JP5830020B2 - カルボキシラート金属錯体及びオレフィン重合用触媒 - Google Patents
カルボキシラート金属錯体及びオレフィン重合用触媒 Download PDFInfo
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- JP5830020B2 JP5830020B2 JP2012531742A JP2012531742A JP5830020B2 JP 5830020 B2 JP5830020 B2 JP 5830020B2 JP 2012531742 A JP2012531742 A JP 2012531742A JP 2012531742 A JP2012531742 A JP 2012531742A JP 5830020 B2 JP5830020 B2 JP 5830020B2
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- 229910052751 metal Inorganic materials 0.000 title claims description 21
- 239000002184 metal Substances 0.000 title claims description 21
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 52
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 37
- -1 carboxylate metal complex Chemical class 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 31
- 125000005843 halogen group Chemical group 0.000 claims description 29
- 125000003545 alkoxy group Chemical group 0.000 claims description 26
- 125000004104 aryloxy group Chemical group 0.000 claims description 25
- 125000003277 amino group Chemical group 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 22
- 125000004423 acyloxy group Chemical group 0.000 claims description 21
- 125000004429 atom Chemical group 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
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- 125000003118 aryl group Chemical group 0.000 claims description 8
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
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- 150000004696 coordination complex Chemical class 0.000 description 76
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- 239000013078 crystal Substances 0.000 description 8
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- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 6
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
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- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
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- 125000000753 cycloalkyl group Chemical group 0.000 description 3
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- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 3
