JP6819669B2 - 重合触媒及びその製造方法、共重合体の製造方法、重合体組成物の製造方法並びに架橋重合体の製造方法 - Google Patents
重合触媒及びその製造方法、共重合体の製造方法、重合体組成物の製造方法並びに架橋重合体の製造方法 Download PDFInfo
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- 229920001155 polypropylene Polymers 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000004551 spreading oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CRNIHJHMEQZAAS-UHFFFAOYSA-N tert-amyl chloride Chemical compound CCC(C)(C)Cl CRNIHJHMEQZAAS-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- PFXYQVJESZAMSV-UHFFFAOYSA-K zirconium(iii) chloride Chemical compound Cl[Zr](Cl)Cl PFXYQVJESZAMSV-UHFFFAOYSA-K 0.000 description 1
Images
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- C08F4/60—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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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Description
[2] 上記[1]の重合触媒を用いて、共役ジエン化合物と炭素数3〜8のα−オレフィンとを重合する、共重合体の製造方法。
[3] β−ケトイミン化合物及びその互変異性体よりなる群から選ばれる少なくとも一種のケトイミン誘導体と、4族及び5族の遷移金属から選ばれる少なくとも一種を含む化合物と、有機アルミニウム化合物と、ハロゲン化合物と、を混合する、重合触媒の製造方法。
[4] 共役ジエン化合物に由来する構造単位MAと、炭素数3〜8のα−オレフィンに由来する構造単位MBとを有し、−15℃〜140℃の範囲内に融点があり、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量が10,000以上であり、かつ前記構造単位MAと前記構造単位MBとのモル比(MA/MB)が55/45〜99/1である、共重合体。
[5] 上記[2]の製造方法により得られた共重合体又は上記[4]の共重合体と、架橋剤とを含む重合体組成物。
[6] 上記[5]の重合体組成物を架橋して得られる架橋重合体。
<重合触媒>
本開示の重合触媒は、β−ケトイミン化合物及びその互変異性体よりなる群から選ばれる少なくとも一種のケトイミン誘導体と、4族及び5族の遷移金属から選ばれる少なくとも一種を含む化合物(以下、単に「遷移金属化合物」とも言う。)とを混合してなる金属錯体を触媒成分として含む。なお、本明細書において「重合触媒」は、単独で触媒作用を示す成分からなる単一系のもの、及び単独で触媒作用を示す成分と助触媒とを組み合わせた多成分系のもの(複合触媒)を含む意味である。
(R6)3−Y1−Cl …(2)
(式(2)中、Y1は炭素原子又はケイ素原子であり、複数のR6はそれぞれ独立にヒドロカルビル基であり、2個のR6が互いに結合して、これらが結合する炭素原子と共に炭素数3〜20の環を形成していてもよい。)
本開示の共重合体の製造方法は、上記で説明した本開示の重合触媒を用いて、共役ジエン化合物と炭素数3〜8のα−オレフィンとを重合する工程を含む。
上記重合に使用する共役ジエン化合物としては、例えば1,3−ブタジエン、イソプレン、2,3−ジメチル−1,3−ブタジエン、1,3−ペンタジエン、1,3−ヘキサジエン、1,3−ヘプタジエン、2−フェニル−1,3−ブタジエン、3−メチル−1,3−ペンタジエン、2−クロロ−1,3−ブタジエン等が挙げられる。これらの中でも、1,3−ブタジエン、イソプレン及び2,3−ジメチル−1,3−ブタジエンが好ましく、1,3−ブタジエンがより好ましい。なお、重合に使用する共役ジエン化合物は、1種であってもよいし2種以上であってもよい。
