JPH03200814A - Hexene-1 copolymer - Google Patents
Hexene-1 copolymerInfo
- Publication number
- JPH03200814A JPH03200814A JP33820489A JP33820489A JPH03200814A JP H03200814 A JPH03200814 A JP H03200814A JP 33820489 A JP33820489 A JP 33820489A JP 33820489 A JP33820489 A JP 33820489A JP H03200814 A JPH03200814 A JP H03200814A
- Authority
- JP
- Japan
- Prior art keywords
- hexene
- copolymer
- measured
- directly bonded
- main chain
- 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
- 229920001577 copolymer Polymers 0.000 title abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 25
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 18
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 11
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims abstract description 6
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 239000004711 α-olefin Substances 0.000 abstract description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009102 absorption Effects 0.000 abstract 2
- 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 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- PJLHTVIBELQURV-UHFFFAOYSA-N pentadecene Natural products CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はヘキセン−１の共重合体に関する。詳しくは、
特定の構造を有するヘキセン−１と他のα−オレフィン
の共重合体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to copolymers of hexene-1. For more information,
This invention relates to a copolymer of hexene-1 and other α-olefins having a specific structure.
シンジオタクチックポリプロピレンについては古くより
その存在は知られていたが、従来のバナジウム化合物と
エーテルおよび有機アルミニウムからなる触媒で低温重
合する方法はシンジオタクテイシテイ−が悪く、シンジ
オタクチックなポリプロピレンの特徴を表しているとは
言い難く、ましてや他のオレフィンとプロピレンの共重
合体は結晶性のポリプロピレンとは言い雛いものであっ
た。これに対して、Ｊ、＾、 ＥＷＥＮらにより非対称
な配位子を有する遷移金属触媒とアルミツキサンからな
る触媒によってシンジオタクチックペンタッド分率が０
．７を越えるようなタフティシティ−の良好なポリプロ
ピレンを得られることが初めて発見された（Ｊ、Ａｍ、
Ｃｈｅ−、Ｓｏｃ、、１９８Ｂ、１１０．６２５５−６
２５６） 。The existence of syndiotactic polypropylene has been known for a long time, but the conventional low-temperature polymerization method using a catalyst consisting of a vanadium compound, ether, and organoaluminum has poor syndiotacticity, and the characteristics of syndiotactic polypropylene Furthermore, copolymers of other olefins and propylene could hardly be called crystalline polypropylene. On the other hand, a syndiotactic pentad fraction of 0 was achieved using a catalyst consisting of a transition metal catalyst with an asymmetric ligand and alumituxane by J, ^, EWEN et al.
．． It was discovered for the first time that polypropylene with good toughness exceeding 7 could be obtained (J, Am,
Che-, Soc, 198B, 110.6255-6
256).
一方本発明者らによれば上記触媒の純度の高いものを利
用してヘキセン、１を重合すると高シンジオタクテイシ
テイ−を有するポリヘキセン−１が得られることが判明
した。On the other hand, the present inventors have found that polyhexene-1 having high syndiotacticity can be obtained by polymerizing hexene-1 using the above catalyst with high purity.
上記Ｊ、Ａ、ＥＷＥＮらの触媒を利用すると遷移金属当
たりの活性が良好で、しかも得られるポリマーのタフテ
イシテイ−が高いポリヘキセンｌが得られるが、シンジ
オタクチックな構造を保持したへ；トセンーｌの共重合
体は従来に無い特性を有することが期待でき、他のポリ
オレフィンとのブレンド素材などとしても期待できる。When using the catalysts of J, A, and EWEN et al., polyhexene 1 can be obtained which has good activity per transition metal and high toughness of the obtained polymer, but it is possible to obtain polyhexene 1 which maintains a syndiotactic structure; The copolymer is expected to have properties not found in the past, and can also be used as a blend material with other polyolefins.
本発明者らは、上記目的で新しい構造のヘキセン−１の
共重合体について鋭意探索して本発明を完成した。The present inventors have completed the present invention by intensively searching for a copolymer of hexene-1 with a new structure for the above-mentioned purpose.
