合物と併用する。以下、(3)のCl/Brイオン含有化合物について説明する。これらの化合物の作用については、詳細は解明されていない。本発明者らの検討によれば、これらの化合物を併用することで、(2)の有機化合物中に導入されている「式1、2の基」の構造中の臭素が、(3)のCl/Brイオン含有化合物と、臭素-臭素交換或いは臭素-塩素交換し、その際にラジカルが発生し、そこに(1)のモノマーが挿入されて、そこから重合が起こると考えられる。また、(3)のCl/Brイオン含有化合物が酸化還元の触媒として作用して、(1)のモノマーの重合を進行させる可能性もある。以下、(3)のCl/Brイオン含有化合物を、「(3)のハロゲン化剤」と記載する場合がある。
本発明のポリマーの製造方法では、以上で説明した(1)~(3)の材料を使用し、これらを混合及び加温(加熱)する重合工程で、(1)のモノマーのラジカル重合が、前記「式1、2の基」から開始して進行し、ポリマーが得られる。本発明者らの検討によれば、上記(1)~(3)の材料に加え、さらに、必要に応じて、(4)のイミド基、N-ブロモイミド基、N-アイオドイミド基及び有機塩基の群から選ばれる基を有する化合物のいずれかを添加し、上記重合工程を行うことが好ましい。本発明者らの検討によれば、これらの材料をさらに添加することで、前記した、本発明の重合工程で生じるラジカル重合の停止反応を防止することができ、高分子量化やゲル化を防止することができる。その作用は不明であるが、本発明者らは、(4)の化合物をさらに併用することで、例えば、臭素やアミノ基がラジカルとなって、成長ラジカルのカップリング防止に寄与するのではないかと考えている。以下、(4)の成分を、簡易的に「触媒」或いは「(4)の触媒」と称す場合がある。
以下に、本発明のポリマーの製造方法に用いることができる他の材料について説明する。本発明のポリマーの製造方法の重合工程は、有機溶媒を使用して重合する溶液重合が好ましい。本発明者らの検討によれば、(3)のハロゲン化剤は、その反応系中に溶解していなくても、その効果を発揮することができる。好ましくは、(3)のハロゲン化剤が、反応系に溶解して均一化しているとよい。一方で、(1)のモノマーに、Cl/Brイオン含有化合物である(3)のハロゲン化剤のようなイオン性の材料を溶解することができない場合があり、また、(2)の有機化合物に導入した「式1、2の基」の構造中の臭素と、(3)のハロゲン化剤のハロゲンイオンの交換は、前記したようなハロゲン化剤を溶解して行う必要があり、そのためには、下記に挙げるような極性が高い有機溶剤が、一部又は全部に使用されることが好ましい。
以上が本発明のポリマーの製造方法に必要な材料であって、本発明では、これらの材料を混合して、加温(加熱)することで、「式1、2の基」からモノマーのラジカル重合が開始して進行し、ポリマーを得ることができる。その重合条件としては特に限定はなく、従来公知の方法がとられる。より好ましい具体的な条件を列記すると、窒素やアルゴン雰囲気にしたり、バブリングしたりした方が、酸素の影響がなく、よく重合が進行する。また、温度としては、室温以上であればよく、40℃以上あればよいが、室温程度であると重合時間が多大にかかるので、好ましくは60℃以上、さらには70℃以上で重合させることが、実用の製造においての好ましい製造時間を実現できる点で適している。また、撹拌速度は特に重合に影響はなく、また、遮光が必ずしも必要ではない。重合率も任意であり、完全にモノマーが消費されていなくてもよい。
本発明のポリマーの製造方法では、以上のような条件の下、先に述べたそれぞれの材料を用意して、混合し、加温することで、ポリマーを簡便に作製することができる。さらには、本発明を特徴づける(2)の有機化合物(本発明のラジカル重合の開始基含有化合物)の形態を適宜に設計することで、さらには、必要に応じて(4)の触媒を使用することで、より容易に、所望する特異(複雑)な構造のポリマーを工業的に得ることができる。すなわち、本発明の重合手法を利用することで、下記に挙げるような多様な形態に制御された所望のポリマーを容易に提供できる。本発明によって提供されるポリマーとしては、直鎖状のポリマー、ABブロックコポリマー、ABAブロックコポリマー、分岐型ポリマー、グラフトポリマー、スターポリマー(星型ポリマー)、濃厚ポリマーブラシ、ボトルブラシポリマーなどが挙げられる。
(a)重合開始基含有ポリマーの調製
