JPS61120814A - Production of polydicyclopentadiene - Google Patents

Abstract

PURPOSE:To produce the titled polymer excellent in heat resistance and solvent resistance in a mold without permitting polymerization at room temperature, by adding an alcohol to the second organoaluminum compound-containing part of a composite catalyst system comprising two parts and polymerizing dicyclo pentadiene by a RIM process. CONSTITUTION:In a process for producing polydicyclopentadiene by a RIM process by using a catalyst system comprising a W compound and an organoaluminum compound, the first part of the composite catalyst system contains the W compound, the second part contains the organoaluminum compound, at least one of these parts contains dicyclopentadiene as a monomer to be polymerized, and an alcohol as an activating modifier is added to the said part containing the organoaluminum compound. No polymerization of the monomer occurs at room temperature, and therefore no large force is necessary for mixing the catalyst solutions and they can be poured into a mold by using a low pressure. It is also possible to premix the catalyst solutions. Because the polymerization reaction can proceed gently without violent generation of heat, a polymer excellent in uniformity, heat resistance and solvent resistance can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to polydicyclopentadiene [hereinafter referred to as poly(D
Regarding the manufacturing method of ``oPD'', for more details, please refer to the reaction injection molding (hereinafter referred to as ``RIM'') method.
Regarding the manufacturing method of J (DCFD).

Prior Art □ Methods for producing poly(DOPD) using catalyst systems consisting of tungsten compounds and organoaluminum compounds are known. However, this method has the problem of producing insoluble by-products. In addition, US Pat.
．． 5° recently disclosed in No. 492.245,
A method has been proposed in which dicyclopentadiene (hereinafter referred to as DO'FD) is polymerized by the RI'M method using a metathesis catalyst system consisting of two parts (Japanese Patent Laid-Open No. 5'8-1).
29013).

The first part of this two-part metathesis catalyst system contains a tungsten compound, the second part contains an organoaluminum compound, and at least one of these two parts contains the polymerizable monomer DCPD. . The catalyst system of this second part then contains an ester, ether, keto/or nitrile as an activity modifier.

However, when the polymerization monomers and the two-part metathesis catalyst system are mixed in the presence of the above-mentioned activity modifiers, the polymerization reaction begins immediately at room temperature, so mixing must be done immediately before filling the mold. Moreover, there are disadvantages such as requiring a large force at the mixing stage and also requiring a large pressure to fill the mold. Furthermore, the generated poly(DCFD
) also have insufficient heat resistance and solvent resistance.

Problems to be Solved by the Invention The present invention shows that when DCPD and a metathesis catalyst system are mixed, it is possible to produce poly(DIOPD) which does not undergo a polymerization reaction at room temperature and has excellent heat resistance and solvent resistance. (D.O.
The purpose of this invention is to provide a method for producing PD.

Means for Solving the Problems Summary of the Invention As a result of intensive research, the present inventors have developed a second compound containing an organoaluminum compound of a metathesis catalyst system consisting of two parts.
The present invention was achieved by discovering that the object of the present invention can be achieved by using alcohol as an activity regulator in a method of polymerizing by the DOPD'jzRIM method using an activity regulator in combination with the moiety. .

That is, the gist of the present invention is to mix a solution (A) and a solution (B), at least one of which contains dicyclopentadiene, to form a mixed solution, and then to mix the mixed solution. A method for producing polydicyclopentadiene comprising injecting it into a mold and polymerizing it (a) A solution containing a tungsten compound (A), (b)
Solution containing organoaluminum compound and alcohol (B
), It is in.

Metathesis Catalyst System One of the two-part metathesis catalyst system is a solution containing a tungsten compound (solution A). Examples of the tungsten compound include tungsten hexachloride and tungsten oxytetrachloride, and preferably large tungsten chloride.

Another metathesis catalyst system is a solution containing an organoaluminum compound and an alcohol (solution B). Examples of organoaluminum compounds include trialkylaluminum such as triethylaluminum and triisobutylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride,
Dialkyl aluminum chloride such as dialkyl aluminum chloride, ethyl aluminum dichloride, n-
Examples include alkylaluminum dichlorides such as butylaluminum dichloride, and among these, dialkylaluminum chloride is preferred, and diethylaluminum chloride is particularly preferred. Two or more types of these organoaluminum compounds can be used.

Examples of the alcohol contained in the solution (B) as an activity regulator include aliphatic alcohols having 1 to 6 carbon atoms, and among them, ethanol and n-propanol are preferable.

Solution (A) contains a tungsten compound, and solution (B) contains an organoaluminum compound and alcohol, respectively.
D and/or by dissolving it in a solvent.

Examples of solvents that can be used include benzene, triene, chlorobenzene, dichlorobenzene, trichlorobenzene, and the like.

One of solution (A) and solution (El) is DOPD
However, preferably both solutions contain D
The solution is a solution containing OPD, and more preferably both solutions are solutions containing DOPD as a solvent.