即ち、本発明は１．２．４− ）リクロロベンゼン溶液
で測定した” Ｃ−ＮＭＲで、ヘキセン−１単位の主鎖
に直接結合した側鎖のメチレン基の吸収のうちテトラメ
チルシランを基準として約３４．４ｐｐｍに観測される
吸収強度が、約３４．４〜３５．３ｐｐ−に観測される
主鎖に直接結合した側鎖のメチレン基の全吸収の吸収強
度の０．３以上であり、ヘキセン−１の含量が５０−Ｌ
％〜９９．９ｗｔχであり、１３５ ’Ｃテトラリン溶
液で測定した極限粘度が０．０５以上であるヘキセン−
１の共重合体である。That is, the present invention is based on 1.2.4-) C-NMR measured in a dichlorobenzene solution, based on tetramethylsilane, of the absorption of the methylene group in the side chain directly bonded to the main chain of hexene-1 unit. The absorption intensity observed at about 34.4 ppm is 0.3 or more of the absorption intensity of the total absorption of the methylene group of the side chain directly bonded to the main chain, which is observed at about 34.4 to 35.3 ppm, The content of hexene-1 is 50-L
Hexene-
It is a copolymer of No. 1.
本発明のヘキセン−１と他のα−オレフィンの共重合体
を製造するに用いる触媒としては、上記文献に記載され
た化合物が例示できるが、異なる構造であってもヘキセ
ン−１の単独重合体を製造した時、得られる重合体の口
Ｃ−Ｎ？ｌＲで、ヘキセン−１単位の主鎖に直接結合し
た側鎖のメチレン基の吸収のうちテトラメチルシランを
基準として約３４．４ｐｐｍに観測される吸収強度が、
約３４．４〜３５．３ｐｐ−に観測される主鎖に直接結
合した側鎖のメチレン基の全吸収の吸収強度が０．５以
上と比較的タフティシティ−が高い重合体を与える触媒
系であれば利用可能であり、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。Examples of the catalyst used for producing the copolymer of hexene-1 and other α-olefins of the present invention include the compounds described in the above-mentioned documents, but homopolymers of hexene-1 may also be used even if they have different structures. When producing C-N? of the obtained polymer? In IR, the absorption intensity observed at about 34.4 ppm based on tetramethylsilane among the absorption of the side chain methylene group directly bonded to the main chain of hexene-1 unit is
A catalyst system that provides a polymer with relatively high toughness, with a total absorption intensity of 0.5 or more for methylene groups in side chains directly bonded to the main chain observed at approximately 34.4 to 35.3 pp-. For example, a catalyst system consisting of a transition metal compound having an asymmetric ligand and aluminoxane is effective.
本発明の共重合体を製造するに好適な触媒系としては上
記文献に記載されたイソプロピル（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、あるい
はイソプロピル（シクＵペンタジェニルー１−フルオレ
ニル）ジルコニウムジクロリドなどが例示され、またア
ルミノキサンとしては、
一般式、Ｒ−（Ａ Ｉ＜ ｏ） 、−Ａ １ｔ−Ｉｔｚ
あるいは口！を武ＲＲ
（式中Ｒは炭素数１〜３の炭化水素残基。）で表される
化合物が例示でき、特にＲがメチル基であるメチルアル
ミノキサンでｎが５以上、好ましくはｌ０以上のものが
利用される。上記遷移金属触媒に対するアル泉ツキサン
の使用割合とし°ζは１０〜１００００００モル倍、通
常５０〜５０００モル倍である。また重合条件について
は特に制限はなく不活性媒体を用いる溶媒重合法、或い
は実質的に不活性媒体の存在しない塊状重合法、気相重
合法も利用できる。 重合温度としては一１００〜２０
０℃、重合圧力としては常圧〜１ＧＧ ｋｇ／ｃｄで行
うのが一般的である。好ましくは一１００〜１００℃、
常圧〜５Ｇｋｇ／Ｃ−である。Catalyst systems suitable for producing the copolymer of the present invention include isopropyl (cyclopentagenyl-1-fluorenyl) hafnium dichloride or isopropyl (cyclopentagenyl-1-fluorenyl) zirconium dichloride described in the above-mentioned literature. Examples of aluminoxane include general formulas, R-(AI<o), -A lt-Itz
Or the mouth! Examples include compounds represented by TakeRR (in the formula, R is a hydrocarbon residue having 1 to 3 carbon atoms), particularly methylaluminoxane where R is a methyl group, and n is 5 or more, preferably 10 or more. is used. The ratio of the aluminium chloride to the above transition metal catalyst is 10 to 1,000,000 times by mole, usually 50 to 5,000 times by mole. Further, there are no particular limitations on the polymerization conditions, and solvent polymerization methods using an inert medium, bulk polymerization methods in which substantially no inert medium is present, and gas phase polymerization methods can also be used. The polymerization temperature is -100 to 20
The polymerization is generally carried out at 0° C. and at a pressure of normal pressure to 1 GG kg/cd. Preferably -100 to 100°C,
Normal pressure to 5Gkg/C-.
