JPH01190708A - Production of poly(substituted norbornene) - Google Patents

Abstract

PURPOSE:To obtain the title polymer improved in low-temperature curability, curing rate and impact resistance, by mixing two specified solutions together, immediately pouring the mixture into a mold and polymerizing it. CONSTITUTION:100 pts.wt. 5-alkenylbicyclo[2,2,1]hept-2-ene of formula I (wherein R<1> is a 2-5C alkenyl, R<2> is H or a 1-3C alkyl, m is 0-1) and/or 5- alkylidenebicyclo[2,2,1]hept-2-ene (C) of formula II (wherein R<3-5> are each R<2>, and n is m) are added to at least either a solution (A) containing a double decomposition catalyst which is a catalyst for a metathesis reaction or a solution (B) containing an activator for the double decomposition catalyst and a reaction modifier. After 2-100 pts.wt. dicyclopentadiene resin (D) of a number- average MW of 400-1500 is added to at least component A or component B, component A is mixed with component B and the mixture is immediately poured into a mold and polymerized for 10sec-20min at 35-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to 5-alkenylbicyclo[2,2,1]hept-2-enes and/or 5-alkylidenebicycloC2,2,1]hept-2-enes. This invention relates to a method for producing polymers of the following types. More specifically, the present invention uses a reaction injection molding method (hereinafter abbreviated as RIM) using a metathesis catalyst system to produce 5-alkenylbicyclo[2,2,1]hept-2-enes and/or 5-alkylidenebicyclo(2 , 2, 1) A method for producing polysubstituted norbornene, which comprises polymerizing hept-2-enes.

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 Japanese Patent Application Laid-open No. 58-129013.
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.

Furthermore, in order to improve productivity, there is a need to shorten the time required for one molding cycle, that is, a faster curing rate.

The present invention produces polysubstituted norbornenes with lower curing temperatures and injection pressures, faster curing rates, and superior physical properties, particularly impact resistance.

Means for Solving the Problems The inventors of the present invention have conducted extensive research into a manufacturing method for obtaining plastic molded products with excellent physical properties and manufacturing processes, and have found that 5-alkenylbicycloC2,2
,1]hept-2-enes and/or 5-alkylidenebicyclo[2゜2.1]hept-2-enes by RI
By polymerizing using the M method, it has lower curing temperatures, injection pressures, faster curing speeds, and excellent physical properties, especially impact resistance.

The present invention was achieved by discovering that excellent polysubstituted norbornene can be produced.

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-alkenylbicyclo[2,2 , 11 hept-
2-enes and/or 5-alkylidene bicyclo[
A solution containing 2,2,11 hept-2-enes and a dicyclopentadiene resin is mixed with at least one of the solutions A and B, and the mixture is immediately poured into a mold and polymerized. The present invention relates to a method for producing polysubstituted norbornene, characterized by the following.

5-Alkenylbicyclo(2) used in the present invention
,2,1')hept-2-enes are represented by the following general formula (1
) is a compound represented by

Here, R1 is alkeni/14 having 2 to 5 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is O
or 1.

A specific compound is 5-vinylbicyclo[2,2
,1]hept-2-ene, 5-propenylbicyclo(2
,2,1]hept-2-ene, 5-impropenylbicyclo[2,2,1]hept-2-ene, methyl-5-vinylbicyclo[2゜2.1]hept-2-ene, dimethyl- Examples include 5-vinylbicyclo(2,2,1)hept-2-ene. Among these, 5-vinylbicyclo[2
゜2.1] Hept-2-ene is preferred because it is industrially easily available.

5-Alkylidenebicyclo[
2,2,1) Hept-2-enes represent an atom or an alkyl group having 1 to 3 carbon atoms, and n is 0 or 1.

Specific compounds include 5-ethylidenebicycloC2,
2,1) hept-2-ene, 5-propylidenebicyclo(2,2,1]hept-2-ene, 5-isopropylidenebicyclo(2,2,11hept-2-ene, methyl-
5-ethylidenebicyclo[2,2,1]hept-2-ene, dimethyl-5-ethylidenebicyclo[2,2,1)
Hept-2-ene is mentioned. Among these, 5-ethylidenebicyclo[2,2,1)hept-2-ene is preferred because it is industrially available. In particular, 5-alkylidenebicycloC2,2,1]hept-2-enes are preferred because they provide a fast curing rate.

In the present invention, 5-alkenylbicyclo[2゜2.1
]Hept-2-enes and 5-alkylidenebicycloC2,2,1]Hept-2-enes were added to solution A and solution B.
At least one of the solutions is contained in one. Preferably, it is contained in both hot liquids.

Furthermore, in the present invention, 5-alkenylbicycloC2,2
, 1) Norbornene compounds other than hept-2-enes and 5-alkylidenebicyclo[2,2,1]hept-2-enes (for example, dicyclopentadiene) can also be used in combination. In this case, the other norbornene compound is 5-alkenylbicyclo[2,2,1:lhept-2-
Enes and 5-alkylidene bicyclo[2,2,11
Although it can be used in an amount not exceeding 50 wt% of the total amount of hept-2-enes, it is preferably 30 wt% or less.

