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WO2007142188A1 - Polymerization initiator, and process for polymerization of (meth)acrylic acid derivative - Google Patents

Polymerization initiator, and process for polymerization of (meth)acrylic acid derivative Download PDF

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Publication number
WO2007142188A1
WO2007142188A1 PCT/JP2007/061289 JP2007061289W WO2007142188A1 WO 2007142188 A1 WO2007142188 A1 WO 2007142188A1 JP 2007061289 W JP2007061289 W JP 2007061289W WO 2007142188 A1 WO2007142188 A1 WO 2007142188A1
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WO
WIPO (PCT)
Prior art keywords
butyl
polymerization
meth
zincate
acrylic acid
Prior art date
Application number
PCT/JP2007/061289
Other languages
French (fr)
Japanese (ja)
Inventor
Masanobu Uchiyama
Toshiyuki Kaneko
Original Assignee
The University Of Tokyo
Tosoh Finechem Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by The University Of Tokyo, Tosoh Finechem Corporation filed Critical The University Of Tokyo
Priority to JP2008520560A priority Critical patent/JP5374151B2/en
Publication of WO2007142188A1 publication Critical patent/WO2007142188A1/en

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    • 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
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/50—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc 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
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals

Definitions

  • the present invention relates to a polymerization initiator composed of a specific zinc art complex and a method for polymerizing a (meth) acrylic acid derivative using the zinc art complex as a polymerization initiator.
  • Patent Document 3 Proposed that tetra-n-butylzinc barium salt is useful as a polymerization catalyst for butadiene, isoprene, etc.
  • Patent Document 4 In the polymerization of P-trifluoromethylstyrene, in addition to n-butyllithium and the like, it is known that an organozinc ate complex such as n-ptyljetyllithium zincate also serves as a polymerization initiator (Patent Document 4).
  • Patent Document 5 As an initiator of stereoregular polymerization of acrylonitrile, art complexes such as di-n-butyl cetyl dizyl zincate can be used as in the case of ordinary organometallic compounds (Patent Document 5).
  • n-butyllithium does not function as a polymerization initiator, whereas organozinc compounds, organoaluminum compounds and their art complexes are excellent as polymerization initiators.
  • n-Putyljetyl lithium zincate is exemplified as a suitable example (Patent Document 6).
  • tetra-t-butylzinc zincate is useful as a polymerization catalyst for N-isopropylacrylamide, N, N-dimethylacrylamide, hydroxyethyl methacrylate, and the like. It has been proposed as an epoch-making method capable of allowing living polymerization polymerization to proceed even in a solution containing water (Patent Document 7).
  • Patent Document 7 a solution containing water
  • an organic solvent is generally used. In this case, an organic solvent waste liquid is generated, which requires only a step of separating and recovering the solvophilic polymer. Become.
  • Di-lithium tetra-t-butylzincate that satisfies this requirement can be prepared by reacting zinc chloride with 4-fold molar amount of t-butyllithium in an ether solvent.
  • the solution of t-butyllithium is a pyrophoric substance and is also expensive, so that it was difficult to handle industrially in large quantities.
  • a large amount of lithium chloride generated during catalyst synthesis remains, there is a problem that salt may remain in the polymer.
  • a zinc art complex having magnesium as a counter cation was used as a polymerization initiator, although it can be adjusted relatively easily compared to a zinc art complex in which the cation is lithium. Examples were limited. Although tetraethylmagnesium zincate has been used as a polymerization initiator for acrylic esters or N-substituted maleimides, the polymerization activity was lower than that of zinc ate complexes having lithium as a counter cation. (Non-patent documents 1, 2). Furthermore, it was not known that it has a polymerization initiating function of a monomer having an active proton or a polymerization initiating function in a protic solvent.
  • Patent Document 2 Japanese Patent Publication No. 44-27741
  • Patent Document 3 Japanese Patent Publication No. 45-40303
  • Patent Document 4 Japanese Patent Laid-Open No. 63-103189
  • Patent Document 5 Japanese Patent Publication No. 7-103189
  • Patent Document 6 Japanese Patent Laid-Open No. 3-103409
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2004-292328
  • Non-patent literature l Makromolekulare Chemie, 1986, 187 ⁇ , 731- 737
  • Non-patent literature 2 Makromolekulare Chemie, Rapid Communications, 1987, 8 ⁇ , 167-70
  • An object of the present invention has been made to solve the above-described problems, and relates to a polymerization initiator using an organic zincate complex and a method for polymerizing a (meth) acrylic acid derivative.
  • the present invention relates to the general formula (1)
  • n represents an integer of 1 to 3
  • R represents an alkyl group having 1 to 12 carbon atoms which may be the same or different, an alkyl group, an aryl group, or an aryl alkyl group.
  • the present invention relates to a method for polymerizing a (meth) acrylic acid derivative, wherein the zinc ate complex represented by the general formula (1) or (2) is used as a polymerization initiator.
  • organozinc art complex according to the present invention as a polymerization initiator, a polymer can be obtained in a high yield even when a monomer having an active proton and Z or a solvent are used.
  • the polymerization initiator of the present invention has the general formula (1)
  • organozinc ate complex having at least one t-butyl group.
  • n is an integer selected from 13 and R is the same or different carbon number.
  • alkyl group alkenyl group, aryl group or aryl alkyl group, specifically, methyl group, ethyl group, i-propyl group, n-propyl group, n butyl group, i-butyl group, s butyl group, n pentyl group, t-amyl group, n xyl group, n propyl group, n-octyl group, n-nor group, n-decyl group, bur group, cyclopentagel group, phenol -Represents a benzyl group.
  • M represents lithium magnesium or MgX (X represents chlorine, bromine or iodine).
  • m represents 1 or 2.
  • organozinc ate complex used in the present invention include those represented by the general formula (1) t- Bu R ZnM (1)
  • organic zinc ate complex represented by the formula include di-1-trimethyl tri-butylmethylzincate, dilithium tri-1-butylethylzirconate, tri-1-butyl-n-propyldiethyl zincate, tri-tri- Dilithium 1-butyl-i-propylzinc zincate, dilithium tri-1-butyl-n-butylzinc zincate, dilithium tri-1-butyl-i-butylzinc zincate, di-1-tributyl-1-S-butylzinclate Titanium, Dilithium dimethyldi-t-butylzinc zincate, Jetyldi-t-butylzinc zincate, Di-t-butyldi-n-propylzinc zincate, Di-t-butyldi-i-propylzincate dilithium, Di-n -Butyl di-n-butyl dizinc zincate, di-n-butyl di-i-buty
  • These zinc art complexes can be used as polymerization initiators either individually or as a mixture.
  • the zinc art complex having a t-butyl group of the present invention can be synthesized by a reaction between a zinc compound and an organolithium compound or an organomagnesium compound in an inert gas atmosphere. .
  • halogenated zinc such as salted zinc
  • 3-4 equivalents of zinc It can be synthesized by reacting an organolithium reagent or an organomagnesium reagent.
  • the zinc ate complex in the present invention can be synthesized by using an organomagnesium reagent having at least one equivalent of t-butyllithium or t-butyl group.
  • reaction solvents such as tetrahydrofuran, jetyl ether, dibutyl ether, cyclopentyl methyl ether or hydrocarbon solvents such as pentane, hexane, heptane, toluene, and mixtures thereof.
  • ether solvents such as tetrahydrofuran, jetyl ether, dibutyl ether, cyclopentyl methyl ether or hydrocarbon solvents such as pentane, hexane, heptane, toluene, and mixtures thereof.
  • an ether solvent from the viewpoint of controlling the temperature during the reaction or maintaining uniformity.
  • the solution of the synthesized zinc ate complex can be used for polymerization as it is.
  • Examples of the monomer used for the polymerization include (meth) acrylic acid derivatives.
  • (Meth) acrylic acid derivatives include (meth) acrylic acid esters such as acrylic acid, methacrylic acid and methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and hydroxyethyl methacrylate.
  • Examples include (meth) acrylic acid amides such as —isopropylacrylamide, acrylamide, N-isopropylpyrmethacrylamide. These can be used alone If necessary, they can be used in combination with two or more components or other key-on polymerizable monomers to produce a copolymer.
  • a normal organic metal such as hydroxyethyl methacrylate, N-isopropylacrylamide, acrylamide, N-isopropylmethacrylamide is used.
  • the zinc art complex of the present invention can advance polymerization without impairing the polymerization initiation function.
  • the solvent used for the polymerization may be a commonly used solvent, for example, a hydrocarbon solvent such as toluene, xylene, hexane, cyclohexane, heptane, an ether solvent system such as THF, diethyl ether, Examples include alcohols such as methanol, ethanol and isopropanol, and water. In general, water and alcohols easily react with an organometallic compound. Therefore, when they are used as a solvent, the organometallic compound is said to lose its polymerization initiation function. However, the zinc art complex of the present invention can be used even when a protic solvent system such as a hydrogen alcohol solvent is used as a polymerization solvent. A polymer can be obtained in a high yield without losing performance.
  • a protic solvent system such as a hydrogen alcohol solvent
  • the amount of the zinc ate complex used in the polymerization of the (meth) acrylic acid derivative in the present invention is not particularly limited, but is 0.001 to 10 mol per 100 mol of the (meth) acrylic acid derivative. Preferred to use in a range. If it is less than this range, sufficient polymerization activity may not be obtained. If this range is exceeded, a large amount of metal residue may be contained in the obtained polymer, and it is removed. A process may be required.
  • Example 1 except that 30. lg (70 mmol) of 9 wt% — n-butyllithium in hexane and 20.5 g (69.1 mmol) of 21.6 wt% —t butyllithium in pentane were used. In the same manner as above, a THF solution of 38.9 wt% (t-Bu) (n-Bu) ZnLi was obtained.
  • the mer was recovered.
