JPH02173013A - Polymer - Google Patents
PolymerInfo
- Publication number
- JPH02173013A JPH02173013A JP32619288A JP32619288A JPH02173013A JP H02173013 A JPH02173013 A JP H02173013A JP 32619288 A JP32619288 A JP 32619288A JP 32619288 A JP32619288 A JP 32619288A JP H02173013 A JPH02173013 A JP H02173013A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- ethylene
- toluene
- polycyclic
- solvent
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 125000003367 polycyclic group Chemical group 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 8
- 238000005266 casting Methods 0.000 abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- ZTHNOZQGTXKVNZ-UHFFFAOYSA-L dichloroaluminum Chemical compound Cl[Al]Cl ZTHNOZQGTXKVNZ-UHFFFAOYSA-L 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- -1 3-pentadiene Chemical class 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- PDCHSSDBMXIYIJ-UHFFFAOYSA-N cyclopenta-1,3-diene;1h-indene Chemical compound C1C=CC=C1.C1=CC=C2CC=CC2=C1 PDCHSSDBMXIYIJ-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 101100497923 Viola odorata Voc1 gene Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229920005567 polycyclic polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 101150075827 sra-12 gene Proteins 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は透明性、耐熱性に優れ、かつ溶剤に可溶な新規
な重合体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel polymer that has excellent transparency and heat resistance and is soluble in solvents.
〔従来の技術］
従来、透明性が良く耐熱性にすぐれるオレフィン系ポリ
マーとしては、１−４．５・８−ジメタノ−１，２，３
，４，４ａ、５．８．８ａ−オクタヒドロナフタレン類
（ＤＭＯＮ類）とエチレンとからなるランダム共重合体
（特開昭６０−１６８７０８号公報等）が知られている
が、この重合体は、溶剤に対する溶解性に劣るため、溶
剤を利用したキャスト法等の成形法が利用できないとい
う欠点を有していた。[Prior Art] Conventionally, as an olefin polymer with good transparency and excellent heat resistance, 1-4.5.8-dimethanol-1,2,3 has been used.
, 4, 4a, 5.8.8a - A random copolymer consisting of octahydronaphthalenes (DMONs) and ethylene (Japanese Unexamined Patent Application Publication No. 168708/1984, etc.) is known, but this polymer However, since the solubility in solvents is poor, molding methods such as casting methods using solvents cannot be used.
［発明が解決しようとする課題］
本発明の目的は透明性および耐熱性にすぐれ、溶媒を利
用したキャスト法等の成形法が利用できる重合体を提供
することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide a polymer that has excellent transparency and heat resistance and can be used in molding methods such as casting using a solvent.
［課題を解決するための手段］
そこで、本発明者らはかかる欠点を改良すべく鋭意研究
を重ねた結果、特定の構造を持つ多環モノマーをエチレ
ンと共正合させることにより透明性、耐熱性にすぐれ、
溶媒に可溶な重合体かえられることを見出し、本発明に
到達した。[Means for Solving the Problems] Therefore, the present inventors have conducted extensive research in order to improve these drawbacks, and as a result, by co-merging a polycyclic monomer with a specific structure with ethylene, transparency and heat resistance can be improved. Excellent sex,
The inventors have discovered that a polymer soluble in a solvent can be changed, and have arrived at the present invention.
すなわち下記−形式（りで示される多環モノ（ｎ：１〜
５の整数）
及びエチレンとからなる共重合体であって、多環モノマ
ー／エチレンの組成比が９９／１〜１／９９（モル１モ
ル）であり、３０℃、トルエン中で８−１定した極限粘
度がｏ、ｏｏｉ〜１０ｄｊ！／ｒである重合体に関する
。That is, polycyclic mono (n: 1 to
5) and ethylene, the polycyclic monomer/ethylene composition ratio is 99/1 to 1/99 (1 mole), and the copolymer has a constant of 8-1 in toluene at 30°C. The intrinsic viscosity is o, ooi~10dj! /r.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で使用される多環モノマーは、インデンとシクロ
ペンタジェンのＤｉｅｔｓ−Ａｌｄｅｒ反応により合成
でき、反応するシクロペンタジェンの数によりｎは決定
される。ｎ−１の場合、多環モノマーの名称は１・４−
メタノ−１，４，４ａ＋９ａ−テトラヒドロフルオレン
である。The polycyclic monomer used in the present invention can be synthesized by Diets-Alder reaction of indene and cyclopentadiene, and n is determined by the number of cyclopentadiene reacted. In the case of n-1, the name of the polycyclic monomer is 1,4-
Methanol-1,4,4a+9a-tetrahydrofluorene.
