JP7276963B2 - エチレン/アルファ-オレフィン共重合体及びその製造方法 - Google Patents
エチレン/アルファ-オレフィン共重合体及びその製造方法 Download PDFInfo
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Description
本出願は、2018年5月4日付韓国特許出願2018-0052045に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
以下、本発明のエチレン/アルファ-オレフィン共重合体を詳しく説明する。
本発明の一実施形態によるエチレン/アルファ-オレフィン共重合体は、下記i)からiv)の条件を満たす:
i)粘度:180℃の温度で測定時6,000cPから40,000cP、
ii)分子量分布(MWD):1.5から3.0、
iii)炭素原子1,000個当たりの総不飽和官能基の数:0.8個以下、
iv)下記数式1によるRvd値:0.5以下
i)粘度:180℃の温度で測定時6,000cPから40,000cP、
ii)密度:0.85から0.89g/cc,
iii)分子量分布(MWD):1.5から3.0,
iv)炭素原子1000個当たりの総不飽和官能基の数:0.8個以下、
v)数平均分子量(Mn):9,000から25,000,
vi)ASTM D1238による190℃、2.16kg荷重での溶融指数(MI):200から1,300dg/分、及び
vii)下記数式1によるRvd値:0.5以下
一方、前記のような物性特徴を有するエチレン/アルファ-オレフィン共重合体は、下記化学式1の遷移金属化合物を含む触媒組成物の存在下で、水素を45から100cc/分で投入し、エチレン及びアルファ-オレフィン系単量体を重合する段階を含む製造方法によって製造されてよい。これにより、本発明の他の一実施形態によれば、前記のエチレン/アルファ-オレフィン共重合体の製造方法が提供される:
R2aからR2eは、それぞれ独立して、水素;ハロゲン;炭素数1から20のアルキル;炭素数3から20のシクロアルキル;炭素数2から20のアルケニル;炭素数1から20のアルコキシ;又は炭素数6から20のアリールであり、
R3は、水素;ハロゲン;炭素数1から20のアルキル;炭素数3から20のシクロアルキル;炭素数2から20のアルケニル;炭素数6から20のアリール;炭素数7から20のアルキルアリール;炭素数7から20のアリールアルキル;炭素数1から20のアルキルアミド;又は炭素数6から20のアリールアミド;ハロゲン、炭素数1から20のアルキル、炭素数3から20のシクロアルキル、炭素数2から20のアルケニル、炭素数1から20のアルコキシ及び炭素数6から20のアリールでなる群から選択された1種以上で置換されたフェニルであり、
R4からR9は、それぞれ独立して、水素;シリル;炭素数1から20のアルキル;炭素数3から20のシクロアルキル;炭素数2から20のアルケニル;炭素数6から20のアリール;炭素数7から20のアルキルアリール;炭素数7から20のアリールアルキル;又は炭素数1から20のヒドロカルビルで置換された14族金属のメタロイドラジカルであり;前記R6からR9のうち互いに隣接する2個以上は、互いに連結されて環を形成してよく、
Qは、Si又はCであり、
Mは、4族の遷移金属であり、
X1及びX2は、それぞれ独立して、水素;ハロゲン;炭素数1から20のアルキル;炭素数3から20のシクロアルキル;炭素数2から20のアルケニル;炭素数6から20のアリール;炭素数7から20のアルキルアリール;炭素数7から20のアリールアルキル;炭素数1から20のアルキルアミノ;又は炭素数6から20のアリールアミノである。
より具体的に、前記R3は、水素;炭素数1から12のアルキル;又はフェニルであってよい。
前記R6からR9のうち互いに隣接する2個以上は、互いに連結されて炭素数5から20の脂肪族環又は炭素数6から20の芳香族環を形成してよく;前記脂肪族環又は芳香族環は、ハロゲン、炭素数1から20のアルキル、炭素数2から12のアルケニル、又は炭素数6から12のアリールで置換されてよい。
より具体的に、前記X1及びX2は、それぞれ独立して水素又は炭素数1から12のアルキルであってよい。
R41-[Al(R42)-O]n-R43
前記化学式2において、
R41、R42及びR43は、それぞれ独立して、水素、ハロゲン、炭素数1から20のヒドロカルビル基及びハロゲンで置換された炭素数1から20のヒドロカルビル基のうち何れか一つであり、
nは2以上の整数であり、
[化学式3]
D(R44)3
前記化学式3において、Dはアルミニウム又はホウ素であり、
R44は、それぞれ独立して、ハロゲン、炭素数1から20のヒドロカルビル基、及びハロゲンで置換された炭素数1から20のヒドロカルビル基のうち何れか一つであり、
[化学式4]
[L-H]+[Z(A)4]-又は[L]+[Z(A)4]-
前記化学式4において、
Lは、中性又は陽イオン性ルイス塩基であり、Hは、水素原子であり、
Zは、13族元素であり、Aは、それぞれ独立して、炭素数1から20のヒドロカルビル基;炭素数1から20のヒドロカルビルオキシ基;及びこれら置換基の1以上の水素原子が、ハロゲン、炭素数1から20のヒドロカルビルオキシ基及び炭素数1から20のヒドロカルビルシリル基のうち1以上の置換基で置換された置換基のうち何れか一つである。