  • a reaction was carried out in the same manner as in Example 6 from 3.8 g (30.8 mmol) of jetil zinc, 30 ml of toluene and 19.8 g (62.6 mmol) of a pentane solution of 20.3 wt% -t-butyllithium. Thereafter, the precipitated solid was filtered under a nitrogen atmosphere, and then the solvent was distilled off to obtain a 29.4 wt% toluene solution of t-Bu Et ZnLi.
  • the polymer was recovered.
  • N-isopropylacrylamide (5.6 g, 44.4 mmol) was added to an aqueous solution of 18.2 wt% n-BuEt ZnLi in THF (0.8 g) prepared in Synthesis Example 2. Addition It was stirred at room temperature for 1 hour. Thereafter, the mixture was stirred at 50 ° C. for 30 minutes, but no solid was precipitated and the polymer could not be recovered.
  • N-isopropylacrylamide 5.lg (45.0 mmol) in an aqueous solution was added with 4 g of THF solution of 34.4 wt% PhEt ZnLi prepared in Synthesis Example 3,
  • N-isopropylacrylamide (5.3 g, 46.8 mmol) in an aqueous solution at 20 ° C was mixed with 23.4 wt% (TH-solution of n-BuEt ZnLi in 0.8 g prepared in Synthesis Example 2).
  • the zinc ate complex having no t-butyl group has a protic solution such as water.
  • a protic solution such as water.
  • the medium was used, it was confirmed that it did not function as a polymerization initiator.
  • the present invention is useful for the polymerization of (meth) acrylic acid derivatives.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerization Catalysts (AREA)

Abstract

[PROBLEMS] To provide a polymerization initiator which enables to polymerize a (meth)acrylic acid derivative under the conditions where a monomer and/or a solvent has an active proton. [MEANS FOR SOLVING PROBLEMS] Disclosed is a polymerization initiator comprising a zinc ate complex represented by the following general formula (1) or (2): t-BunR3-nZnM (1) t-BunR4-nZnMm (2) wherein n represents an integer ranging from 1 to 3; R's independently represent an alkyl, alkenyl, aryl or arylalkyl group having 1 to 12 carbon atoms; M represents lithium, magnesium or a magnesium halide represented by the formula: MgX [wherein X represents a chlorine, a bromine or an iodine]; and m represents 1 or 2. Also disclosed is a process for polymerization of a (meth)acrylic acid derivative using the polymerization initiator.

Description

明 細 書  Specification
重合開始剤および (メタ)アクリル酸誘導体の重合方法  Polymerization initiator and polymerization method of (meth) acrylic acid derivative
技術分野  Technical field
[0001] 本発明は特定の亜鉛アート錯体からなる重合開始剤および該亜鉛アート錯体を重 合開始剤として用いる (メタ)アクリル酸誘導体の重合方法に関する。  The present invention relates to a polymerization initiator composed of a specific zinc art complex and a method for polymerizing a (meth) acrylic acid derivative using the zinc art complex as a polymerization initiator.
背景技術  Background art
[0002] 有機亜鉛のアート錯体は、他の有機金属化合物と同様、ァ-オン重合性モノマー の開始剤として用いることができる。例えば、古川らはテトラェチル亜鉛のアルキル土 類金属塩が、メチルビ二ルケトンの重合に有用な触媒であることを提案しており（特許 文献 1)、中塚らはジ—n—ブチルジェチル亜鉛のジリチウム塩がアクリロニトリル類の 重合触媒として有用であることを提案している (特許文献 2)。また、案西らはテトラ— n—ブチル亜鉛のバリウム塩がブタジエン、イソプレン等の重合触媒として有用なこと を提案している（特許文献 3)。 P-トリフルォロメチルスチレンの重合には、 n—ブチル リチウムなどの他に n—プチルジェチル亜鉛酸リチウムなどの有機亜鉛アート錯体も 重合開始剤となることが知られている (特許文献 4)。また、アクリロニトリルの立体規則 性重合の開始剤として、通常の有機金属化合物同様、ジー n プチルジェチル亜鉛 酸ジリチウムなどのアート錯体を用いることが可能であることも示されている（特許文 献 5)。 a フルォロアクリル酸エステルの重合においては、 n—ブチルリチウムでは 重合開始剤として機能しないのに対して、有機亜鉛化合物や、有機アルミニウムィ匕 合物およびそれらのアート錯体が重合開始剤として優れており、 n プチルジェチル 亜鉛酸リチウムが好適な例として例示されて ヽる（特許文献 6)。  [0002] Art complexes of organozinc can be used as initiators for ar polymerizable monomers, as with other organometallic compounds. For example, Furukawa et al. Have proposed that alkyl earth metal salts of tetraethyl zinc are useful catalysts for the polymerization of methyl vinyl ketone (Patent Document 1), and Nakatsuka et al. Dilithium salts of di-n-butyljetyl zinc. Has been proposed to be useful as a polymerization catalyst for acrylonitriles (Patent Document 2). In addition, Dr. Nishiki et al. Proposed that tetra-n-butylzinc barium salt is useful as a polymerization catalyst for butadiene, isoprene, etc. (Patent Document 3). In the polymerization of P-trifluoromethylstyrene, in addition to n-butyllithium and the like, it is known that an organozinc ate complex such as n-ptyljetyllithium zincate also serves as a polymerization initiator (Patent Document 4). It has also been shown that, as an initiator of stereoregular polymerization of acrylonitrile, art complexes such as di-n-butyl cetyl dizyl zincate can be used as in the case of ordinary organometallic compounds (Patent Document 5). a In the polymerization of fluoroacrylates, n-butyllithium does not function as a polymerization initiator, whereas organozinc compounds, organoaluminum compounds and their art complexes are excellent as polymerization initiators. n-Putyljetyl lithium zincate is exemplified as a suitable example (Patent Document 6).
[0003] ただし、これらの有機亜鉛錯体は、触媒機能が発揮させるためには、 Vヽずれも無水 条件下で重合を行なうことが必須である。  [0003] However, it is essential that these organozinc complexes be polymerized under anhydrous conditions so that the catalytic function is exerted.
[0004] 一方、テトラ t—ブチル亜鉛酸ジリチウムが N—イソプロピルアクリルアミド、 N, N— ジメチルアクリルアミド、ヒドロキシェチルメタクリル酸エステル等の重合触媒として有 用であり、さらにこの触媒は、含水 THF等の水を含む溶液中でもリビング重合的ァ- オン重合を進行させることができる画期的な方法として提案されて 、る (特許文献 7) [0005] 有機金属を開始剤とした重合に際しては一般に有機溶剤が使用されるが、この場 合、溶媒力 ポリマーを分離、回収する工程が必要となるだけでなぐ有機溶媒廃液 が生成することとなる。それに対して、水溶媒でも反応を行うことができれば、これらの 問題を回避することができることから、そのような開始剤の開発が望まれていた。その 要求を満たす、テトラ t—ブチル亜鉛酸ジリチウムは、エーテル系溶媒中、塩化亜鉛と 4倍モル量の t—ブチルリチウムとの反応により調製する事ができる。し力しながら、 t —プチルリチウムの溶液は自然発火性物質であり、また高価でもあることから工業的 に多量取り扱うのは困難であった。また、触媒合成時に生成した塩化リチウムが多量 残存するため、ポリマー中に塩が残存する可能性があるといった問題があった。 [0004] On the other hand, tetra-t-butylzinc zincate is useful as a polymerization catalyst for N-isopropylacrylamide, N, N-dimethylacrylamide, hydroxyethyl methacrylate, and the like. It has been proposed as an epoch-making method capable of allowing living polymerization polymerization to proceed even in a solution containing water (Patent Document 7). [0005] In the polymerization using an organic metal as an initiator, an organic solvent is generally used. In this case, an organic solvent waste liquid is generated, which requires only a step of separating and recovering the solvophilic polymer. Become. On the other hand, if the reaction can be carried out even with an aqueous solvent, these problems can be avoided, and therefore development of such an initiator has been desired. Di-lithium tetra-t-butylzincate that satisfies this requirement can be prepared by reacting zinc chloride with 4-fold molar amount of t-butyllithium in an ether solvent. However, the solution of t-butyllithium is a pyrophoric substance and is also expensive, so that it was difficult to handle industrially in large quantities. In addition, since a large amount of lithium chloride generated during catalyst synthesis remains, there is a problem that salt may remain in the polymer.
[0006] また、これまで、テトラー t—ブチル亜鉛のジリチウム塩以外の亜鉛アート錯体力 活 性プロトンを有するモノマーの重合開始剤となること、ある 、はプロトン性溶媒での重 合開始剤となると 、うことは知られて 、なかった。  [0006] In addition, until now, it becomes a polymerization initiator for monomers having a zinc ate complex power-active proton other than the dilithium salt of tetra-t-butylzinc, or a polymerization initiator in a protic solvent. It wasn't known to be.
[0007] さらに、マグネシウムを対カチオンとして有する亜鉛アート錯体に関しては、対カチ オンがリチウムである亜鉛アート錯体に比べ、比較的容易に調整する事が可能であ るものの、重合開始剤として用いた例は限られていた。アクリル酸エステルあるいは N —置換マレイミドの重合開始剤としてテトラエチル亜鉛酸マグネシウムが用いられたこ とがあるものの、リチウムを対カチオンとして有する亜鉛アート錯体に比べると、重合 活性は低いものであった。（非特許文献 1, 2)。さらには活性プロトンを有するモノマ 一の重合開始機能を有すること、あるいはプロトン性溶媒中での重合開始機能を有 することは知られて 、なかった。  [0007] Furthermore, a zinc art complex having magnesium as a counter cation was used as a polymerization initiator, although it can be adjusted relatively easily compared to a zinc art complex in which the cation is lithium. Examples were limited. Although tetraethylmagnesium zincate has been used as a polymerization initiator for acrylic esters or N-substituted maleimides, the polymerization activity was lower than that of zinc ate complexes having lithium as a counter cation. (Non-patent documents 1, 2). Furthermore, it was not known that it has a polymerization initiating function of a monomer having an active proton or a polymerization initiating function in a protic solvent.