撹拌機、還流コンデンサー、温度計及び窒素導入管を取り付けた反応装置に、溶媒として3-メトキシ-N,N-ジメチルプロパンアミド(以下、MDPAと略記)を561.0部、ヨウ素を1.0部、ラジカル重合開始剤である2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)〔商品名:V-70、和光純薬社製〕を3.7部、メタクリル酸2-ヒドロキシエチルを208.0部、N-アイオドスクシンイミド(以下、NISと略記)を0.113部添加し、窒素をバブリングしながら、65℃で7時間重合した。重合率は、ほぼ100%であった。また、N,N-ジメチルホルムアミド溶媒を用いたゲルパーミエーションクロマトグラフィー(以下、GPCと略記)にて分子量を測定した結果、数平均分子量(以下、Mnと略記)が18500、分子量分布(重量平均分子量/数平均分子量、以下、PDIと略記)が1.35であった。
(合成例1)
前記の重合開始基含有ポリマーの調製の際に用いたと同様の反応装置を使用して、MDPAを131.1部、(1)のモノマーとして、メタクリル酸メチル(以下、MMAと略記)を50部、(2)の有機化合物として、先に(a)で調製した、「式2の基」を有するポリマーであるKP-1を2.7部、(3)の臭化物イオン含有化合物として、テトラブチルアンモニウムブロミド(以下、TBABと略記)を3.5部添加し、80℃で8時間重合した。重合が進行し、高粘度の液体となったのでサンプリングし、重合率を測定したところ85%であった。また、THF溶媒のGPCにて分子量を測定したところ、Mnが340500、PDIが2.43であった。上記重合に使用したKP-1のMnが26000であったことから、アゾ系や過酸化物系のラジカル重合開始剤を使用することなく、KP-1の構造中の「式2の基」からMMAの重合が開始してグラフトコポリマーを得ることができることが確認された。
合成例1と同様の反応装置を使用し、表1に示した材料をそれぞれに用い、合成例1と同様の操作にて、グラフトコポリマーを調製した。表1中の、(1)は、各合成例で使用したラジカル重合性モノマー、(2)のKP-1は、(a)で調製した重合開始基が分子内に1個以上導入されている有機化合物に該当する重合開始基含有ポリマー、(3)は、塩化物イオン又は臭化物イオン含有化合物、(4)は、イミド基や有機塩基を有する化合物で、ラジカル重合の停止反応を防止することができる触媒的な機能を示すものである。
合成例1で使用したと同様の反応装置を使用し、MDPAを100部、(2)の有機化合物に該当する、「式2の基」を4個有するペンタエリスリトールテトラキス(2-ブロモイソブチレート)を1.83部、(1)のモノマーとして、MMAを100.0部、(3)の臭化物イオン含有化合物として、TBABを3.8部仕込んで、窒素をバブリングしながら75℃に加温した。次いで、(4)の触媒として、有機塩基であるトリエチルアミン(以下、TEAと記載)0.74部を加え、7時間重合した。得られたポリマーの重合率は94.7%、Mnは25600、PDIは1.48であった。このことから、4本鎖の多分岐ポリマーが得られることが確認できた。
合成例1で使用したと同様の反応装置に以下のものを仕込み、下記のようにして、コアとなるポリマーを合成した。MDPAを400部、(2)の有機化合物に該当する、「式2の基」を有するラジカル重合性モノマーである、2-(2-ブロモイソブチリロキシ)エチルメタクリレート(合同資源社製、以下、BEMAと略記)を40部、(1)のモノマーとして、MMAを160部、(3)の塩化物イオン含有化合物として、ラウリルトリメチルアンモニウムクロライド(以下、LTMACと略記)を41.6部仕込んで撹拌し、75℃に加温した。LTMACが溶解し、全体が均一になった後、(4)の触媒として、有機塩基であるTEAを2.8部添加し、上記の温度を維持して7時間重合した。サンプリングし、固形分を測定したところ38.8%であり、これに基づいて算出した重合率はほぼ100%であった。GPCにて分子量を測定したところ、Mnが7600、PDIが1.53であった。以上のようにしてコアポリマー溶液を得た。
