JPS6397610A - Production of poly(substituted norbornene) - Google Patents

Abstract

PURPOSE:To obtain the title polymer excellent in impact resistance, by mixing a solution containing 5-vinyl-(or 5-ethylidene)bicyclo[2.2.1]hept-2-ene and a double decomposition catalyst with a solution containing an activator for the catalyst and a reaction modifier, pouring the combined solution into a mold and polymer izing the compound. CONSTITUTION:5-Vinylbicyclo[2.2.1]hept-2-ene (VBH) is dissolved in a solution formed by suspending a double decomposition catalyst (e.g., WCl6) in an inert organic solvent such as benzene or toluene to obtain a solution A. 5-Ethylidene- bicyclo[2.2.1]hept-2-ene (EBH) is dissolved in a solution containing an activator for said catalyst (e.g., triethylaluminum) and a reaction modifier (e.g., isopropyl ether) to obtain a solution B. Solution A is mixed with solution B such that the molar ratio of VBH to EBH may fall in the range of 1:1,000-15,000, and the combined solution is poured into a mold and polymerized therein at 35-150 deg.C for 10sec-2min.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to 5-vinylbicyclo(2,2,1]hept-2
-ene (hereinafter abbreviated as VBH) and/or 5-vinylidenebicyclo[2,2,1]hept-2-ene (hereinafter abbreviated as E
This invention relates to a method for producing a polymer (abbreviated as BB). More specifically, the present invention relates to a method for producing polysubstituted norbornene, which is characterized by polymerizing VBB and/or EBB by a reaction injection molding method (hereinafter abbreviated as RIM) using a metathesis catalyst system.

Prior Art and Problems to be Solved by the Invention As a method for producing plastic molded products, the RIM method is known, in which two or more components are mixed in a mold and subjected to a curing reaction. In particular, urethane RIM made from diisocyanate and diol is widely used, but it has drawbacks in physical properties such as insufficient rigidity, and drawbacks in process such as curing temperature and injection pressure not being lowered as expected. There is.

In addition, recently, the RIM method using dicyclopentadiene as a raw material using a metathesis catalyst system has been published in JP-A-58-12901].
It is disclosed in Japanese Patent Application Laid-Open No. 58-206661. Polydicyclopentadiene obtained by this method has physical properties such as a good balance between rigidity and impact resistance, and manufacturing process advantages such as low curing temperature and low injection pressure, but it also has higher performance. Physical properties such as impact resistance are still insufficient for use in automobile outer panels, etc., which require high performance.

The present invention has lower curing temperature and injection pressure, excellent physical properties,
The purpose is to produce polysubstituted norbornenes with particularly high impact resistance.

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on manufacturing methods for obtaining plastic molded products with excellent physical properties and manufacturing processes.
The present invention was achieved by discovering that polysubstituted norbornene with excellent physical properties, particularly impact resistance, can be produced at lower curing temperatures and injection pressures by polymerizing using the IM method.

That is, the present invention consists of a solution A containing a metathesis catalyst and a solution B containing an activator and a reaction regulator for the metathesis catalyst, and at least one of the solutions A and B contains 5-vinylbicyclo[2,2 ,1) Hepto-2-
ene and/or 5-vinylidene bicyclo(2,2,
1) Mix solution A and solution B containing hept-2-ene,
This invention relates to a method for producing polysubstituted norbornene, which is characterized by immediately injecting it into a mold and polymerizing it.

The VBH used in the present invention is a compound represented by the following formula (1), and usually includes cyclopentadiene and 1.3-
Produced by Diels-Alder reaction of butadiene.

EBH is a compound represented by the following formula (2), and usually V
Produced by isomerization of BH.

In the present invention, VBH and/or EBH are contained in at least one of solution A and solution B. Preferably, V contained in the re-solution is also used in the present invention.
Norbornene compounds other than BH and EBH (e.g.
Dicyclopentadiene) can also be used in combination. In this case, other norbornene compounds can be used within a range not exceeding 50wt% of the total amount of VBH and EBH, but 30vt%
% or less.

The metathesis catalyst as used in the present invention refers to a catalyst that causes a metathesis reaction. Metathesis reaction is a reaction in which two olefin bonds form a complex and undergo a four-membered ring transition state to form two new olefins.

In this reaction, a ring expansion reaction proceeds as follows for a suitable cyclic olefin.

As the metathesis catalyst used in the present invention, tungsten compounds are preferably used, and specific examples include tungsten hexachloride and tungsten oxytetrachloride.

