JPH10512600A - 長鎖分岐を有する重合体及びそれらの製造 - Google Patents
長鎖分岐を有する重合体及びそれらの製造Info
- Publication number
- JPH10512600A JPH10512600A JP8514092A JP51409296A JPH10512600A JP H10512600 A JPH10512600 A JP H10512600A JP 8514092 A JP8514092 A JP 8514092A JP 51409296 A JP51409296 A JP 51409296A JP H10512600 A JPH10512600 A JP H10512600A
- Authority
- JP
- Japan
- Prior art keywords
- ziegler
- monomer
- natta polymerization
- polymerization
- polymer
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
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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
- C08F4/60—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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 請求するのは: 1.下記a)〜c)の単量体類であって、 i) 直鎖状で、六個未満又は少なくとも七個の炭素原子を有するか ; ii) 直鎖状以外であるか;又は iii)それらの組み合わせである ものを含む、少なくとも三種の単量体類から誘導される共重合体であって 、下記d)〜g)の性質を有する共重合体: a) チグラー・ナッタ重合が可能な単結合を有する一つのモノオレフィ ン; b) チグラー・ナッタ重合が可能な結合を少なくとも一つ有する第二の 単量体;及び c) チグラー・ナッタ重合が可能な結合を少なくとも二つ有する第三の 単量体、 及び d) 炭素−炭素不飽和結合を、数平均分子量につき、少なくとも一つ有 する; e) チグラー・ナッタ重合が可能な結合を少なくとも二つ有する種を除 いて同じ単量体類から誘導される線状主鎖を有する共重合体よりも、少なくとも 1kcal/モル大きい粘弾性活性化エネルギー(Ea)を有する; f) 結晶化度水準が10%〜50%の範囲内である;及び g) Mz/Mwが少なくとも1.7である。 2.前記のチグラー・ナッタ重合が可能な結合を少なくとも一つ有する一つの モノオレフィンがエチレンである、請求項1の共重合体。 3.前記第三の単量体がジエンである、先行する請求項のいずれかの共重合体 。 4.前記ジエンが、1,3−ブタジエン、1,4−ペンタジエン、1,6−ヘ プタジエン、1,7−オクタジエン、1,8−ノナジエン、1,9−デカジエン ,1,10−ウンデカジエン、1,11−ドデカジエンから、又は、シクロヘキ サジエン、シクロオクタジエン、ノルボルナジエン、ビニルノルボルネンからな る群から選ばれる、先行する請求項のいずれかの共重合体。 5.チグラー・ナッタ重合が可能な結合を少なくとも一つ有する一つの種が、 プロピレン、ブテン−1、ペンテン−1、ヘキセン−1、ヘプテン−1、オクテ ン−1、ノネン−1、デセン−1、ウンデセン−1、ドデセン−1、ヘキサデセ ン−1、オクタデセン−1、及び4−メチルペンテン−1からなる群から選ばれ る、先行する請求項のいずれかの共重合体。 6.a) 前記モノオレフィンがi)エチレンであり、ii)前記第二の単量 体が、プロピレン、ブテン−1、ペンテン−1、ヘキセン−1、ヘプテン−1、 オクテン−1、ノネン−1、デセン−1、ウンデセン−1、ドデセン−1、ヘキ サデセン−1、オクタデセン−1、及び4−メチルペンテン−1からなる群から 選ばれ、 b) 前記第三の単量体が、i)1,3−ブタジエン、1,4−ペンタジ エン、1,6−ヘプタジエン、1,7−オクタジエン、1,8−ノナジエン、1 ,9−デカジエン、1,10−ウンデカジエン、1,11−ドデカジエンから、 又はii)ノルボルナジエン、ビニルノルボルネン、シクロヘキサジエン、シク ロオクタジエン、シクロデカジエン、分岐非環状ジエンからなる群から選ばれる 、 先行する請求項のいずれかの共重合体。 7.数平均分子量につき、1〜8の、好ましくは2〜8の範囲内の不飽和炭 素−炭素結合を有する、先行する請求項のいずれかの共重合体。 8.下記a)〜c)の単量体類であって、 i) 直鎖状で、六個未満又は少なくとも七個の炭素原子を有するか ; ii) 直鎖状以外であるか;又は iii)それらの組み合わせである ものを共重合する方法であって、下記d)及びe)の工程を含む方法: a) チグラー・ナッタ重合が可能な単結合を有する一つのモノオレフィ ン; b) チグラー・ナッタ重合が可能な結合を少なくとも一つ有する第二の 単量体;及び c) チグラー・ナッタ重合が可能な結合を少なくとも二つ有する第三の 単量体、 及び d) 単量体類を、チグラー・ナッタ触媒、その誘導体又はそれらの組み 合わせに接触させる;及び e) 共重合体を回収する。 9.共重合が、100バール未満の圧力下に行われる、請求項8の方法。 10.