JPH01294681A - Dimethanooctahydronaphthalene derivative with organic silyl group - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to polyolefin polymers used for substrate materials, etc., and in particular to organic polyolefin polymers suitable for producing polyolefin polymers that have good adhesion to metals or inorganic insulators. The present invention relates to a novel dimetanooctahydronaphthalene derivative having a silyl group.

[Conventional Technique I] In recent years, dimetanooctahydronaphthalene derivatives have been used in the production of polyolefin polymers or copolymers with excellent transparency (Japanese Patent Laid-Open No. 168708/1983).
. However, this conventional polyolefin polymer does not contain metals such as copper or silicon nitride! It had the disadvantage of poor adhesion to insulators.

[The problem that the invention tries to solve! ! ] As a result of extensive research in order to solve the drawback that conventional polyolefin polymers have poor adhesion to metals and inorganic insulators, the present inventors have developed dimetanooctahydronaphthalene, which has an olefin and an organic silyl group. We have discovered that by copolymerizing with derivatives, it is possible to obtain a polyolefin copolymer that has extremely good adhesion to inorganic insulators such as silicon nitride compounds, metals, adhesives, etc., and has a high glass transition temperature.

An object of the present invention is to provide a dimetanooctahydronaphthalene derivative having an organic silyl group, which is a novel compound from which a polyolefin copolymer having a high glass transition temperature and excellent adhesiveness can be produced. It is in.

[Means for Solving the Problems] The object of the present invention is to achieve the following: General formula (wherein R is an alkyl group having 1 to 5 carbon atoms,
X is a halogen atom, a substituent selected from alkoxy groups having 1 to 5 carbon atoms, and a is 0 to 3. This is achieved by

Further, as the dimetanooctahydronaphthalene derivative having an organic silyl group of the present invention, a compound represented by the general formula (wherein R represents an alkyl group having 1 to 5 carbon atoms) can be used.

Furthermore, the dimetanooctahydronaphthalene derivative having an organic silyl group of the present invention has the general formula (wherein R is an alkyl group having 1 to 5 carbon atoms.

R' may be a substituent selected from a methyl group, an ethyl group, a propyl group, and a butyl group, and a represents 1 or 2.

[Function] The method for synthesizing the dimetanooctahydronaphthalene derivative having an organic silyl group of the present invention is as follows: (i) Robert F. Canio, "Diels-Alder of α,β-unsaturated trihalosilanes using cyclopentadiene"; Reaction (Diene Synthesis)” [Robert F.

Cun1orTha Dials-Alder Rea
ction of a, β-unsaturated
Trihalosilanas with Cycle
openta-dianaJ (J, Org, cham
, , Vol. 36 (1971) & 7. p. 929)
] According to the synthesis method shown in the literature, bicyclo[2,2,1]hept-2-
xcy5yl-silane (bicyclo[2,2.

1 ] ] hept-2-ena-5-ylsilan
(n) Niss B. Soloway "Stereochemistry of the Molten Norcamphene System J(S,B.

Soloway r The 5tereoche+5
istry of FusedNorcamphane
SystemsJ (J, Am, Chew@Sa
c.

Vol, 74 (1952), p, 1072) (7) According to the tail synthesis method shown in the literature, the following reaction formula (2)
Dimethanooctahydronaphthalene having an organic silyl group is synthesized by

Examples of the diene compound used in the synthesis of dimethanoloctahydronaphthalene having an organic silyl group of the present invention include cyclopentadiene and dicyclopentadiene.

In addition, as a compound represented by the general cH,=:c)lSiRmXs-s, for example, trimethylvinylsilane,
triethylvinylsilane, tripropylvinylsilane,
Dimethylmethoxyvinylsilane, dimethylethoxyvinylsilane, dimethylpropoxyvinylsilane, dimethylbutoxyvinylsilane, methyldimethoxysilane, methyljethoxyvinylsilane, methyldipropoxyvinylsilane, methyldibutoxyvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxyvinylsilane, tributoxyvinylsilane , trichlorovinylsilane, methyldichlorovinylsilane, dimethylchlorovinylsilane, and the like.

Cyclopentadiene and CH, = CHS i Ra X
The reaction with the 3-m compound was carried out at 160-180°C under pressure (1,0-10 kg/cd) in an inert gas atmosphere.
The reaction temperature is preferably 160 to 170°C. Examples of the inert gas include nitrogen gas and argon gas.

Cyclopentadiene and CHz = CHS i Ra
The reaction with the X)-m compound is carried out in a Diels-Alder reaction using equimolar amounts, but it is preferable to carry out the Diels-Alder reaction using a slight excess of cyclopentadiene.