特許文献 1：特公昭 39 - 18944号公報  Patent Document 1: Japanese Patent Publication No. 39-18944
特許文献 2：特公昭 44 - 27741号公報  Patent Document 2: Japanese Patent Publication No. 44-27741
特許文献 3：特公昭 45—40303号公報  Patent Document 3: Japanese Patent Publication No. 45-40303
特許文献 4：特開昭 63 - 103189号公報  Patent Document 4: Japanese Patent Laid-Open No. 63-103189
特許文献 5：特公平 7 - 103189号公報  Patent Document 5: Japanese Patent Publication No. 7-103189
特許文献 6：特開平 3 - 103409号公報  Patent Document 6: Japanese Patent Laid-Open No. 3-103409
特許文献 7：特開 2004— 292328号公報 非特許文献 l : Makromolekulare Chemie, 1986年， 187卷， 731— 737頁 非特許文献 2： Makromolekulare Chemie, Rapid Communications, 1987 年， 8卷， 167— 70頁 Patent Document 7: Japanese Patent Application Laid-Open No. 2004-292328 Non-patent literature l: Makromolekulare Chemie, 1986, 187 卷, 731- 737 Non-patent literature 2: Makromolekulare Chemie, Rapid Communications, 1987, 8 卷, 167-70
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0008] 本発明の目的は、上記問題点を解決するためになされたものであり、有機亜鉛ァ 一ト錯体を用いた重合開始剤および (メタ)アクリル酸誘導体の重合方法に関するも のである。 [0008] An object of the present invention has been made to solve the above-described problems, and relates to a polymerization initiator using an organic zincate complex and a method for polymerizing a (meth) acrylic acid derivative.
課題を解決するための手段  Means for solving the problem
[0009] 本発明者らは、本課題を解決するために鋭意努力を行った結果、亜鉛原子上に t- ブチル基を少なくとも 1つもつ有機亜鉛アート錯体がァ-オン重合性モノマーの重合 開始剤として好適であることを見出し本発明を完成するに至った。 [0009] As a result of diligent efforts to solve this problem, the inventors of the present invention have started the polymerization of an ion-polymerizable monomer from an organozinc ate complex having at least one t-butyl group on a zinc atom. As a result, the present invention was found to be suitable as an agent.
[0010] すなわち本発明は、一般式（1) That is, the present invention relates to the general formula (1)
t-Bu R ZnM (1)  t-Bu R ZnM (1)
または一般式 (2)  Or general formula (2)
t-Bu R ZnM (2)  t-Bu R ZnM (2)
n 4— n m  n 4— n m
(ただし式中、 nは 1〜3の整数、 Rは各々同一でも異なっていてもよぐ炭素数 1〜12 のアルキル基、ァルケ-ル基、ァリール基、またはァリールアルキル基を示す。 Mはリ チウム、マグネシウムあるいは MgX(Xは塩素、臭素、ヨウ素のいずれかを表す）で示 されるハロゲン化マグネシウムを表す。 mは 1ないし 2を示す。）  (In the formula, n represents an integer of 1 to 3, and R represents an alkyl group having 1 to 12 carbon atoms which may be the same or different, an alkyl group, an aryl group, or an aryl alkyl group. Represents a magnesium halide represented by lithium, magnesium, or MgX (where X represents chlorine, bromine, or iodine. M represents 1 to 2).
で示される亜鉛アート錯体力ゝらなることを特徴とする重合開始剤および  A polymerization initiator characterized by comprising a zinc ate complex
前記一般式（1)または (2)で示される亜鉛アート錯体を重合開始剤として用いること を特徴とする (メタ)アクリル酸誘導体の重合方法に関するものである。  The present invention relates to a method for polymerizing a (meth) acrylic acid derivative, wherein the zinc ate complex represented by the general formula (1) or (2) is used as a polymerization initiator.
発明の効果  The invention's effect
[0011] 本発明に係る有機亜鉛アート錯体を重合開始剤として用いることで、活性プロトン を有するモノマーおよび Zまたは溶媒を用いても、高収率で重合体を得ることができ る。 発明を実施するための最良の形態 [0011] By using the organozinc art complex according to the present invention as a polymerization initiator, a polymer can be obtained in a high yield even when a monomer having an active proton and Z or a solvent are used. BEST MODE FOR CARRYING OUT THE INVENTION
[0012] 本発明の重合開始剤は一般式 ( 1)  [0012] The polymerization initiator of the present invention has the general formula (1)
t- Bu R ZnM ( 1)  t- Bu R ZnM (1)
または一般式 (2)  Or general formula (2)
t- Bu R ZnM (2)  t- Bu R ZnM (2)
n 4— n m  n 4— n m
で示される少なくとも 1つの t ブチル基を有する有機亜鉛アート錯体である。  And an organozinc ate complex having at least one t-butyl group.
[0013] ここで、 nは 1 3から選ばれる整数、 Rは各々同一でも異なっていてもよぐ炭素数  [0013] where n is an integer selected from 13 and R is the same or different carbon number.
1 12のアルキル基、ァルケ-ル基、ァリール基またはァリールアルキル基であり、 具体的にはメチル基、ェチル基、 i—プロピル基、 n—プロピル基、 n ブチル基、 i— ブチル基、 s ブチル基、 n ペンチル基、 t-アミル基、 n キシル基、 n プチ ル基、 n—ォクチル基、 n—ノ-ル基、 n—デシル基、ビュル基、シクロペンタジェ-ル 基、フエ-ル基、ベンジル基を示す。 Mはリチウム、マグネシウムあるいは MgX (Xは 塩素、臭素、ヨウ素のいずれかを表す)で示されるハロゲンィ匕マグネシウムを表す。 m は 1ないし 2を示す。  1 12 alkyl group, alkenyl group, aryl group or aryl alkyl group, specifically, methyl group, ethyl group, i-propyl group, n-propyl group, n butyl group, i-butyl group, s butyl group, n pentyl group, t-amyl group, n xyl group, n propyl group, n-octyl group, n-nor group, n-decyl group, bur group, cyclopentagel group, phenol -Represents a benzyl group. M represents lithium magnesium or MgX (X represents chlorine, bromine or iodine). m represents 1 or 2.
[0014] 本発明に用いられる有機亜鉛アート錯体のより具体的な例としては、一般式（1) t- Bu R ZnM ( 1)  [0014] More specific examples of the organozinc ate complex used in the present invention include those represented by the general formula (1) t- Bu R ZnM (1)
で示される化合物として、（t プチル)ジメチル亜鉛酸リチウム、（t—プチル)ジェチ ル亜鉛酸リチウム、（tーブチル）ジブチル亜鉛酸リチウム、（tーブチル）ジビュル亜鉛 酸リチウム、（n—ブチル）ジ t ブチル亜鉛酸リチウム、ビス（tーブチル）フエ-ル亜 鉛酸リチウム、トリ t—ブチル亜鉛酸リチウム等の有機亜鉛酸リチウムや、（t—プチル） ジメチル亜鉛酸マグネシウムクロライド、（tーブチル）ジメチル亜鉛酸マグネシウムブ ロマイド、（tーブチル）ジメチル亜鉛酸マグネシウムアイオダイド、ジ (tーブチル)メチ ル亜鉛酸マグネシウムクロライド、ジ（t ブチル）メチル亜鉛酸マグネシウムブロマイ ド、ジ（tーブチル)メチル亜鉛酸マグネシウムアイオダイド、ジェチル（tーブチル）亜 鉛酸マグネシウムクロライド、ジェチル (tーブチル）亜鉛酸マグネシウムブロマイド、ジ ェチル (t ブチル）亜鉛酸マグネシウムアイオダイド、ェチルジ (t ブチル）亜鉛酸 マグネシウムクロライド、ェチルジ（tーブチル）亜鉛酸マグネシウムブロマイド、ェチル ジ（t ブチル）亜鉛酸マグネシウムアイオダイド、 (t ブチル）ジブチル亜鉛酸マグ ネシゥムクロライド、（tーブチル）ジブチル亜鉛酸マグネシウムブロマイド、（t ブチル )ジブチル亜鉛酸マグネシウムアイオダイド、ジ (tーブチル）ブチル亜鉛酸マグネシゥ ムクロライド、ジ（t ブチル）ブチル亜鉛酸マグネシウムブロマイド、ジ（t ブチル）ブ チル亜鉛酸マグネシウムアイオダイド、（tーブチル）ジビュル亜鉛酸マグネシウムクロ ライド、 (t ブチル）ジビュル亜鉛酸マグネシウムブロマイド、 (t ブチル）ジビニル亜 鉛酸マグネシウムアイオダイド、ジフエ-ル (t ブチル）亜鉛酸マグネシウムクロライド 、ジフエ-ル（tーブチル）亜鉛酸マグネシウムブロマイド、ジフエ-ル（tーブチル）亜 鉛酸マグネシウムアイオダイド、フエ-ルジ (t ブチル）亜鉛酸マグネシウムクロライド 、フエ-ルジ（tーブチル）亜鉛酸マグネシウムブロマイド、フエ-ルジ（tーブチル）亜 鉛酸マグネシウムアイオダイド、トリ t ブチル亜鉛酸マグネシウムクロライド、トリ tーブ チル亜鉛酸マグネシウムブロマイド、トリ t ブチル亜鉛酸マグネシウムアイオダイド等 の有機亜鉛酸マグネシウムハロゲンィ匕物が例示される。 (T-butyl) lithium dimethylzincate, (t-butyl) lithium lithium zincate, (t-butyl) lithium dibutylzincate, (t-butyl) lithium dibutyrate, (n-butyl) diethyl t Lithium butyl zincate, lithium bis (tert-butyl) phenyl phosphite, tri-lithium lithium zincate such as lithium zincate, (t-butyl) dimethylzinc zincate chloride, (tert-butyl) dimethyl Magnesium zincate bromide, (t-butyl) dimethylmagnesium zinc iodide, di (t-butyl) methylmagnesium chloride, di (t-butyl) methylmagnesium bromide, di (t-butyl) methylzinc acid Magnesium Iodide, Jetyl (t-Butyl) Magnesium Chlorite, Jetyl ( t-butyl) magnesium zinc bromide, dimethyl (t butyl) magnesium zinc iodide, ethyl di (t butyl) magnesium chloride, ethyl di (t-butyl) magnesium bromide, ethyl di (t butyl) magnesium zinc Dido, (t-butyl) dibutyl zincate mug Nesmuchloride, (t-butyl) dibutylmagnesium zinc bromide, (tbutyl) dibutylzincmagnesium iodide, di (t-butyl) butylzincmagnesium chloride, di (tbutyl) butylmagnesium bromide, di ( (t-Butyl) Butylzinc Zinc Magnesium Iodide, (t-Butyl) Dibulu Magnesium Zinc Oxide Chloride, (t-Butyl) Dibulu Magnesium Magnesium Bromide, (t-Butyl) Divinyl Magnesium Plumite Iodide, Diphenyl (t-Butyl) ) Magnesium Zinc Acid Chloride, Diphenyl (t-butyl) Magnesium Zinc Acid Bromide, Diphenyl (t-butyl) Magnesium Zincite Iodide, Ferrule (t-butyl) Magnesium Zinc Acid Chloride, Ferrule (t-butyl) ) Magnesium zincate Organomagnesium halides such as mubromide, ferrule (t-butyl) magnesium phosphite iodide, tri-t-butylzinc zincate chloride, tri-tert-butylzincmagnesium bromide, tri-t-butylzincmagnesium iodide Examples are illustrated.