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- AKJFBIZAEPTXIL-UHFFFAOYSA-N chloro(dicyclohexyl)phosphane Chemical compound C1CCCCC1P(Cl)C1CCCCC1 AKJFBIZAEPTXIL-UHFFFAOYSA-N 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 239000011737 fluorine Substances 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
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Images
Classifications
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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Description
一般的に、配位重合に用いる触媒系として、金属−水素結合、または金属−炭素結合をもつ金属錯体が使用されてきた。
J. Am. Chem. Soc., 127, 5132 (2005)(非特許文献1)には、周期律表第10族の金属錯体を使用した酢酸ビニルの重合における重合機構と触媒失活機構が示されている。特に、触媒失活機構の1つとして、金属−アルキル結合への酢酸ビニル挿入後のβ−アセトキシ脱離を提唱しているが、これは、β−アセトキシ脱離により生成する金属−アセトキシ錯体が重合活性を有しないことを示しており、一般に金属−酸素結合へのオレフィン挿入は起こり得ないと認識されていた。
[1]一般式(C1)
で示されるカルボキシラート金属錯体。
[2]一般式(C1)で示されるカルボキシラート金属錯体が、一般式(C2)
で示される[1に記載のカルボキシラート金属錯体。
[3]一般式(C2)中のMが、NiまたはPdである[2]に記載のカルボキシラート金属錯体。
[4]一般式(C2)中のR1が、ハロゲン原子で置換されていてもよい炭素原子数1〜30の炭化水素基である[2]または[3]に記載のカルボキシラート金属錯体。
[5]一般式(C2)中のR1がメチル基またはトリフルオロメチル基である[4]に記載のカルボキシラート金属錯体。
[6]一般式(C2)中のR1がメチル基である[5]に記載のカルボキシラート金属錯体。
[7]一般式(C2)中のR2及びR3がともにイソプロピル基またはシクロヘキシル基である[2]〜[6]のいずれかに記載のカルボキシラート金属錯体。
[8]一般式(C2)中のR4がすべて水素原子である[2]〜[7]のいずれかに記載のカルボキシラート金属錯体。
[9]一般式(C2)中のLが2,6−ジメチルピリジンであり、nが1である[2]〜[8]のいずれかに記載のカルボキシラート金属錯体。
[10][1]〜[9]のいずれかに記載のカルボキシラート金属錯体を主成分とするオレフィン重合用触媒。
[11][1]〜[9]のいずれかに記載のカルボキシラート金属錯体を触媒として使用し、一般式(1)
で示されるオレフィンを単独であるいは2種以上を組み合わせて重合するか、または前記一般式(1)で示されるオレフィンと一般式(2)
で示される極性基含有オレフィンとを共重合することを特徴とする重合体の製造方法。
なお、本明細書では「炭化水素」は飽和、不飽和の脂肪族炭化水素、脂環式炭化水素、及び芳香族炭化水素を含む。
Mは周期律表第10族の元素を表す。周期律表第10族の元素としては、ニッケル(Ni)、パラジウム(Pd)、白金(Pt)が挙げられるが、Ni及びPdが好ましく、Pdがより好ましい。
中性の電子供与性配位子としては、硫黄原子を有するものとしてジメチルスルホキシド(DMSO)が挙げられる。窒素原子を有するものとして、炭素原子数1〜10のトリアルキルアミン、ジアルキルアミン、ピリジン、2,6−ジメチルピリジン、キノリン、2−メチルキノリン、アニリン、2,6−ジメチルアニリン、2,6−ジイソプロピルアニリン、N,N,N’,N’−テトラメチルエチレンジアミン(TMEDA)、4−(N,N−ジメチルアミノ)ピリジン(DMAP)、アセトニトリル、ベンゾニトリルなどが挙げられる。リン原子を有するものとして、トリメチルホスフィン、トリイソプロピルホスフィン、トリブチルホスフィン、トリ(t−ブチル)ホスフィン、トリフェニルホスフィン、トリス(o−トリル)ホスフィン、トリフリルホスフィンなどが挙げられる。酸素原子を有するものとして、ジエチルエーテル、テトラヒドロフラン、1,4−ジオキサン、1,2−ジメトキシエタンなどが挙げられる。合成手法の観点から、窒素原子を有するもの、リン原子を有するものが好ましく、特に窒素原子を有するものが好ましい。
R12が表すハロゲン原子としては、塩素原子、臭素原子、またはヨウ素原子が挙げられ、経済性の面から塩素原子または臭素原子が好ましい。
第3のモノマーとしては、エチルビニルエーテル、プロピルビニルエーテル、ノルボルネン、一酸化炭素などが挙げられる。
重合方法は特に制限されるものではなく、一般に使用される方法で重合可能である。すなわち、溶液重合法、懸濁重合法、気相重合法などのプロセス法が可能であるが、特に溶液重合法、懸濁重合法が好ましい。また重合様式は、バッチ様式でも連続様式でも可能である。また、一段重合でも、多段重合でも行うこともできる。