さらに、本発明の重合体の特徴を損なわないかぎり、第
３成分として重合可能なモノマーを使用することができ
る。この共重合可能なモノマーとしては、たとえば、プ
ロピレン、ブテン−１等のα−オレフィン、スチレン、
メチルスチレン等のスチレン類、シクロペンテン、シク
ロヘキセン等のシクロオレフィン、ノルボルネン、ジシ
クロペンタジェン等の多環モノマー類、ブタジェン、１
゜３−ペンタジェン等のジエン類、シクロオクタジエン
、エチリデンノルボルネン等の環状又は多環ジエン類を
挙げることができる。このｔ８３成分として使用可能な
モノマーの使用量は多環モノマーに対し５０ｍｏ １％
以下であることが好ましい。Furthermore, as long as the characteristics of the polymer of the present invention are not impaired, a polymerizable monomer can be used as the third component. Examples of the copolymerizable monomer include propylene, α-olefins such as butene-1, styrene,
Styrenes such as methylstyrene, cycloolefins such as cyclopentene and cyclohexene, polycyclic monomers such as norbornene and dicyclopentadiene, butadiene, 1
Examples include dienes such as 3-pentadiene, and cyclic or polycyclic dienes such as cyclooctadiene and ethylidene norbornene. The amount of monomer that can be used as this t83 component is 50mo 1% based on the polycyclic monomer.
It is preferable that it is below.
本発明の重合体を製造するためには、多環上ツマ−とエ
チレンとを通常のチーグラー触媒を使用して重合すれば
よい。In order to produce the polymer of the present invention, a polycyclic polymer and ethylene may be polymerized using a conventional Ziegler catalyst.
遷移金属成分としては、−形式ＴｉＸｎ−ｍ（ＯＲ）ｍ
（ｎ ： ３または４．ｍ：０成ｍ≦ｎ。As a transition metal component, -form TiXn-m(OR)m
(n: 3 or 4. m: 0 m≦n.
Ｒ；炭素数１〜１２の炭化水素残基、Ｘ：へロゲン）で
示されるＴＩ化合物又は、−形式ＶＸｓ。R: a hydrocarbon residue having 1 to 12 carbon atoms, X: herogen) or -form VXs.
ＶＯＸｔ （ＯＲ）ｓ−ｔ （ｓ ： ３または４．ｔ
：０≦ｔ≦３．Ｒ：炭素数１〜１２の炭化水素残基。VOXt (OR)s-t (s: 3 or 4.t
:0≦t≦3. R: Hydrocarbon residue having 1 to 12 carbon atoms.
Ｘ：ハロゲン）で示されるＶ化合物が使用できる。A V compound represented by (X: halogen) can be used.
具体的には、ＴｉＣｌ３．ＴｉＢｒ３゜ＴｉＣｌ４．Ｔ
ｉＢｒ４．Ｔｌ （ＯＣＨｌ）４゜Ｔｉ（ＯＣ２Ｈう）
４．Ｔｌ （ＱＣｓ Ｈｔ ）ｓ 。Specifically, TiCl3. TiBr3°TiCl4. T
iBr4. Tl (OCHL)4゜Ti (OC2H)
4. Tl(QCsHt)s.
Ｔｉ （ＱＣ４Ｈｅ ）ａ 、Ｔｌ （ＯＣ６Ｈｔ３）
４ 。Ti (QC4He)a, Tl (OC6Ht3)
4.
Ｔｉ （ＯＣＨ３）！ 、ＴＩ （ＯＣ２Ｈ５）ｓ 。Ti (OCH3)! , TI (OC2H5)s.
ＴＬ （ＯＣＩ Ｈｔ）ｓ、ＶＣｌｉ、ＶＢｒ３゜Ｖ
ＣＩ ａ 、 Ｖ Ｂ ｒ ４ 、 Ｖ ＯＣ１ｍ 、
Ｖ ＯＢ ｒ ３ 。TL (OCI Ht)s, VCli, VBr3°V
CIa, VBr4, VOC1m,
VOBr3.