一般式（2)  General formula (2)
t-Bu R ZnM (2)  t-Bu R ZnM (2)
n 4— n m  n 4— n m
で示される有機亜鉛アート錯体の具体例としては、トリ- 1-ブチルメチル亜鉛酸ジリチ ゥム、トリ- 1-ブチルェチル亜鉛酸ジリチウム、トリ- 1-ブチル -n-プロピル亜鉛酸ジリチ ゥム、トリ- 1-ブチル -i-プロピル亜鉛酸ジリチウム、トリ- 1-ブチル -n-ブチル亜鉛酸ジリ チウム、トリ- 1-ブチル -i-ブチル亜鉛酸ジリチウム、トリ- 1-ブチル -S-ブチル亜鉛酸ジリ チウム、ジメチルジ -t-ブチル亜鉛酸ジリチウム、ジェチルジ -t-ブチル亜鉛酸ジリチウ ム、ジ -t-ブチルジ- n-プロピル亜鉛酸ジリチウム、ジ -t-ブチルジ- i-プロピル亜鉛酸 ジリチウム、ジ- n-ブチルジ- n-ブチル亜鉛酸ジリチウム、ジ- n-ブチルジ- i-ブチル亜 鉛酸ジリチウム、ジ- n-ブチルジ- s-ブチル亜鉛酸ジリチウム、メチルェチルジ -t-ブチ ル亜鉛酸ジリチウム、メチル -n-ブチル -ジ -t-ブチル亜鉛酸ジリチウム、メチル -S-ブ チル-ジ -t-ブチル亜鉛酸ジリチウム、ェチル -n-ブチル -ジ -t-ブチル亜鉛酸ジリチウ ム、ェチル -S-ブチル -ジ -t-ブチル亜鉛酸ジリチウム、ジメチルェチル -t-ブチル亜鉛 酸ジリチウム、ジメチル- n-ブチル -t-ブチル亜鉛酸ジリチウム、ジメチル -S-ブチル -t- ブチル亜鉛酸ジリチウム、ジメチルェチル -t-ブチル亜鉛酸ジリチウム、ジェチルメチ ル -t-ブチル亜鉛酸ジリチウム、ジェチル- n-ブチル -t-ブチル亜鉛酸ジリチウム、ジ ェチル -s-ブチル -t-ブチル亜鉛酸ジリチウム等の有機亜鉛酸ジリチウムや、トリ- 1-ブ チルメチル亜鉛酸マグネシウム、トリ- 1-ブチルェチル亜鉛酸マグネシウム、トリ- 1-ブ チル- n-プロピル亜鉛酸マグネシウム、トリ- 1-ブチル -トプロピル亜鉛酸マグネシウム 、トリ- 1-ブチル -n-ブチル亜鉛酸マグネシウム、トリ- 1-ブチル -i-ブチル亜鉛酸マグネ シゥム、トリ- 1-ブチル -S-ブチル亜鉛酸マグネシウム、ジメチルジ -t-ブチル亜鉛酸マ グネシゥム、ジェチルジ -t-ブチル亜鉛酸マグネシウム、ジ -t-ブチルジ- n-プロピル 亜鉛酸マグネシウム、ジ -t-ブチルジ- i-プロピル亜鉛酸マグネシウム、ジ- n-ブチルジ -n-ブチル亜鉛酸マグネシウム、ジ- n-ブチルジ- i-ブチル亜鉛酸マグネシウム、ジ -n -ブチルジ- s-ブチル亜鉛酸マグネシウム、メチルェチルジ -t-ブチル亜鉛酸マグネシ ゥム、メチル -n-ブチル -ジ -t-ブチル亜鉛酸マグネシウム、メチル -S-ブチル -ジ -t-ブ チル亜鉛酸マグネシウム、ェチル -n-ブチル -ジ -t-ブチル亜鉛酸マグネシウム、ェチ ル- s-ブチル -ジ -t-ブチル亜鉛酸マグネシウム、ジメチルェチル -t-ブチル亜鉛酸マ グネシゥム、ジメチル- n-ブチル -t-ブチル亜鉛酸マグネシウム、ジメチル -S-ブチル -t -ブチル亜鉛酸マグネシウム、ジメチルェチル -t-ブチル亜鉛酸マグネシウム、ジェチ ルメチル -t-ブチル亜鉛酸マグネシウム、ジェチル- n-ブチル -t-ブチル亜鉛酸マグネ シゥム、ジェチル- s-ブチル -t-ブチル亜鉛酸マグネシウム等の有機亜鉛酸マグネシ ゥムを挙げる事ができる。 Specific examples of the organic zinc ate complex represented by the formula include di-1-trimethyl tri-butylmethylzincate, dilithium tri-1-butylethylzirconate, tri-1-butyl-n-propyldiethyl zincate, tri-tri- Dilithium 1-butyl-i-propylzinc zincate, dilithium tri-1-butyl-n-butylzinc zincate, dilithium tri-1-butyl-i-butylzinc zincate, di-1-tributyl-1-S-butylzinclate Titanium, Dilithium dimethyldi-t-butylzinc zincate, Jetyldi-t-butylzinc zincate, Di-t-butyldi-n-propylzinc zincate, Di-t-butyldi-i-propylzincate dilithium, Di-n -Butyl di-n-butyl dizinc zincate, di-n-butyl di-i-butyl dilithium phosphite, di-n-butyl di-s-butyl dizinc zincate, methylethyl di-t-butylzinc zincate, methyl-n -Butyl-di-t-butyl Dilithium zincate, methyl-S-butyl-di-t-butyldilithium zincate, ethyl-n-butyl-di-t-butyldilithium zincate, ethyl-S-butyl-di-t-butyldilithium zincate , Dimethylethyl-t-butylzinc zincate, dimethyl-n-butyl-t-butylzinclate, dimethyl-S-butyl-t-butylzinclate, dimethylethyl-t-butylzinclate, jetylmethyl-t- Dilithium butyl zincate, Jetyl-n-Butyl-t-butyl dilithium zincate, Di Diethyllithium zincate such as ethyl-s-butyl-t-butylzinczate, magnesium tri-1-butylmethylzinc zincate, magnesium tri-1-butylethylzincate, tri-1-butylbutyl-n-propylzinc Magnesium acetate, magnesium tri-1-butyl-topropyl zincate, magnesium tri-1-butyl-n-butyl magnesium zinc, tri-1-butyl-magnesium i-butylzinc, tri-1-butyl-S-butyl Magnesium zincate, magnesium dimethyldi-t-butylzinc zincate, jetyldi-t-butylmagnesium zincate, di-t-butyldi-n-propylmagnesium zincate, di-t-butyldi-i-propylmagnesium zincate, di -n-Butyldi-n-butylmagnesium zincate, di-n-butyldi-i-butylmagnesium zincate, di-n-butyldi-s-butylmagnesium zincate, methylethyldi-t- Magnesium til zincate, methyl-n-butyl-di-t-butylmagnesium zincate, methyl-S-butyl-di-t-butylmagnesium zincate, ethyl-n-butyl-di-t-butylzinc Magnesium oxide, ethyl-s-butyl-di-t-butylmagnesium zincate, dimethylethyl-t-butylmagnesium magnesium, dimethyl-n-butyl-t-butylmagnesium zincate, dimethyl-S-butyl-t -Butylmagnesium zincate, dimethylethyl -t-butylmagnesium zincate, methylmethyl-t-butylmagnesium zincate, jetyl-n-butyl-t-butylzincmagnesium, jetyl-s-butyl-t-butylzincacid Mention may be made of magnesium organic zincate such as magnesium.
[0016] これらの亜鉛アート錯体は、単品でもあるいは混合物としても重合開始剤として用 いることがでさる。 [0016] These zinc art complexes can be used as polymerization initiators either individually or as a mixture.
[0017] 本発明の t—ブチル基を有する亜鉛アート錯体は、不活性ガス雰囲気下、亜鉛ィ匕 合物と、有機リチウム化合物ある 、は有機マグネシウム化合物との反応により合成す ることがでさる。  The zinc art complex having a t-butyl group of the present invention can be synthesized by a reaction between a zinc compound and an organolithium compound or an organomagnesium compound in an inert gas atmosphere. .