Solution (A) may contain a phenolic compound to increase the solubility of the tungsten compound. Examples of the phenol compound include phenol, alkylphenol, halogenated phenol, etc., and alkylphenols such as t-butylphenol, t-octylphenol, and nonylphenol are particularly desirable. The amount of phenol compound used is usually 1 to 1 mole of tungsten compound.
It is 6 moles. Furthermore, the solution fA) contains DCF in the solution
To prevent early polymerization of D, tungsten compound 1
Each mole can contain from about 1 to about 5 moles of Lewis base or chelating agent. Preferred chelating agents are acetylacetone, acetoacetic acid alkyl esters, etc., and preferred Lewis bases are nitrites such as benzonitrile and ethers such as tetrahydrofuran.

The molar ratio of the organoaluminum compound and alcohol in the solution (Bl) is 17Q, 1 to 1/5.O1, preferably 1102 to 1/30, particularly preferably 1/0.
The molar ratio of DOPD and tungsten compound in the polymerization system is 5 to 1/1.7.
1,000/1 to 1,500/1, preferably 2,00
0/1 to 5,000/1, and the molar ratio of polymerized DOPD to organoaluminum compound is 100/1 to 2,000/1.
1, preferably 200/1 to 500/1, and this can be adjusted by appropriately changing the concentrations of both solution (A) and solution (B). or,
The ratio of the tungsten compound and the organoaluminum compound used is 1 mole of the tungsten compound and 2 to 20 moles of the organoaluminum compound, preferably 5 to 10 moles. B) is further mixed with D" OP D as necessary, and the resulting mixture is injected into a mold and reacted. The mixing of both solutions is usually done by injecting into a mold. However, it is also possible to pre-mix.The method according to the invention is advantageously carried out using conventional RIM equipment.

In the polymerization reaction, it is necessary to avoid as much as possible the contamination of moisture, oxygen, etc., which inhibit the reaction.

In addition, it is an effective means to carry out the polymerization reaction in the presence of an inert gas such as dry nitrogen gas1. This is carried out at 100° C. for 50 seconds to 2 minutes.

Effects of the Invention According to the method of the present invention, polymerization does not occur at room temperature. Therefore, no great force is required to mix the solution (A) and the solution (B), and low pressure is sufficient for injection into the mold.

It is also possible to prepare and mix solution (A) and solution (B) in advance.

Furthermore, since the polymerization reaction proceeds slowly without rapid heat generation, uniform IJ (DCFD) can be produced, and the resulting polymer has excellent heat resistance and solvent resistance.

Example Hereinafter, the present invention will be explained in detail with reference to Examples.

In addition, the word "chi" in the example is based on Shigeyoshi.

Example 1 Tungsten hexachloride (WCl2) 1.58y, p-
A catalyst solution was prepared by mixing t-butylphenol 1152y and toluene 35- in the presence of nitrogen gas. Next, in the presence of nitrogen gas, g 5 ml of this catalyst solution, D
OP D 10”rl and tetrahydrofuran n[
]66m to form solution (A) (WCl60.053
mol/1) was prepared.

In the presence of nitrogen gas, diethyl aluminum chloride (D
Equal moles of KAC and n-glopanol DOP
Dissolve in D, solution (B) (DtAoo2 mol/z)
was prepared.

Then, in the presence of nitrogen gas, D OP D 25 m1
1 solution (A) 2.8 art and solution (B) 4.6
5 ml were mixed.

It remained a homogeneous solution at room temperature. This solution could be poured into a mold at 70° C. without applying pressure. Upon injection, the solution immediately hardened to yield poly(DOPD).

The Vicat softening point and solvent resistance of this poly(DOPD) were measured, and the results are shown in the table below. Diisopropyl ether DBA'01
Solution (B) was prepared in the same manner as in Example 1 except that 92 mol per mol was used.

D OjD 2.5ml and solution (B) 4.6511/
were mixed in advance, and the solution prepared in Example 1 (
A) When 2.8rnl was added, it immediately generated heat and hardened, and a homogeneous solution was not obtained3. Therefore,
Injection into the mold used in Example 1 was not possible.

Comparative example 2 p, DOPD by RIM machine for polyurethane production.

DCFD was polymerized using the solution (A) prepared in Example 1 and the solution (B) prepared in Comparative Example 1 in the same proportions as in Comparative Example 1. The Picat softening point and solvent resistance of the obtained poly(DOPD) were measured and the results are shown in the table.

Example 2 BoIJ (DOPD) was produced in the same manner as in Example 1, except that ethanol was used in equimolar amounts as DEAC instead of the n-propanol used when preparing the solution (B) in the actual flow side 1. was manufactured. Note that the solution before being injected into the mold was a homogeneous solution at room temperature), and the injection into the mold was also the same as in Example 1.

The physical properties of the obtained BoI) (DOPD) are shown in the table. .

Examples 6 and 4 When preparing the solution (B) of Example 1, n-propanol was added to DKAC in an amount equivalent to 1 mol, 0.7 mol (Example 3), or 1,
Po! was carried out in the same manner as in Example 1 except that 3 mol (Example 4) was used. j (DOPD) was produced.

The physical properties of the obtained poly(DOPD) are shown in the table. In addition,
The state of the solution before injection into the mold and the conditions of injection into the mold were the same as in Example 1.

Claims (1)

[Claims] Two solutions having the following composition, at least one of which contains dicyclopentadiene (A) and solution (B) are mixed to form a mixed solution, and then the mixed solution is placed in a mold. (a) A solution containing a tungsten compound (A); (b) A solution containing an organoaluminum compound and alcohol (B)
.