本発明において用いるα−オレフィンとしてはエチレン
の他に一般式１１ｉＣ−ＣＩ−（ＣＨ，）−ＣＨｓ （
ａはｌ、２．４以上の整数）あるいは上記−（ＣＨＩ）
−ＣＨＩ３が分岐構造を有するものなどが例示でき炭素
数３〜２５程度のものが利用できる。具体的にはプロピ
レン、ブテン−１、ペンテン−１，ヘプテン−１１オク
テン−１１ノネン−１、デセン−１１ウンデセン−１１
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
などの直鎖α・オレフィンあるいは、３−メチルブテン
−１，４−メチルペンテン−１，４，４−ジメチルペン
テン−１などの分岐α−オレインが例示される。In addition to ethylene, the α-olefin used in the present invention has the general formula 11iC-CI-(CH,)-CHs (
a is l, an integer of 2.4 or more) or the above - (CHI)
Examples include those in which -CHI3 has a branched structure, and those having about 3 to 25 carbon atoms can be used. Specifically, propylene, butene-1, pentene-1, heptene-11 octene-11 nonene-1, decene-11 undecene-11
Dodecene-1, Tridecene-1, Pentadecene-1, Hexadecene-1, Heptadecene-1, Octadecene-1
Examples include straight chain α-olefins such as, and branched α-oleins such as 3-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1.
本発明において、重要なのはヘキセン−１とαオレフィ
ンの重合割合がα−オレフィン含量で０゜１〜５０ｗｔ
χとなるように単量体の重合系への導入量を制御するこ
と、そして共重合の１．２．４− トリクロロベンゼン
溶液で測定した目Ｃ−Ｎ１’ｌＲで、ヘキセン−１単位
の主鎖に直接結合した側鎖のメチレン基の吸収のうちテ
トラメチルシランを基準として約３４．４ＰＰ−に観測
される吸収強度が、約３４．４〜３５．３ｐｐ−に観測
される主鎖に直接結合した側鎖のメチレン基の全吸収の
吸収強度の０．４以上となるように単量体の量比、重合
温度などを制御することでｌ１Ｉａされる。このヘキセ
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。In the present invention, what is important is that the polymerization ratio of hexene-1 and α-olefin is 0°1 to 50wt in terms of α-olefin content.
The amount of monomer introduced into the polymerization system is controlled so that Of the absorption of the methylene group in the side chain directly bonded to the chain, the absorption intensity observed at about 34.4 PP- based on tetramethylsilane is the absorption intensity directly attached to the main chain, which is observed at about 34.4 to 35.3 pp-. l1Ia is achieved by controlling the monomer ratio, polymerization temperature, etc. so that the absorption intensity of the total absorption of the methylene group of the bonded side chain is 0.4 or more. The absorption spectrum pattern of the methylene group, which is thought to be caused by the steric structure of hexene-1, has not been previously known, and this is thought to characterize 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°Ｃ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
ーミニ−シラ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として約１０００以上である。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 usually 0.05. As mentioned above, the number average molecular weight in terms of propylene measured by gel perminisilane chromatography is about 1000 or more.
以下に実施例を示しさらに本発明を説明する。 The present invention will be further explained with reference to Examples below.