[0018] 例えば、ジアルキル亜鉛やジァリール亜鉛、ジアルケニル亜鉛などの有機亜鉛ィ匕 合物に対して 1〜 2当量の t-ブチルリチウムある!/ヽは t ブチル基を有する有機マグ ネシゥム試薬とを反応させることで合成することができる。また、ジ t ブチル亜鉛に対 して 1〜2当量の有機リチウム試薬または有機マグネシウム試薬を反応させたものを 用いることちでさる。  [0018] For example, there are 1 to 2 equivalents of t-butyllithium to an organozinc compound such as dialkylzinc, dialylzinc and dialkenylzinc! /! Reacts with an organomagnesium reagent having a tbutyl group. Can be synthesized. It is also possible to use one obtained by reacting 1 to 2 equivalents of an organolithium reagent or an organomagnesium reagent with dibutylzinc.
[0019] あるいは、塩ィ匕亜鉛などのハロゲンィ匕亜鉛を出発源とし、亜鉛に対し 3〜4当量の 有機リチウム試薬あるいは有機マグネシウム試薬を反応させることで合成することが できる。この際、少なくとも 1当量の t—ブチルリチウムあるいは t—ブチル基を有する 有機マグネシウム試薬を使用することで、本発明における亜鉛アート錯体を合成する ことができる。 [0019] Alternatively, starting from halogenated zinc such as salted zinc, 3-4 equivalents of zinc It can be synthesized by reacting an organolithium reagent or an organomagnesium reagent. At this time, the zinc ate complex in the present invention can be synthesized by using an organomagnesium reagent having at least one equivalent of t-butyllithium or t-butyl group.
[0020] これらの合成には、反応溶媒として、テトラヒドロフラン、ジェチルエーテル、ジブチ ルエーテル、シクロペンチルメチルエーテルなどのエーテル系溶媒あるいはペンタン 、へキサン、ヘプタン、トルエンなどの炭化水素系溶媒およびそれらの混合液を用い ることができる。なかでも、反応時の温度の制御あるいは均一性の保持の観点から、 エーテル系溶媒を用いるのが好ま 、。  [0020] In these syntheses, as reaction solvents, ether solvents such as tetrahydrofuran, jetyl ether, dibutyl ether, cyclopentyl methyl ether or hydrocarbon solvents such as pentane, hexane, heptane, toluene, and mixtures thereof. Can be used. In particular, it is preferable to use an ether solvent from the viewpoint of controlling the temperature during the reaction or maintaining uniformity.
[0021] 合成した亜鉛アート錯体の溶液はそのまま重合に使用することができる。  [0021] The solution of the synthesized zinc ate complex can be used for polymerization as it is.
[0022] 重合に用いられるモノマーとして、（メタ)アクリル酸誘導体が挙げられる。（メタ)ァク リル酸誘導体としては、アクリル酸、メタクリル酸およびアクリル酸メチル、メタクリル酸 メチル、アクリル酸ェチル、メタクリル酸ェチル、ヒドロキシェチルメタタリレートなどの（ メタ）アクリル酸エステル類、 N—イソプロピルアクリルアミド、アクリルアミド、 N—イソプ 口ピルメタクリルアミドなど (メタ)アクリル酸アミド類が例示できる。これらは単独で用い られる力 必要に応じて、 2成分以上あるいは他のァ-オン重合性モノマーと併用し、 共重合体を製造することも出来る。  [0022] Examples of the monomer used for the polymerization include (meth) acrylic acid derivatives. (Meth) acrylic acid derivatives include (meth) acrylic acid esters such as acrylic acid, methacrylic acid and methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and hydroxyethyl methacrylate. Examples include (meth) acrylic acid amides such as —isopropylacrylamide, acrylamide, N-isopropylpyrmethacrylamide. These can be used alone If necessary, they can be used in combination with two or more components or other key-on polymerizable monomers to produce a copolymer.
[0023] 特に、ヒドロキシェチルメタタリレート、 N—イソプロピルアクリルアミド、アクリルアミド 、 N—イソプロピルメタクリルアミドなど、通常の有機金属を用いた場合には失活する ような、活性プロトンを有する (メタ)アクリル誘導体に対しても、本発明の亜鉛アート錯 体は、重合開始機能を損なうことなぐ重合を進行させることができる。  [0023] In particular, (meth) acrylic having an active proton that is deactivated when a normal organic metal such as hydroxyethyl methacrylate, N-isopropylacrylamide, acrylamide, N-isopropylmethacrylamide is used. Even for the derivatives, the zinc art complex of the present invention can advance polymerization without impairing the polymerization initiation function.
[0024] 重合に用いられる溶媒としては、通常用いられる溶媒であればよぐ例えばトルエン 、キシレン、へキサン、シクロへキサン、ヘプタンなどの炭化水素系溶媒、 THF、ジェ チルエーテルなどのエーテル溶媒系、メタノール、エタノール、イソプロパノールなど のアルコール類および水等が挙げられる。一般に、水やアルコール類は、有機金属 化合物と容易に反応を起こすため、それらを溶媒に用いた場合、有機金属化合物は 重合開始機能を失うとされている。しかしながら、本発明の亜鉛アート錯体は、水ゃァ ルコール系溶媒といったプロトン性溶媒系を重合溶媒として使用しても、重合開始機 能を失うことがなぐ高収率で重合体を得ることが出来る。 [0024] The solvent used for the polymerization may be a commonly used solvent, for example, a hydrocarbon solvent such as toluene, xylene, hexane, cyclohexane, heptane, an ether solvent system such as THF, diethyl ether, Examples include alcohols such as methanol, ethanol and isopropanol, and water. In general, water and alcohols easily react with an organometallic compound. Therefore, when they are used as a solvent, the organometallic compound is said to lose its polymerization initiation function. However, the zinc art complex of the present invention can be used even when a protic solvent system such as a hydrogen alcohol solvent is used as a polymerization solvent. A polymer can be obtained in a high yield without losing performance.
[0025] 本発明における、（メタ）アクリル酸誘導体の重合において使用される亜鉛アート錯 体の量は特に制限はないが、（メタ）アクリル酸誘導体 100モルに対して 0. 001-10 モルの範囲で用いることが好ま 、。この範囲より少な 、場合には十分な重合活性が 出ないことがあり、この範囲を超えた場合には、得られたポリマー中に多量の金属残 渣が含まれることがあり、それを除去する工程が必要となることがある。  [0025] The amount of the zinc ate complex used in the polymerization of the (meth) acrylic acid derivative in the present invention is not particularly limited, but is 0.001 to 10 mol per 100 mol of the (meth) acrylic acid derivative. Preferred to use in a range. If it is less than this range, sufficient polymerization activity may not be obtained. If this range is exceeded, a large amount of metal residue may be contained in the obtained polymer, and it is removed. A process may be required.
[0026] 以下に本発明の実施例を示すが、本発明はこれらに限定されるものではない。  Examples of the present invention are shown below, but the present invention is not limited to these.
実施例 1  Example 1
[0027] t-BuEt ZnLiの [0027] t-BuEt ZnLi
2 M  2 M
窒素雰囲気下、 lOOmLナスフラスコに THF30mL,ジェチル亜鉛 3. 72g (30. 1ミ リモル)をカ卩え、 70°Cに冷却した。攪拌条件下、 20. 3wt%の t—ブチルリチウムの ペンタン溶液 9. 35g (29. 7ミリモル)を滴下した。滴下後、 70°Cにて 30分攪拌し た後、室温まで昇温した。溶媒を減圧濃縮し、 32. 2 ％の1;ー：61^ ZnLiの THF  Under a nitrogen atmosphere, 30 mL of THF and 3.72 g (30.1 mmol) of jetyl zinc were placed in an lOOmL eggplant flask and cooled to 70 ° C. Under stirring conditions, 9.35 g (29.7 mmol) of a 20.3 wt% t-butyllithium pentane solution was added dropwise. After dropping, the mixture was stirred at 70 ° C for 30 minutes, and then warmed to room temperature. The solvent was concentrated under reduced pressure, 32.2% 1;-: 61 ^ ZnLi in THF
2  2
溶液を得た。  A solution was obtained.
1H-NMR (THF-d6) d 1.36 (t, 6H), 1.03 (s, 9H), -0.06 (q, 4H)  1H-NMR (THF-d6) d 1.36 (t, 6H), 1.03 (s, 9H), -0.06 (q, 4H)
また、本溶液を希硫酸にて分解し、発生ガス量を測定したところ、 Znに対して 3倍モ ル量のガスが発生することを確認した。  In addition, when this solution was decomposed with dilute sulfuric acid and the amount of gas generated was measured, it was confirmed that 3 times the amount of gas was generated with respect to Zn.
上記分析結果より、 t-BuEt ZnMgClが生成している事を確認した。  From the above analysis results, it was confirmed that t-BuEt ZnMgCl was produced.
2  2
[0028] N イソプロピルアクリルアミドの重合  [0028] Polymerization of N-isopropylacrylamide
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. 0g (44. 4ミリモル）の水 溶液に、合成例 1にて調製した 32. 3 ％の1；一 BuEt ZnLiの THF溶液 0. 28gを  N-isopropylacrylamide 5.0 g (44.4 mmol) in an aqueous solution at 20 ° C under nitrogen atmosphere 32.3% 1 prepared in Synthesis Example 1; 1 BuEt ZnLi THF solution 0.28 g The
2  2
加え、常温で 1時間間攪拌した。その後、 50°Cにて 30分間攪拌したところ、固体が析 出。 4. Ogのポリマーを回収した。  In addition, the mixture was stirred at room temperature for 1 hour. After stirring for 30 minutes at 50 ° C, solids were precipitated. 4. The Og polymer was recovered.
実施例 2  Example 2
[0029] t-BuEt ZTIM CWM . [0029] t-BuEt ZTIM CWM.
