JPH0625213B2 - Method for producing hydrogenated dicyclopentadiene-ethylene copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a hydrogenated dicyclopentadiene-ethylene copolymer, more specifically, an olefinic unsaturated bond contained in the dicyclopentadiene-ethylene copolymer. The present invention relates to hydrogenation of a dicyclopentadiene-ethylene copolymer excellent in hot melt processability obtained by hydrogenating a part or all of the above with hydrogen in the presence of a hydrogenation catalyst.

Conventionally, a dicyclopentadiene-ethylene copolymer itself is known (for example, Angew, Macromo.
1, Chem. 20, 141, (1971)). However, since this copolymer has an unsaturated bond in its structure, it has a drawback that it is prone to thermal deterioration and is inferior in hot-melt molding processability. On the other hand, 4,7-methano-2,3,3a, 4,7,7a-hexahydro-1H represented by the following formula
-The copolymer of indene (abbreviated as MHI) and ethylene (U.S. Pat. No. 2,883,372) has no unsaturated bond and is excellent in hot melt processability. MHI, which is a monomer component, is difficult to obtain economically.

As a method for synthesizing the monomer MHI, there are, for example, two methods represented by the following formula.

(I) (II) However, the method (I) has a low yield and the method (II) has complicated steps. Further, in both cases, purification of the monomer is required. Therefore, there is a drawback that a large amount of capital investment is required and it is not economical.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As a result of intensive studies to solve the above-mentioned drawbacks, the present inventors have used an easily available dicyclopentadiene-ethylene copolymer and used an olefin-based copolymer contained in the copolymer. By hydrogenating a part or all of the saturated bonds using a hydrogenation catalyst, it is possible to easily obtain a hydride of dicyclopentadiene-ethylene copolymer excellent in hot melt processability by a simple process. They have found the present invention and have completed the present invention based on this finding.

Means for Solving the Problems Thus, according to the present invention, a part or all of the olefinic unsaturated bonds contained in the dicyclopentadiene-ethylene copolymer are hydrogenated with hydrogen in the presence of a hydrogenation catalyst. Provides a method for producing a hydrogenated dicyclopentadiene-ethylene copolymer having excellent hot melt processability.

Hereinafter, the components of the present invention will be described in detail.

(Dicyclopentadiene-Ethylene Copolymer) The dicyclopentadiene-ethylene copolymer used in the present invention has a molecular weight of 1,000 to 1,500,000, preferably 5,000 to 700,000, more preferably 10,000 to 5.
It is 100,000 and can be obtained by the known method as described above.

Further, to the extent that the object of the present invention is not impaired, an alkyl-substituted dicyclopentadiene substituted with an alkyl group such as a methyl group or an ethyl group, or an olefinic monomer such as propylene or 1-butene is copolymerized as a third monomer. It may be a copolymer.

(Hydrogenation Method) The hydrogenation method of the dicyclopentadiene-ethylene copolymer in the present invention is usually carried out in a polymer organic solvent solution. As the solvent, a hydrocarbon solvent such as cyclohexane, methylcyclohexane, benzene, toluene or xylene is used. Dicyclopentadiene-
Although the concentration of the ethylene copolymer solution can be appropriately determined, hydrogenation is usually carried out at a concentration of 0.1 to 30% by weight, preferably 1 to 20% by weight.

The hydrogenation catalyst used in the method of the present invention includes:
Any catalyst that is commonly used for hydrogenating olefin compounds can be used and is not particularly limited,
For example: As the heterogeneous catalyst, nickel, palladium, platinum, or a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, or titanium oxide, for example, nickel / silica, nickel / diatomaceous earth, palladium / Examples thereof include carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like. Further, as the nickel-based catalyst, in the platinum-based catalyst such as Raney nickel catalyst,
There are also platinum oxide catalysts and platinum black. Homogeneous catalysts based on metals of Group VIII of the Periodic Table, such as cobalt naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum, etc.
Examples of the compound include an o compound and an organometallic compound of a Group I to III metal of the Periodic Table, or a Rh compound.

In addition, MS Saloen
Ziegler-based hydrogenation catalyst (J. Am.
Chem. Soc. 85, 4014 (1963)) can also be used effectively. Examples of these catalysts include the following.