In the present invention, the dicyclopentadiene resin is contained in at least one of solution A and solution B.

The dicyclopentadiene resin in the present invention is mainly composed of cyclopentadiene, dicyclopentadiene, or an alkyl-substituted derivative thereof, and is heated or treated with BF3.
It is a resin polymerized using a cationic catalyst such as 0Ph2 or AfCfi, and also includes a copolymerized resin with an unsaturated hydrocarbon compound that can be copolymerized with these. The unsaturated hydrocarbon compounds mentioned here include aromatic olefins such as styrene, vinyltoluene and indene, aliphatic olefins such as isoprene and piperylene, and alicyclic olefins such as cyclopentene.

As the dicyclopentadiene resin of the present invention, one having a number average molecular weight of about 400 to 1,500 is usually used.

The amount of dicyclopentadiene resin used is 100 parts by weight of the total amount of 5-alkenylbicyclo(2,2,1)hept-2-enes and 5-alkylidenebicyclo[2,2,1]hept-2-enes. The amount is 2 to 100 parts by weight, preferably 5 to 70 parts by weight. If the amount of dicyclopentadiene resin used is less than 2 parts by weight, the effect of its addition will not be fully realized and the rigidity will not improve, and if it exceeds 100 parts by weight, the viscosity of the solution will increase and the mold will not be affected. Injection becomes difficult and impact resistance is also significantly reduced.

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 double decomposition 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 phenol compound to the tungsten compound to make the tungsten compound soluble. 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.

5 contained in the metathesis catalyst and solution A and/or solution B
-Alkenylbicyclo(2,2,1)hept-2-enes, 5-alkylidenebicyclo(2,2,13hept-2-enes)
The molar ratio of the 2-enes and the total amount of dicyclopentadiene resin is 1:1000 to 1:1500.
0, preferably in the range of 1:2000 to 1:5000.

In addition, solution A is 5-alkenylbicyclo[2゜2.1]
When containing hept-2-enes and/or 5-alkylidenebicyclo(2,2,1)hept-2-enes,
5-alkenylbicycloC,2,2,1) in solution A
Adding 1 to 5 moles of a chelate compound or Lewis base per mole of metathesis catalyst to prevent polymerization of hept-2-enes and/or 5-alkylidenebicyclo(2,2゜1]hept-2-enes. 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 aluminum 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 these, diethylaluminum chloride is particularly preferred.

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

5-alkenylbicyclo(2,2,1)hept-2-enes contained in the activator and solution A and/or solution B;
5-Alkylidene bicyclo[2゜2,1]hept-2-
The molar ratio of the enes and the dicyclopentadiene resin to the total amount is 1:100 to 1:2000, preferably 1:200 to 1:500, and the ratio of the activator to the metathesis catalyst is 1:500. The amount of activator is 2 to 20 moles, preferably 5 to 10 moles, per mole of catalyst.

Furthermore, the B solution of the present invention contains a reaction regulator to prevent instantaneous polymerization when both the A and B solutions are mixed. 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 ratio of anti-window modifier and activator used is 1.5:1 to 5:1 in molar ratio.
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, in one solution, 5-alkenylbicyclo[2°2.1]hept-2
-enes and/or 5-alkylidene bicycloC2
, 2, 1) Metathesis catalyst-containing A containing hept-2-enes
The solution and B solution containing the metathesis catalyst activator and reaction regulator are prepared in separate containers.The two solutions are then mixed, heated to some extent in advance, 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 20 minutes, preferably at 50 to 100°C for 30 seconds to 5 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 100°C.
Post-curing at 90° C. for 10 minutes to 1 hour, preferably 20 to 40 minutes is sufficient. Furthermore, in order to increase the mixing efficiency of solutions A and B, or to maintain the optimum viscosity of the solution 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, but the present invention is not limited thereto.

Preparation of catalyst and activator Add 4.0 g of tungsten hexachloride in 92 ml of dry toluene under a nitrogen atmosphere, then add 1.64 g of p-ter, t-butylphenol to 6 ml of dry toluene.
A 0.1 mol tungsten-containing catalyst solution was prepared by adding a solution containing tungsten and purging with nitrogen gas overnight.

Similarly, 7.7 m of diethylaluminium chloride was added to 25.9 m of dry toluene under a nitrogen atmosphere to prepare a 1.8 mol diethylaluminum chloride solution.

Synthesis side of synchlopentadiene resin 500 g of dicyclopentadiene with a purity of 96% and 500 g of mixed xylene were mixed in an autoclave under stirring for 260 g.
The reaction was carried out by heating at ℃ for 1.5 hours.

After the reaction was completed, the autoclave was cooled, and the contents were distilled to remove unreacted monomers, low polymers, and xylene, and 348 g of dicyclopentadiene resin was obtained as a residue. The softening point of this dicyclopentadiene resin is 82℃
, the number average molecular weight determined by vapor pressure osmometer method is 45
It was 0.