一般式(1)で示されるオレフィンの圧が内部圧力の大半を占める重合圧力については、常圧から20MPaの範囲内、好ましくは常圧から10MPaの範囲内で行われる。
(共)重合体は、通常の熱可塑性樹脂の条件で、ペレット状、フィルム状、シート状などに成形することができる。
実施例で得た金属錯体1及び金属錯体2の構造は、リガク(株)製CCD型単結晶X線回折装置(Mercury CCD)を用いたX線結晶構造解析により決定した。X線としてはMoのKα線(λ=0.71069Å)を用い、2θ=50°までの反射を用いた。反射強度はローレンツ効果により補正した。構造はSIR−97による直接法により解き、SHELXL-97により最適化した。水素以外の原子は異方的に最適化し、水素原子はAFIX instructionを用いて配置した。
実施例で得た重合体の構造は、日本電子(株)製JNM−ECS400を用いた各種NMR解析により決定した。一般式(2)で示される極性基含有オレフィンに由来するモノマーユニットの含有率と共重合体末端構造は、溶媒として1,2,4−トリクロロベンゼン(0.55mL)及び緩和試薬としてCr(acac)3(10mg)を用い、120℃において、逆ゲート付きデカップリング法を用いた13C−NMR(9.0マイクロ秒の90°パルス、スペクトル幅:31kHz、緩和時間:10秒、取り込み時間:10秒、FIDの積算回数5,000〜10,000回)によって決定した。
アルゴン雰囲気下、ベンゼンスルホン酸(東京化成工業製、0.66g,4.2mmol)のテトラヒドロフラン(THF)溶液(20mL)に、n−ブチルリチウム(関東化学製、1.65Mヘキサン溶液,5.1mL,8.4mmol)を0℃で加え、室温で2.5時間撹拌した。反応容器を−78℃に冷却した後にクロロジシクロヘキシルホスフィン(Sigma-Aldrich社製,0.89g,3.8mmol)を−78℃で加え、室温で24時間撹拌した。反応をトリフルオロ酢酸(東京化成工業製、0.50M THF溶液,8.4mL,4.2mmol)で停止した後に、生じた沈殿をろ過によって回収し減圧下乾燥し、2−(ジシクロヘキシルホスフィノ)ベンゼンスルホン酸(2-(dicyclohexylphosphino)benzenesulfonic acid)(化合物1a)を得た。収量は0.66g(85%)であった。
13C−NMR(101MHz,CDCl3):δ 25.0 (s), 25.6-26.2 (m), 28.8 (br), 30.3 (br), 34.6 (br d, 1JPC = 40 Hz), 113.4 (br d, 1JPC = 87 Hz), 128.8 (d, JPC = 9 Hz), 130.1 (d, JPC = 9 Hz), 135.4 (br), 137.1 (br), 150.5 (br);
31P−NMR(162MHz,CDCl3):δ 52.8 (d, 1JPH = 370 Hz) (90%), 20.8 (d, 1JPH = 530 Hz) (10%);
Anal. calcd for C18H27O3PS, C, 60.99; H, 7.68. found: C, 60.90; H, 7.55。
アルゴン雰囲気下、化合物1a;2−(ジシクロヘキシルホスフィノ)ベンゼンスルホン酸(0.43g,1.2mmol)とジイソプロピルエチルアミン(和光純薬工業製、1.1mL,6.0mmol)の塩化メチレン溶液(16mL)に、(COD)PdMeCl(文献:「Inor. Chem., 1993, 32, 5769-5778」に従って合成。COD=1,5−シクロオクタジエン、0.32g,1.2mmol)の塩化メチレン溶液(6mL)を加え、室温で1時間撹拌した。溶液を濃縮した後に、ろ過により沈殿物を取り除き、溶液をヘキサン中に加えた。生じた沈殿をろ過によって回収し、ヘキサンで洗浄した後に減圧下乾燥し、金属錯体1bを得た。収量は0.66g(85%)であった。
13C−NMR(101MHz,CDCl3):δ -7.3 (s, PdCH3), 12.0 (s, HNCH2CH3), 17.9 (s, HNCH(CH3)2), 19.2 (s, HNCH(CH3)2), 26.0 (s), 26.9-27.4 (m), 28.7 (s), 29.4 (d, JPC = 4 Hz), 35.6 (d, 1JPC = 25 Hz), 42.4 (s, HNCH2CH3), 54.6 (s, HNCH(CH3)2), 125.5 (d, 1JPC = 33 Hz), 128.3 (d, JPC = 7 Hz), 128.9 (d, JPC = 6 Hz), 130.3 (s), 132.5 (s), 150.9 (d, 2JPC = 11 Hz);
31P−NMR(162MHz,CDCl3):δ 31.7;
Anal. calcd for C27H49ClNO3PPdS, C, 50.62; H, 7.71; N, 2.19. found: C, 50.49; H, 8.00, N, 2.12。
