JPH03200810A - 4-methylpentene-1 polymer - Google Patents
4-methylpentene-1 polymerInfo
- Publication number
- JPH03200810A JPH03200810A JP2134041A JP13404190A JPH03200810A JP H03200810 A JPH03200810 A JP H03200810A JP 2134041 A JP2134041 A JP 2134041A JP 13404190 A JP13404190 A JP 13404190A JP H03200810 A JPH03200810 A JP H03200810A
- Authority
- JP
- Japan
- Prior art keywords
- methylpentene
- observed
- measured
- ppm
- 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.)
- Granted
Links
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 28
- 239000004711 α-olefin Substances 0.000 claims abstract description 19
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims abstract description 18
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 5
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 229920001519 homopolymer Polymers 0.000 claims description 7
- 238000001103 continuous-wave nuclear magnetic resonance spectrum Methods 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 238000005277 cation exchange chromatography Methods 0.000 claims 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 abstract description 9
- 230000000379 polymerizing effect Effects 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 3
- 230000009102 absorption Effects 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000000862 absorption spectrum Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- -1 polypropylene Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PGOXJIBERNIRFR-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)[Hf+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C(C)(C)[Hf+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 PGOXJIBERNIRFR-UHFFFAOYSA-L 0.000 description 1
- PDBMBIIQRMIHJS-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)[Zr+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C(C)(C)[Zr+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 PDBMBIIQRMIHJS-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000017168 chlorine Nutrition 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/14—Monomers containing five or more carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は実質的にシンジオタクチック構造を有する、立
体規則性の高い４−メチルペンテン−１の重合体に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a highly stereoregular 4-methylpentene-1 polymer having a substantially syndiotactic structure.
［従来の技術］
シンジオタクチック構造を有するα−オレフィンの重合
体は、古くからその存在が知られており、その一つはシ
ンジオタクチックポリプロピレンである。しかしながら
、バナジウム化合物とエーテル及び有機アルミニウム化
合物とからなる触媒を用いてプロピレンを低温において
重合する方法により得られたシンジオタクチックポリプ
ロピレンはシンジオタクテイシテイ−が悪く、シンジオ
タクチックポリプロピレンとしての特徴を有するとは云
い難かった。[Prior Art] The existence of α-olefin polymers having a syndiotactic structure has been known for a long time, and one of them is syndiotactic polypropylene. However, syndiotactic polypropylene obtained by polymerizing propylene at low temperatures using a catalyst consisting of a vanadium compound, an ether, and an organoaluminum compound has poor syndiotacticity and is not characterized as syndiotactic polypropylene. It was hard to say.
Ｊ、Ａ、Ｅｗｅｎらは、非対称な配位子を有する遷移金
属ｆｌｌｆ及びＺｒ）化合物とメチルアルミノキサンと
からなる重合触媒を用いてプロピレンを重合することに
より、”Ｃ−ＮＭＲによるシンジオタクヂックペンタッ
ド分率が０．７を越えるタフティシティ−の良好なプロ
ピレンが得られることを、はじめて見出した（Ｊ、Ａｓ
＋ｅｒ、Ｃｈｅｍ、 Ｓｏｃ、 、 １９８８．１１０
゜６２５５−６２５６１゜
上記のＪ、Ａ、Ｅｗｅｎらの方法は遷移金属当りの活性
が良好であって、得られたシンジオタクチックポリプロ
ピレンのシンジオタクテイシテイ−も高く、しかも、そ
の物性もかなり優れたものであった。しかしながら、Ｅ
ｖｅｎらは４−メチルペンテン−１の重合については、
なんら開示していない。J. A. Ewen et al. reported that a "syndiotagic pen by C-NMR" was obtained by polymerizing propylene using a polymerization catalyst consisting of a transition metal (Fllf and Zr) compound having an asymmetrical ligand and methylaluminoxane. It was discovered for the first time that propylene with good toughness and a Tad fraction exceeding 0.7 can be obtained (J, As
+er, Chem, Soc, , 1988.110
゜6255-62561゜The above method of J, A, Ewen et al. has good activity per transition metal, the syndiotactic polypropylene obtained has high syndiotacticity, and its physical properties are also quite good. It was something like that. However, E
Regarding the polymerization of 4-methylpentene-1, Ven et al.
Nothing has been disclosed.
４−メチルペンテン−１の重合体については、アイソタ
クチック及びアタクチックのものが知られており、また
シンジオタクチック構造を有する４−メチルペンテン−
１の重合体もＡ、Ｚａｍｂｅｌｌｉらによって報告され
ている（Ｍａｃｒｏｒｎｏｌｅｃｕｌｅｓ １９Ｂ９゜
２２．２１２６−２１２８） 。Ｚａｍｂｅｌｌｉらの
方法は、シンジオタクチック構造を有する４−メチル−
１，３−ペンタジェンの１．２−重合体を水素添加して
シンジオタクチック構造を有する４−メチルペンテン−
１の重合体とするものである。Isotactic and atactic polymers of 4-methylpentene-1 are known, and 4-methylpentene-1 having a syndiotactic structure is known.
A polymer of No. 1 has also been reported by Zambelli et al. (Macronolecules 19B9°22.2126-2128). Zambelli et al.'s method uses 4-methyl-
Hydrogenating a 1,2-polymer of 1,3-pentadiene to produce 4-methylpentene having a syndiotactic structure.
1 polymer.
しかしながら、上記１，２−重合体の規則性があまり高
くないので、その水素添加物である４−メチルペンテン
−１の重合体の立体規則性が低く、結果的に４−メチル
ペンテン−１の重合体の結晶性が低くなる。またＺａｍ
ｂｅｌｌｉらの方法では４−メチルペンテン−１と他の
α−オレフィンの共電体を製造することができないとい
う問題がある。However, since the regularity of the above 1,2-polymer is not very high, the stereoregularity of the polymer of 4-methylpentene-1, which is its hydrogenated product, is low, and as a result, the stereoregularity of the 4-methylpentene-1 polymer is low. The crystallinity of the polymer decreases. Zam again
The method of Belli et al. has a problem in that it cannot produce a conjugate of 4-methylpentene-1 and other α-olefins.
