JPH0813823B2 - Dimethanooctahydronaphthalene derivative having organic silyl group - Google Patents
Dimethanooctahydronaphthalene derivative having organic silyl groupInfo
- Publication number
- JPH0813823B2 JPH0813823B2 JP63121746A JP12174688A JPH0813823B2 JP H0813823 B2 JPH0813823 B2 JP H0813823B2 JP 63121746 A JP63121746 A JP 63121746A JP 12174688 A JP12174688 A JP 12174688A JP H0813823 B2 JPH0813823 B2 JP H0813823B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- organic silyl
- silyl group
- dimethanooctahydronaphthalene
- derivative
- 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.)
- Expired - Lifetime
Links
- XBFJAVXCNXDMBH-GEDKWGBFSA-N molport-035-785-283 Chemical class C1[C@@H](C23)C=C[C@H]1C3[C@@H]1C[C@H]2CC1 XBFJAVXCNXDMBH-GEDKWGBFSA-N 0.000 title claims description 17
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- -1 silicon nitride compound Chemical class 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- CHHWNYBAWJMTRY-UHFFFAOYSA-N 1,2,2-tributoxyethenylsilane Chemical compound CCCCOC([SiH3])=C(OCCCC)OCCCC CHHWNYBAWJMTRY-UHFFFAOYSA-N 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
- UCMZDKNUMKBJAA-UHFFFAOYSA-N 2,2-diethoxyethenyl(methyl)silane Chemical compound C[SiH2]C=C(OCC)OCC UCMZDKNUMKBJAA-UHFFFAOYSA-N 0.000 description 1
- QRWXZUPBHVGCNF-UHFFFAOYSA-N 2-butoxyethenyl(dimethyl)silane Chemical compound C(CCC)OC=C[SiH](C)C QRWXZUPBHVGCNF-UHFFFAOYSA-N 0.000 description 1
- IDYHGSXNTVTKAC-UHFFFAOYSA-N 2-methoxyethenyl(dimethyl)silane Chemical compound COC=C[SiH](C)C IDYHGSXNTVTKAC-UHFFFAOYSA-N 0.000 description 1
- KDDUIBSPBYQWCE-UHFFFAOYSA-N 5-propyloct-4-en-4-ylsilane Chemical compound C(CC)C(=C(CCC)CCC)[SiH3] KDDUIBSPBYQWCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- VHZMTMWDTJSOAB-UHFFFAOYSA-N dimethyl(2-propoxyethenyl)silane Chemical compound C(CC)OC=C[SiH](C)C VHZMTMWDTJSOAB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- HBWGDHDXAMFADB-UHFFFAOYSA-N ethenyl(triethyl)silane Chemical compound CC[Si](CC)(CC)C=C HBWGDHDXAMFADB-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 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
- 229920005672 polyolefin resin Polymers 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は基材材料などに用いられるピリオレフィン重
合体に関し、特に金属あるいは無機絶縁物との接着性が
良好なポリオレフィン重合体の製造に好適な有機シリル
基を有する新規なジメタノオクタヒドロナフタレン誘導
体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a pyriolefin polymer used as a base material and the like, and is particularly suitable for producing a polyolefin polymer having good adhesion to a metal or an inorganic insulator. To a novel dimethanooctahydronaphthalene derivative having a novel organic silyl group.
［従来の技術］ 近年、透明性に優れたポリオレフィン重合体または共
重合体の製造に、ジメタノオクタヒドロナフタレン誘導
体が用いられている。（特開昭60−168708号公報）。し
かし、この従来のポリオレフィン重合体は、銅などの金
属や窒化シリコンなどの無機絶縁物との接着性に劣ると
いう欠点があった。[Prior Art] In recent years, a dimethanooctahydronaphthalene derivative has been used for producing a polyolefin polymer or copolymer having excellent transparency. (JP-A-60-168708). However, this conventional polyolefin polymer has a drawback that it is inferior in adhesiveness to a metal such as copper and an inorganic insulator such as silicon nitride.