2  2
窒素雰囲気下、 lOOmLナスフラスコに THF30mL,ジェチル亜鉛 9. 65g (78. 1ミ リモル)をカ卩え、 50°Cに冷却した。攪拌条件下、 13. Owt%の t—ブチルマグネシ ゥムクロライドの THF溶液 70g (78. 1ミリモル）を滴下した。滴下後、 50°Cにて 30 分攪拌した後、室温まで昇温し、 17 ％の1; 81^ ZnMgClの THF溶液を得た。 Under a nitrogen atmosphere, 30 mL of THF and 9.65 g (78.1 mmol) of jetyl zinc were placed in an lOOmL eggplant flask and cooled to 50 ° C. Under stirring conditions, 70 g (78.1 mmol) of THF solution of 13. Owt% t-butylmagnesium chloride was added dropwise. After dropping, 30 at 50 ° C After stirring for minutes, the temperature was raised to room temperature, and a THF solution of 17% 1; 81 ^ ZnMgCl was obtained.
2  2
1H-NMR (THF-d6) d 1.31 (t, 6H), 1.10 (s, 9H),—0.03 (q, 4H)  1H-NMR (THF-d6) d 1.31 (t, 6H), 1.10 (s, 9H), — 0.03 (q, 4H)
また、本溶液を希硫酸による分解にて生成する、亜鉛アート錯体由来のブタンおよ びェタン力 なるガス量を測定したところ、 Znに対して 3倍モル量のガスが発生するこ とを確認した。  In addition, when the amount of butane and ethane power derived from the zinc ate complex produced by the decomposition of this solution with dilute sulfuric acid was measured, it was confirmed that a 3-fold molar amount of gas was generated relative to Zn. did.
上記分析結果より、 t-BuEt ZnMgClが生成している事を確認した。  From the above analysis results, it was confirmed that t-BuEt ZnMgCl was produced.
2  2
[0030] N イソプロピルアクリルアミドの重合  [0030] Polymerization of N-isopropylacrylamide
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. 5g (48. 7ミリモル）の水 溶液に、合成例 1にて調製した 17wt%の t— BuEt ZnMgClの THF溶液 0. 8gを加  Under a nitrogen atmosphere, 20 g of N-isopropylacrylamide at 5.5 g (48.7 mmol) in water was added with 0.8 g of the 17 wt% t-BuEt ZnMgCl THF solution prepared in Synthesis Example 1.
2  2
え、常温で 1時間間攪拌した。その後、 50°Cにて 30分間攪拌したところ、固体が析出 。 5. 5gのポリマーを回収した。  It was stirred at room temperature for 1 hour. Then, when it stirred for 30 minutes at 50 degreeC, solid precipitated. 5. 5 g of polymer was recovered.
実施例 3  Example 3
[0031] t— Bu Zn sClの [0031] t— Bu Zn sCl
3 S  3 S
蜜素雰囲気下、 300mLナスフラスコに THF70mL,塩ィ匕亜 )4. 73g (34. 7ミリモ ル)をカ卩え、 0°Cに冷却した。攪拌条件下、 13. Owt%の t ブチルマグネシウムクロ ライドの THF溶液 94g (104. 4ミリモル)を滴下した。滴下後、室温室温まで昇温し、 濾過後 7wt%の t Bu ZnMgClの THF溶液を得た。  Under a honey atmosphere, 4.7 mL (34.7 millimoles) of THF (70 mL, salt) was added to a 300 mL eggplant flask and cooled to 0 ° C. Under stirring conditions, 94 g (104.4 mmol) of THF solution of 13. Owt% t-butylmagnesium chloride was added dropwise. After the dropwise addition, the temperature was raised to room temperature, and after filtration, a THF solution of 7 wt% t Bu ZnMgCl was obtained.
3  Three
1H-NMR (THF-d6) d 1.15 (s, 27H)  1H-NMR (THF-d6) d 1.15 (s, 27H)
[0032] N イソプロピルアクリルアミドの重合 [0032] Polymerization of N-isopropylacrylamide
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. lg (40. 1ミリモル）の水 溶液に、合成例 1にて調製した 7wt%の t—Bu ZnMgClの THF溶液 0. 6gを加え、  Under a nitrogen atmosphere at 20 ° C, add 0.6 g of a 7 wt% t-Bu ZnMgCl THF solution prepared in Synthesis Example 1 to an aqueous solution of 5.lg (40.1 mmol) of N-isopropylacrylamide.
3  Three
常温で 1時間間攪拌した。その後、 50°Cにて 30分間攪拌したところ、固体が析出。 4 . 9gのポリマーを回収した。  Stir at room temperature for 1 hour. Thereafter, the mixture was stirred at 50 ° C for 30 minutes, and a solid precipitated. 4.9 g of polymer was recovered.
実施例 4  Example 4
[0033] t-Buin-Bul ZnLiの調製 [0033] Preparation of t-Buin-Bul ZnLi
3 2  3 2
窒素雰囲気下、 300mLナスフラスコに無水塩化亜鉛の 1M— THF溶液 35mL (3 5ミリモル）を加え、 70°Cに冷却。攪拌条件下、 14. 9wt%—n—ブチルリチウムの へキサン溶液 45. 3g ( 105ミリモル）を滴下した。更に、 70°C、攪拌条件下 21. 6w t%— t—ブチルリチウムのペンタン溶液 10. 2g (34. 3ミリモル）を滴下した。滴下後 、— 70°Cにて 30分攪拌した後、室温まで昇温した。溶媒を減圧除去し、 39. 2wt% の ー：611 (11—：611) ZnLiの THF溶液を得た。 In a nitrogen atmosphere, add 35 mL (35 mmol) of 1M THF solution of anhydrous zinc chloride to a 300 mL eggplant flask and cool to 70 ° C. Under stirring conditions, 45.3 g (105 mmol) of a hexane solution of 14.9 wt% -n-butyllithium was added dropwise. Furthermore, 21.6 w under stirring at 70 ° C 10.2 g (34.3 mmol) of t% —t-butyllithium in pentane was added dropwise. After dropping, the mixture was stirred at -70 ° C for 30 minutes, and then warmed to room temperature. The solvent was removed under reduced pressure to obtain 39.2 wt% of THF solution of —611 (11—611) ZnLi.
3 2  3 2
[0034] N イソプロピルアクリルアミドの重合  [0034] Polymerization of N-isopropylacrylamide
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. lg (45. 0ミリモル）の水 溶液に、 t— Bu (n— Bu) ZnLiの THF溶液 0. 5gをカ卩え、常温で 1時間間攪拌した  In a nitrogen atmosphere at 20 ° C, add 0.5 g of t-Bu (n-Bu) ZnLi in THF to an aqueous solution of N-isopropylacrylamide (5 lg, 45.0 mmol) at room temperature. Stir for hours
3 2  3 2
。その後、 50°Cにて 30分間攪拌したところ、固体が析出。 4. 3gのポリマーを回収し た。  . Thereafter, the mixture was stirred at 50 ° C for 30 minutes, and a solid precipitated. 4. 3 g of polymer was recovered.
実施例 5  Example 5
[0035] It Bu). in Bui ZnLiの調製  [0035] Preparation of It Bu). In Bui ZnLi
2 2 2  2 2 2
14. 9wt%— n—ブチルリチウムのへキサン溶液 30. lg (70ミリモル）と 21. 6wt% —t ブチルリチウムのペンタン溶液 20. 5g (69. 1ミリモル）を用いた以外は、実施 例 1と同様にして、 38. 9wt%の（t— Bu) (n-Bu) ZnLiの THF溶液を得た。  14. Example 1 except that 30. lg (70 mmol) of 9 wt% — n-butyllithium in hexane and 20.5 g (69.1 mmol) of 21.6 wt% —t butyllithium in pentane were used. In the same manner as above, a THF solution of 38.9 wt% (t-Bu) (n-Bu) ZnLi was obtained.
2 2 2  2 2 2
[0036] N イソプロピルアクリルアミドの重合  [0036] Polymerization of N-isopropylacrylamide
実施例 4と同様な方法により、 38. 9wt%の（t— Bu) (n-Bu) ZnLiの THF溶液  In the same manner as in Example 4, 38.9 wt% of (t—Bu) (n-Bu) ZnLi in THF solution
2 2 2  2 2 2
0. 5gより、ポリマー 4. 8gを得た。  From 0.5 g, 4.8 g of a polymer was obtained.
実施例 6  Example 6
[0037] t Buin-Bu) Et ZnLiの調製 [0037] Preparation of t Buin-Bu) Et ZnLi
2 2  twenty two
窒素雰囲気下、 lOOmLナスフラスコに THF30mL,ジェチル亜鉛 4. 26g (34. 5ミ リモル）をカ卩え、 70°Cに冷却。攪拌条件下、 14. 9wt%—n ブチルリチウムのへ キサン溶液 14. 9g (34. 8ミリモル)を滴下した。更に— 70°C、攪拌条件下 21. 6t% t ブチルリチウムのペンタン溶液 10. lg (34. 0ミリモル）を滴下した。滴下後、 70°Cにて 30分攪拌した後、室温まで昇温した。溶媒を減圧除去し、 36. 8wt%のt -Bu (n-Bu) Et ZnLiの THF溶液を得た。  In a nitrogen atmosphere, add 30 mL of THF and 4.26 g (34.5 mmol) of jetyl zinc in an lOOmL eggplant flask and cool to 70 ° C. Under stirring conditions, 14.9 g (34.8 mmol) of a hexane solution of 14.9 wt% -n butyllithium was added dropwise. Further, 10. lg (34.0 mmol) of a 21.6 t% t-butyl lithium pentane solution was added dropwise at 70 ° C. under stirring conditions. After dropping, the mixture was stirred at 70 ° C for 30 minutes, and then warmed to room temperature. The solvent was removed under reduced pressure to obtain a THF solution of 36.8 wt% t 2 -Bu (n-Bu) Et ZnLi.