実施例１
内容積３００ ｍのオートクレーブで常法に従って台底
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し、さらに
梢製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と東洋
アクゾ■製の重合度約１６のメチルアルミツキサン０．
６７ｇをヘキセン−１１５０ｇに溶解し、３０℃でプロ
ピレンを１００ ｇ挿入して３０°Ｃで２時間攪拌した
。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°Ｃで減圧乾燥して１８０ ｇのポ
リマーを得た。 １．２゜４−トリクロロベンゼン溶液
で測定した口Ｃ−ＮＭＲではテトラメチルシランを基準
として約３４．４ｐｐｍに観測される吸収強度は、約３
４．４〜３５．３ｐｐ■の吸収強度の０．６５であり、
プロピレンを３０．５ｗｔＸ含有していた。また、１３
５°Ｃテトラリン溶液で測定した極限粘度（以下、ηと
記す）は０．７１であり、ゲルパーミニ−シランクロマ
トグラフィーで１３５°Ｃの１．２．４−）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（以下、ＭＷ／ＭＮと記す）は２．１であった。Example 1 In an autoclave with an internal volume of 300 m, isopropylcyclopentadienyl-1fluorene was lithiated using a conventional method, reacted with zirconium tetrachloride, and further processed to obtain isopropyl(cyclopentadienyl-1).
-fluorenyl) 5 mg of zirconium dichloride and 0.0 mg of methylaluminoxane with a degree of polymerization of about 16 manufactured by Toyo Akzo ■.
67g was dissolved in 1150g of hexene, 100g of propylene was added at 30°C, and the mixture was stirred at 30°C for 2 hours. 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 180 g of polymer. In the C-NMR measured with a 1.2° 4-trichlorobenzene solution, the absorption intensity observed at about 34.4 ppm based on tetramethylsilane is about 3
It is 0.65 of the absorption intensity of 4.4 to 35.3 pp■,
It contained 30.5wtX propylene. Also, 13
The intrinsic viscosity (hereinafter referred to as η) measured in a tetralin solution at 5°C is 0.71, and the weight average molecular weight measured in a 1.2.4-)lichlorobenzene solution at 135°C by gel permini-silane chromatography. and the number average molecular weight (hereinafter referred to as MW/MN) was 2.1.
また１ ａｒｍのプレスシートを作製して以下の物性を
測定した。In addition, a 1 arm press sheet was produced and the following physical properties were measured.
・引張降伏強さ： ｋｇ／ｃｊ ＡＳＴＭ Ｄ６３
８ （２３°Ｃ）・伸び：％ ＡＳＴＭ
Ｄ６３８ （２３°Ｃ）・アイゾツト （ノツチ付
）衝撃強度：ｋｇ−ｃ■／ｃｍＡＳＴＭ Ｄ２５６
（２３℃、−１０℃）・ヘイズニ％ ＡＳＴＭ ０１
００３に準拠した。・Tensile yield strength: kg/cj ASTM D63
8 (23°C)・Elongation:% ASTM
D638 (23°C) Izot (with notch) Impact strength: kg-c/cm ASTM D256
(23°C, -10°C) Haze % ASTM 01
Compliant with 003.
引張降伏強さは１ｋｇ／ｃｊ、伸びは６７χ、アイゾツ
ト衝撃強度は２３°Ｃ，−１０℃ともに８０ｋｇ−ｃｍ
／ｃ−以上であり、ヘイズは２３％であった。Tensile yield strength is 1kg/cj, elongation is 67χ, and Izod impact strength is 80kg-cm at both 23°C and -10°C.
/c- or more, and the haze was 23%.
実施例２ ヘキセン−１の使用量を９５ｇとしプロピレンをｌ。Example 2 The amount of hexene-1 used was 95 g, and the amount of propylene was 1.
ｇとした他は実施例１と同様にしたところプロピレン含
量１０．７ｗｔχの共重合体を６５ｇ得た。 ”Ｃ−Ｎ
ＭＲで測定した約３４．４ｐＰｍに観測される吸収強度
は、約３４．４〜３５．３ｐｐ−の吸収強度の０．７８
であり、ηは０．８１であり、ＭＷ／ＭＮは２．２であ
った。The same procedure as in Example 1 was carried out except that 65 g of a copolymer with a propylene content of 10.7 wtχ was obtained. “C-N
The absorption intensity observed at about 34.4 pPm measured by MR is 0.78 of the absorption intensity of about 34.4 to 35.3 pp-.
