JP2009052058A5 - - Google Patents
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- JP2009052058A5 JP2009052058A5 JP2008314091A JP2008314091A JP2009052058A5 JP 2009052058 A5 JP2009052058 A5 JP 2009052058A5 JP 2008314091 A JP2008314091 A JP 2008314091A JP 2008314091 A JP2008314091 A JP 2008314091A JP 2009052058 A5 JP2009052058 A5 JP 2009052058A5
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 43
- 239000005977 Ethylene Substances 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 30
- -1 polypropylene Polymers 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229920001155 polypropylene Polymers 0.000 claims description 19
- 229920001400 block copolymer Polymers 0.000 claims description 18
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 17
- 238000010828 elution Methods 0.000 claims description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000005194 fractionation Methods 0.000 claims description 8
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-Dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229940117389 Dichlorobenzene Drugs 0.000 claims description 2
- 230000001747 exhibiting Effects 0.000 claims description 2
- 150000008040 ionic compounds Chemical class 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000000737 periodic Effects 0.000 claims description 2
- 230000000630 rising Effects 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 2
- 238000004132 cross linking Methods 0.000 claims 1
- 238000005227 gel permeation chromatography Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 230000001681 protective Effects 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 6
- 241000282941 Rangifer tarandus Species 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-Dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-EICOSENE Drugs 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-Hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-Methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical compound CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N Decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N Hafnium Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N Octadecene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N Pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N icos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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Description
本発明者らは、上記目的を達成すべく鋭意研究を行った結果、少なくとも２種の異なる立体特異性を示すメタロセン化合物とアルミノキサン化合物および／または非配位性イオン化合物からなる触媒の存在下に、ポリプロピレン成分とプロピレンとエチレンとの共重合体成分とをそれぞれ段階的に特定量製造したブロック共重合体の開発に成功し、かかるブロック共重合体が、上記目的をすべて満たすことを見出し本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have found that in the presence of a catalyst composed of a metallocene compound, an aluminoxane compound and / or a non-coordinating ion compound exhibiting at least two different stereospecificities. , the found that successful the copolymer component of the polypropylene component and the propylene and ethylene with the development of each stepwise specific amount produced block copolymer, such a block copolymer, satisfy all of the above objects Completed the invention.
即ち、本発明は、少なくとも２種の異なる立体特異性を示すメタロセン化合物とアルミノキサン化合物および／または非配位性イオン化合物からなる触媒の存在下にポリプロピレン成分とプロピレンとエチレンとの共重合体成分をそれぞれ段階的に製造してなり、ポリプロピレン成分とプロピレンとエチレンとの共重合体成分とから構成され、ｏ−ジクロロベンゼン溶媒を用いた温度昇温溶離分別法による８０℃までの温度で溶出する成分が全体の４０〜９９重量％で、８０℃以上の温度で溶出する成分が、全体の６０〜１重量％で、ＡＳＴＭ−Ｄ１２３８に準拠して２３０℃、２．１６ｋｇ荷重下で測定されるメルトフローレートが０．０１〜５０ｇ／１０分であるプロピレン系ブロック共重合体を提供する。
また、本発明は、ポリプロピレン成分とプロピレンとエチレンとの共重合体成分とから構成され、ｏ−ジクロロベンゼン溶媒を用いた温度昇温溶離分別法による８０℃までの温度で溶出する成分が全体の４０〜９９重量％で、８０℃以上の温度で溶出する成分が、全体の６０〜１重量％で、ＡＳＴＭ−Ｄ１２３８に準拠して２３０℃、２．１６ｋｇ荷重下で測定されるメルトフローレートが０．０１〜５０ｇ／１０分であるプロピレン系ブロック共重合体を提供する。
本発明は、上記ポリプロピレン系ブロック共重合体を成形してなるフィルムを提供する。
That is, the present invention is a copolymer component of the polypropylene component and the propylene and ethylene with the presence of a catalyst comprising a metallocene compound showing at least two different stereospecificity and aluminoxane compound and / or a non-coordinating ionic compound Are produced in stages, and are composed of a polypropylene component and a copolymer component of propylene and ethylene, and are eluted at a temperature up to 80 ° C. by a temperature-temperature elution fractionation method using an o-dichlorobenzene solvent. Ingredients account for 40-99% by weight of the total, and components eluting at a temperature of 80 ° C. or higher are measured at 60-1% by weight of the total, at 230 ° C. under a load of 2.16 kg according to ASTM-D1238 A propylene-based block copolymer having a melt flow rate of 0.01 to 50 g / 10 min is provided .