上記重合に使用するα−オレフィンとしては、炭素数3〜8であって炭素−炭素二重結合がα位にあるアルケンであれば特に制限されず、例えばプロピレン、1−ブテン、1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン等が挙げられる。これらの中でも、プロピレン及び1−ブテンが好ましく、プロピレンがより好ましい。なお、重合に使用するα−オレフィンは、1種であってもよいし2種以上であってもよい。
(重合体成分)
本開示の重合体組成物は、重合体成分として、上述した本開示の共役ジエン化合物/α−オレフィン共重合体を含む。重合体組成物中の上記共重合体の含有割合は、重合体組成物の全体量に対して、20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましい。また、当該含有割合の上限は、重合体組成物の全体量に対して、例えば99質量%以下とすることができる。
上記重合体組成物は、架橋剤(加硫剤)を含む。架橋剤としては、硫黄、ハロゲン化硫黄、有機過酸化物、キノンジオキシム類、有機多価アミン化合物、メチロール基を有するアルキルフェノール樹脂などが挙げられる。架橋剤としては通常、硫黄が使用される。硫黄の配合割合は、重合体組成物に含まれる重合体成分の合計量100質量部に対して、好ましくは0.1〜5質量部、より好ましくは0.5〜3質量部である。
ポリエチレン以外の重合体については、以下の条件で、ゲルパーミエーションクロマトグラフィー(商品名「HLC−8320GPC EcoSEC」、東ソー社製)を使用してポリスチレン換算を求めた。
カラム:商品名「TSK gel Multipore HXL−M」(東ソー社製)
カラム温度:40℃
移動相;テトラヒドロフラン
流速;1.0ml/分
サンプル濃度;10mg/20ml
・ポリエチレンの重量平均分子量Mw及び数平均分子量Mn
ポリエチレンについては、以下の条件で、高温ゲルパーミエーションクロマトグラフィー(商品名「PL−GPC 220」、Agilent社製)を使用してポリスチレン換算を求めた。
カラム:商品名「PLgel Olexis」(Agilent社製)
カラム温度:135℃
移動相;オルトジクロロベンゼン
流速;1.0ml/分
サンプル濃度;4mg/4ml
重合体の全構造単位に対するブタジエン構造単位の含有割合[モル%]、及びプロピレン構造単位の含有割合[モル%]を、重クロロホルムを溶媒として測定した400MHzの1H−NMRスペクトルから次のようにして求めた。なお、以下では、ブタジエン構造単位のうちcis−1,4−結合成分を構造単位(Ubc14)、trans−1,4−結合成分を構造単位(Ubt14)、及び1,2−結合成分を構造単位(Ub12)と表し、プロピレン構造単位を構造単位(Upp)と表す。
<1H−NMR>
以下の(a)〜(c)のピークの積分値から、共重合体中における構造単位(Ubc14)及び構造単位(Ubt14)の合計と、構造単位(Ub12)と、構造単位(Upp)との含有比率((Ubc14+Ubt14):Ub12:Upp[モル比])を下記数式(1)により算出し、該算出した含有比率から、共重合体中における各構造単位の含有割合(モル%)を算出した。
(a)構造単位(Ubc14)及び構造単位(Ubt14)の合計の含有量:δ5.36
(b)構造単位(Ub12)の含有量:δ4.95
(c)構造単位(Upp)の含有量:δ0.84
FT−IR(商品名「Frontier」)を用いてATR(Attenuated Total Reflection)法により特性吸収帯(cis−1,4−結合は740cm−1、trans−1,4−結合は967cm−1)から解析した。
・ガラス転移温度Tg[℃]、融点Tm[℃]及び融解エンタルピーΔH[J/g]
DSC(商品名「DSC Q20」、ティー・エイ・インスツルメント・ジャパン社製)を用いて測定を行い、測定により得られた融解曲線から求めた。測定用サンプルは、アルミニウム製サンプルパン(型番「900786.901」と「900779.901」、ティー・エイ・インスツルメント・ジャパン社製)に5mgの重合体を封入して作製した。測定は、測定用サンプルを200℃で1分間保持した後、−150℃まで10℃/分の速度で冷却し、次いで−150℃で1分間保持した後、200℃まで20℃/分の速度で昇温する方法で行った。この−150℃から200℃に昇温する工程における結晶融解に起因する吸熱量の総和を融解エンタルピーΔHとし、吸熱量がピークを示す温度を融点Tmとした。
[調製例1]