[Example] Examples of the present invention will be given below and will be explained in more detail.

(1) Synthesis of 5-exo-15-endo-trimethylsilylbicyclo[2,2,1]hept-2-ene.

220 g (2.2 mol) trimethylvinylsilane 160 g (2.42 mol) slightly excess cyclopentadiene
was placed in an IQ autoclave, nitrogen gas was introduced to make the initial pressure 1.6 kg/cJ, and the temperature was maintained at 165-175°C for 6 hours and 20 minutes (maximum pressure 9.9 kg/cd).
. 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, BP69.5~70.5℃/2
0-22IwHg, synthetic component 187.7g (yield 55
%), and 24.0 g of residual pickles were obtained.

(2) Synthesis of 2-trimethylsilyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

5exo-15endo-trimethylsilylbicyclo[2
,2,l]hept-2-ene 150 g (0.9 mol) and a slight excess of cyclopentadiene 88,ag (1,3
4 mol) was placed in a 12 autoclave, nitrogen gas was introduced, the initial pressure was 5 kg/aJ, and the temperature was 175-185°C.
The temperature was maintained for 12 hours (maximum pressure 9.5 kg/aJ)
, after cooling the autoclave container, 227 g of reaction product
I took it out. The insoluble filtrate in the reaction product was filtered, washed away with a small amount of hexane, and 223 g of the filtrate was collected, placed in a flask, and distilled under reduced pressure. Light weight: 73.0g, BP
120-130℃/3 pus Hg fraction 98.3g (yield 65
．． 5%), and 54.2 g of residual pickles were obtained.

(3) Synthesis (polymerization) of polyolefin resin A stirring blade, a gas inlet tube, and a thermometer were attached to a thoroughly dried 3Q, three-row flask, and the inside of the reaction vessel was sufficiently purged with nitrogen gas. 6 Next, 100 mQ of dehydrated and dried toluene was put into this flask, and while nitrogen gas was flowing, vOCΩ was adjusted to 0.4.
Add 8.7 g (0,0374 mol) of 2-trimethylsilyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene and turn the flask into a liquid. 4 mmol of ethylaluminum sesquichloride was placed in a 6-dropping funnel that had been cooled with nitrogen and vacuum degassed twice.

Next, 35ffi/h of ethylene gas was passed through the gas introduction pipe.
While a mixed gas of 150 Q/h of nitrogen gas was passed through the flask maintained at 10° C. for 10 minutes, ethylaluminum sesquichloride was added dropwise from the dropping funnel to start the copolymerization reaction, and polymerization was carried out for 60 minutes.

5 ml (l) of methanol was added to the obtained polymer solution to stop the polymerization reaction.

After stopping the reaction, the polymerization solution was poured into a large amount of methanol to precipitate a copolymer, and after further washing with methanol,
It was vacuum dried at 0°C to obtain 8.5g of copolymer. This polymer was hot-pressed at 240° C. to produce a press-molded sheet with a thickness of 1 m. A 0.5 μm thick Si
When N was formed into a film, a sheet with extremely good adhesiveness was obtained.

(Comparative example) 1.4,5.8-dimethano-1,2,3,4°4a,5
, 8.8a A copolymerization reaction was carried out in the same manner as in the above example except that 6 g of a-octahydronaphthalene was used. As a result,
8.4 g of copolymer was obtained.

This polymer was hot-pressed at 240° C. to produce a 1 m thick press-molded sheet, and a 0.5 μm thick SiN film was formed on the sheet in the same manner as in the above example, but the film had poor adhesion and peeled off.

[Effects of the Invention] As explained in detail above, the polyolefin polymer using the dimethanooctahydronaphthalene derivative having an organic silyl group according to the present invention has extremely good adhesion to metals or insulating inorganic materials, and has high adhesive properties. An excellent substrate material with a glass transition temperature is obtained.

Claims (1)

[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R is an alkyl group having 1 to 5 carbon atoms, X is a halogen atom, and A dimetanooctahydronaphthalene derivative having an organic silyl group, characterized in that it is a compound represented by the following formula: a substituent selected from alkoxy groups, l represents 0 to 3. 2. In claim 1, the dimetanooctahydronaphthalene derivative having an organic silyl group has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R represents an alkyl group having 1 to 5 carbon atoms) A dimethanooctahydronaphthalene derivative having an organic silyl group, characterized in that it is a compound represented by: 3. In claim 1, the dimetanooctahydronaphthalene derivative having an organic silyl group has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R is an alkyl group having 1 to 5 carbon atoms, R' is a substituent selected from methyl group, ethyl group, propyl group, and butyl group, and l represents 1 or 2. Octahydronaphthalene derivative.