［発明が解決しようとする課題］ 本発明者らは、従来のポリオレフィン重合体が金属や
無機絶縁物との接着性に劣るという欠点を解決するため
に鋭意研究を重ねた結果、オレフィンと有機シリル基を
有するジメタノオクタヒドロナフタレン誘導体とを共重
合させることにより、窒化ケイ素化合物などの無機絶縁
物、金属や接着剤などとの接着性が極めて良好で、高い
ガラス転移温度を有するポリオレフィン共重合体が得ら
れることを見い出した。[Problems to be Solved by the Invention] As a result of intensive studies conducted by the present inventors in order to solve the drawback that conventional polyolefin polymers have poor adhesiveness to metals and inorganic insulators, olefins and organosilyl groups have been investigated. By copolymerizing with a dimethanooctahydronaphthalene derivative having a group, a polyolefin copolymer having excellent adhesion to an inorganic insulator such as a silicon nitride compound, a metal or an adhesive, and a high glass transition temperature I found that
本発明の目的は、高いガラス転移温度を有し、かつ接
着性の優れたポリオレフィン共重合体を製造することの
できる新規な化合物である有機シリル基を有するジメタ
ノオクタヒドロナフタレン誘導体を提供することにあ
る。An object of the present invention is to provide a dimethanooctahydronaphthalene derivative having an organic silyl group, which is a novel compound having a high glass transition temperature and capable of producing a polyolefin copolymer having excellent adhesiveness. It is in.
［課題を解決するための手段］ 上記本発明の目的は、 一般式 （但し、式中、Ｒは炭素原子数１〜５個のアルキル基、
Ｘはハロゲン原子、炭素原子数１〜５個のアルコキシ基
のうちより選択される置換基、ｌは０〜３を表わす。） で示される有機シリル基を有するジメタノオクタヒド
ロナフタレン誘導体を用いることにより、達成される。[Means for Solving the Problems] The object of the present invention is to provide a compound represented by the general formula: (In the formula, R is an alkyl group having 1 to 5 carbon atoms,
X represents a substituent selected from a halogen atom and an alkoxy group having 1 to 5 carbon atoms, and l represents 0 to 3. ) Is achieved by using a dimethanooctahydronaphthalene derivative having an organic silyl group represented by
また、本発明の有機シリル基を有するジメタノオクタ
ヒドロナフタレン誘導体は、 一般式 （式中、Ｒは炭素原子数１〜５個のアルキル基を表わ
す。） で示される化合物を用いることができる。The dimethanooctahydronaphthalene derivative having an organic silyl group of the present invention has the general formula (In the formula, R represents an alkyl group having 1 to 5 carbon atoms).
さらに、本発明の有機シリル基を有するジメタノオク
タヒドロナフタレン誘導体は、 一般式 （式中、Ｒは炭素原子数１〜５個のアルキル基、Ｒ′は
メチル基、エチル基、プロピル基、ブチル基のうちより
選択される置換基、ｌは１または２を表わす。） で示される化合物であってもよい。Furthermore, the dimethanooctahydronaphthalene derivative having an organosilyl group of the present invention has the general formula (In the formula, R is an alkyl group having 1 to 5 carbon atoms, R'is a substituent selected from a methyl group, an ethyl group, a propyl group, and a butyl group, and l represents 1 or 2.) It may be a compound shown.
［作用］ 本発明の有機シリル基を有するジメタノオクタヒドロ
ナフタレン誘導体の合成法は、まず、（ｉ）ロバート・
エフ・カニオ「シクロペンタジエンによるα、β不飽和
トリハローシランのディールスーアンダー反応（ジエン
合成）」「Robert F.Cunio「The Diels−Alder Reactio
n of α，β−Unsaturated Trihalosilanes with Cyclo
penta−diene」（J.Org・chem.,Vol.36（1971）No.7,p.
929）］の文献に示されている合成法に従い、次に示す
反応式（１）で示されるビシクロ［2,2,1］ヘプト−２
−エン−５イル−シラン（bicyclo［2,2,1］hept−２−
ene−５−y1−silane）を合成し、 次に、（ii）エス・ビー・ソロウェイ「溶融ノールカ
ンフェンシステムの立体化学」（S.B.Soloway「The St
ereochemistry of Fused Norcamphane Systems」（J.A
m.Chem.Soc.,Vol.74（1952）,p.1072）の文献に示され
ている合成法に従い、次に示す反応式（２）によって有
機シリル基を有するジメタノオクタヒドロナフタレンが
合成される。[Operation] The synthesis method of the dimethanooctahydronaphthalene derivative having an organic silyl group of the present invention is as follows.
F. Canio "Decaus-under reaction of α, β-unsaturated trihalosilane with cyclopentadiene (diene synthesis)""Robert F. Cunio" The Diels-Alder Reactio
n of α, β-Unsaturated Trihalosilanes with Cyclo
penta-diene '' (J.Org.chem., Vol.36 (1971) No.7, p.