［発明が解決しようとする課題］
本発明の目的は、立体規則性が高い４−メチルペンテン
−１の重合体及び共重合体を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide 4-methylpentene-1 polymers and copolymers with high stereoregularity.
本発明のいま一つの目的は、物性、特に耐衝撃性が良好
で耐衝撃性と剛性のバランスが良好であり、かつ透明性
の良好な実質的にシンジオタクチックＦＲ造を有する４
−メチルペンテン−１とその他のα−オレフィンとの共
重合体を提供することにある。Another object of the present invention is to have a substantially syndiotactic FR construction having good physical properties, particularly impact resistance, a good balance between impact resistance and rigidity, and good transparency.
- To provide a copolymer of methylpentene-1 and other α-olefins.
［課題を解決するための手段１
本発明によって、次の４−メチルペンテン−１の重合体
が提供される。[Means for Solving the Problems 1] The present invention provides the following 4-methylpentene-1 polymer.
４−メチルペンテン−１以外のα−オレフィン単位を０
〜３０モル％含有する実質的にシンジオタクチック構造
を有する４−メチルペンテン−１の重合体。α-olefin units other than 4-methylpentene-1 are 0
A polymer of 4-methylpentene-1 having a substantially syndiotactic structure containing ~30 mol%.
−ｈ記重合体が４−メチルペンテン−１の単独重合体の
場合は、１．２．４− トリクロロベンゼン溶液で測定
した”Ｃ−ＮＭＲの吸収スペクトルにおいて、テトラメ
チルシランを基準として約４３． １ｐｐｍに観−１１
される吸収強度が、約４２〜４４ｐｐ＋ｓに観測される
吸収強度の総和の０．５以上であり、ゲルパーミェーシ
ョンクロマトグラフィーで測定した分子量が１０００以
上であり、かつＸ＃ｉ１回折により面間隔約９入に最大
回折線が観測される重合体である。- When the polymer described in h is a homopolymer of 4-methylpentene-1, in the "C-NMR absorption spectrum measured with a 1.2.4-trichlorobenzene solution, it has an absorption spectrum of about 43% based on tetramethylsilane. 1ppm -11
The absorption intensity of This is a polymer in which maximum diffraction lines are observed at intervals of about 9 degrees.
また、上記重合体が４−メチルペンテン−１とその他の
α−オレフィンとの共重合体の場合は、１．２．４−１
−リクロロベンゼン溶液で測定した１３Ｃ−ＮＭＨの吸
収スペクトルにおいて、テトラメチルシランを基準とし
て約４３．１ｐｐｍに観測される４−メチルペンテン−
１単位の吸収強度が約４２〜４４ ｐｐｍに観測される
４−メチルペンテン−１単位の吸収強度の総和の０°、
３以上であり、上記α−オレフィン単位を０．１〜３０
モル％含有し、テトラリン溶液として１３５℃において
測定した極限粘度が０．０５以上である共重合体である
。In addition, if the above polymer is a copolymer of 4-methylpentene-1 and other α-olefins, 1.2.4-1
-4-Methylpentene- observed at about 43.1 ppm based on tetramethylsilane in the absorption spectrum of 13C-NMH measured in a dichlorobenzene solution
0° of the total absorption intensity of 4-methylpentene-1 unit, where the absorption intensity of 1 unit is observed at about 42 to 44 ppm,
3 or more, and the α-olefin unit is 0.1 to 30
It is a copolymer containing mol% of tetralin and having an intrinsic viscosity of 0.05 or more when measured as a tetralin solution at 135°C.
本発明による４−メチルペンテン−１の重合体及び共重
合体は触媒の存在下に４−メチルペンテン−１単独また
はこれ以外のａ−オレフィン単位とともに重合すること
により得られる。重合触媒としては、 Ｊ、Ａ、Ｅｗｅ
ｎらの前記文献に記載された化合物が例示されるが、異
なる構造であってもプロピレンの単独重合体を製造した
とき、得られる重合体の１３Ｃ−ＮＭＲの吸収スペクト
ルにより測定したシンジオタクチックペンタッド分率が
０．７以上の比較的タフティシティ−の高い重合体を与
える触媒系を用いることができる０例えば、非対称な配
位子を有する遷移金属化合物とアルミノキサンとからな
る触媒系が有効である。The polymers and copolymers of 4-methylpentene-1 according to the present invention are obtained by polymerizing 4-methylpentene-1 alone or together with other a-olefin units in the presence of a catalyst. As a polymerization catalyst, J, A, Ewe
The syndiotactic pen measured by the 13C-NMR absorption spectrum of the resulting polymer when a propylene homopolymer is produced, even if it has a different structure, is exemplified by the compounds described in the above-mentioned literature by N et al. It is possible to use a catalyst system that provides a polymer with a relatively high toughness with a Tad fraction of 0.7 or more. For example, a catalyst system consisting of a transition metal compound having an asymmetrical ligand and aluminoxane is effective. It is.
非対称な配位子を有する遷移金属化合物の例はＪ、Ａ、
Ｅｗｅｎらの開示しているイソプロピル（シクロペンタ
ジェニル−１−フルオレニル）ハフニウムジクロリドお
よびイソプロピル（シクロペンタジェニル−１−フルオ
レニル）ジルコニウムジクロリドであり、さらにこれら
の塩素の１もしくは２をその他のハロゲンもしくは炭素
数１−５のアルキル基で置換したものも挙げることがで
きる。Examples of transition metal compounds with asymmetric ligands are J, A,
Ewen et al. disclose isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride and isopropyl (cyclopentajenyl-1-fluorenyl) zirconium dichloride, and furthermore, one or two of these chlorines are replaced by other halogens or Those substituted with an alkyl group having 1 to 5 carbon atoms can also be mentioned.