A solution of the tungsten compound can be obtained by suspending it in a solvent that does not react with the tungsten compound, such as benzene, toluene, chlorobenzene, or hexane, or by adding a small amount of alcohol or a phenol compound to the tungsten compound to make it ``soluble.'' A method is used. In particular, a method of making it soluble with a phenol compound is preferably employed.

As the phenol compound, p-tert-butylphenol, p-tert-octylphenol, and p-nonylphenol are preferred. The amount of the phenol compound used is usually 1 to 3 moles per mole of the tungsten compound.

V contained in the metathesis catalyst and solution A and/or solution B
The molar ratio of BH and/or EBH is 1:
1000-1:15000, preferably 1;2
The range is from 000 to 1:5000.

In addition, when solution A contains VBH and/or EBH,
To prevent polymerization of VBH and/or EBH in solution A, 1 to 5 moles of a chelate compound or Lewis base can be added per mole of metathesis catalyst. In this case, the chelate compound is preferably acetylacetone, acetoacetic acid alkyl ester, etc., and the Lewis base is preferably a nitrile such as benzonitrile, an ether such as tetrahydrofuran, etc.

An organoaluminum compound is used as an activator for the double decomposition catalyst contained in Solution B of the present invention.

Examples of organoaluminum compounds include trialkylaluminums such as triethylaluminum and triisobutylaluminum, dialkylaluminum chlorides such as diethylaluminum chloride and diisobutylaluminum chloride, and alkylaluminum dichlorides such as ethylaluminum dichloride and n-butylaluminum dichloride. Among them, diethylaluminum chloride is particularly preferred.

It is also possible to use two or more types of these organoaluminum compounds.

Activator and VBH contained in solution A and/or solution B
and/or the ratio of EBH used is 1:1 in molar ratio
00-1:2000, preferably 1:200-1
; 500, and the ratio of the activator to the metathesis catalyst is 2 to 20, preferably 5 to 10 mol, of the activator per 1 mol of the metathesis catalyst.

Furthermore, the B solution of the present invention contains a reaction regulator to prevent instantaneous polymerization during mixing of both the A and B solutions. Examples of reaction regulators include esters such as ethyl benzoate, ethers such as isopropyl ether and butyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, nitriles such as benzonitrile, and alcohols such as ethanol and n-propanol. Among these, ethyl benzoate and butyl ether are particularly preferred. The molar ratio of reaction regulator and activator is 1.5:1 to 5:1.
It is.

Furthermore, in the present invention, the properties of the polysubstituted norbornene obtained can be changed by blending various additives as necessary, as long as they do not affect the polymerization.

For example, by using fillers such as glass, carbon black, and talc as additives, it is possible to increase rigidity and reduce mold shrinkage. Furthermore, impact resistance can be improved by adding an elastomer such as natural rubber, isoprene rubber, or styrene-butadiene rubber, or a plasticizer such as dioctyl phthalate or dioctyl phthalate. Furthermore, oxidation of the unsaturated portions of the polysubstituted norbornene can be prevented by adding a phenolic or amine antioxidant. Preferred antioxidants include 2,6-tert-butyl-p-cresol, N,N''-diphenyl-p-phenylenediamine, and the like.

The polysubstituted norbornene in the present invention is produced and molded by the RIM method. More specifically, at least one solution contains a metathesis catalyst containing VBH and/or EBH, and a solution B contains a metathesis catalyst activator and a reaction regulator.
The solution is prepared in a separate container, then the two solutions are mixed, heated to some extent beforehand, and poured into a mold.
Polysubstituted norbornene moldings are produced by immediate polymerization in a mold.

Polymerization using a metathesis catalyst system is inhibited by oxygen and moisture, so it is necessary to remove oxygen and moisture from each polymerization component and store and handle it under an inert gas atmosphere such as nitrogen gas.

The polymerization reaction in the mold is usually carried out at 35 to 150°C for 10 seconds to
It is carried out for 5 minutes, preferably at 50 to 100°C for 30 seconds to 2 minutes. In addition, in order to reduce residual odor and improve final physical properties, the molded product taken out from the mold may be post-cured, usually at 150 to 200°C, preferably at 160 to 19°C.
It is sufficient to post-cure at 0° C. for 10 minutes to 1 hour, preferably 20 to 40 minutes. Furthermore, in order to increase the mixing efficiency of solutions A and B, or to maintain the optimum viscosity to facilitate injection into the mold, both solutions A and B were mixed at a temperature below which polymerization would not occur immediately. Preferably, heating and cooling may be performed at a temperature of 50° C. or lower.

EXAMPLES The content of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Preparation of catalyst and activator 4.0 g of tungsten hexachloride is added in 92 mf of dry toluene under a nitrogen atmosphere, and to this is added a solution of 1.64 g of p-tert-butylphenol in 6 mf of dry toluene. The solution was then purged with nitrogen gas overnight to prepare a 0.1 mol tungsten-containing catalyst solution.