In addition, the present invention is composed of a polypropylene component and a copolymer component of propylene and ethylene, and the components eluting at a temperature up to 80 ° C. by the temperature rising elution fractionation method using an o-dichlorobenzene solvent are entirely contained. The component that elutes at a temperature of 40 to 99% by weight at a temperature of 80 ° C. or higher is 60 to 1% by weight of the total, and the melt flow rate measured under a load of 230 ° C. and 2.16 kg according to ASTM-D1238 Provided is a propylene-based block copolymer of 0.01 to 50 g / 10 min.
The present invention provides a film formed by molding the above polypropylene-based block copolymer.
本発明のプロピレン系ブロック共重合体は、ポリプロピレン成分と、プロピレンとエチレンとの共重合体成分とから構成される。 Propylene block copolymer of the present invention is composed of a polypropylene component, a copolymer component of propylene and ethylene Len.
上記ポリプロピレン成分とプロピレンと、エチレンとの共重合体成分との比率は、ｏ−ジクロロベンゼンを溶媒として用いた温度昇温溶離分別（以下ＴＲＥＦという）法による溶出曲線から求められる溶出成分量によって特定することができる。 And propylene to the polypropylene component, the ratio of the copolymer component of ethylene Len, by elution component weight determined from the elution curve by o- temperature rise elution fractionation using dichlorobenzene as a solvent (hereinafter referred to as TREF) method Can be identified.
即ち、ポリプロピレン成分は、ＴＲＥＦ法による溶出曲線において主として８０℃以上の溶出成分からなる。また、プロピレンとエチレンとの共重合体成分は、主として８０℃に至るまでの温度で溶出する成分からなる。 That is, the polypropylene component mainly comprises an elution component at 80 ° C. or higher in the elution curve by the TREF method. Further, the copolymer component of propylene and ethylene Len consists components eluted at temperatures up to mainly 80 ° C..
本発明において、本発明の効果である柔軟性、低温耐衝撃性、耐熱性、透明性、応力緩和性に優れるという特徴は、ポリプロピレン成分と、プロピレンとエチレンとの共重合体成分の構成比率を間接的に表すＴＲＥＦ法で測定した溶出成分の比率（結晶性の分布）が極めて重要である。 In the present invention, flexibility is the effect of the present invention, low-temperature impact resistance, heat resistance, transparency, is characterized of excellent stress relaxation properties, and polypropylene component, propylene and the component ratio of the copolymer component of ethylene Len The ratio of the eluted components (crystallinity distribution) measured by the TREF method that indirectly represents is extremely important.
本発明のプロピレン系ブロック共重合体において、８０℃以上での溶出成分（以下、高温溶出成分という）は、プロピレン単位含有量が９７〜１００重量％であることが好ましい。具体的には、高温溶出成分は、プロピレンの単独重合体、或いはプロピレンを主成分とし、エチレンよりなる単量体単位が３重量％以下、好ましくは１．５重量％以下、更に好ましくは１重量％以下のランダム共重合体であることが、耐熱性が良好となるため好ましい。 In the propylene-based block copolymer of the present invention, the elution component at 80 ° C. or higher (hereinafter referred to as a high temperature elution component) preferably has a propylene unit content of 97 to 100% by weight. Specifically, the high temperature eluting component, a propylene homopolymer, or a main component of propylene monomer units is 3 wt% consisting of ethylene Len or less, preferably 1.5 wt% or less, more preferably A random copolymer of 1% by weight or less is preferable because heat resistance is improved.