アルミノキサンとしては、
＼
（式中、Ｒは炭素数１−３の炭化水素残基である。）で
表わされる化合物が例示され、特にＲがメチルでｎが５
以上、特に好ましくは１０−１００のものが好ましく用
いられる。Examples of aluminoxane include compounds represented by \ (in the formula, R is a hydrocarbon residue having 1 to 3 carbon atoms);
Above, those having a molecular weight of 10 to 100 are particularly preferably used.
上記遷移金属化合物に対するアルミノキサンの使用割合
は１０−１，０００，０００モル倍、好ましくは５０−
５，０００モル倍である。The ratio of aluminoxane used to the above transition metal compound is 10 to 1,000,000 times, preferably 50 to 1,000,000 times by mole.
5,000 moles.
重合条件は特に制限はなく、公知の不活性溶媒を用いる
溶媒重合法、実質的に不活性溶媒の存在しない重合系で
の塊状重合法、又は気相重合法が用いられる。通常、重
合温度は一１００℃〜２００℃、重合圧力は常圧〜１０
０ ｋｇ／ｃｍ２−Ｇである。−１００℃〜１００℃、
常圧〜５０ ｋｇ／ｃｍ２−Ｇにおける重合が特に好ま
しい。The polymerization conditions are not particularly limited, and a solvent polymerization method using a known inert solvent, a bulk polymerization method in a polymerization system substantially free of an inert solvent, or a gas phase polymerization method may be used. Usually, the polymerization temperature is -100℃ to 200℃, and the polymerization pressure is normal pressure to 10℃.
0 kg/cm2-G. -100℃～100℃,
Polymerization at normal pressure to 50 kg/cm2-G is particularly preferred.
本発明において、４−メチルペンテン−１の単独重合体
は上記触媒を用い比較的低温で重合することにより製造
できる。必要に応じてペンタン、ヘキサン、ヘプタンな
どの炭素数５〜２０程度の飽和炭化水素化合物、ベンゼ
ン、トルエン、キシレン、エチルベンゼンなどの芳香族
炭化水素化合物、あるいはこれらの水素の一部または全
部がハロゲンで置換された化合物、炭素数１〜２０のア
ルコール類、炭素数２〜２０のエーテル、エステル類な
どで洗浄して、比較的低立体規則性の４−メチルペンテ
ン−１の重合体を除去することで高度に立体規則性の４
−メチルペンテン−１の単独重合体とすることができる
。In the present invention, the homopolymer of 4-methylpentene-1 can be produced by polymerizing at a relatively low temperature using the above catalyst. If necessary, saturated hydrocarbon compounds having about 5 to 20 carbon atoms such as pentane, hexane, and heptane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene, or some or all of these hydrogens are halogens. Removal of relatively low stereoregular 4-methylpentene-1 polymer by washing with substituted compounds, alcohols with 1 to 20 carbon atoms, ethers, esters with 2 to 20 carbon atoms, etc. The highly stereoregular 4
-Methylpentene-1 homopolymer.
このようにして得られた４−メチルペンテン−１の重合
体は、１，２．４−トリクロロベンゼン溶液で測定した
１３Ｃ−ＮＭＲの吸収スペクトルにおいて、テトラメチ
ルシランを基準として約４３．１ｐｐｍに観測される吸
収強度が約４２〜４４ ｐｐｍに観測される吸収強度の
総和の０．５以上である。The thus obtained 4-methylpentene-1 polymer was observed at approximately 43.1 ppm based on tetramethylsilane in the 13C-NMR absorption spectrum measured with a 1,2.4-trichlorobenzene solution. The absorption intensity observed is 0.5 or more of the total absorption intensity observed at about 42 to 44 ppm.
重合体を３００℃で一度溶融した後１０℃／ｌｌｌ１ｎ
で降温することにより測定した結晶温度は１６０℃以上
である。After melting the polymer once at 300°C, 10°C/lll1n
The crystal temperature measured by lowering the temperature at 160° C. or higher is 160° C. or higher.
また、本発明の４−メチルペンテン−１の重合体は、Ｘ
線回折スペクトルにおいて面間隔約９．０入に最大回折
線が現れることも特徴である。Moreover, the polymer of 4-methylpentene-1 of the present invention is
Another feature is that the maximum diffraction line appears at a lattice spacing of about 9.0 in the line diffraction spectrum.
本発明による４−メチルペンテン−１の単独重合体の分
子量は、この重合体を成形に用いるので、ゲルパーミェ
ーションクロマトグラフィーで測定した重量平均分子量
（Ｍｗ）が１，０００以上、特に５，０００以上である
ことが好ましい。分子量の測定は、例えば１，２．４−
トリクロロベンゼン溶液として１３５℃において測定し
、ポリプロピレンに換算した分子量として算出される。Since the homopolymer of 4-methylpentene-1 according to the present invention is used for molding, the weight average molecular weight (Mw) measured by gel permeation chromatography is 1,000 or more, especially 5 ,000 or more is preferable. For example, the molecular weight can be measured using 1,2.4-
It is measured as a trichlorobenzene solution at 135°C and calculated as the molecular weight in terms of polypropylene.
また、重合体の重量平均分子量（Ｍｗ）と数平均分子量
（Ｍｎ）との比（Ｍｗ／Ｍｎ）については用途に応じて
Ｚｒ触媒とＨｆ触媒とを混合することで種々の値のもの
を製造することができるが、通常１．５〜２０である。In addition, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (Mw/Mn) can be manufactured with various values by mixing Zr catalyst and Hf catalyst depending on the application. However, it is usually 1.5 to 20.