アルゴン雰囲気下、炭酸カリウム(0.42g,3.0mmol)と2,6−ルチジン(東京化成工業製、0.33g,3.1mmol)の塩化メチレン懸濁液(2mL)に、金属錯体1b(0.19g,0.30mmol)の塩化メチレン溶液(4mL)を加え、室温で1時間撹拌した。溶媒を減圧下留去して残った固体をジエチルエーテルで洗浄した後に、塩化メチレンで抽出した。抽出液をセライト(乾燥珪藻土)でろ過し、ゆっくりとヘキサン(40mL)中に加えた。生じた沈殿をろ過によって回収し、ヘキサンで洗浄した後に減圧下乾燥し、金属錯体1cを得た。収量は0.12g(70%)であった。
13C−NMR(101MHz,CDCl3):δ -9.4 (d, 2JPC = 4.8 Hz, PdCH3), 26.3 (s, CH3 of lutidine), 26.9-27.5 (m), 28.6 (s), 29.6 (d, JPC = 3 Hz), 35.5 (d, 1JPC = 26 Hz), 122.5 (s),122.5 (s), 124.6 (d, 1JPC = 35 Hz), 128.9 (d, JPC = 7 Hz), 129.0 (d, JPC = 6 Hz), 130.7 (s), 132.4 (s), 138.1 (s). 151.0 (d, 2JPC = 12 Hz), 159.0 (s);
31P−NMR(162MHz,CDCl3):δ 27.5;
Anal. calcd for C26H38NO3PPdS, C, 53.65; H, 6.58; N, 2.51. found: C, 53.51; H, 6.74; N, 2.40。
上記化合物1aの合成において、クロロジシクロヘキシルホスフィンの代わりにクロロジイソプロピルホスフィン(Sigma-Aldrich製,19.0g,125mmol)を用いたほかは同様にして2−(ジイソプロピルホスフィノ)ベンゼンスルホン酸(2-(diisopropylphosphino)benzenesulfonic acid)(化合物2a)を得た。収量は26.8g(78%)であった。
13C−NMR(101MHz,CDCl3):δ19.4 (s), 24.5-27.7 (m), 114.4 (br d, J = 93 Hz), 129.1 (d, J = 8.6 Hz), 130.3 (d, J = 12.5 Hz), 134.7-137.1 (m), 150.7 (br s);
31P−NMR(162MHz,CDCl3):δ62.5 (d, 1JPH = 380 Hz) (83%), 31.0 (d, 1JPH = 460 Hz) (17%)。
上記金属錯体1bの合成において、化合物1aの代わりに化合物2a(2−(ジイソプロピルホスフィノ)ベンゼンスルホン酸)(16.3g,59.3mmol)を用い同様にして金属錯体2bを得た。収量は33.7g(99%)であった。
13C−NMR(101MHz,CDCl3):δ-7.79 (s), 12.16 (s), 17.91 (s), 18.54 (s), 19.21-19.28 (m), 25.93 (d, J = 25.9 Hz), 42.58 (s), 54.69 (s), 125.25 (s), 125.58 (s), 128.8 (d, J = 6.7 Hz), 129.13 (d, J = 5.8 Hz), 130.58 (s), 132.48 (s), 150.89 (d, J = 10.5 Hz);
31P−NMR(162MHz,CDCl3):δ38.4 (s)。
上記金属錯体1cの合成において、金属錯体1bの代わりに金属錯体2b(33.7g,58.5mmol)を用い同様にして金属錯体2cを得た。収量は27.6g(94%)であった。
13C−NMR(101MHz,CDCl3):δ-10.10 (d, J = 4.8 Hz), 18.44 (s), 19.29 (d, J = 4.8 Hz), 25.91 (d, J = 25.9 Hz), 26.20 (s), 122.72 (d, J = 3.8 Hz), 124.56 (d, J = 35.5 Hz), 129.19 (t, J = 6.7 Hz), 131.03 (d, J = 1.9 Hz), 132.39 (s), 138.30 (s), 151.13 (d, J = 10.5 Hz), 159.17 (s);
31P−NMR(162MHz,CDCl3):δ34.4 (s);
Anal. calcd for C20H30NO3PPdS, C, 47.86; H, 6.02; N, 2.79. found: C, 47.92; H, 5.98; N, 2.51。
13C−NMR(101MHz,CDCl3):δ 22.7(s), 24.7 (s), 26.1 (s), 27.1-27.3 (m),28.1 (d, 1Jpc = 19 Hz), 34.7 (d, 1Jpc = 25 Hz),121.7 (s), 122.1 (s), 122.8 (d, Jpc = 3 Hz), 128.7 (d, Jpc = 7 Hz), 130.1 (d, Jpc = 6 Hz),131.9 (s),132.1 (s),138.7 (s), 148.9 (d, Jpc = 10 Hz), 160.1 (s), 176.7 (s).