本発明のプロピレン系ブロック共重合体において、８０℃までの温度で溶出する成分（以下、低温溶出成分という）は、プロピレンとエチレンとの共重合体であることが好ましい。 In the propylene block copolymer of the present invention, components eluted at temperatures up to 80 ° C. (hereinafter, referred to as low-temperature eluting component) is preferably a copolymer of propylene and ethylene Len.
また、上記プロピレンとエチレンとの共重合体は、製品に柔軟性、低温耐衝撃性、透明性、応力緩和性を有効に付与するために、プロピレンとエチレンとをランダム共重合してなる共重合体であることが好ましい。 Further, a copolymer of the propylene and ethylene Len, flexible products, low-temperature impact resistance, transparency, in order to effectively impart stress relaxation properties, formed by random copolymerization of propylene and ethylene Len A copolymer is preferred.
低温溶出成分中のエチレン単位含有量は、柔軟性、透明性、耐熱性、低温耐衝撃性、応力緩和性を勘案すると４〜５０重量％であることが好ましい。さらには５〜２０重量％、より好ましくは６〜１５重量％のエチレン単位を含む主に低結晶性のプロピレン系共重合体である。 Ethylene Ren unit content in the low-temperature eluting component, flexibility, transparency, heat resistance, low-temperature impact resistance, it is preferred that the stress relaxation properties 4-50 wt% In consideration of. Furthermore 5-20 wt%, more preferably predominantly low-crystalline propylene copolymer containing ethylene lens unit 6 to 15 wt%.
本発明のプロピレン系樹脂組成物は、樹脂成分として、上記したポリプロピレン成分およびプロピレンとエチレンの共重合体成分に加えて、本発明のプロピレン系樹脂組成物の効果を阻害しない範囲で、例えば５重量％以下の範囲で他のα−オレフィンの重合体を成分として含んでいてもよい。α−オレフィンとしては、１−ブテン、１−ペンテン、３−メチル−１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、４，４−ジメチル−１−ペンテン、１−ヘプテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、３−エチル−１−ヘキセン、４−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン等を例示することができる。 Propylene resin composition of the present invention, as a resin component, in addition to the copolymer component of the polypropylene component and the propylene and ethylene Ren described above, in a range not impairing the effect of the propylene resin composition of the present invention, for example 5 Another α-olefin polymer may be contained as a component in the range of not more than% by weight. Examples of the α-olefin include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene, 4- Methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-octadecene, 1-eicosene and the like can be exemplified.
アイソタクチックな立体特異性を有するメタロセン化合物は、公知の化合物が何ら制限なく使用できるが、その中でも下記一般式（１）で表されるキラルなラセミ型の化合物を好適に用いることができる。
Ｑ（Ｃ５Ｈ４−ｍＲ１ ｍ）（Ｃ５Ｈ４−ｎＲ２ ｎ）ＭＸ１Ｘ２ （１）
（式中、Ｍは、周期律表第ＩＶｂ族の遷移金属原子を示す。（Ｃ５Ｈ４−ｍＲ１ ｍ）、（Ｃ５Ｈ４−ｎＲ２ ｎ）は置換シクロペンタジエニル基を示し、ｍおよびｎは、１〜３の整数であり、Ｒ１およびＲ２は、互いに同一でも異なっていてもよく、炭素原子数が１〜２０の炭化水素基、ケイ素含有炭化水素基、またはシクロペンタジエニル環上の２個の炭素原子と結合して炭化水素基で置換されていてもよい１つ以上の炭化水素環を形成している炭化水素基である。Ｑは、（Ｃ５Ｈ４−ｍＲ１ ｍ）および（Ｃ５Ｈ４−ｎＲ２ ｎ）を架橋可能な基であって、２価の、炭化水素基、非置換シリレン基または炭化水素置換シリレン基である。Ｘ１およびＸ２は、同一または異なっていてもよく水素、ハロゲンまたは炭化水素基を示す。）
より好ましくは、上記式（１）において、Ｍがジルコニウム、ハフニウム原子であり、Ｒ１、Ｒ２が同一もしくは異なる炭素数１〜２０の炭化水素基、Ｘ１およびＸ２が、同一もしくは異なるハロゲン原子または炭化水素基、Ｑが、炭化水素置換シリレン基であるキラルなラセミ型のメタロセン化合物が好適である。
（Ｃ ５ Ｈ ４−ｍ Ｒ １ ｍ ）および（Ｃ ５ Ｈ ４−ｎ Ｒ ２ ｎ ）は、具体的には２−メチル−ベンズインデニル基が挙げられる。
As the metallocene compound having isotactic stereospecificity, known compounds can be used without any limitation. Among them, a chiral racemic compound represented by the following general formula (1) can be preferably used.