段階1:リガンド化合物(1a-1)の製造
250mLのシュレンクフラスコに1,2-ジメチル-3H-ベンゾ[b]シクロペンタ[d]チオフェン10g(1.0eq、49.925mmol)と100mLのTHFを入れ、n-BuLi 22 mL(1.1eq、54.918mmol、2.5M inヘキサン)を-30℃で滴加した後、常温で3時間撹拌した。撹拌したLi-complex THF溶液をジクロロ(メチル)(フェニル)シラン8.1mL(1.0eq、49.925mmol)と70mLのTHFが入っているシュレンクフラスコに-78℃でカニュレーション後、常温で一晩中撹拌した。撹拌してから真空乾燥した後、ヘキサン100mLで抽出した。
100mLのシュレンクフラスコに前記化学式1a-1のリガンド化合物4.93g(12.575mmol、1.0eq)とトルエン50mL(0.2M)を入れ、n-BuLi 10.3mL(25.779mmol、2.05eq、2.5M inヘキサン)を-30℃で滴加した後、常温で一晩中撹拌した。撹拌後にMeMgBr 12.6mL(37.725mmol、3.0 eq、3.0M inジエチルエーテル)を滴加した後、TiCl4 13.2mL(13.204mmol、1.05eq、1.0M inトルエン)を順に入れて常温で一晩中撹拌した。撹拌してから真空乾燥した後、ヘキサン150 mLで抽出し、50mLまで溶媒を除去してからDME 4mL(37.725mmol、3.0eq)を滴加した後、常温で一晩中撹拌した。再び真空乾燥した後、ヘキサン150mLで抽出した。溶媒乾燥してから茶色の固体2.23g(38%、dr=1:0.5)を得た。
実施例1
1.5Lのオートクレーブ連続工程反応器にヘキサン溶媒(5.0kg/h)と1-オクテン(1.00kg/h)を満たした後、反応器上部の温度を150℃に予熱した。トリイソブチルアルミニウム化合物(0.05mmol/分)、触媒として前記合成例で製造した遷移金属化合物(1a)(0.40μmol/分)、ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート助触媒(1.20μmol/分)を同時に反応器へ投入した。次いで、前記オートクレーブ反応器の中にエチレン(0.87kg/h)及び水素ガス(50cc/分)を投入し、89barの圧力及び重合温度125℃で60分以上維持しながら共重合反応を連続進行して共重合体を製造した。
下記の表1に記載された含量で反応物質を投入することを除いては、前記実施例1と同一の方法で行い重合体を製造した。
実験例1
前記実施例及び比較例で製造したエチレン/アルファ-オレフィン共重合体に対し、下記の方法で物性を測定して表2に示した。
-カラム:PL Olexis
-溶媒:TCB(トリクロロベンゼン;Trichlorobenzene)
-流速:1.0ml/分
-試料濃度:1.0mg/ml
-注入量:200μl
-カラム温度:160℃
-検出器(Detector):Agilent High Temperature RI detector
-標準(Standard):ポリスチレン(Polystyrene)(3次関数で補正)
Claims (8)
- 密度が0.85から0.89g/ccである、請求項1に記載のエチレン/アルファ-オレフィン共重合体。
- 重量平均分子量が17,000から40,000g/molである、請求項1又は2に記載のエチレン/アルファ-オレフィン共重合体。
- 粘度が180℃の温度で測定時、8,500から35,000cPである、請求項1~3のいずれか一項に記載のエチレン/アルファ-オレフィン共重合体。
- 前記アルファ-オレフィンは、プロピレン、1-ブテン、1-ペンテン、4-メチル-1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-デセン、1-ウンデセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン及び1-エイコセンで構成される群から選択される1種以上を含む、請求項1~4のいずれか一項に記載のエチレン/アルファ-オレフィン共重合体。
- 前記アルファ-オレフィンは、1-ブテン、1-ヘキセン及び1-オクテンでなる群から選択される1種以上である、請求項1~5のいずれか一項に記載のエチレン/アルファ-オレフィン共重合体。
- 前記アルファ-オレフィンは、共重合体の総重量に対して0超過99モル%以下の含量で含まれる、請求項1~6のいずれか一項に記載のエチレン/アルファ-オレフィン共重合体。
- 下記v)からvii)の条件をさらに満たす、請求項1~7のいずれか一項に記載のエチレン/アルファ-オレフィン共重合体:
v)炭素原子1000個当たりの総不飽和官能基の数:0.8個以下、
vi)数平均分子量(Mn):9,000から25,000、
vii)ASTM D1238による190℃、2.16kg荷重での溶融指数(MI):200から1,300dg/分。
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