31P−NMR(162MHz,CDCl3):δ 17.0 (s)
13C−NMR(101MHz,CDCl3):δ 17.7 (s), 17.8 (s), 22.5 (s), 24.5 (s, CH3 of lutidine), 25.0 (d, 1JPC = 26.5 Hz), 121.4 (d, 1JPC = 39.8 Hz), 122.6 (s), 128.5 (d, JPC = 5.7 Hz), 129.8 (d, JPC = 5.8 Hz), 131.6 (s), 131.8 (s), 138.5 (s), 148.5 (d, 2JPC = 8.3 Hz), 159.8 (s), 176.7 (s)。
金属錯体2cと金属錯体2の酢酸存在下での安定性の比較実験を実施した。すなわち、金属錯体2c(0.0037mmol)及び金属錯体2(0.0037mmol)をそれぞれのNMRチューブ(内径5mm)に充填し、酢酸の重トルエン溶液(0.062M、0.6mL、0.037mmol)を加え、1H−NMR測定をした。このNMRチューブを80度で10時間に加熱した後、再度1H−NMR測定を行った。金属錯体2cを含む反応液には、金属錯体2c由来のピーク以外に、金属錯体2由来のピーク(δ1.74ppm,3.44ppm,8.22ppm)及び分解して中心金属から解離した2,6−ジメチルピリジン(ルチジン)由来のピーク(δ2.38ppm)が観測された。これらの存在比率は、ルチジンベースの積算値から、金属錯体2c(81.7%)、金属錯体2(10.6%)、解離ルチジン(7.7%)と算出した。一方、金属錯体2を含む反応液には、金属錯体2由来のピーク以外は錯体由来のピークが観測されなかった。なお、酢酸のピークは、1.59ppm及び9.80ppmに観測され、上記の金属錯体2、金属錯体2c、及びルチジンのピークと区別することができる。
酢酸やアクリル酸などのプロトン酸は、重合モノマーである極性基含有オレフィン中に不純物として存在している。参考例1の結果は、本発明の金属錯体がその不純物に対して非常に安定であり、重合反応中でもそれによる分解が起こりにくいことを示している。
窒素雰囲気下、120mLオートクレーブ中に、金属錯体触媒2(0.50mmol)のトルエン溶液(75mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、15分撹拌した。室温に冷却後、反応液をメタノール(400mL)に加えた。生じた重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体1を得た。収量は0.24g、数平均分子量は19,000、重量平均分子量は42,000、Mw/Mnは2.2であった。
窒素雰囲気下、酢酸アリル(37.5mL,34.9g,350mmol)を含む120mLオートクレーブ中に、金属錯体触媒2(0.10mmol)のトルエン溶液(37.5mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、5時間撹拌した。室温に冷却後、反応液をメタノール(400mL)に加えた。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体2を得た。収量は2.7g、数平均分子量は12,000、重量平均分子量は25,000、Mw/Mnは2.1であった。重合体2中の酢酸アリル含有率は、逆ゲート付きデカップリング法を用いた13C−NMRにより、モル分率で3.1%と決定した。
窒素雰囲気下、酢酸アリル(37.5mL,34.9g,350mmol)を含む120mLオートクレーブ中に、金属錯体触媒2(0.010mmol)のトルエン溶液(37.5mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、25時間撹拌した。室温に冷却後、反応液をメタノール(400mL)に加えた。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体3を得た。収量は2.2g、数平均分子量は12,000、重量平均分子量は28,000、Mw/Mnは2.3であった。共重合体中の酢酸アリル含有率は、逆ゲート付きデカップリング法を用いた13C−NMRにより、モル分率で3.4%と決定した。