温度計を取り付けた2リッターの3口丸型フラスコ反応装置に、溶媒として、酢酸エチル670g、(1)のモノマーとして、ジエチレングリコールジメタクリレート(以下、DEGDMAと略記)65部、(2)の有機化合物に該当する、「式2の基」を有するラジカル重合性モノマーである、BEMAを5.7部添加し、緩く栓をして、70℃の湯浴に浸漬させた。別容器に、酢酸エチル20部、ラジカル重合開始剤である2,2’-アゾビスイソブチロニトリルを2.2部溶解させ、(2)に該当する有機化合物のポリマー微粒子を作製するための開始剤溶液を作成した。ついで、ガラス瓶(丸型フラスコ)の系全体が65℃に達したところで、別容器から開始剤溶液を添加して、その温度で10時間反応させた。その結果、系が白濁し、粒子が凝集して析出した。重合反応終了後、冷却した。溶液を濾過し、よく酢酸エチルで洗浄し、70℃の送風乾燥機にて乾燥し、白色粉末の微粒子(ビーズ)を69.7部得た。収率より、ほぼすべてのモノマーが反応したと考えられる。すなわち、ビーズ(微粒子)の質量中、(2)の有機化合物に該当するBEMAの含有量は8.1%、DEGDMAが91.9%の構成である。
合成例1と同様の装置を使用して、MDPAを200部、(1)のモノマーとして、MMAを30部、(2)の有機化合物に該当する「式2の基」を有するポリマーとして、先に調製したKP-1を5.5部、(3)の塩化物イオン含有化合物として、塩化リチウム(LiCl)を0.38部、(4)の触媒として、イミド基を有する化合物である、コハク酸イミドを0.1部添加し、75℃で8時間重合した。重合が進行し、高粘度の液体となったのでサンプリングし、重合率を測定したところ81%であった。また、Mnが261000、PDIが1.41であった。
Claims (16)
- (1)不飽和結合を有するラジカル重合性モノマーと、(2)該モノマーの重合開始基として機能する下記一般式1で表せる構造の基が、分子内に1個以上導入されている有機化合物と、(3)金属塩化物塩、金属臭化物塩、第四級アンモニウムクロライド塩、第四級アンモニウムブロマイド塩、第四級ホスホニウムクロライド塩及び第四級ホスホニウムブロマイド塩からなる群から選ばれる1種以上の、塩化物イオン及び/又は臭化物イオン含有化合物とを、混合及び加温することで、前記構造の基から、前記(1)のモノマーの停止反応を伴うラジカル重合が始まる重合工程を有することを特徴とするポリマーの製造方法。
(一般式1中、R1は、H又はアルキル基又はアシル基又はアリール基のいずれかを表し、R2は、アルキル基又はアリール基を表し、Yは、O又はNHを表す。) - 前記重合工程で、アゾ系ラジカル重合開始剤、過酸化物系ラジカル重合開始剤及び光ラジカル重合開始剤のいずれについても使用しない請求項1に記載のポリマーの製造方法。
- さらに、前記重合工程で、(4)イミド基、N-ブロモイミド基、N-アイオドイミド基及び有機塩基の群から選ばれるいずれかの基を有する化合物を使用する請求項1又は2に記載のポリマーの製造方法。
- さらに、前記重合工程の際に、有機溶媒を使用する請求項1~3のいずれか1項に記載のポリマーの製造方法。
- 前記有機溶媒が、アルコール系、グリコール系、アミド系、尿素系、スルホキシド系及びイオン液体からなる群から選ばれる少なくともいずれかである請求項4に記載のポリマーの製造方法。
- 前記(1)不飽和結合を有するラジカル重合性モノマーが、メタクリル酸系モノマーである請求項1~5のいずれか1項に記載のポリマーの製造方法。
- アゾ系ラジカル重合開始剤、過酸化物系ラジカル重合開始剤及び光ラジカル重合開始剤のいずれについても使用せずに、不飽和結合を有するラジカル重合性モノマーの、停止反応を伴うラジカル重合を行わせるためのラジカル重合の開始基含有化合物であって、
金属塩化物塩、金属臭化物塩、第四級アンモニウムクロライド塩、第四級アンモニウムブロマイド塩、第四級ホスホニウムクロライド塩及び第四級ホスホニウムブロマイド塩からなる群から選ばれる1種以上の、塩化物イオン及び/又は臭化物イオン含有化合物と併用することで、前記ラジカル重合性モノマーの重合開始基としての機能が発現する構成の下記一般式1で表せる構造の基が、分子内に1個以上導入されている有機体であることを特徴とするラジカル重合の開始基含有化合物。
(一般式1中、R1は、H又はアルキル基又はアシル基又はアリール基のいずれかを表し、R2は、アルキル基又はアリール基を表し、Yは、O又はNHを表す。) - 前記有機体が、前記一般式1で表せる構造の基を分子内に2個以上導入してなる有機体である請求項8又は9に記載のラジカル重合の開始基含有化合物。
- 前記有機体が、一般式1又は2で表せる構造の基を分子内に2個以上導入してなるポリマーである請求項8又は9に記載のラジカル重合の開始基含有化合物。