929)], the bicyclo [2,2,1] hept-2 represented by the following reaction formula (1) is used.
-En-5yl-silane (bicyclo [2,2,1] hept-2-
ene-5-y1-silane), Next, (ii) S. B. Soloway, "Stereochemistry of Molten Norcamphene System" (SB Soloway, "The St.
ereochemistry of Fused Norcamphane Systems "(JA
m.Chem.Soc., Vol.74 (1952), p.1072) was used to synthesize dimethanooctahydronaphthalene having an organic silyl group by the following reaction formula (2). To be done.
本発明の有機シリル基を有するジメタノオクタヒドロ
ナフタレンの合成に用いられるジエン化合物として、シ
クロペンタジエン、ジシクロペンタジエンが挙げられ
る。 Examples of the diene compound used in the synthesis of the dimethanooctahydronaphthalene having an organic silyl group of the present invention include cyclopentadiene and dicyclopentadiene.
また、一般的CH2＝CHSiRlX3-lで示される化合物とし
て、例えば、トリメチルビニルシラン、トリエチルビニ
ルシラン、トリプロピルビニルシラン、ジメチルメトキ
シビニルシラン、ジメチルエトキシビニルシラン、ジメ
チルプロポキシビニルシラン、ジメチルブトキシビニル
シラン、メチルジメトキシシラン、メチルジエトキシビ
ニルシラン、メチルジプロポキシビニルシラン、メチル
ジブトキシビニルシラン、トリメトキシビニルシラン、
トリエトキシビニルシラン、トリプロポキシビニルシラ
ン、トリブトキシビニルシラン、トリクロロビニルシラ
ン、メチルジクロロビニルシラン、ジメチルクロロビニ
ルシランなどが挙げられる。Further, as a compound represented by general CH 2 = CHSiR l X 3-l , for example, trimethylvinylsilane, triethylvinylsilane, tripropylvinylsilane, dimethylmethoxyvinylsilane, dimethylethoxyvinylsilane, dimethylpropoxyvinylsilane, dimethylbutoxyvinylsilane, methyldimethoxysilane. , Methyldiethoxyvinylsilane, methyldipropoxyvinylsilane, methyldibutoxyvinylsilane, trimethoxyvinylsilane,
Examples thereof include triethoxyvinylsilane, tripropoxyvinylsilane, tributoxyvinylsilane, trichlorovinylsilane, methyldichlorovinylsilane and dimethylchlorovinylsilane.
シクロペンタジエンとCH2＝CHSiRlX3-l化合物との反
応は、不活性ガス雰囲気の加圧（1.0〜10kg/cm2）下
で、160〜180℃の温度で約５〜15時間で反応は完了す
る。反応温度は、好ましくは160〜170℃である。不活性
ガスとしては、窒素ガスまたはアルゴンガスが挙げられ
る。The reaction between cyclopentadiene and CH 2 ＝ CHSiR l X 3-l compound is carried out under pressure (1.0 to 10 kg / cm 2 ) in an inert gas atmosphere at a temperature of 160 to 180 ° C for about 5 to 15 hours. Is complete. The reaction temperature is preferably 160 to 170 ° C. Examples of the inert gas include nitrogen gas and argon gas.
シクロペンタジエンとCH2＝CHSiRlX3-l化合物との反
応は等モルでディールス−アルダー（Diels−Alder）反
応を行うが、好ましくは、シクロペンタジエンをやや過
剰に用いてディールス−アルダー反応を行う方がよい。The reaction between cyclopentadiene and a CH 2 ═CHSiR l X 3-l compound is carried out in an equimolar manner and a Diels-Alder reaction is carried out, but preferably, a Diels-Alder reaction is carried out with a slight excess of cyclopentadiene. Better.
［実施例］ 以下に本発明の実施例を挙げ、さらに詳細に説明す
る。[Examples] Examples of the present invention will be described below in more detail.
（１）５エキソ−、５エンド−トリメチルシリルビシク
ロ［2,2,1］ヘプト−２−エンの合成。(1) Synthesis of 5 exo-5, endo-trimethylsilylbicyclo [2,2,1] hept-2-ene.