本発明による４−メチルペンテン−１の共重合体におい
て４−メチルペンテン−１と共重合せしめられるα−オ
レフィンの例は４−メチルペンテン−１を除く炭素数２
−２５のものであり、具体的にはエチレンおよびＨ２（
：Ｊｌ：Ｈ−（ＧＤ３）−Ｃ）Ｉ３（式中ｎは０〜２２
の整数）の直鎖α−オレフィン、具体的には、プロピレ
ン、ブテン−１、ペンテン−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、ト
リデセン−１、ペンタデセン−１、ヘキサデセン−１、
ヘプタデセン−１、オクタデセン−１、エイコセン−１
、ベンタコセン−１など、並びに−（ＧＤ３）、、１１
：Ｈｓ基が枝分かれしたアルキル基であるもの、具体的
には３−メチルブテン−１，４，４−ジメチルペンテン
−１などの枝分かれしたα−オレフィンである。Examples of α-olefins copolymerized with 4-methylpentene-1 in the 4-methylpentene-1 copolymer according to the present invention include 2 carbon atoms, excluding 4-methylpentene-1.
-25, specifically ethylene and H2 (
:Jl:H-(GD3)-C)I3 (in the formula, n is 0 to 22
(an integer of -1, hexadecene-1,
heptadecene-1, octadecene-1, eicosene-1
, bentacocene-1, etc., and -(GD3), 11
: Those in which the Hs group is a branched alkyl group, specifically branched α-olefins such as 3-methylbutene-1,4,4-dimethylpentene-1.
これらのα−オレフィンは１種を用いてもよいし、２種
以上併用することもできる。これらのα−オレフィン単
位は総和で共重合体中に０．１〜３０モル％、好ましく
は０．２〜２５モル％、最も好ましくは０．３〜２０モ
ル％含有される。これらのα−オレフィン単位が３０モ
ル％を越えると剛性が低下するので好ましくない。These α-olefins may be used alone or in combination of two or more. These α-olefin units are contained in the copolymer in a total amount of 0.1 to 30 mol%, preferably 0.2 to 25 mol%, and most preferably 0.3 to 20 mol%. If the content of these α-olefin units exceeds 30 mol %, the rigidity decreases, which is not preferable.
重合は４−メチルペンテン−１以外のα−オレフィン単
量体の重合系への導入量を共重合体中のその他のα−オ
レフィン単位の含量が上記の範囲になるように制御し、
かつ得られる共重合体の１．２．４− トリクロロベン
ゼン溶液で測定した１３Ｃ−ＮＭＲの吸収スペクトルに
おいて、４−メチルペンテン−１単位のテトラメチルシ
ランを基準として約４３．１ｐｐｍに観測される吸収強
度が、約４２〜４４ ｐｐｍに観測される４−メチルペ
ンテン−１単位の吸収強度の０．３以上となるように、
各単量体の量比、重合温度を前記の範囲内で制御するこ
とにより行われる。In the polymerization, the amount of α-olefin monomers other than 4-methylpentene-1 introduced into the polymerization system is controlled so that the content of other α-olefin units in the copolymer is within the above range,
In the 13C-NMR absorption spectrum measured with a 1.2.4-trichlorobenzene solution of the obtained copolymer, an absorption observed at about 43.1 ppm based on 4-methylpentene-1 unit of tetramethylsilane. so that the intensity is 0.3 or more of the absorption intensity of 4-methylpentene-1 unit observed at about 42 to 44 ppm,
This is carried out by controlling the quantitative ratio of each monomer and the polymerization temperature within the above-mentioned ranges.
この共重合体４−メチルペンテン−１の単独重合体と同
様に溶媒洗浄に付して立体規則性を高めることができる
。Similar to the homopolymer of 4-methylpentene-1, this copolymer can be washed with a solvent to improve its stereoregularity.
この４−メチルペンテン−１の立体構造に起因すると考
えられるメチレン基の吸収スペクトルのパターンは従来
知られておらず、これが従来にない物性を有する共重合
体を特徴ずけるものと考えられる。The absorption spectrum pattern of the methylene group, which is thought to be caused by the steric structure of 4-methylpentene-1, has not been previously known, and it is thought that this characterizes the copolymer with unprecedented physical properties.
本発明において、共重合体の分子量としては通常の重合
体として利用できる限り特に制限はないが、通常、成形
樹脂として使用するという点からは１３５℃のテトラリ
ン溶液で測定した極限粘度として０，０５以上、ゲルパ
ーミェーションクロマトグラフィーで測定したプロピレ
ン換算の数平均分子量（Ｍｎ）として約１０００以上、
好ましくは５，０００以上である。また、この共重合体
の重量平均分子量と数平均分子量の比（Ｍｗ／Ｍｎ）は
、好ましくは１．５〜２０である。In the present invention, the molecular weight of the copolymer is not particularly limited as long as it can be used as a normal polymer, but from the point of view of use as a molding resin, the intrinsic viscosity measured in a tetralin solution at 135°C is 0.05. As mentioned above, the number average molecular weight (Mn) in terms of propylene measured by gel permeation chromatography is about 1000 or more,
Preferably it is 5,000 or more. Further, the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) of this copolymer is preferably 1.5 to 20.
本発明による４−メチルペンテン−１の単独重合体の成
形体は比較的もろく通常の物性の測定条件では物性が評
価できず、単独で通常の用途に利用するのは困難と思わ
れる。しかしながら、この重合体を他の重合体とブレン
ドして成形に用いることは、もちろん可能である。The molded product of the 4-methylpentene-1 homopolymer according to the present invention is relatively brittle and its physical properties cannot be evaluated under normal physical property measurement conditions, and it seems difficult to use it alone for general purposes. However, it is of course possible to blend this polymer with other polymers and use it for molding.