- 前記有機体が、一般式1又は2で表せる構造の基を分子内に3個以上導入してなる化合物である請求項8又は9に記載のラジカル重合の開始基含有化合物。
- 前記有機体が、一般式1又は2で表せる構造の基を分子内に3個以上導入してなるビニルポリマーである請求項8又は9に記載のラジカル重合の開始基含有化合物。
- 前記有機体が、一般式1又は2で表せる構造の基を分子内に1個以上導入したモノマーと、基材表面に結合する反応性基を有するモノマーとの共重合体である請求項8又は9に記載のラジカル重合の開始基含有化合物。
- (1)の不飽和結合を有するラジカル重合性モノマーと、請求項8~14のいずれか1項に記載の、下記一般式1で表せる構造の基が、分子内に1個以上導入されている(2)のラジカル重合の開始基含有化合物と、(3)の、金属塩化物塩、金属臭化物塩、第四級アンモニウムクロライド塩、第四級アンモニウムブロマイド塩、第四級ホスホニウムクロライド塩及び第四級ホスホニウムブロマイド塩からなる群から選ばれる1種以上の、塩化物イオン及び/又は臭化物イオン含有化合物とを、混合及び加温させて、前記(2)の開始基含有化合物に導入されているラジカル重合性モノマーの重合開始基から前記(1)の不飽和結合を有するラジカル重合性モノマーがラジカル重合してなる構成のものであることを特徴とするポリマー。
(一般式1中、R1は、H又はアルキル基又はアシル基又はアリール基のいずれかを表し、R2は、アルキル基又はアリール基を表し、Yは、O又はNHを表す。) - 前記(2)のラジカル重合の開始基含有化合物が、2-(2-ブロモイソブチリルオキシ)エチルメタクリレートを少なくとも構成成分とするポリマーである請求項15に記載のポリマー。
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EP4194204A4 (en) * | 2020-08-06 | 2024-03-20 | Dainichiseika Color Chem | SURFACE TREATMENT FILM, RELATED MANUFACTURING METHOD AND ARTICLE |
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JP6254239B2 (ja) * | 2016-02-29 | 2017-12-27 | 大日精化工業株式会社 | ポリマーの製造方法 |
CN111871394A (zh) * | 2020-07-30 | 2020-11-03 | 河南省农产品质量安全检测中心(河南省绿色食品发展中心) | 一种新型双功能基混合模式有机聚合物整体柱、其制备方法和其应用 |
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EP4194204A4 (en) * | 2020-08-06 | 2024-03-20 | Dainichiseika Color Chem | SURFACE TREATMENT FILM, RELATED MANUFACTURING METHOD AND ARTICLE |
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CA3057048C (en) | 2020-03-10 |
TWI729280B (zh) | 2021-06-01 |
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US10995159B2 (en) | 2021-05-04 |
US20200385496A1 (en) | 2020-12-10 |
KR20190125495A (ko) | 2019-11-06 |
CA3057048A1 (en) | 2018-09-27 |
JP6245719B1 (ja) | 2017-12-13 |
CN110446725B (zh) | 2020-09-22 |
KR102057958B1 (ko) | 2020-01-22 |
TW201841947A (zh) | 2018-12-01 |
AU2018239715A1 (en) | 2019-09-26 |
JP2018162333A (ja) | 2018-10-18 |
EP3604354A4 (en) | 2021-01-13 |
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