トロメチルビニルシラン220g（2.2モル）やや過剰の
シクロペンタジエン160g（2.42モル）を１のオートク
レーブに入れ、窒素ガそスを導入して初圧を1.6kg/cm2
とし、165〜175℃の温度で６時間20分保持した（最高圧
力9.9kg/cm2）。オートクレーブ容器を冷却後、反応生
成物370gを取り出した。反応生成物300gを採取して減圧
蒸留した。軽量分85.0g、BP66.5〜70.5℃/20〜22mmHg、
合成成分187.7g（収率55％）、残渣物24.0gを得た。220 g (2.2 mol) of tromethylvinylsilane, 160 g (2.42 mol) of cyclopentadiene in a slight excess were placed in an autoclave of 1, and nitrogen gas was introduced to bring the initial pressure to 1.6 kg / cm 2
And maintained at a temperature of 165-175 ° C. for 6 hours and 20 minutes (maximum pressure 9.9 kg / cm 2 ). After cooling the autoclave container, 370 g of the reaction product was taken out. 300 g of the reaction product was collected and distilled under reduced pressure. Light weight 85.0g, BP66.5-70.5 ℃ / 20-22mmHg,
187.7 g of synthetic components (55% yield) and 24.0 g of residue were obtained.
（２）２−トリメチルシリル−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の合成。(2) 2-trimethylsilyl-1,4,5,8-dimethano-1,
Synthesis of 2,3,4,4a, 5,8,8a-octahydronaphthalene.
５エキソ−、５エンド−トリメチルシリルビシクロ
［2,2,1］ヘプト−２−エン150g（0.9モル）と、やや過
剰のシクロペンタジエン88.3g（1.34モル）を１のオ
ートクレーブに入れ、窒素ガスを導入して初圧を5kg/cm
2として、175〜185℃の温度に12時間保った（最高圧力
9.5kg/cm2）。オートクレープ容器を冷却後、反応生成
物227gを取出した。この反応生成物中の不溶解分をろ過
し、少量のヘキサンで洗い流して、ろ液223gを採取し、
フラスコに入れて減圧蒸留した。軽量分73.0g、BP120〜
130℃/3mmHg留分98.3g（収率65.5％）、残渣物54.2gを
得た。150 g (0.9 mol) of 5 exo-, 5 endo-trimethylsilylbicyclo [2,2,1] hept-2-ene and 88.3 g (1.34 mol) of cyclopentadiene in a slight excess were placed in 1 autoclave, and nitrogen gas was introduced. And the initial pressure is 5 kg / cm
2 was maintained at a temperature of 175-185 ℃ for 12 hours (maximum pressure
9.5 kg / cm 2 ). After cooling the autoclave container, 227 g of the reaction product was taken out. The insoluble matter in this reaction product was filtered, rinsed with a small amount of hexane, and 223 g of the filtrate was collected,
It was put in a flask and distilled under reduced pressure. Light weight 73.0g, BP120 ~
130 ° C./3 mmHg fraction 98.3 g (yield 65.5%) and a residue 54.2 g were obtained.
（３）ポリオレフィン樹脂の合成（重合） 充分乾燥した3lの、三の口フラスコに攪拌羽根、ガス
導入管、温度計をとりつけ、反応容器内を充分に窒素ガ
スで置換した。このフラスコに脱水乾燥したトルエン10
0mlを入れた。次に、窒素ガスを流しながらVOCl3を0.4
ミリモル、２−トリメチルシリル−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8.7g
（0.0374モル）を入れ、フラスコを液体窒素で冷して真
空脱気を２回繰返した。滴下ロートにエチルアルミニウ
ムセスキクロリドを４ミリモル入れた。(3) Synthesis (Polymerization) of Polyolefin Resin A well-dried 3 l three-necked flask was equipped with a stirring blade, a gas introduction tube and a thermometer, and the inside of the reaction vessel was sufficiently replaced with nitrogen gas. Dehydrated and dried toluene 10 in this flask
I added 0 ml. Then, while flowing nitrogen gas, VOCl 3 is adjusted to 0.4
Mmol, 2-trimethylsilyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene 8.7 g
(0.0374 mol) was charged, the flask was cooled with liquid nitrogen, and vacuum degassing was repeated twice. 4 mmol of ethyl aluminum sesquichloride was added to the dropping funnel.