一方、４−メチルペンテン−１とその他のα−オレフィ
ンとの本発明による共重合体の成形体は耐衝撃性が良好
であり、かつ剛性と耐？ＩＩ撃性とのバランスが良好で
ある。On the other hand, the molded product of the copolymer of 4-methylpentene-1 and other α-olefins according to the present invention has good impact resistance, and has good rigidity and durability. Good balance with II impact resistance.
［実施例］
以下に、本発明を実施例を示して具体的に説明するが、
これらの実施例は本発明を説明するためのものであり、
限定するものではない。[Example] The present invention will be specifically explained below with reference to Examples.
These examples are intended to illustrate the invention;
It is not limited.
実施例１
常法に従って合成したイソプロピルシクロペンタジェニ
ル−１−フルオレンをリチウム化し、四塩化ジルコニウ
ムと反応させることにより得たイソプロピル（シクロペ
ンタジェニル−１−フルオレニル）ジルコニウムジクロ
リド５ｍｇと、六水和硫酸銅とトリメチルアルミニウム
をトルエン中で反応させることにより得られた重合度約
１５のメチルアルミノキサン０．３４ｇとを、１００ｇ
の４−メチルペンテン−１に添加して内容積３００ｍ１
のフラスコに装入し、２５℃で５時間重合した。得られ
た重合混合物を多量のメタノールに投入してメタノール
不溶分としてポリ４−メチルペンテン−１を５．７ｇ得
た。Example 1 5 mg of isopropyl (cyclopentajenyl-1-fluorenyl) zirconium dichloride obtained by lithiation of isopropylcyclopentajenyl-1-fluorene synthesized according to a conventional method and reacting with zirconium tetrachloride, and hexahydrate. 100 g of 0.34 g of methylaluminoxane with a degree of polymerization of about 15 obtained by reacting copper sulfate and trimethylaluminum in toluene.
When added to 4-methylpentene-1, the internal volume was 300ml.
The mixture was placed in a flask and polymerized at 25°C for 5 hours. The obtained polymerization mixture was poured into a large amount of methanol to obtain 5.7 g of poly-4-methylpentene-1 as a methanol-insoluble component.
ウォターズ■製ＧＰ（：１５０Ｇゲルパーミ・ニージョ
ンクロマトグラフにより１３５℃で測定しポリプロピレ
ン換算の数平均分子量Ｍｎは３５，４００、重量平均分
子量Ｍｗは６４，３００であった。 １，２．４トリク
ロロベンゼン溶液を測定することによって得られた１３
Ｃ−ＮＭＲの吸収スペクトルにおいてテトラメチルシラ
ンを基準とした時の吸収ピークとして２３．４． ２５
．９ 、３１．６． ４３．１および４６．０ｐｐｍに
５本観測された。また示差走査熱量分析装置で１０℃／
ｍｉｎで昇温、降温して測定した融点は２０５．５℃、
結晶化温度は１６９．２℃であった。1,2.4 trichlorobenzene manufactured by Waters ■ GP (measured at 135°C using a 150G gel permeable knee chromatograph, the number average molecular weight Mn in terms of polypropylene was 35,400, and the weight average molecular weight Mw was 64,300. 13 obtained by measuring the solution
In the C-NMR absorption spectrum, the absorption peak is 23.4 when based on tetramethylsilane. 25
．． 9, 31.6. Five lines were observed at 43.1 and 46.0 ppm. In addition, 10℃/
The melting point measured by increasing and decreasing the temperature at 205.5℃,
The crystallization temperature was 169.2°C.
一方、触媒として１．２−エチレンビスインデニルジル
コニウムジクロリドを用いて４−メチルペンテン−１を
重合することにより得られたアイソタクチックポリ４−
メチルペンテン−１につき、上記と同様にして”Ｃ−Ｎ
ＭＲの吸収スペクトルを測定すると、約２３．５． ２
５．９ 、３１．４． ４２．６および４６．０ｐＰｆ
ｆｌにピークが観測された。また融点は２２７．５℃、
結晶化温度は２０７．８℃であった。On the other hand, isotactic poly(4-) obtained by polymerizing 4-methylpentene-1 using 1,2-ethylenebisindenylzirconium dichloride as a catalyst
For methylpentene-1, “C-N
When the MR absorption spectrum was measured, it was approximately 23.5. 2
5.9, 31.4. 42.6 and 46.0 pPf
A peak was observed at fl. Also, the melting point is 227.5℃,
The crystallization temperature was 207.8°C.
主鎖のＣＨ２基に帰属する吸収の４３．１ｐｐｍのシン
ジオタクチックベンタド結合による吸収は、主鎖の０１
１２基に帰属する４３．１ｐｐｍの吸収及び全側鎖のＣ
Ｈ２基のうち主鎖に直接結合したＣＨ２基による吸収に
対し０．８１であった。これらの１３Ｃ−ＮＭＲの吸収
スペクトルの測定結果は第１図に、赤外吸収スペクトル
の測定結果は第２図及び第３図に示す。The absorption due to the syndiotactic bentad bond of 43.1 ppm of the absorption attributed to the CH2 group of the main chain is
Absorption of 43.1 ppm attributed to 12 groups and total side chain C
Of the H2 groups, the absorption due to CH2 groups directly bonded to the main chain was 0.81. The measurement results of these 13C-NMR absorption spectra are shown in FIG. 1, and the measurement results of the infrared absorption spectra are shown in FIGS. 2 and 3.
またＣυ−にα線を用いて測定したＸ線回折の測定結果
を第４図に示す。Furthermore, the results of X-ray diffraction measurements using α rays for Cυ- are shown in FIG.