Example 1 5-vinylbicycloC2,2, dried under nitrogen atmosphere
1] Hept-2-ene (hereinafter abbreviated as VBH) 100 m,
10 g of dicyclopentadiene resin obtained in the synthesis example
A solution A was prepared by adding 0.2 ml of 1 benzonitrile and 7.2 ml of a catalyst solution containing 0.1 mol of tungsten.

Similarly, VBHIoomf was dried under nitrogen atmosphere.
10 g of the cyclopentadiene-16 resin obtained in the synthesis example, 1.2 mJ of isopropyl ether, and 1.8 mol of diethylaluminium chloride solution 2.
A solution B was prepared by adding 4m and f:.

First, 5ml each of solution A and solution B! , in a test tube 2
Mixed at 5°C and immersed in a 90°C oil bath.

Thereafter, the time required for the temperature to reach 130°C due to the exothermic reaction of the polymerization reaction (hereinafter referred to as exothermic time) was investigated.

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 2 minutes to complete the polymerization reaction in the mold to obtain a polysubstituted norbornene molded product. Take out this molded product from the mold and
Post-curing was carried out at 20°C for 30 minutes.

The physical properties of the polysubstituted norbornene thus obtained were measured, and the results are shown in the table along with the heat generation time.

Example 2 In place of the VBH 100m°C contained in solution A of Example 1, dried 5-ethylidenebicyclo[2°2.1]hept-2-ene (hereinafter abbreviated as EBH) 94.2m, 5,B
Dry EBH instead of VBH100m℃ contained in solution
A polysubstituted norbornene molded product was produced in the same manner as in Example 1 using 2 ml of 94°. The physical properties of the obtained molded product and the exothermic time measured in the same manner as in Example 1 are shown in the table.

Example 3 VBH contained in solution B of Example 1 is 100 mJ! .

A polysubstituted norbornene molded product was obtained in the same manner using dry EBH94.2mf instead. The physical properties and exothermic time measured in the same manner as in Example 1 are shown in the table.

Example 4 The amount of dicyclopentadiene resin contained in solution A and solution B of Example 1 was 20 g each, and 20 g of liquid imprene rubber (LIR-30 manufactured by Kuraray) was added to solution A. A polysubstituted norbornene molded product was produced in a similar manner. The physical properties and exothermic time measured in the same manner as in Example 1 are shown in the table.

Comparative Example 1 VBHroom, f! contained in solution A of Example 1. and 98.5 ml of dried dicyclopentadiene instead of 10 g of dicyclopentadiene resin, vB contained in solution B.
H100mj! and 98.5 m of dried dicyclopentadiene instead of 10 g of dicyclopentadiene resin, I:
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 and the exothermic time measured in the same manner as in Example 1 are shown in the table.

Comparative Example 2 Dried dicyclopentadiene 78°5m,5,B was used instead of vBaloom,e contained in solution A of Example 1.
VBHroom contained in the solution, t! A polysubstituted norbornene molded product was produced in the same manner as in Example 1, using dried dicyclopentadiene at 78.5 m°C instead of. The physical properties and exothermic time measured in the same manner as in Example 1 are shown in the table.

Comparative Example 3 Dry 5-ethylbicyclo[2,2°1]hept-
2-ene 94.2 mJl, B solution number included VBHL
If dried instead of oomf, use monoethylbicyclo[2,
2,1] Hept-2-ene 94.2ml! ,Using,
A polysubstituted norbornene molded article was produced in the same manner as in Example 1. The physical properties of the obtained molded product and the exothermic time measured in the same manner as in Example 1 are shown in the table.

Table 1. Effects of the Invention As is clear from the examples, the present invention has been achieved by using the RIM method.
-alkenylbicycloC2,2', 1.1 to 7' l-
-Producing polysubstituted norbornene using lower curing temperature and injection pressure using 2-enes and/or 5-alkylidene vinylidene vinyl[2,2,1]hept-2-enes and dicyclopentadiene resin as raw materials Moreover, the impact resistance and rigidity of the molded product obtained are superior to molded products made from dicyclopentadiene as a raw material. Also,
Vine gives faster curing time.

Patent applicant: Nippon Oil Co., Ltd.

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 has the following general formula: 5-alkenylbicyclo[2
,2,1]Hept-2-enes▲Mathematical formulas, chemical formulas, tables, etc.▼...(1) (R^1 is an alkenyl group with 2 to 5 carbon atoms, R^2 is a hydrogen atom or a carbon number 1 to 3 alkyl groups, m is 0 or 1) and/or 5-alkylidenebicyclo[2,2,1]hept-2-enes represented by the following general formula (2) ▲ Numerical formula, There are chemical formulas, tables, etc.▼...(2) (R^3, R^4 and R^5 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 0 or 1.) A method for producing polysubstituted norbornene, which comprises mixing a solution A and a solution B containing a dicyclopentadiene resin with at least one of the solutions A and B, and immediately injecting the mixture into a mold and polymerizing the solution.