次に、ガス導入管を通してエチレンガス35l/h、窒素
ガス150l/hの混合ガスを10℃に保持したフラスコに10分
間通しながら、滴下ロートからエチルアルミニウムセス
キクロリドを滴下して共重合反応を開始し、60分間重合
した。得られたポリマ溶液にメタノール5mlを加えて重
合反応を停止した。Next, while passing a mixed gas of 35 l / h of ethylene gas and 150 l / h of nitrogen gas through a gas introduction pipe through a flask kept at 10 ° C for 10 minutes, ethyl aluminum sesquichloride was added dropwise from the dropping funnel to start the copolymerization reaction. And polymerized for 60 minutes. 5 ml of methanol was added to the obtained polymer solution to stop the polymerization reaction.
反応停止後の重合溶液を、大量のメタノール中に投入
して共重合体を析出させ、さらにメタノールで洗浄後、
70℃で真空乾燥し、共重合体8.5gを得た。このポリマを
240℃のホットプレスで1mm厚さのプレス成形シートを作
製した。このシートに、0.5μｍ厚さのSiNを成膜したと
ころ極めて接着性の良いシートが得られた。After the termination of the reaction, the polymerization solution is poured into a large amount of methanol to precipitate the copolymer, and further washed with methanol,
It was vacuum dried at 70 ° C. to obtain 8.5 g of a copolymer. This polymer
A 1 mm thick press-formed sheet was prepared by hot pressing at 240 ° C. When a 0.5 μm-thick SiN film was formed on this sheet, a sheet with extremely good adhesiveness was obtained.
（比較例） 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6gを用いる以外は上記実施例と同様にして
共重合反応を行なった結果、共重合体8.4gを得た。この
ポリマを、240℃のホットプレスで1mm厚さのプレス成形
シートを作製し、上記実施例と同様にしてシート上に0.
5μｍ厚さのSiNを成膜したが接着性が悪く剥離した。(Comparative Example) A copolymerization reaction was performed in the same manner as in the above Example except that 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene was used. As a result, 8.4 g of a copolymer was obtained. This polymer, a hot press at 240 ° C. to prepare a press-formed sheet of 1 mm thickness, on the sheet in the same manner as in the above example.
A 5 μm thick SiN film was formed, but the adhesion was poor and the film peeled off.
［発明の効果］ 以上詳細に説明したごとく、本発明による有機シリル
基を有するジメタノオクタヒドロナフタレン誘導体を用
いたポリオレフィン重合体は、金属あるいは絶縁性無機
材料との接着性が極めて良好で、高いガラス転移温度を
有する優れた基板材料が得られる。[Effects of the Invention] As described in detail above, the polyolefin polymer using the dimethanooctahydronaphthalene derivative having an organic silyl group according to the present invention has extremely good adhesiveness to a metal or an insulating inorganic material, An excellent substrate material having a glass transition temperature is obtained.
Claims (3)
ロゲン原子、炭素原子数１〜５個のアルコキシ基から選
択される置換基、ｌは０〜３を表わす。） で示される化合物であることを特徴とする有機シリル基
を有するジメタノオクタヒドロナフタレン誘導体。1. A general formula (Wherein R represents an alkyl group having 1 to 5 carbon atoms, X represents a halogen atom, a substituent selected from an alkoxy group having 1 to 5 carbon atoms, and 1 represents 0 to 3). A dimethanooctahydronaphthalene derivative having an organic silyl group, which is a compound described below.
するジメタノオクタヒドロナフタレン誘導体が、 一般式 （式中、Ｒは炭素原子数１〜５個のアルキル基を表わ
す。） で示される化合物であることを特徴とする有機シリル基
を有するジメタノオクタヒドロナフタレン誘導体。2. The dimethanooctahydronaphthalene derivative having an organic silyl group according to claim 1, wherein (In the formula, R represents an alkyl group having 1 to 5 carbon atoms.) A dimethanooctahydronaphthalene derivative having an organic silyl group, which is a compound represented by the formula:
するジメタノオクタヒドロナフタレン誘導体が、 一般式 （式中、Ｒは炭素原子数１〜５個のアルキル基、Ｒ′は
メチル基、エチル基、プロピル基、ブチル基のうちより
選択される置換基、ｌは１または２を表わす。） で示される化合物であることを特徴とする有機シリル基
を有するジメタノオクタヒドロナフタレン誘導体。3. The dimethanooctahydronaphthalene derivative having an organic silyl group according to claim 1, (In the formula, R is an alkyl group having 1 to 5 carbon atoms, R'is a substituent selected from a methyl group, an ethyl group, a propyl group, and a butyl group, and l represents 1 or 2.) A dimethanooctahydronaphthalene derivative having an organic silyl group, which is a compound shown.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63121746A JPH0813823B2 (en) | 1988-05-20 | 1988-05-20 | Dimethanooctahydronaphthalene derivative having organic silyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63121746A JPH0813823B2 (en) | 1988-05-20 | 1988-05-20 | Dimethanooctahydronaphthalene derivative having organic silyl group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01294681A JPH01294681A (en) | 1989-11-28 |