実施例２
実施例１と同様にして得たイソプロピル（シクロペンタ
ジェニル−１−フルオレニル）ジルコニウムジクロリド
５ｍｇと、東ソーアクゾ■製の重合度約１６のメチルア
ルミノキサン０．６７ｇとを４−メチルペンテン−１４
００ｍ１に溶解し、内容積３００ ｍｌのオートクレー
ブに装入した。３０℃でプロピレンを１０ｇ装入して３
０℃で２時間攪拌し重合させた。未反応のプロピレンを
パージし、多量のメタノールを加え濾別した後８０℃で
減圧乾燥して８２ｇのポリマーを得た。Example 2 5 mg of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride obtained in the same manner as in Example 1 and 0.67 g of methylaluminoxane with a degree of polymerization of about 16 manufactured by Tosoh Akzo ■ were mixed with 4-methylpentene- 14
00ml and charged into an autoclave with an internal volume of 300ml. Charge 10g of propylene at 30℃
The mixture was stirred at 0° C. for 2 hours to polymerize. Unreacted propylene was purged, a large amount of methanol was added, the mixture was filtered, and the mixture was dried under reduced pressure at 80° C. to obtain 82 g of polymer.
１．２．４− トリクロロベンゼン溶液で測定した”Ｃ
−ＮＭＲの吸収スペクトルでは、テトラメチルシランを
基準として約４３．１ｐｐｍに観測される吸収強度は、
約４２．５〜４３．１ｐｐｍの吸収強度の総和の０．８
５であり、またプロピレン単位を８゜Ｏｗｔ％含有して
いた。また、１３５℃テトラリン溶液で測定した極限粘
度（以下ηと略記する。）は０．４０であり、ゲルパー
ミェーションクロマトグラフィーにより１３５℃の１．
２．４− トリクロロベンゼン溶液で測定した重量平均
分子量と数平均分子量の比（Ｍｗ／Ｍｎ）は２．１であ
った。共重合体パウダーを２１０℃でプレス成型し１ｍ
ｍのシートを作製して以下の物性を測定した。1.2.4- “C” measured in trichlorobenzene solution
- In the NMR absorption spectrum, the absorption intensity observed at about 43.1 ppm based on tetramethylsilane is:
0.8 of the total absorption intensity of about 42.5 to 43.1 ppm
5, and contained 8° Owt% of propylene units. Further, the intrinsic viscosity (hereinafter abbreviated as η) measured with a tetralin solution at 135°C was 0.40, and the intrinsic viscosity at 135°C was 1.40 by gel permeation chromatography.
2.4- The ratio of weight average molecular weight to number average molecular weight (Mw/Mn) measured with a trichlorobenzene solution was 2.1. Copolymer powder is press-molded at 210℃ to 1m.
A sheet of m was prepared and the following physical properties were measured.
・引張降伏強さ： ｋｇ／ｃｍ２ＡＳＴＭ Ｈ３８（２
３℃）・伸び：％ ＡＳＴＭ Ｄ６３８
（２３℃）・アイゾツト（ノツチ付）衝撃強度： ｋｇ
−ｃｍ／ｃｍＡＳＴＭ Ｄ２５６（２３℃、
一１０℃）
・ヘイズ：％ ＡＳＴＭ ０１００３引張降
伏強さは４ ｋｇ／ｃｍ２、伸びは５００％以上、アイ
ゾツト衝撃強度は２３℃、−１０℃ともに８０ ｋｇ−
ｃｍ／ｃｍ以上であり、ヘイズは５２％であった。・Tensile yield strength: kg/cm2 ASTM H38 (2
3℃)・Elongation:% ASTM D638
(23℃) Izot (with notch) Impact strength: kg
-cm/cm ASTM D256 (23℃, -10℃) Haze: % ASTM 01003 tensile yield strength is 4 kg/cm2, elongation is 500% or more, Izot impact strength is 80 kg- at both 23℃ and -10℃
cm/cm or more, and the haze was 52%.
実施例３
プロピレン１０ｇにかえエチレン５ｇを用いた他は実施
例２と同様に重合を行った。未反応のエチレンをパージ
し、濾過した後８０℃で減圧乾燥して７４ｇのポリマー
を得た。１，２．４−トリクロロベンゼン溶液で測定し
た”Ｃ−ＮＭＨの吸収スペクトルにおいてテトラメチル
シランを基準として約４３．１ｐｐ１１に観測される吸
収強度は、約４２〜４４ ｐｐｍの吸収強度の総和の０
．７２であり、エチレン単位を２．６ｗｔ！に含有して
いた。また、ηは０．４０あり、Ｍｗ／Ｍｎは２゜１で
あった。Example 3 Polymerization was carried out in the same manner as in Example 2, except that 5 g of ethylene was used instead of 10 g of propylene. Unreacted ethylene was purged, filtered, and dried under reduced pressure at 80° C. to obtain 74 g of polymer. In the absorption spectrum of "C-NMH" measured in a 1,2.4-trichlorobenzene solution, the absorption intensity observed at about 43.1 ppm with respect to tetramethylsilane is 0 of the total absorption intensity of about 42 to 44 ppm.
．． 72, and the ethylene unit is 2.6wt! contained in. Further, η was 0.40, and Mw/Mn was 2°1.
実施例２と同様にして物性を測定した結果、引張降伏強
さは２０５ ｋｇ／ｃｍ２、伸びは６２０％、アイゾツ
ト衝撃強度は２３℃、−１０℃でそれぞれ２０ ｋｇ−
ｃｒｎ ７ｃｍ、８ ｋｇ−ｃｍ／ｃｍであり、ヘイズ
は４８％であった。As a result of measuring the physical properties in the same manner as in Example 2, the tensile yield strength was 205 kg/cm2, the elongation was 620%, and the Izot impact strength was 20 kg- at 23°C and -10°C, respectively.
The crn was 7 cm, 8 kg-cm/cm, and the haze was 48%.