ＶＯＣ１２（ＯＣＨ３）。VOC12 (OCH3).
ＶＯＣｌ ２ （ＯＣ２Ｈｓ ） 。VOCl 2 (OC2Hs).
ＶＯＣ１２（ＯＣＩ Ｈｅ ）。VOC12 (OCI He).
ＶＯＣｌ ｚ （ＯＣ４Ｈｅ ） ｊＶＯＣ１２（Ｏ
Ｃ６ＨＩＭ） 。VOCl z (OC4He ) jVOC12(O
C6HIM).
ＶＯＣｌ （ＯＣＩ３）２ 。VOCl (OCI3)2.
ＶＯＣ１（ＯＣ２Ｈｓ ） ２ 。VOC1 (OC2Hs) 2.
ＶＯＣｌ （ＱＣｓ Ｈｔ ） ２ 。VOCl (QCs Ht) 2.
ＶＯＣＩ Ｃ０Ｃ４Ｈｑ ）２ 。VOCI C0C4Hq)2.
ＶＯＣＩ Ｃ０Ｃ６ＨＩ３）２等が使用できる。VOCI C0C6HI3)2 etc. can be used.
有機金属成分としては一般式ＡＩＸｕＲ３−ｕ（ｕ：０
≦Ｕ≦２．Ｒ：炭素数１〜１２の炭化水素残基、Ｘ：ハ
ロゲン）で示される有機アルミニウム化合物が使用され
る。The organometallic component has the general formula AIXuR3-u (u:0
≦U≦2. An organoaluminum compound represented by R: a hydrocarbon residue having 1 to 12 carbon atoms, X: halogen is used.
具体的には、Ａ ｌ （ＣＨ３） ｓ 。Specifically, A1 (CH3) s.
Ａｌ （Ｃ２Ｈｓ） ３．ＡＩ （ＣＩ Ｈｔ）３
゜Ａｌ （Ｃ４Ｈｅ ） ３． ＡＩ （Ｃ６ＨＩ３
） ＊ 。Al (C2Hs) 3. AI (CI Ht)3
゜Al (C4He) 3. AI (C6HI3
) *.
Ａｌ （Ｃｓ Ｈ１？）ｓ、ＡｌＣｌ （ＣＨ３）
２゜ＡｌＣｌ （Ｃ２Ｈｓ）２゜
ＡｌＣｌ （Ｃｉ Ｈｙ）ｚ。Al (Cs H1?)s, AlCl (CH3)
2゜AlCl (C2Hs) 2゜AlCl (Ci Hy)z.
ＡｌＣｌ （Ｃ４Ｉ（９）２゜ Ａ Ｉ ＣＩ （Ｃ６Ｈ＋ｉ） ２ 。AlCl (C4I(9)2゜ A I CI (C6H+i) 2.
ＡｌＣｌ （Ｃ１ｌＨＩ？）２゜
ＡｌＢｒ （（Ｈ３）２．ＡｌＢｒ （Ｃ２Ｈ％）２゜
ＡｌＢｒ （Ｃｉ Ｈｙ） ２゜
ＡＩＢｒ（Ｃ４Ｈ＊）ｚ。AlCl (C1lHI?)2°AlBr ((H3)2.AlBr (C2H%)2°AlBr (Ci Hy) 2°AIBr(C4H*)z.
Ａ Ｉ Ｂ ｒ （Ｃａ Ｈｒｓ） ｚ ＋Ａ ｔＢｒ
（ＣｓＨ＋７） ２ 。A I B r (Ca Hrs) z +A tBr
(CsH+7) 2 .
Ａ １２ Ｃ１３（ＣＨｉ ） ！ 。A 12 C13 (CHi)! .
Ａ１２ Ｃ１３（Ｃｚ Ｈｓ）ｓ。A12 C13 (Cz Hs)s.
Ａ１２ Ｃ１３（Ｃ３Ｈ７）３ 。A12 C13 (C3H7)3.
Ａ１２ Ｃ１３（Ｃ４Ｈ９） ｓ 。A12 C13 (C4H9) s.