窒素置換した内容積1Lのガラス製容器に、脱水トルエン700ml、ケトイミン誘導体として下記式(1−A)で表される化合物7.5g、及び遷移金属化合物としてバナジウムオキシトリイソプロポキシド5.2gを加えて、20時間還流させた。次に、反応液を室温に戻した後、真空下で溶媒を留去することで黒色固体を得た。この黒色固体から70℃の脱水アセトニトリルを用いて抽出を行い、窒素雰囲気下で抽出溶液を空冷したところ、黒色結晶が析出した。次に、上澄みを取り除き、真空下でアセトニトリルを留去することで黒色結晶状のバナジウム化合物6.0gを得た。このバナジウム化合物1.1gとテトラヒドロフラン(THF)0.38gを脱水トルエン53mlに溶解させたものを、バナジウム触媒溶液として重合に用いた。
[実施例1]
窒素置換した500mLのガラス製重合管中に、室温でトルエンを29mL添加してから、その重合管を−55℃の低温槽に沈積した。次に、重合管中にモノマーとしてプロピレン0.9g及びブタジエン5.8gを加え、さらに有機金属アルミニウム化合物としてメチルアルミノキサンのトルエン溶液(10質量%、アルベマール社製)1.8mLと、ハロゲン化合物として2−クロロ−2−メチルプロパンのトルエン溶液(1.0mol/L、和光純薬社製)0.3mLを加え、重合管を0℃に昇温した。次に、実施例1で調製したバナジウム触媒溶液0.5mLを加えて、3時間重合反応を行った。重合後、メタノール2.0mLを加えて反応を停止させ、更に大量のメタノールで凝固反応を行い、60℃で真空乾燥して重合体(これを「共重合体A」とする。)を得た。得られた共重合体Aの収量は0.5gであった。
[実施例2〜5]
使用するプロピレン及びブタジエンの量をそれぞれ下記表1に記載の通りに変更した以外は実施例1と同様にして重合を行い、共重合体B〜Eを得た。下記表1に収量及び収率を併せて示した。
窒素置換した500mLのガラス製重合管中に、室温でトルエンを6.9mL添加してから、その重合管を0℃の低温槽に沈積した。次に、重合管内をエチレンガスで置換し、さらに有機金属アルミニウム化合物としてメチルアルミノキサンのトルエン溶液(10質量%、アルベマール社製)5.8mL、ハロゲン化合物として2−クロロ−2−メチルプロパンのトルエン溶液(1.0mol/L、和光純薬社製)0.8mL、及び調製例1で得たバナジウム触媒溶液1.6mLを加えて、3時間重合反応を行った。重合後、メタノール2.0mLを加えて反応を停止させ、更に大量のメタノールで凝固反応を行い、60℃で真空乾燥して重合体(これを「重合体Q」とする。)を得た。得られた重合体Qの収量は0.8g、収率は50.7%であった。
[参考例2]
窒素置換した500mLのガラス製重合管中に、室温でトルエンを29mL添加してから、その重合管を0℃の低温槽に沈積した。次に、ブタジエン3.5gを加え、さらに有機金属アルミニウム化合物としてメチルアルミノキサンのトルエン溶液(10質量%、アルベマール社製)1.8mL、ハロゲン化合物として2−クロロ−2−メチルプロパンのトルエン溶液(1.0mol/L、和光純薬社製)0.3mL、及び実施例1で調製したバナジウム触媒溶液0.5mLを加えて、3時間重合反応を行った。重合後、メタノール2.0mLを加えて反応を停止させ、更に大量のメタノールで凝固反応を行い、60℃で真空乾燥して重合体(これを「重合体R」とする。)を得た。得られた重合体Rの収量は0.2g、収率は5.2%であった。
Claims (9)
- 前記遷移金属が5族の元素である、請求項1に記載の重合触媒。
- 前記ハロゲン化合物は、3級炭素又は3級ケイ素と、塩素とが結合した構造を有する化合物である、請求項2に記載の重合触媒。
- 前記有機アルミニウム化合物がアルミノキサン化合物である、請求項1〜3のいずれか一項に記載の重合触媒。
- β−ケトイミン化合物及びその互変異性体よりなる群から選ばれる少なくとも一種のケトイミン誘導体と、4族及び5族の遷移金属から選ばれる少なくとも一種を含む化合物とを混合してなる金属錯体、有機アルミニウム化合物、及び、ハロゲン化合物を含む重合触媒を用いて、共役ジエン化合物と炭素数3〜8のα−オレフィンとを重合する、共重合体の製造方法。
- 重合温度が−50℃〜50℃の範囲内である、請求項5に記載の共重合体の製造方法。
- 請求項5又は6に記載の製造方法により得られた共重合体と、架橋剤とを含む重合体組成物の製造方法。
- 請求項8に記載の製造方法により得られた重合体組成物を架橋して得られる架橋重合体の製造方法。
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