2 2  twenty two
[0038] N—イソプロピルアクリルアミドの重合  [0038] Polymerization of N-isopropylacrylamide
実施例 4と同様な方法により、 t-Bu(n-Bu) Et ZnLiの THF溶液 0. 5gより 4. lg  In the same manner as in Example 4, from 0.5 g of a THF solution of t-Bu (n-Bu) Et ZnLi to 4. lg
2 2  twenty two
のポリマーを回収した。  Of polymer was recovered.
実施例 7 [0039] t-Bu Et ZnLiの調製 Example 7 [0039] Preparation of t-Bu Et ZnLi
2 2 2  2 2 2
ジェチル亜鉛 3. 26g (26. 4ミリモル）と 20. 3wt%— t—ブチルリチウムのペンタン 溶液 16. 2g (51. 3ミリモノレ）より、実施 ί列 6と同様な方法により 22. 3wt%の t— Bu Ε  Jetylzinc 3.26 g (26.4 mmol) and 20. 3 wt% —t-butyllithium in pentane solution 16.2 g (51.3 millimonoles) — Bu Ε
2 t ZnLiの THF溶液を得た。  A THF solution of 2 t ZnLi was obtained.
2 2  twenty two
[0040] N—イソプロピルアクリルアミドの重合  [0040] Polymerization of N-isopropylacrylamide
実施例 4と同様な方法により、 t-Bu Et ZnLiの THF溶液 0. 5gより、 3. 9gのポリ  In the same manner as in Example 4, from 0.5 g of t-Bu Et ZnLi in THF, 3.9 g of poly
2 2 2  2 2 2
マーを回収した。  The mer was recovered.
実施例 8  Example 8
[0041] t-Bu Et ZnLiの調製 [0041] Preparation of t-Bu Et ZnLi
2 '2 2  2 '2 2
ジェチル亜鉛 3. 8g (30. 8ミリモル）、トルエン 30ml及び 20. 3wt%— t—ブチルリ チウムのペンタン溶液 19. 8g (62. 6ミリモル)より、実施例 6と同様な方法により反応 を行なった後、析出した固体を窒素雰囲気下でろ過した後、溶媒を溜去し 29. 4wt %の t—Bu Et ZnLiのトルエン溶液を得た。  A reaction was carried out in the same manner as in Example 6 from 3.8 g (30.8 mmol) of jetil zinc, 30 ml of toluene and 19.8 g (62.6 mmol) of a pentane solution of 20.3 wt% -t-butyllithium. Thereafter, the precipitated solid was filtered under a nitrogen atmosphere, and then the solvent was distilled off to obtain a 29.4 wt% toluene solution of t-Bu Et ZnLi.
2 2 2  2 2 2
[0042] N—イソプロピルアクリルアミドの重合  [0042] Polymerization of N-isopropylacrylamide
実施例 4と同様な方法により、 t-Bu Et ZnLiのトルエン溶液 0. 5gより、 3. 8gの  In the same manner as in Example 4, from 0.5 g of a toluene solution of t-Bu Et ZnLi, 3.8 g
2 2 2  2 2 2
ポリマーを回収した。  The polymer was recovered.
[0043] (比較例 1)  [0043] (Comparative Example 1)
n-BuEt ZnLiの  n-BuEt ZnLi
2 S  2 S
窒素雰囲気下、 lOOmLナスフラスコに THF30mL,ジェチル亜鉛 4. 10g (33. 2ミ リモル)をカ卩え、— 70°Cに冷却した。攪拌条件下、 14. 9wt%の n—ブチルリチウム のへキサン溶液 14. 4g (32. 2ミリモル)を滴下した。滴下後、— 70°Cにて 30分攪拌 した後、室温まで昇温した。溶媒を減圧濃縮し、 18. 2wt%のn—BuEt ZnLiの TH In a nitrogen atmosphere, 30 mL of THF and 4.10 g (33.2 mmol) of jetyl zinc were placed in an lOOmL eggplant flask and cooled to -70 ° C. Stirring conditions, hexanes 14 to the 14. 9 wt% of n- butyl lithium. Was added dropwise 4g (32. 2 mmol). After dropping, the mixture was stirred at -70 ° C for 30 minutes, and then warmed to room temperature. The solvent was concentrated under reduced pressure, 18.2 wt% n-BuEt ZnLi TH
2  2
F溶液を得た。  F solution was obtained.
1H-NMR (THF-d6) d 1.71 (m, 2H), 1.37 (m, 2H), 1.32 (t, 6H), 0.95 (t, 3H), -0.05 (t, 2H), -0.16 (q, 4H)  1H-NMR (THF-d6) d 1.71 (m, 2H), 1.37 (m, 2H), 1.32 (t, 6H), 0.95 (t, 3H), -0.05 (t, 2H), -0.16 (q, 4H)
[0044] N—イソプロピルアクリルアミドの重合 [0044] Polymerization of N-isopropylacrylamide
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. 6g (44. 4ミリモル）の水 溶液に、合成例 2にて調製した 18. 2wt%の n— BuEt ZnLiの THF溶液 0. 8gを加 え、常温で 1時間間攪拌した。その後、 50°Cにて 30分間攪拌したものの、固体は析 出せず、ポリマーは回収できなかった。 In a nitrogen atmosphere at 20 ° C, N-isopropylacrylamide (5.6 g, 44.4 mmol) was added to an aqueous solution of 18.2 wt% n-BuEt ZnLi in THF (0.8 g) prepared in Synthesis Example 2. Addition It was stirred at room temperature for 1 hour. Thereafter, the mixture was stirred at 50 ° C. for 30 minutes, but no solid was precipitated and the polymer could not be recovered.
[0045] (比較例 2) [0045] (Comparative Example 2)
PhEt ZnUの言歴  History of PhEt ZnU
2  2
窒素雰囲気下、 lOOmLナスフラスコに THF30mL,ジェチル亜鉛 4. 03g (32. 6ミ リモル)をカ卩え、— 70°Cに冷却した。攪拌条件下、 12. 3 ％のフエ-ルリチウムの エーテル—シクロへキサン溶液 22. lg (32. 3ミリモル）を滴下した。滴下後、— 70°C にて 30分攪拌した後、室温まで昇温した。溶媒を減圧濃縮し、 34. 4wt%の PhEt  Under a nitrogen atmosphere, 30 mL of THF and 4.03 g (32.6 mmol) of jetyl zinc were placed in an lOOmL eggplant flask and cooled to -70 ° C. Under stirring conditions, 22. lg (32.3 mmol) of 12.3% phenol lithium in ether-cyclohexane was added dropwise. After dropping, the mixture was stirred at -70 ° C for 30 minutes, and then warmed to room temperature. Concentrate the solvent under reduced pressure to 34.4 wt% PhEt
2 2
ZnLiの THF溶液を得た。 A THF solution of ZnLi was obtained.
1H-NMR (THF-d6) d 7.88(d,2H), 7.05 (t, 2H), 6.98 (d, 1H) , 1.45 (t, 6H), 0.06 ( 1H-NMR (THF-d6) d 7.88 (d, 2H), 7.05 (t, 2H), 6.98 (d, 1H), 1.45 (t, 6H), 0.06 (
Q, Q,
4H)  4H)
[0046] N—イソプロピルアクリルアミドの重合  [0046] Polymerization of N-isopropylacrylamide
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. lg (45. 0ミリモル）の水 溶液に、合成例 3にて調製した 34. 4wt%の PhEt ZnLiの THF溶液 0. 6gを加え、  Under a nitrogen atmosphere at 20 ° C, N-isopropylacrylamide 5.lg (45.0 mmol) in an aqueous solution was added with 4 g of THF solution of 34.4 wt% PhEt ZnLi prepared in Synthesis Example 3,
2  2
常温で 1時間間攪拌した。その後、 50°Cにて 30分間攪拌したものの、固体は析出せ ず、ポリマーは回収できなかった。  Stir at room temperature for 1 hour. Thereafter, the mixture was stirred at 50 ° C. for 30 minutes, but no solid precipitated and the polymer could not be recovered.
[0047] (比較例 3) [0047] (Comparative Example 3)
s— BuEt ZnLiの  s—BuEt ZnLi
2  2
窒素雰囲気下、 lOOmLナスフラスコに THF30mL,ジェチル亜鉛 3. 92g (31. 7ミ リモル)をカ卩え、— 70°Cに冷却した。攪拌条件下、 10. 5wt%の s—ブチルリチウムの シクロへキサン溶液 19. 8g (32. 4ミリモル）を滴下した。滴下後、— 70°Cにて 30分 攪拌した後、室温まで昇温した。溶媒を減圧濃縮し、 32. 8wt%の s— BuEt ZnLiの  Under a nitrogen atmosphere, 30 mL of THF and 3.92 g (31.7 mmol) of jetyl zinc were placed in an lOOmL eggplant flask and cooled to -70 ° C. Under stirring conditions, 19.8 g (32.4 mmol) of 10.5 wt% s-butyllithium in cyclohexane was added dropwise. After dropping, the mixture was stirred at -70 ° C for 30 minutes, and then warmed to room temperature. The solvent was concentrated under reduced pressure and 32.8 wt% s—BuEt ZnLi
2  2
THF溶液を得た。  A THF solution was obtained.