Ａ １２ Ｃｌｉ （Ｃ６ＨＩ３）３ 。A 12 Cli (C6HI3) 3.
Ａ １ ２ Ｃ１） （Ｃ８ＨＩＴ） ３
。A 1 2 C1) (C8HIT) 3
.
Ａ １２ Ｂ ｒ３ （ＣＨｉ ） ３
＋ＡｌｚＢｒｓ （ＣｚＨ５）ｉ。A 12 B r3 (CHi) 3
+AlzBrs(CzH5)i.
Ａ１２ Ｂｒｉ （Ｃ３Ｈ？）ｓｒＡ １２
Ｂ ｒ３ （Ｃ４Ｈ９） ３−Ａ １２ Ｂ
ｒ ３ （Ｃ６ＨＩ３） ３ ＋Ａ １２
Ｂ ｒｉ （Ｃ８ＨＩ７） ３ 。A12 Bri (C3H?)srA 12
B r3 (C4H9) 3-A 12 B
r 3 (C6HI3) 3 +A 12
B ri (C8HI7) 3 .
ＡｌＣｌ２ （ＣＨ３）、 ＡｌＣｌ２ （Ｃ２
Ｈ５）。AlCl2 (CH3), AlCl2 (C2
H5).
Ａ ＩＣ１２（Ｃ３Ｈ７）。A IC12 (C3H7).
ＡｌＣｌ２ （Ｃ４Ｈ９）、 ＡＩＣ１２（Ｃ６１
１３）ＡｌＣｌ２ （Ｃｓ Ｈａｔ）、 ＡｌＢ
ｒ２ （ＣＨ３）ＡｌＢｒ２（ＣｚＨラ ）。AlCl2 (C4H9), AIC12 (C61
13) AlCl2 (Cs Hat), AlB
r2(CH3)AlBr2(CzHra).
ＡｌＢｒ ２ （ＣｉＨ７）、 ＡｌＢｒ２ （Ｃ
４Ｈ９）等を例示できる。AlBr2 (CiH7), AlBr2 (C
4H9) etc. can be exemplified.
遷移金属成分と有機金属成分との混合は、Ａｌ／（Ｔｉ
及び／又はｖ）で１〜１０００（モル比）の範囲で行え
ば良い。The mixture of the transition metal component and the organometallic component is Al/(Ti
and/or v) in a range of 1 to 1000 (molar ratio).
重合に際し、多環モノマーを溶媒兼コモノマーとして用
いることもできるが、更に不活性溶媒を用いることもで
きる。この不活性溶媒としては、当該技術分野で通常用
いられるものであればいずれも使用できるが、特に炭素
数４〜２０の脂肪族炭化水素、芳香族炭化水素、／１０
ゲン化炭化水素を用いることができる。より具体的には
、ヘキサン、ヘプタン、ペンタン、オクタン、デカン、
シクロヘキサン、ベンゼン、トルエン、キシレン。During polymerization, a polycyclic monomer can be used as a solvent and a comonomer, but an inert solvent can also be used. As this inert solvent, any solvent commonly used in the technical field can be used, but in particular, aliphatic hydrocarbons having 4 to 20 carbon atoms, aromatic hydrocarbons, /10
Generated hydrocarbons can be used. More specifically, hexane, heptane, pentane, octane, decane,
Cyclohexane, benzene, toluene, xylene.
クロルベンゼン、二塩化エチレン、灯油などが挙げられ
る。Examples include chlorobenzene, ethylene dichloride, and kerosene.
触媒の使用量は、ＴＩ及び／又はＶとして０．００１〜
１０００１００Ｏ／溶媒ｇ、好ましくは０．０１〜１０
０ｍｍｏ １／溶媒ｇである。The amount of catalyst used is from 0.001 to TI and/or V.
1000100O/g of solvent, preferably 0.01-10
0 mmo 1/g of solvent.
重合条件は特に限定されないが、重合温度としては、例
えば−７８〜３００℃、重合圧力としては、１〜２００
ｋｇ／ｃｄＧ、重合時間としては、１分〜２４時間の範
囲である。また、分子量調節のため適宜、水素などのよ
うな分子量調節剤の存在下で重合させることもできる。The polymerization conditions are not particularly limited, but the polymerization temperature is, for example, -78 to 300°C, and the polymerization pressure is 1 to 200°C.
kg/cdG and polymerization time range from 1 minute to 24 hours. In addition, polymerization can be carried out in the presence of a molecular weight regulator such as hydrogen, if necessary, to control the molecular weight.