Q (C 5 H 4-m R 1 m) (C 5 H 4-n R 2 n) MX 1 X 2 (1)
(In the formula, M represents a transition metal atom of Group IVb of the periodic table. (C 5 H 4-m R 1 m ) and (C 5 H 4-n R 2 n ) are substituted cyclopentadienyl groups. M and n are integers of 1 to 3, and R 1 and R 2 may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, Or a hydrocarbon group which is bonded to two carbon atoms on the cyclopentadienyl ring to form one or more hydrocarbon rings which may be substituted with a hydrocarbon group, Q is (C 5 H 4-m R 1 m ) and (C 5 H 4-n R 2 n ) are crosslinkable groups, and are divalent hydrocarbon groups, unsubstituted silylene groups, or hydrocarbon-substituted silylene groups. .X 1 and X 2 are the same or different and have good hydrogen, halogen or hydrocarbon Are shown.)
More preferably, in the above formula (1), M is a zirconium or hafnium atom, R 1 and R 2 are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and X 1 and X 2 are the same or different halogens. A chiral racemic metallocene compound in which an atom or a hydrocarbon group and Q is a hydrocarbon-substituted silylene group is preferred.
(C 5 H 4-m R 1 m) and (C 5 H 4-n R 2 n) , specifically 2-methyl - include benzindenyl group.
成分［Ｉ］および成分［ＩＩ］からなる触媒の存在下にポリプロピレン成分（Ａ）とプロピレンと少なくとも２個以上の非共役のビニル基を有する化合物とエチレンとの共重合体成分（Ｂ）を段階的に製造する方法において、必要に応じて有機アルミニウム化合物（以下成分［ＩＩＩ］と略す）を併用することもできる。成分［ＩＩＩ］は、一般式（５）で表わされる化合物である。 Component [I] and the component compounds in the presence of a catalyst consisting of [II] the polypropylene component (A) and propylene having at least two non-conjugated vinyl groups and a copolymer component of ethylene-les emission (B) Can be used in combination with an organoaluminum compound (hereinafter abbreviated as component [III]) as necessary. Component [III] is a compound represented by general formula (5).
ポリプロピレン成分の重合は、プロピレン単独または、本発明の要件を満足する範囲内でのプロピレンと、エチレンの混合物を供給して実施すればよい。ポリプロピレン成分の重合における重合温度は、０〜１００℃、好ましくは、２０〜８０℃の範囲から採用することが好適である。 The polymerization of the polypropylene component is propylene alone or a propylene in the range satisfying the requirements of the present invention may be carried out by feeding a mixture of ethylene Ren. The polymerization temperature in the polymerization of the polypropylene component is 0 to 100 ° C, preferably 20 to 80 ° C.