1H-NMR (THF-d6) d 1.67 (m, 2H), 1.34 (t, 9H) , 1.03 (t, 3H), 0.27(m, 1H), -0.1 5 (q, 4H)  1H-NMR (THF-d6) d 1.67 (m, 2H), 1.34 (t, 9H), 1.03 (t, 3H), 0.27 (m, 1H), -0.1 5 (q, 4H)
[0048] N—イソプロピルアクリルアミドの重合  [0048] Polymerization of N-isopropylacrylamide
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. 3g (46. 8ミリモル）の水 溶液に、合成例 4にて調製した 32. 8wt%の s— BuEt ZnLiの THF溶液 0. 7gをカロ N-isopropylacrylamide 5.3 g (46.8 mmol) water at 20 ° C under nitrogen atmosphere To the solution, add 0.7 g of 32.8 wt% s-BuEt ZnLi in THF prepared in Synthesis Example 4
2  2
え、常温で 1時間間攪拌した。その後、 50°Cにて 30分間攪拌したものの、固体は析 出せず、ポリマーは回収できなかった。  It was stirred at room temperature for 1 hour. Thereafter, the mixture was stirred at 50 ° C. for 30 minutes, but no solid was precipitated and the polymer could not be recovered.
[0049] (比較例 4) [0049] (Comparative Example 4)
n-BuEt ZnMgClの言膽  n-BuEt ZnMgCl
2  2
窒素雰囲気下、 lOOmLナスフラスコに THFlOmL,ジェチル亜鉛 2. 54g (20. 6ミ リモル)をカ卩え、 50°Cに冷却した。攪拌条件下、 24. 4wt%の n—プチマグネシゥ ムクロライドの THF溶液 9. 85g (20. 6ミリモル）を滴下した。滴下後、 50°Cにて 30 分攪拌した後、室温まで昇温し、 23. 4wt%( n-BuEt MgClの THF溶液を得た。  Under a nitrogen atmosphere, THF10 mL and 2.54 g (20.6 mmol) of jetylzinc were placed in a 10 mL eggplant flask and cooled to 50 ° C. Under stirring conditions, 9.85 g (20.6 mmol) of a THF solution of 24.4 wt% n-petitmagnesium chloride was added dropwise. After the dropwise addition, the mixture was stirred at 50 ° C. for 30 minutes, and then warmed to room temperature to obtain 23.4 wt% (n-BuEt MgCl in THF solution).
2  2
1H-NMR (THF-d6) d 1.66 (m, 2H), 1.41 (m, 2H), 1.29 (t, 6H), 1.01 (t, 3H), 0.08 (t, 2H), -0.05 (q, 4H)  1H-NMR (THF-d6) d 1.66 (m, 2H), 1.41 (m, 2H), 1.29 (t, 6H), 1.01 (t, 3H), 0.08 (t, 2H), -0.05 (q, 4H )
[0050] N—イソプロピルアクリルアミドの重合 [0050] Polymerization of N-isopropylacrylamide
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. 3g (46. 8ミリモル）の水 溶液に、合成例 2にて調製した 23. 4wt%( n-BuEt ZnLiの THF溶液 0. 8gを加  In a nitrogen atmosphere, N-isopropylacrylamide (5.3 g, 46.8 mmol) in an aqueous solution at 20 ° C was mixed with 23.4 wt% (TH-solution of n-BuEt ZnLi in 0.8 g prepared in Synthesis Example 2). Addition
2  2
え、常温で 1時間間攪拌した。その後、 50°Cにて 30分間攪拌したものの、固体は析 出せず、ポリマーは回収できなかった。  It was stirred at room temperature for 1 hour. Thereafter, the mixture was stirred at 50 ° C. for 30 minutes, but no solid was precipitated and the polymer could not be recovered.
[0051] (比較例 5) [0051] (Comparative Example 5)
n-Bu Et ZnLiの調製  Preparation of n-Bu Et ZnLi
2 2 2  2 2 2
窒素雰囲気下、 lOOmLナスフラスコに THF30mL,ジェチル亜鉛 2. 75g (22. 2ミ リモル）を加え、—70°Cに冷却。攪拌下、 15. 3wt%— n—ブチルリチウムのへキサ ン溶液 19. 0g (45. 5ミリモル)を滴下した。滴下後、 70°Cにて 30分攪拌した後、 室温まで昇温した。溶媒を減圧除去し、 38. lwt%の  In a nitrogen atmosphere, add 30 mL of THF and 2.75 g (22.2 mmol) of jetyl zinc to an lOOmL eggplant flask and cool to -70 ° C. Under stirring, 19.3 g (45.5 mmol) of a 15.3 wt% n-butyllithium hexane solution was added dropwise. After dropping, the mixture was stirred at 70 ° C for 30 minutes, and then warmed to room temperature. Remove the solvent under reduced pressure and 38.
n-Bu Et ZnLiの THF溶液を得た。  A THF solution of n-Bu Et ZnLi was obtained.
2 2 2  2 2 2
[0052] N イソプロピルアクリルアミドの重合例  [0052] Example of N-isopropylacrylamide polymerization
窒素雰囲気下、 20°Cにて N—イソプロピルアクリルアミド 5. 0g (44. 1ミリモル）の水 溶液に、 n-Bu Et ZnLiの THF溶液 0. 5gをカ卩え、常温で 2時間攪拌した。その後  Under a nitrogen atmosphere, 0.5 g of a THF solution of n-Bu Et ZnLi was placed in an aqueous solution of 5.0 g (44.1 mmol) of N-isopropylacrylamide at 20 ° C. and stirred at room temperature for 2 hours. afterwards
2 2 2  2 2 2
、 50°Cにて 30分間攪拌した。固体は析出せず、ポリマーは得られな力つた。  And stirred for 30 minutes at 50 ° C. The solid did not precipitate and the polymer was vigorous.
[0053] 本結果より、 t ブチル基を有さな 、亜鉛アート錯体では、水のようなプロトン性溶 媒を用いた場合には、重合開始剤として機能しないことを確認した。 産業上の利用可能性 [0053] From this result, it is found that the zinc ate complex having no t-butyl group has a protic solution such as water. When the medium was used, it was confirmed that it did not function as a polymerization initiator. Industrial applicability
本発明は (メタ)アクリル酸誘導体の重合に有用である。  The present invention is useful for the polymerization of (meth) acrylic acid derivatives.

Claims

請求の範囲 The scope of the claims
[1] 一般式 (1)  [1] General formula (1)
t-Bu R ZnM (1)  t-Bu R ZnM (1)
または一般式 (2)  Or general formula (2)
t-Bu R ZnM (2)  t-Bu R ZnM (2)
n 4— n m  n 4— n m
(ただし式中、 nは 1〜3の整数、 Rは各々同一でも異なっていてもよぐ炭素数 1〜12 のアルキル基、ァルケ-ル基、ァリール基、またはァリールアルキル基を示す。 Mはリ チウム、マグネシウムあるいは MgX(Xは塩素、臭素、ヨウ素のいずれかを表す）で示 されるハロゲン化マグネシウムを表す。 mは 1ないし 2を示す。）  (In the formula, n represents an integer of 1 to 3, and R represents an alkyl group having 1 to 12 carbon atoms which may be the same or different, an alkyl group, an aryl group, or an aryl alkyl group. Represents a magnesium halide represented by lithium, magnesium, or MgX (where X represents chlorine, bromine, or iodine. M represents 1 to 2).
で示される亜鉛アート錯体力ゝらなることを特徴とする重合開始剤。  A polymerization initiator characterized by having a zinc ate complex strength represented by:
[2] 請求項 1に記載の一般式（1)または (2)で示される亜鉛アート錯体を重合開始剤とし て用いることを特徴とする (メタ)アクリル酸誘導体の重合方法。  [2] A method for polymerizing a (meth) acrylic acid derivative, wherein the zinc ate complex represented by the general formula (1) or (2) according to claim 1 is used as a polymerization initiator.
[3] 重合に用いられる溶媒がプロトン性溶媒であることを特徴とする請求項 2に記載の (メ タ）アクリル酸誘導体の重合方法。  [3] The method for polymerizing a (meth) acrylic acid derivative according to claim 2, wherein the solvent used for the polymerization is a protic solvent.
[4] プロトン性溶媒が水であることを特徴とする請求項 3に記載の (メタ)アクリル酸誘導体 の重合方法。  [4] The method for polymerizing a (meth) acrylic acid derivative according to [3], wherein the protic solvent is water.
[5] (メタ)アクリル酸誘導体が活性プロトンを有する化合物であることを特徴とする請求項 2〜4の 、ずれか 1項に記載の (メタ）アクリル酸誘導体の重合方法。  [5] The method for polymerizing a (meth) acrylic acid derivative according to any one of claims 2 to 4, wherein the (meth) acrylic acid derivative is a compound having an active proton.
PCT/JP2007/061289 2006-06-05 2007-06-04 Polymerization initiator, and process for polymerization of (meth)acrylic acid derivative WO2007142188A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013064085A (en) * 2011-09-20 2013-04-11 Tosoh Finechem Corp Method for polymerizing sulfonic acid group-containing vinyl monomer
JP2013064088A (en) * 2011-09-20 2013-04-11 Tosoh Finechem Corp Polymerization initiator, and method for polymerizing vinyl monomer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292328A (en) * 2003-03-26 2004-10-21 Univ Tokyo Organozinc complex and method for producing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292328A (en) * 2003-03-26 2004-10-21 Univ Tokyo Organozinc complex and method for producing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HSIEH H.L.: "Effects of Diethylzinc in Alkyllithium-Initiated Polymerizations", JOURNAL OF POLYMER SCIENCE: POLYMER CHEMISTRY EDITION, vol. 14, no. 2, February 1976 (1976-02-01), pages 379 - 386, XP003019759 *
KOBAYASHI M. ET AL.: "A New Chemoselective Anionic Polymerization Method for Poly(N-isopropylacrylamide)(PNIPAm) in Aqueous Media: Design and Application of Bulky Zincate Possessing Little Basicity", MACROMOLECULES, vol. 37, no. 12, June 2004 (2004-06-01), pages 4339 - 4341, XP001196825 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013064085A (en) * 2011-09-20 2013-04-11 Tosoh Finechem Corp Method for polymerizing sulfonic acid group-containing vinyl monomer
JP2013064088A (en) * 2011-09-20 2013-04-11 Tosoh Finechem Corp Polymerization initiator, and method for polymerizing vinyl monomer

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