このようにして得られたｍ合体は、溶剤に易溶である。The m-coalescence thus obtained is easily soluble in a solvent.
溶解のために使用可能な溶剤としては、例えば、ベンゼ
ン、トルエン等の芳香族炭化水素又は、クロロホルム、
０−ジクロロベンゼン等のハロゲン化炭化水素が使用で
きる。Examples of solvents that can be used for dissolution include aromatic hydrocarbons such as benzene and toluene, chloroform,
Halogenated hydrocarbons such as 0-dichlorobenzene can be used.
又、本発明の重合体には必要に応じて充填剤、安定剤、
帯電防止剤、滑剤、酸化防止剤などの各種添加剤を添加
してもよい。In addition, the polymer of the present invention may contain fillers, stabilizers,
Various additives such as antistatic agents, lubricants, and antioxidants may be added.
［実施例］
以下、本発明を実施例によって更に具体的に説明を行う
が、本発明はこれらの実施例によって同等限定されるも
のではない。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the same extent by these Examples.
実施例１
充分に窒素置換した１ｆＩ丸底フラスコにトルエン５０
０ｍ１．インデン・シクロペンタジェン１：１反応物（
ｎ−１）３０ｇおよびエチルアルミニウムセスキクロラ
イド１０ｍｍｏｌを加えた。さらにガス吹き込み管から
エチレン３０ρ／ ｈ ｒ 。Example 1 50% of toluene was added to a 1fI round bottom flask that was sufficiently purged with nitrogen.
0m1. Indene-cyclopentadiene 1:1 reactant (
30 g of n-1) and 10 mmol of ethylaluminum sesquichloride were added. Furthermore, 30 ρ/hr of ethylene was added from the gas blowing pipe.
窒素６０ ｊ！ ／ ｈ ｒからなる混合ガスを吹き込
み、系内を０℃に設定後、ジクロロメトキシバナジウム
ｌ、１ｍｍｏｌを圧入して共重合を開始した。Nitrogen 60j! After blowing a mixed gas consisting of /hr and setting the inside of the system at 0°C, 1 mmol of dichloromethoxyvanadium was introduced under pressure to start copolymerization.
３０分後、塩酸−エタノールを注入して重合を停止した
。内容物は多量のメタノールに投入して析出した生成物
は濾過後乾燥した。After 30 minutes, hydrochloric acid-ethanol was injected to stop the polymerization. The contents were poured into a large amount of methanol, and the precipitated product was filtered and dried.
収量は２１．３ｇ、”Ｃ−ＮＭＲスペクトルで求めたポ
リマー中のエチレン含量は７３モル％、示差熱走査熱量
計（セイコー電子製、商品名ｒＤｓｃ２００Ｊ）で求め
たＴｇは１２８℃であり、３０℃、トルエン溶液中での
極限粘度［η］は０．３６ｄｊ）／ｇであった。またこ
のポリマーはクロロホルム、トルエン、ベンセンに１ｍ
ｇ／ｍＯで溶解した。The yield was 21.3 g, the ethylene content in the polymer determined by C-NMR spectrum was 73 mol%, and the Tg determined by a differential thermal scanning calorimeter (manufactured by Seiko Electronics, trade name rDsc200J) was 128 °C, 30 °C , the intrinsic viscosity [η] in a toluene solution was 0.36 dj)/g.This polymer was dissolved in chloroform, toluene, and benzene for 1 m
g/mO.