上記ポリプロピレン成分を得るための重合に続いて、プロピレンとエチレンのランダム共重合が行われる。プロピレンとエチレンとのランダム共重合は、プロピレン自身を溶媒とするスラリー重合の場合には前記プロピレン重合に引き続いてエチレンガスを供給することで、また気相重合の場合はプロピレンとエチレンの混合ガスを供給することで実施される。 Following polymerization for obtaining the polypropylene component, the random copolymer of propylene and ethylene Len is performed. Random copolymer of propylene and ethylene Len, in the case of slurry polymerization of propylene itself as a solvent by feeding ethylene gas subsequent to the propylene polymer, also in the case of gas phase polymerization mixture of propylene and ethylene Len This is done by supplying gas.
本発明のプロピレンとエチレンのランダム共重合ではプロピレン重合に続いて１段のランダム共重合を行うことが好ましいが、エチレンの供給濃度を多段階に変化させて製造することもできる。プロピレンとエチレンのランダム共重合の重合温度は、０〜１００℃、好ましくは、２０〜８０℃の範囲から採用することが好適である。また、必要に応じて分子量調節剤として水素を用いることもでき、その際の水素濃度を多段階または連続的に変化させて重合を実施することもできる。 The random copolymerization of propylene and ethylene Len of the invention it is preferable to carry out the random copolymerization of one stage following the propylene polymer can also be prepared by changing the feed concentration of ethylene Ren in multiple stages. The polymerization temperature for a random copolymer of propylene and ethylene Len, 0 to 100 ° C., preferably, it is preferred to employ the range of 20 to 80 ° C.. Further, if necessary, hydrogen can be used as a molecular weight regulator, and the polymerization can be carried out by changing the hydrogen concentration at that time in multiple steps or continuously.
プロピレンとエチレンのランダム共重合は回分式、半回分式、連続式のいずれの方法でもよく、重合を多段階に分けて実施することもできる。また、本工程の重合は、スラリー重合、気相重合、溶液重合のいずれの方法を採用してもよい。 Propylene and random copolymerization batch of ethylene Ren, semi-batch, may be any method of continuous, it may be performed separately polymerized in multiple stages. Further, the polymerization in this step may employ any method of slurry polymerization, gas phase polymerization, and solution polymerization.
参考例１
実施例１の前段で重合時間を６０分、後段重合における気相エチレン濃度を７．１ｍｏｌ％とするとともに、液化ブテン−１を気相ブテン−１濃度で５．０ｍｏｌ％まで張り込み、重合時間を８０分とした以外は実施例１と同様に行った。結果を表１、表２に示す。
Reference example 1
The polymerization time was 60 minutes in the former stage of Example 1, the gas phase ethylene concentration in the latter stage polymerization was 7.1 mol%, and liquefied butene-1 was added to 5.0 mol% in the gas phase butene-1 concentration. The same operation as in Example 1 was performed except that the time was 80 minutes. The results are shown in Tables 1 and 2.
Claims (12)
Ｑ（２−メチル−ベンズインデニル）Q (2-methyl-benzindenyl) ２2 ＭＸMX １1 ＸX ２2
（式中、Ｍは、周期律表第ＩＶｂ族の遷移金属原子を示す。Ｑは、２−メチル−ベンズインデニル基および２−メチル−ベンズインデニル基を架橋可能な基であって、２価の、炭化水素基、非置換シリレン基または炭化水素置換シリレン基である。Ｘ(In the formula, M represents a transition metal atom of Group IVb of the periodic table. Q is a group capable of cross-linking 2-methyl-benzindenyl group and 2-methyl-benzindenyl group, A hydrogen group, an unsubstituted silylene group or a hydrocarbon-substituted silylene group, X. １1 およびＸAnd X ２2 は、同一または異なっていてもよく水素、ハロゲンまたは炭化水素基を示す。）で表される化合物である請求項２に記載のプロピレン系ブロック共重合体。May be the same or different and each represents a hydrogen, halogen or hydrocarbon group. The propylene-based block copolymer according to claim 2, which is a compound represented by
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| JP36901799A Division JP2001181360A (en) | 1999-12-27 | 1999-12-27 | Propylene block copolymer |
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