| JPH0813823B2 true JPH0813823B2 (en) | 1996-02-14 |
Family
ID=14818860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63121746A Expired - Lifetime JPH0813823B2 (en) | 1988-05-20 | 1988-05-20 | Dimethanooctahydronaphthalene derivative having organic silyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813823B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7741423B2 (en) | 2006-04-20 | 2010-06-22 | Shin-Etsu Chemical Co, Ltd. | Highly oxygen permeable polymer |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004175784A (en) * | 2002-09-30 | 2004-06-24 | Mitsubishi Chemicals Corp | Method for producing norbornene derivative having organosilyl group |
| JP4889097B2 (en) * | 2005-08-11 | 2012-02-29 | 信越化学工業株式会社 | Polycycloolefin functional polysiloxane |
| JP2007051251A (en) * | 2005-08-19 | 2007-03-01 | Shin Etsu Chem Co Ltd | Reactive silyl group-modified norbornene-based resin and method for producing the same |
| JP6207287B2 (en) * | 2013-08-05 | 2017-10-04 | 信越化学工業株式会社 | Silyl group-containing norbornene compound and method for producing the same |
-
1988
- 1988-05-20 JP JP63121746A patent/JPH0813823B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7741423B2 (en) | 2006-04-20 | 2010-06-22 | Shin-Etsu Chemical Co, Ltd. | Highly oxygen permeable polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01294681A (en) | 1989-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3176609B2 (en) | Method for producing syndiotactic polyolefin, metallocene used in the method and catalyst containing the same | |
| JP3176608B2 (en) | Method for producing syndiotactic polyolefin and catalyst used therefor | |
| US9187583B2 (en) | Catalysts | |
| KR100284726B1 (en) | Metallocenes containing benzo fused indenyl derivatives as ligands and methods for preparing the same | |
| JP2001519825A (en) | Substituted metallocene compounds for olefin polymerization catalyst systems, intermediates thereof, and methods for preparing the same | |
| JP2010174099A (en) | Cycloolefin addition polymer and method for producing the same | |
| WO2006067950A1 (en) | Method for producing cyclic olefin addition copolymer, cyclic olefin addition copolymer and use thereof | |
| JPH0813823B2 (en) | Dimethanooctahydronaphthalene derivative having organic silyl group | |
| US5489662A (en) | Process for the preparation of organosilicon polymer | |
| US3893986A (en) | Process for the preparation of novel hydrocarbon resins | |
| JPH01132591A (en) | Dimerized vinylcycloheptyl group-containing silicon compound and its production | |
| Peulecke et al. | ansa‐Titanocene and‐Zirconocene η2‐Alkyne Complexes‐Synthesis, Spectral Characteristics, and X‐ray Crystal Structure | |
| JP2002529555A (en) | Method for producing EP (D) M using bridged pentadienyl-fluorenyl transition metal complex | |
| US3164573A (en) | Allyl esters of bicyclic carboxylic acids and polymers thereof | |
| Kroll et al. | Cyclopentadienyl-aluminum compounds I. The reactions of cyclopentadiene with aluminum alkyls | |
| KR20020016923A (en) | (Co)polymerization of olefins | |
| JPS6244577B2 (en) | ||
| US5300605A (en) | Cross-linkable poly(unsaturated carbosilane) homopolymers and copolymers and method of making same | |
| JP2020164828A (en) | Olefin polymerization catalyst, transition metal complex, and method for producing olefin copolymer | |
| Ko et al. | Synthesis and characterization of poly (3, 4-benzo-1-phenyl-1-silapentene) and poly (3, 4-benzo-1-silapentene) | |
| JP2020164632A (en) | Olefin polymerization catalyst, transition metal complex, and method for producing olefin copolymer | |
| JP3474234B2 (en) | Vinylcyclopropane compound having cyclic carbonate and polymer obtained therefrom | |
| JP3859577B2 (en) | Bicyclic conjugated diene polymer | |
| JPH10120767A (en) | Cyclic olefin-based copolymer and its production | |
| KR100503371B1 (en) | Addition polymers derived from pauson-khand type norborbene monomers and preparation method therof |