実施例４
プロピレンの使用量を３ｇとした他は実施例２と同様に
して重合を行ったところ、プロピレン単位を２．１ ｗ
ｔ！に含む重合体を７６ｇ得た。１３ｃ −ＮＭＲで測
定した約４３．１ｐｐｍに観測される吸収強度は、約４
２〜４４ ｐｐｍの吸収強度の総和の０．８７であり、
ηは０．４３であり、Ｍｗ／Ｍｎは２．１であった。Example 4 Polymerization was carried out in the same manner as in Example 2 except that the amount of propylene used was 3 g, and the propylene unit was 2.1 w.
T! 76g of the polymer contained in the mixture was obtained. The absorption intensity observed at about 43.1 ppm measured by 13c-NMR is about 4
It is 0.87 of the total absorption intensity of 2 to 44 ppm,
η was 0.43, and Mw/Mn was 2.1.
実施例２と同様にして物性を測定した結果引張降伏強さ
は１８５ ｋｇ／ｃｍ２、伸びは４８０％、アイゾツト
衝撃強度は２３℃、−１０℃でそれぞれ２５ ｋｇ−ｃ
ｍ／ｃｍ、 ６．５ ｋｇ−ｃｍ／ｃｍであり、ヘイズ
は４６％であった。The physical properties were measured in the same manner as in Example 2, and the tensile yield strength was 185 kg/cm2, the elongation was 480%, and the Izot impact strength was 25 kg-c at 23°C and -10°C, respectively.
m/cm, 6.5 kg-cm/cm, and haze was 46%.
第１図は実施例１で得たポリ４−メチルペンテン−１（
ａはシンジオタクチックポリ４−メチルペンテン−１、
ｂはアイソタクチックポリ４−メチルペンテン−１）の
１３Ｃ−ＮＭＲの吸収スペクトル、第２図は実施例１で
得たシンジオタクチックポリ４−メチルペンテン−１の
赤外吸収スペクトル、第３図は実施例１で得たアイソタ
クチックポリ４−メチルペンテン−１の赤外吸収スペク
トル塁耘−１第４図はシンジオタクチックポリ４−メチ
ルペンテン−１のＸ線回折スペクトルである。Figure 1 shows poly-4-methylpentene-1 (
a is syndiotactic poly4-methylpentene-1,
b is the 13C-NMR absorption spectrum of isotactic poly-4-methylpentene-1), FIG. 2 is the infrared absorption spectrum of syndiotactic poly-4-methylpentene-1 obtained in Example 1, and FIG. Figure 4 shows the X-ray diffraction spectrum of syndiotactic poly-4-methylpentene-1.
Claims (1)
単位を０〜３０モル％含有する実質的にシンジオタクチ
ック構造を有する４−メチルペンテン−１の重合体。 ２、１，２，４−トリクロロベンゼン溶液で測定した＾
１＾３Ｃ−ＮＭＲの吸収スペクトルにおいて、テトラメ
チルシランを基準として約４３．１ｐｐｍに観測される
吸収が約４２．０〜４３．５ｐｐｍに観測される吸収強
度の総和の０．５以上であり、ゲルパーミェーションク
ロマトグラフィーで測定した分子量が１．０００以上で
あるシンジオタクチックポリ４−メチルペンテン−１。 ３、１，２，４−トリクロロベンゼン溶液で測定した＾
１＾３Ｃ−ＮＭＲの吸収スペクトルにおいて、テトラメ
チルシランを基準として約４３．１ｐｐｍに観測される
吸収強度が、約４２〜４４ｐｐｍに観測される吸収強度
の総和の０．５以上であり、ゲルパーミエーションクロ
マトグラフィーで測定した分子量が１．０００以上であ
り、かつＸ線回折により面間隔約９Åに最大回折線が観
測される、実質的にシンジオタクチック構造を有する４
−メチルペンテン−１の単独重合体。 ４、１，２，４−トリクロロベンゼン溶液で測定した＾
１＾３Ｃ−ＮＭＲで、４−メチルペンテン−１単位のテ
トラメチルシランを基準として約４３．１ｐｐｍに観測
される吸収強度が、約４２．５〜４３．１ｐｐｍに観測
される４−メチルペンテン−１単位の吸収強度の０．５
以上であり、プロピレン含量が０．１ｗｔ％〜２０ｗｔ
％であり、１３５℃テトラリン溶液で測定した極限粘度
が０．０５以上である４−メチルペンテン−１とプロピ
レンの共重合体。 ５、１，２，４−トリクロロベンゼン溶液で測定した＾
１＾３Ｃ−ＮＭＲの吸収スペクトルにおいて、テトラメ
チルシランを基準として約４３．１ｐｐｍに観測される
４−メチルペンテン−１単位の吸収強度が約４２〜４４
ｐｐｍに観測される４−メチルペンテン−１単位の吸収
強度の総和の０．３以上であり、４−メチルペンテン−
１単位以外のα−オレフィン単位を０．１〜３０モル％
含有し、テトラリン溶液として１３５℃において測定し
た極限粘度が０．０５以上である、実質的にシンジオタ
クチック構造を有する４−メチルペンテン−１とその他
のα−オレフィンとの共重合体。[Scope of Claims] A 4-methylpentene-1 polymer having a substantially syndiotactic structure containing 0 to 30 mol% of α-olefin units other than 1,4-methylpentene-1 units. Measured with 2,1,2,4-trichlorobenzene solution^
In the 1^3C-NMR absorption spectrum, the absorption observed at about 43.1 ppm based on tetramethylsilane is 0.5 or more of the sum of the absorption intensity observed at about 42.0 to 43.5 ppm, Syndiotactic poly-4-methylpentene-1 having a molecular weight of 1.000 or more as measured by gel permeation chromatography. Measured with 3,1,2,4-trichlorobenzene solution^
In the 1^3C-NMR absorption spectrum, the absorption intensity observed at about 43.1 ppm with respect to tetramethylsilane is 0.5 or more of the sum of the absorption intensities observed at about 42 to 44 ppm. 4 having a substantially syndiotactic structure, with a molecular weight of 1.000 or more as measured by cation chromatography, and a maximum diffraction line observed at an interplanar spacing of about 9 Å by X-ray diffraction.