アルゴン雰囲気下、化合物2b(0.12mmol)とPd2(DBA)3・CHCl3(DBA=ジベンジリデンアセトン,0.10mmol)を含む50mLオートクレーブ中に、塩化メチレン(3.75mL)を加え、10分間撹拌した。このとき、触媒種として、Pd−ヒドリド錯体が形成していると考えられる(参考文献:J. Am. Chem. Soc., 131, 14605 (2009))。その後、触媒液にトルエン(3.75mL)及び酢酸アリル(7.5mL,7.0g,70mmol)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、15時間撹拌した。室温に冷却後、オートクレーブ中にメタノール(約20mL)を加えた。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥して、重合体を得た。収量は1.7g、数平均分子量は4,000、重量平均分子量は9,000、Mw/Mnは2.7であった。共重合体中の酢酸アリル含有率は、逆ゲート付きデカップリング法を用いた13C−NMRにより、モル分率で2.7%と決定した。
窒素雰囲気下、酢酸アリル(188mL,174g,1740mmol)を含む500mLオートクレーブ中に、金属錯体触媒2(0.050mmol)のトルエン溶液(188mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、50時間撹拌した。室温に冷却後、反応液をメタノール(1000mL)に加えた。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体4を得た。収量は23g、数平均分子量は12,000、重量平均分子量は28,000、Mw/Mnは2.3であった。共重合体中の酢酸アリル含有率は、逆ゲート付きデカップリング法を用いた13C−NMRにより、モル分率で3.4%と決定した。
31P−NMR(162MHz,CD2Cl2):δ 16.6 (s)。
窒素雰囲気下、金属錯体触媒3(0.050mmol)を含む50mLオートクレーブ中に、トルエン(6mL)を加えた。エチレンを内圧が3.0MPaとなるまで充填した後、オートクレーブを80℃で、7時間撹拌した。室温に冷却後、オートクレーブ中にメタノール(20mL)を加えた。生じた重合体をろ過によって回収し、メタノールで洗浄した後に減圧下乾燥し、重合体5を得た。収量は0.12g、数平均分子量は2,800、重量平均分子量は9,800、Mw/Mnは3.5であった。
Claims (8)
- 一般式(C2)
で示されるカルボキシラート金属錯体。 - 一般式(C2)中のMが、NiまたはPdである請求項1に記載のカルボキシラート金属錯体。
- 一般式(C2)中のR1がメチル基である請求項1または2に記載のカルボキシラート金属錯体。
- 一般式(C2)中のR2及びR3がともにイソプロピル基またはシクロヘキシル基である請求項1〜3のいずれかに記載のカルボキシラート金属錯体。
- 一般式(C2)中のR4がすべて水素原子である請求項1〜4のいずれかに記載のカルボキシラート金属錯体。
- 一般式(C2)中のLが2,6−ジメチルピリジンであり、nが1である請求項1〜5のいずれかに記載のカルボキシラート金属錯体。
- 請求項1〜6のいずれかに記載のカルボキシラート金属錯体を主成分とするオレフィン重合用触媒。
- 請求項1〜6のいずれかに記載のカルボキシラート金属錯体を触媒として使用し、一般式(1)
で示されるオレフィンを単独であるいは2種以上を組み合わせて重合するか、または前記一般式(1)で示されるオレフィンと一般式(2)
で示される極性基含有オレフィンとを共重合することを特徴とする重合体の製造方法。
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