前記一つのモノオレフィンが、エチレン及びプロピレンからなる群から選 ばれ、前記第二の単量体が、ブテン−1、ペンテン−1、ヘキセン−1、オクテ ン−1、デセン−1、ドデセン−1、オクタデセン−1、及び4−メチルペンテ ン−1からなる群から選ばれ、且つ、前記チグラー・ナッタ重合が可能な結合を 少なくとも二つ有する単量体が、1,7−オクタジエン、1,9−デカジエン、 1,11−ドデカジエン、ノルボルナジエン、ビニルノルボルネン、シクロヘキ サジエン、シクロオクタジエン、及びシクロデカジエンからなる群から選ばれる 、請求項8−9のいずれか の方法。 11.前記チグラー・ナッタ重合が可能な結合を少なくとも二つ有する単量体が 、1,7−オクタジエン、1,9−デカジエン、ノルボルナジエン、及びビニル ノルボルネンからなる群から選ばれる、請求項8−10のいずれかの方法。 12.前記ジエンが、1,3−ブタジエン、1,4−ペンタジエン、1,6−ヘ プタジエン、1,7−オクタジエン、1,8−ノナジエン、1,9−デカジエン 、1,10−ウンデカジエン、1,11−ドデカジエン、シクロヘキサジエン、 シクロオクタジエン、ノルボルナジエン、ビニルノルボルネン、及び分岐非環状 ジエンからなる群から選ばれる、請求項8−11のいずれかの方法。 13.前記第二の単量体が、プロピレン、ブテン−1、ペンテン−1、ヘキセン −1、ヘプテン−1、オクテン−1、ノネン−1、デセン−1、ウンデセン−1 、ドデセン−1、ヘキサデセン−1、オクタデセン−1、及び4−メチルペンテ ン−1からなる群から選ばれる、請求項8−12のいずれかの方法。 14.重合が、メタロセン触媒系を用いて行われる、請求項8−13のいずれか の方法。 15.メタロセン触媒系用の活性化剤として、アルモキサン、嵩高くて化学変化 を起こし易い陰イオン種、又はそれらの組み合わせを含む活性化剤が用いられる 、請求項8−14のいずれかの方法。 16.活性化剤と掃去剤との組み合わせが、メタロセン触媒系と共に用いられる 、請求項8−15のいずれかの方法。 17.エチレンと、チグラー・ナッタ重合が可能な二重結合を少なくとも二つ有 するポリエンを、少なくとも120℃の温度で、嵩高い取付けリガンドを有する 遷移金属化合物から誘導される触媒を用いて重合し、MIRが少なくとも25で 活性化エネルギーが少なくとも9.0kcal/モルのエチレン共重合体を作る ことを含む方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/328,187 | 1994-10-24 | ||
US08/328,187 US6300451B1 (en) | 1994-10-24 | 1994-10-24 | Long-chain branched polymers and their production |
PCT/US1995/013643 WO1996012744A1 (en) | 1994-10-24 | 1995-10-24 | Long-chain branched polymers and their production |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10512600A true JPH10512600A (ja) | 1998-12-02 |
Family
ID=23279893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8514092A Pending JPH10512600A (ja) | 1994-10-24 | 1995-10-24 | 長鎖分岐を有する重合体及びそれらの製造 |
Country Status (13)
Country | Link |
---|---|
US (1) | US6300451B1 (ja) |
EP (1) | EP0788521B1 (ja) |
JP (1) | JPH10512600A (ja) |
KR (1) | KR100358857B1 (ja) |
CN (2) | CN1091774C (ja) |
AU (1) | AU694812B2 (ja) |
BR (1) | BR9509427A (ja) |
CA (1) | CA2202402C (ja) |
DE (1) | DE69506906T2 (ja) |
ES (1) | ES2128786T3 (ja) |
RU (1) | RU2165437C2 (ja) |
TW (1) | TW422857B (ja) |
WO (1) | WO1996012744A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004065435A1 (ja) * | 2003-01-23 | 2004-08-05 | Mitsui Chemicals, Inc. | エチレン・α-オレフィン・非共役ポリエン共重合体の製造方法およびエチレン・α-オレフィン・非共役ポリエン共重合体 |
JP2014530272A (ja) * | 2011-09-23 | 2014-11-17 | エクソンモービル ケミカルパテンツ インコーポレイテッド | 改質ポリエチレン組成物 |
JP2015057461A (ja) * | 2013-08-09 | 2015-03-26 | 三菱化学株式会社 | 熱可塑性エラストマー組成物の製造方法 |
JP2016500723A (ja) * | 2012-10-09 | 2016-01-14 | ライオン コポリマー リミテッド ライアビリティー カンパニー | 制御された長鎖分岐と幅広い分子量分布を有するスポンジポリマー |