- Homopolymer of methylpentene-1. Measured with 4,1,2,4-trichlorobenzene solution^
In 1^3C-NMR, the absorption intensity observed at about 43.1 ppm based on 4-methylpentene-1 unit of tetramethylsilane is 4-methylpentene- observed at about 42.5 to 43.1 ppm. 0.5 of 1 unit of absorption intensity
or more, and the propylene content is 0.1 wt% to 20 wt
% and has an intrinsic viscosity of 0.05 or more as measured in a tetralin solution at 135°C. Measured with 5,1,2,4-trichlorobenzene solution^
In the 1^3C-NMR absorption spectrum, the absorption intensity of 4-methylpentene-1 unit observed at about 43.1 ppm based on tetramethylsilane is about 42-44
It is 0.3 or more of the total absorption intensity of 1 unit of 4-methylpentene observed in ppm, and 4-methylpentene-
0.1 to 30 mol% of α-olefin units other than 1 unit
A copolymer of 4-methylpentene-1 and other α-olefins having a substantially syndiotactic structure and having an intrinsic viscosity of 0.05 or more when measured as a tetralin solution at 135°C.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/535,535 US5157092A (en) | 1989-06-21 | 1990-06-11 | Polymer of 4-methylpentene-1 |
| EP90111248A EP0405236B1 (en) | 1989-06-21 | 1990-06-14 | Copolymer of 4-methylpentene-1 |
| DE69007550T DE69007550T2 (en) | 1989-06-21 | 1990-06-14 | 4-methylpentene-1 copolymers. |
| CA002019361A CA2019361C (en) | 1989-06-21 | 1990-06-20 | Polymer of 4-methylpentene-1 |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-156706 | 1989-06-21 | ||
| JP15670689 | 1989-06-21 | ||
| JP1-277246 | 1989-10-26 | ||
| JP27724689 | 1989-10-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03200810A true JPH03200810A (en) | 1991-09-02 |
| JP2962770B2 JP2962770B2 (en) | 1999-10-12 |
Family
ID=26484390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2134041A Expired - Lifetime JP2962770B2 (en) | 1989-06-21 | 1990-05-25 | 4-methylpentene-1 polymer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2962770B2 (en) |
| KR (1) | KR930005821B1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005121192A1 (en) * | 2004-06-10 | 2005-12-22 | Mitsui Chemicals, Inc. | Olefin polymer and use thereof |
| JP2007161876A (en) * | 2005-12-14 | 2007-06-28 | Mitsui Chemicals Inc | Olefinic polymer and method for producing the same |
| JP2008509273A (en) * | 2004-08-09 | 2008-03-27 | ダウ グローバル テクノロジーズ インコーポレイティド | Functionalized poly (4-methyl-1-pentene) |
| WO2010023906A1 (en) * | 2008-09-01 | 2010-03-04 | 三井化学株式会社 | 4-methylpentene-1 polymer having syndiotactic structure |
| WO2011078054A1 (en) * | 2009-12-21 | 2011-06-30 | 三井化学株式会社 | PROCESS FOR PRODUCTION OF SYNDIOTACTIC α-OLEFIN POLYMER |
| CN114230701A (en) * | 2022-01-13 | 2022-03-25 | 宁夏清研高分子新材料有限公司 | Preparation method of poly 4-methyl-1-pentene material with narrow molecular weight distribution |
-
1990
- 1990-05-25 JP JP2134041A patent/JP2962770B2/en not_active Expired - Lifetime
- 1990-06-20 KR KR1019900009068A patent/KR930005821B1/en not_active IP Right Cessation
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005121192A1 (en) * | 2004-06-10 | 2005-12-22 | Mitsui Chemicals, Inc. | Olefin polymer and use thereof |
| KR100807767B1 (en) * | 2004-06-10 | 2008-02-28 | 미쓰이 가가쿠 가부시키가이샤 | Olefin polymer and use thereof |
| US7803888B2 (en) | 2004-06-10 | 2010-09-28 | Mitsui Chemicals, Inc. | Olefin-based polymers and uses thereof |
| JP2008509273A (en) * | 2004-08-09 | 2008-03-27 | ダウ グローバル テクノロジーズ インコーポレイティド | Functionalized poly (4-methyl-1-pentene) |
| JP2007161876A (en) * | 2005-12-14 | 2007-06-28 | Mitsui Chemicals Inc | Olefinic polymer and method for producing the same |
| WO2010023906A1 (en) * | 2008-09-01 | 2010-03-04 | 三井化学株式会社 | 4-methylpentene-1 polymer having syndiotactic structure |
| JPWO2010023906A1 (en) * | 2008-09-01 | 2012-01-26 | 三井化学株式会社 | 4-methylpentene-1 polymer having a syndiotactic structure |
| WO2011078054A1 (en) * | 2009-12-21 | 2011-06-30 | 三井化学株式会社 | PROCESS FOR PRODUCTION OF SYNDIOTACTIC α-OLEFIN POLYMER |
| US8716418B2 (en) | 2009-12-21 | 2014-05-06 | Mitsui Chemicals, Inc. | Process for producing syndiotactic α-olefin polymer |
| JP5514838B2 (en) * | 2009-12-21 | 2014-06-04 | 三井化学株式会社 | Method for producing syndiotactic alpha-olefin polymer |
| CN114230701A (en) * | 2022-01-13 | 2022-03-25 | 宁夏清研高分子新材料有限公司 | Preparation method of poly 4-methyl-1-pentene material with narrow molecular weight distribution |
Also Published As
| Publication number | Publication date |
|---|---|
| KR930005821B1 (en) | 1993-06-25 |
| JP2962770B2 (en) | 1999-10-12 |
| KR910000820A (en) | 1991-01-30 |
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