実施例２
エチレン５４）／ｈｒ、窒素１（ｌからなる混合ガスを
吹き込んだ以外は実施例１のとおりに行った。収量は１
６．９ｇ、ポリマー中のエチレン含量は６７モル２６、
Ｔｇは１３９℃、トルエン溶液中での極限粘度は０．２
９ｄｊ）／ｇであった。またこのポリマーはクロロホル
ム、トルエン、ベンセンに１ｍｇ／ｍｌ！で溶解した。Example 2 The procedure was as in Example 1 except that a mixed gas consisting of ethylene 54)/hr and nitrogen 1 (l) was blown in. The yield was 1
6.9 g, ethylene content in the polymer is 67 moles26,
Tg is 139℃, intrinsic viscosity in toluene solution is 0.2
9dj)/g. Also, this polymer is 1mg/ml in chloroform, toluene, and benzene! It was dissolved in
実施例３
インデン・シクロペンタジェン１：２反応物（ｎ＝２）
を使用した以外は実施例１のとおりに行った。収量は２
０．６ｇｘポリマー中のエチレン含量は７２モル％、Ｔ
ｇは１４１℃、トルエン溶液中での極限粘度は０．４１
ｄＮ／ｇであった。Example 3 Indene-cyclopentadiene 1:2 reactant (n=2)
The procedure was as in Example 1 except that . Yield is 2
Ethylene content in 0.6gx polymer is 72 mol%, T
g is 141℃, intrinsic viscosity in toluene solution is 0.41
dN/g.
またこのポリマーはクロロホルム、トルエン、ベンセン
に１ｍｇ／ｍｊｐで溶解した。Further, this polymer was dissolved in chloroform, toluene, and benzene at a concentration of 1 mg/mjp.
［発明の効果］
本発明により、透明性および耐熱性にすぐれ、劣化によ
る若色などを引き起こすことなく成形できる溶剤を利用
したキャスト法等の成形法が利用できる重合体が提供で
きる。[Effects of the Invention] According to the present invention, it is possible to provide a polymer that has excellent transparency and heat resistance, and can be molded without causing premature discoloration due to deterioration and can be molded by a molding method such as a casting method using a solvent.
本発明の重合体は、以上の特徴から、光学用レンズ、光
ディスクなどの光学分野、電子レンジ用食器、コーヒー
メーカー アイロン水タンクなどの家庭用電気電子分野
、ビーカー、メスシリンダー フラスコなどの理化学分
野、注射器、医療ｎｊコネクター、輸血セットなどの医
療分野など各種の成形品として広範な分野で使用するこ
とが可能である。Due to the above characteristics, the polymer of the present invention can be used in the optical field such as optical lenses and optical discs, in the household electrical and electronic fields such as microwave tableware, coffee makers and iron water tanks, and in the physical and chemical fields such as beakers, measuring cylinders, and flasks. It can be used in a wide range of fields as various molded products such as syringes, medical NJ connectors, blood transfusion sets, and other medical fields.
特許出願人 東ソー株式会社Patent applicant: Tosoh Corporation
Claims (1)
式、化学式、表等があります▼（ I ） （ｎ：１〜５の整数） 及びエチレンとからなる共重合体であって、多環モノマ
ー／エチレンの組成比が９９／１〜１／９９（モル／モ
ル）であり、３０℃、トルエン中で測定した極限粘度が
０．００１〜１０ｄｌ／ｇである重合体。(1) A polycyclic monomer represented by the general formula (I) below▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) A copolymer consisting of (n: an integer from 1 to 5) and ethylene, A polymer having a ring monomer/ethylene composition ratio of 99/1 to 1/99 (mol/mol) and an intrinsic viscosity of 0.001 to 10 dl/g measured in toluene at 30°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32619288A JPH02173013A (en) | 1988-12-26 | 1988-12-26 | Polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32619288A JPH02173013A (en) | 1988-12-26 | 1988-12-26 | Polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02173013A true JPH02173013A (en) | 1990-07-04 |
Family
ID=18185051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32619288A Pending JPH02173013A (en) | 1988-12-26 | 1988-12-26 | Polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02173013A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020196835A (en) * | 2019-06-05 | 2020-12-10 | 三井化学株式会社 | Molding and medical container |
| US20220064369A1 (en) * | 2018-12-27 | 2022-03-03 | Mitsui Chemicals, Inc. | Cyclic olefin copolymer for medical instrument, cyclic olefin copolymer composition for medical instrument, and molded body |
-
1988
- 1988-12-26 JP JP32619288A patent/JPH02173013A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220064369A1 (en) * | 2018-12-27 | 2022-03-03 | Mitsui Chemicals, Inc. | Cyclic olefin copolymer for medical instrument, cyclic olefin copolymer composition for medical instrument, and molded body |
| JP2020196835A (en) * | 2019-06-05 | 2020-12-10 | 三井化学株式会社 | Molding and medical container |
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