Similarly, 25.9 mj under nitrogen atmosphere! A 1.8 mol diethyl-aluminum chloride solution was prepared by adding 7.7 ml of diethyl aluminum chloride to the dried toluene.

Example 1 Solution A was prepared by adding 0.2 m of benzonitrile and 7.2 m of a 0.1 mol tungsten-containing catalyst solution to 4.1 mf of VBH1 dried under a nitrogen atmosphere.

Similarly, 1.2 m of isopropyl ether and 2.4 m of a 1.8 mol diethylaluminium chloride solution were added to 4.1 m°C of VBH1 dried under a nitrogen atmosphere to prepare solution B.

Next, the A solution and the B solution were mixed under a nitrogen atmosphere, and immediately
It was heated to 0°C and poured into a mold. This temperature was maintained for 1 minute to complete the polymerization reaction in the mold, and a polysubstituted norpoene molded product was obtained. This molded product is removed from the mold,
Post-curing was performed at 120° C. for 30 minutes.

The physical properties of the polysubstituted norbornene thus obtained were measured, and the results are shown in the table.

Example 2 Dry EBH10 instead of VBH1]4.1m contained in solution A of Example 1 7.5m, e, dry EBH10 instead of VBH1 contained in solution B]4.1m, fl:
7.5mJ! A polysubstituted norbornene molded product was produced in the same manner as in Example 1 using the following.

The physical properties of the obtained molded product are shown in the table.

Example 3 VBH1 contained in solution B of Example 1] 4.1 mI! Dry EBH107.5mj instead! A polysubstituted norbornene molded product was obtained in the same manner. The physical properties are shown in the table.

Example 4 Liquid isoprene rubber (-Kuraray L) was added to solution A of Example 1.
A polysubstituted norbornene molded product was produced in the same manner as in Example 1 by adding 15 g of IR-30). The physical properties are shown in the table.

Comparative Example 1 Dried dicyclopentadiene 98°5m was substituted for VBH1]4.1m contained in solution A of Example 1, and dried dicyclopentadiene 98.5m was substituted for VBH1]4.1m contained in the gSB solution. A polysubstituted norbornene molded product was produced in the same manner as in Example 1 using .5m. The physical properties of the obtained molded product are shown in the table.

Comparative Example 2 15 g of liquid isoprene rubber (LIR-30 manufactured by Kuraray) was added to the A solution of Comparative Example 1, and a polysubstituted norbornene molded product was produced in the same manner as in Example 1. The physical properties are shown in the table.

Effects of the Invention As is clear from the examples, the present invention enables the production of polysubstituted norbornene molded products at lower curing temperatures and injection pressures by polymerizing VBH and/or EBH using the RIM method. The impact resistance of the resulting molded product is even better than that of a molded product made from dicyclopentadiene.

Patent Applicant Nippon Oil Co., Ltd. Procedural Amendment September 30, 1988 1, Indication of Case Japanese Patent Application No. 1983-242836 26 Title of Invention Process for Producing Polysubstituted Norbornene 3, Relationship with the Amendment Person Case Patent Applicant name (444) Nippon Oil Co., Ltd. 5, Date of amendment order Voluntary 6, Number of inventions increased by amendment No change 7, Subject of amendment Specification (scope of claims, detailed description of invention) 8, Contents of amendment [1] The scope of claims in the specification is amended as shown in the attached sheet.

[2] Same, on the third line from the bottom of the first page, "5-vinylidene bicyclo" is corrected to "5-ethylidene bicyclo".

[3] "5-vinylidene bicyclo" on page 4, line 1.
Correct the statement to "5-ethylidene bicyclo".

Claims [1] Consisting of solution A containing a metathesis catalyst and solution B containing an activator and a reaction regulator for the metathesis catalyst, at least one of solution A and solution B containing 5-
Mix solution A and solution B containing vinylbicyclo[2,2,1]hept-2-ene and/or 5-ethylidenebicyclo[2,2,1]hept-2-ene and immediately inject into a mold. A method for producing polysubstituted norbornene, which comprises polymerizing it.

Claims (1)

[Scope of Claims] [1] Consisting of a solution A containing a metathesis catalyst and a solution B containing an activator and a reaction regulator for the metathesis catalyst, at least one of the solutions A and B contains 5-
Mix solution A and solution B containing vinylbicyclo[2,2,1]hept-2-ene and/or 5-vinylidenebicyclo[2,2,1]hept-2-ene and immediately inject into the mold. A method for producing polysubstituted norbornene, which comprises polymerizing it.