, η was 0.81, and MW/MN was 2.2.
実施例３
プロピレンに変えエチレンを５ｇ用いた他は実施例２と
同様にしたエチレン含量４．８ｗｔＸの共重合体７２ｇ
を得た。目Ｃ−ＮＭＲで測定した約３４．４ｐｐｍ＋に
観測される吸収強度は、約３４．４〜３５．３ｐｐ−の
吸収強度の０．６５であり、ηは０．６３であり、問／
）ＩＮは２．１であった。Example 3 72 g of a copolymer with an ethylene content of 4.8 wtX made in the same manner as in Example 2 except that 5 g of ethylene was used instead of propylene.
I got it. The absorption intensity observed at about 34.4 ppm+ measured by eye C-NMR is 0.65 of the absorption intensity at about 34.4 to 35.3 pp-, and η is 0.63.
) IN was 2.1.
実施例４
プロピレンに変えブテン−１を用いた他は実施例２と同
様にしたブテン−１含量７．５ｗｔＸの共重合体６２ｇ
を得た。 ”Ｃ−ＮＭＲで測定した約３４．４ｐｐｍに
観測される吸収強度は、約３４．４〜３ｓ、３ｐｐｍの
吸収強度の０．７２であり、ηは０．４８であり、問／
ＭＮは２．０であった。Example 4 62 g of a copolymer with a butene-1 content of 7.5 wtX, which was prepared in the same manner as in Example 2 except that butene-1 was used instead of propylene.
I got it. "The absorption intensity observed at about 34.4 ppm measured by C-NMR is about 34.4~3s, 0.72 of the absorption intensity at 3 ppm, and η is 0.48.
MN was 2.0.
本発明の共重合体は種々の用途に利用が期待でき工業的
に極めて価値がある。The copolymer of the present invention can be expected to be used for various purposes and is extremely valuable industrially.
Claims (1)
３ＣＮＭＲで、ヘキセン−１単位の主鎖に直接結合した
側鎖のメチレン基の吸収のうちテトラメチルシランを基
準として約３４．４ｐｐｍに観測される吸収強度が、約
３４．４〜３５．３ｐｐｍに観測される主鎖に直接結合
した側鎖のメチレン基の全吸収の吸収強度の０．３以上
であり、ヘキセン−１の含量が５０ｗｔ％〜９９．９ｗ
ｔ％であり、１３５℃テトラリン溶液で測定した極限粘
度が０．０５以上であるヘキセン−１の共重合体。Measured with 1,2,4-trichlorobenzene solution ^1^
In 3CNMR, the absorption intensity observed at about 34.4 ppm based on tetramethylsilane among the absorption of the side chain methylene group directly bonded to the main chain of hexene-1 unit is about 34.4 to 35.3 ppm. It is 0.3 or more of the total absorption intensity of the observed methylene group of the side chain directly bonded to the main chain, and the content of hexene-1 is 50 wt% to 99.9 w.
t% and has an intrinsic viscosity of 0.05 or more as measured in a tetralin solution at 135°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33820489A JP2919521B2 (en) | 1989-10-26 | 1989-12-28 | Hexene-1 copolymer |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27724789 | 1989-10-26 | ||
| JP1-277247 | 1989-10-26 | ||
| JP33820489A JP2919521B2 (en) | 1989-10-26 | 1989-12-28 | Hexene-1 copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03200814A true JPH03200814A (en) | 1991-09-02 |
| JP2919521B2 JP2919521B2 (en) | 1999-07-12 |
Family
ID=26552313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33820489A Expired - Fee Related JP2919521B2 (en) | 1989-10-26 | 1989-12-28 | Hexene-1 copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2919521B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446117A (en) * | 1993-08-19 | 1995-08-29 | Queen's University At Kingston | Process for producing amorphous syndiotactic polystyrene |
-
1989
- 1989-12-28 JP JP33820489A patent/JP2919521B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446117A (en) * | 1993-08-19 | 1995-08-29 | Queen's University At Kingston | Process for producing amorphous syndiotactic polystyrene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2919521B2 (en) | 1999-07-12 |
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