_{Ti (O-iC 3 H 7} ) 4 - (iC 4 H 9) 3 Al, Ti (O-iC 3 H 7) 4 - (C 2 H 5) 3 Al, (C 2 H 5) 2 TiCl 2 - _{(C 2 H 5) 3 Al} , Cr (acac) 3 - (iC 4 H 9) 3 Al, Cr (acac) 3 - (C 2 H 5) 3 Al, Mn (acac) 3 - (iC 4 _{H 9) 3 Al, Mn (} acac) 3 - (C 2 H 5) 3 Al, Fe (acac) 3 - (C 2 H 5) 3 Al, Co (acac) 2 - (C 2 H 5) 3 Al _{, (C 7 H 5 COO)} 3 Co- (C 2 H 5) 3 Al hydrogenation reaction, in homogeneous or heterogeneous depending on the type of catalyst, under a hydrogen pressure of 1 to 150 atm, 0 to 180 ° C., preferably Is carried out at a reaction temperature of 20-120 ° C. The hydrogenation rate can be arbitrarily adjusted in the range of 0 to 100% by changing the reaction conditions such as hydrogen pressure, reaction temperature, reaction time, catalyst concentration, and the like. Hydrogenated dicyclopentadiene-ethylene copolymer In order to exhibit excellent heat resistance, and thus good hot melt processability, 50% or more of the olefinic unsaturated bonds in the copolymer are preferably hydrogenated, more preferably 80% or more, Preferably, the hydrogenation rate is 90% or more.

After the hydrogenation reaction, the catalyst is removed by centrifugation, filtration, or in the case of a Ziegler type catalyst, by deactivating the catalyst with an acid,
Then, the reaction product is precipitated in a large amount of a polar solvent such as acetone or alcohol, and then the solvent is removed and dried to obtain a hydride of a dicyclopentadiene-ethylene copolymer.

(Hydrogenated Dicyclopentadiene-Ethylene Copolymer) The hydrogenated dicyclopentadiene-ethylene copolymer thus obtained has excellent heat resistance and is aromatic at the normal temperature, such as toluene and dicyclohexane. It is less soluble in naphthenic hydrocarbons and has better solvent resistance than the polymer before hydrogenation. Also,
By adjusting the hydrogenation rate, it is possible to obtain polymers of various grades in terms of heat resistance, solvent resistance, solubility and the like.

The hydrogenated dicyclopentadiene-ethylene copolymer obtained by the method of the present invention can be molded by a well-known method. Particularly, a polymer having a high hydrogenation rate is 180 ° C. to 250 ° C. without causing crosslinking and oxidative deterioration at high temperature. It can be easily melt-molded at ℃. Moreover, the obtained molded product is transparent and has excellent mechanical strength.

Since the hydrogenated copolymer of the present invention is a polymer having well-balanced heat resistance, transparency, solvent resistance, mechanical properties, etc., it is useful in various fields as various molded products.

For example, photoresist protective film, optical lens, optical field such as optical disk, electric iron water tank, microwave oven product, substrate for liquid crystal display, printed circuit board, electrical field such as transparent conductive sheet and film, syringe, pipette It can be used in many fields, such as medical and chemical fields such as animal gauges, camera bodies, housings for various instruments, films, sheets, helmets, and so on.

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the production method of the present invention is not limited to these examples. Parts and% in the examples and comparative examples are based on weight unless otherwise specified.

Reference Example 1 A well-dried 5 l separable flask was equipped with a stirring blade, a gas blowing tube, a thermometer and a dropping funnel, and was sufficiently replaced with nitrogen.

2.5 l of toluene dehydrated and dried with a molecular sieve was put into this flask.

Dicyclopentadiene (DC
P) 75 g, and ethylene aluminum sesquichloride 2
To the dropping funnel, 2.5 mmol of dichloroethoxyoxovanadium was added.

A dry mixed gas of 60 l / hr of ethylene and 120 l / hr of nitrogen was passed through the gas blowing tube through the above flask controlled at 20 ° C for 5 minutes.

Dichloroethoxyoxovanadium was added dropwise from an appropriate funnel to start the copolymerization reaction, and the copolymerization reaction was carried out at 20 ° C. for 30 minutes while passing the above mixed gas.

The copolymerization reaction was stopped by adding 30 ml of methanol to the polymer solution.

After the termination of the reaction, the polymerization mixture was poured into a large amount of methanol to precipitate the copolymer, and the copolymer was washed with acetone.
It was vacuum dried at ℃ for 24 hours to obtain 68 g of a copolymer. The composition ratio of the dicyclopentadiene component in the copolymer analyzed by ¹ H-NMR was 34 mol%, and the intrinsic viscosity [η] was 0.
It was 65 dl / g and the glass transition point (Tg) was 94 ° C.