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- 1995-10-24 CA CA002202402A patent/CA2202402C/en not_active Expired - Fee Related
- 1995-10-24 EP EP95938287A patent/EP0788521B1/en not_active Revoked
- 1995-10-24 ES ES95938287T patent/ES2128786T3/es not_active Expired - Lifetime
- 1995-10-24 DE DE69506906T patent/DE69506906T2/de not_active Revoked
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- 1995-10-24 RU RU97108600/04A patent/RU2165437C2/ru not_active IP Right Cessation
- 1995-10-24 KR KR1019970702672A patent/KR100358857B1/ko not_active IP Right Cessation
- 1995-10-24 CN CN95195850A patent/CN1091774C/zh not_active Expired - Fee Related
-
1996
- 1996-04-26 TW TW085105107A patent/TW422857B/zh not_active IP Right Cessation
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2001
- 2001-09-06 CN CNB011328118A patent/CN1204157C/zh not_active Expired - Fee Related
Cited By (6)
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WO2004065435A1 (ja) * | 2003-01-23 | 2004-08-05 | Mitsui Chemicals, Inc. | エチレン・α-オレフィン・非共役ポリエン共重合体の製造方法およびエチレン・α-オレフィン・非共役ポリエン共重合体 |
JPWO2004065435A1 (ja) * | 2003-01-23 | 2006-05-18 | 三井化学株式会社 | エチレン・α−オレフィン・非共役ポリエン共重合体の製造方法およびエチレン・α−オレフィン・非共役ポリエン共重合体 |
JP2011052231A (ja) * | 2003-01-23 | 2011-03-17 | Mitsui Chemicals Inc | エチレン・α−オレフィン・非共役ポリエン共重合体 |
JP2014530272A (ja) * | 2011-09-23 | 2014-11-17 | エクソンモービル ケミカルパテンツ インコーポレイテッド | 改質ポリエチレン組成物 |
JP2016500723A (ja) * | 2012-10-09 | 2016-01-14 | ライオン コポリマー リミテッド ライアビリティー カンパニー | 制御された長鎖分岐と幅広い分子量分布を有するスポンジポリマー |
JP2015057461A (ja) * | 2013-08-09 | 2015-03-26 | 三菱化学株式会社 | 熱可塑性エラストマー組成物の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1091774C (zh) | 2002-10-02 |
CA2202402C (en) | 2006-10-17 |
DE69506906T2 (de) | 1999-05-27 |
ES2128786T3 (es) | 1999-05-16 |
US6300451B1 (en) | 2001-10-09 |
CN1204157C (zh) | 2005-06-01 |
BR9509427A (pt) | 1998-01-06 |
DE69506906D1 (de) | 1999-02-04 |
CA2202402A1 (en) | 1996-05-02 |
MX9702954A (es) | 1998-07-31 |
EP0788521A1 (en) | 1997-08-13 |
KR970707184A (ko) | 1997-12-01 |
EP0788521B1 (en) | 1998-12-23 |
AU694812B2 (en) | 1998-07-30 |
TW422857B (en) | 2001-02-21 |
WO1996012744A1 (en) | 1996-05-02 |
CN1161700A (zh) | 1997-10-08 |
KR100358857B1 (ko) | 2003-02-07 |
CN1341672A (zh) | 2002-03-27 |
AU3897095A (en) | 1996-05-15 |
RU2165437C2 (ru) | 2001-04-20 |
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