Example 1 An autoclave equipped with a stirrer having a volume of 1 liter was used as a reactor, 500 g of a cyclohexane solution having a concentration of the polymer obtained in Reference Example 1 of 10% and 5 g of palladium carbon were charged, and the inside of the reactor was replaced with hydrogen and stirred. Meanwhile, the temperature was raised to 120 ° C. When the temperature inside the reactor became constant, the hydrogen pressure was increased to 70 atm. The reaction was carried out for 8 hours while supplementing the hydrogen consumed by the reaction, then the catalyst in the reaction product was removed by centrifugation and filtration, and the product was dissolved in a large amount of acetone-isopropyl alcohol (1: 1) mixed solvent. 45 g after precipitation, filtration and drying
A polymer compound of As a result of ¹ H-NMR analysis, absorption due to an olefinic unsaturated bond at a chemical shift of 5.4 ppm was not observed,
The olefinically unsaturated group was completely hydrogenated.

Example 2 An autoclave equipped with a stirrer having a volume of 1 l was used in a reactor, 500 g of a cyclohexane solution having a concentration of 10% of the polymer obtained in Reference Example 1 was charged, and 5 mmol of triethylaluminum and 1.7 mmol of cobalt octate were previously charged. After the mixed catalyst was added and the inside of the reactor was replaced with hydrogen, the temperature was raised to 90 ° C with stirring. When the temperature became constant, the hydrogen pressure was raised to 70 atm, and the reaction was continued for 3 hours while supplementing the hydrogen consumed by the reaction. After the reaction, the reaction product was converted into hydrochloric acid-acidified acetone-isopropyl alcohol (1:
1) It was precipitated in a mixed solvent to remove the catalyst, washed and dried to obtain 41 g of a polymer compound. As a result of analysis by ¹ H-NMR spectrum, the hydrogenation rate was 100%.

Example 3 An autoclave with a stirrer having a capacity of 1 l was used as a reactor, 500 g of a cyclohexane solution having a concentration of 10% of the polymer obtained in Reference Example 1 and 5 g of palladium carbon were added, and the reactor was replaced with hydrogen and stirred. While raising the temperature to 120 ° C. When the temperature inside the reactor became constant, the hydrogen pressure was increased to 35 atm. The hydrogenation reaction was stopped when the hydrogen pressure reached 20 atm. Thereafter, the catalyst in the reaction product was removed in the same manner as in Example 1 to obtain 45 g of a polymer compound. As a result of ¹ H-NMR analysis, the hydrogenation rate was 83%.

Example 4 By the same method as in Example 3 except that the hydrogen pressure was changed to 35 atm and the pressure was increased to 30 atm, 46 g of a polymer compound was obtained. As a result of ¹ H-NMR analysis, the hydrogenation rate was 58%.

Next, the hydrogenated polymers obtained in Examples 2 to 4 (Experiment Nos. 1-1 to 1-3) and the polymer before hydrogenation (Experiment No. 1-4) obtained in Reference Example 1 were heated at 220 ° C. Each was press-molded and the appearance was observed. The results are shown in Table 1.

Example 5 78 g of a copolymer was obtained in the same manner as in Reference Example 1 except that the ethylene flow rate was 120 l / hr. The composition ratio of the dicyclopentadiene component of the copolymer analyzed by ¹ H-NMR was 27 mol%, and the intrinsic viscosity [η] was 0.7.
It was 6 dl / g and the glass transition point (Tg) was 67 ° C.

When this polymer was subjected to a hydrogenation reaction in the same manner as in Example 1, 43 g of a polymer compound was obtained. As a result of ¹ H-NMR analysis, the hydrogenation rate was 100%.

Effects of the Invention According to the present invention, a polymer excellent in hot melt molding processability,
Water of a desired grade that can be easily obtained from an easily available dicyclopentadiene-ethylene copolymer by a simple hydrogenation method and has different degrees of heat resistance or solvent resistance by adjusting the hydrogenation rate. It can be an accessory. Since the obtained hydrogenated polymer has excellent heat resistance, transparency, solvent resistance, mechanical properties, etc., it can be used in many fields.

Claims (1)

[Claims] 1. A hydrogenated dicyclopentadiene characterized in that a part or all of olefinic unsaturated bonds contained in a dicyclopentadiene-ethylene copolymer are hydrogenated with hydrogen in the presence of a hydrogenation catalyst. Method for producing ethylene copolymer.