JPS63234017A - Production of monomer for ring opening polymerization - Google Patents

Abstract

PURPOSE:To obtain the titled highly active monomer without purification on purpose, capable of giving thermosetting resins having high heat distortion temperature, etc. when subjected to reaction injection molding, by heat treatment of a dicyclopentadiene at specified temperatures. CONSTITUTION:A dicyclopentadiene is heat-treated, pref. in the presence of 100-1,000ppm of an antioxidant (e.g., 4,4-dioxydiphenyl), followed by, if required, mixing a norbornene monomer, thus obtaining the objective monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a monomer for ring-opening polymerization having high polymerization activity from dicyclopentadiene, and more particularly, to a method for producing a monomer for ring-opening polymerization having high polymerization activity from dicyclopentadiene. The present invention relates to a method for producing monomers for ring-opening polymerization which thereby yield thermosetting resins with high activity without special purification and which, when used in reaction injection molding, have a high heat distortion temperature and an improved flexural modulus. .

Prior art In recent years, norbornene derivatives such as dicyclopentadiene and methyltetracyclodecene have been synthesized by reaction injection molding using metathesis catalyst systems.

A method of manufacturing a thermosetting polymer by ring-opening polymerization in a mold is attracting attention.

For example, JP-A-58-129013 discloses a method for producing thermosetting dicyclopentadiene (D CP) homopolymer using a metathesis catalyst system by reaction injection molding method (CRIM method), which is a preferred method. In embodiments, the homopolymer is mixed with a solution consisting of a mixture of a monomer (DCP) and a catalyst component of a metathesis catalyst system, such as tungsten halide, tungsten oxyhalide, and a metathesis catalyst system, such as an alkyl aluminum halide. Reaction injection molding (RIM) of two solutions, one consisting of a catalyst activator and the other consisting of a monomer (DCP)
It is manufactured by combining in a machine and then pouring into a mold.

JP-A No. 59-51911 discloses an opening polymerization method using a mass of cyclic olefin containing a norbornene ring using a metathesis catalyst system in the RIM method. In this bulk polymerization method, the pot life is reduced. The use of alkoxyalkylaluminum halides and aryloxyalkylaluminium halide cocatalysts as cocatalysts (activators) has been proposed to extend the process.

However, in the conventional RIM method, the lithographic D
If CPs are used as they are, the small amount of impurities contained therein will hinder the polymerization and the polymerization activity will not be sufficient. Therefore, for example, reprinted DCP with a purity of 96 to 97% may be further added to M. However, it was necessary to remove impurities such as low-boiling distillates (Japanese Patent Application Laid-Open No. 1290-1980)
No. 13).

In order to purify DCPE, distillation has been repeated to increase its purity. However, this method lowers the recovery rate of DCP, and even when purified to a high degree of purity, it often becomes inert to the polymerization reaction conditions in reaction injection molding.

Recently, a method has been proposed in which the reprinted DCP is distilled and further treated with adsorbents such as sieves, alumina, and silica gel to remove impurities that interfere with polymerization (U.S. Pat. No. 4,584,425). ), however, this method has insufficient distillation performance, requiring a large amount of initial distillation and residue to be left behind, resulting in a low yield of high-purity DCP. There are disadvantages from an industrial perspective, such as an increase in the number of processing steps using adsorbents and disposal of waste adsorbents.

Moreover, the ring-opened polymers produced by these disclosed methods are
Although it has relatively good performance in various physical properties required for engineering plastics such as impact resistance, high modulus of elasticity, and thermal properties of i+, it is still not necessarily sufficient considering the recent strict performance requirements. For example, the glass transition temperature of the DCP homopolymer obtained by these methods is usually around 90° C., which is somewhat insufficient as a material for fields requiring thermal properties.

Incidentally, in this case, as the norbornene monomer used becomes polycyclic, that is, as the number of cyclic structural units in the monomer increases, the heat distortion temperature of the resulting polymer increases. However, it is difficult to obtain high-purity polycyclic monomers, and since they are often solid, RI
Injection into a mold using the M method becomes difficult.

JP-A-61-179214 discloses that in order to increase the glass transition temperature (Tg) and improve the heat distortion temperature of a polymer product, a norbornene monomer such as DCP and, for example, trimethylolpropane-tris-(5-norbornene −
A copolymerization method with a comonomer having 11 or more reactive double bonds, such as 2-carboxylate), which increases the number of crosslinks by cleavage during one polymerization, has been disclosed. This method requires the use of special comonomers that are difficult to obtain, and is economically disadvantageous.

Problems to be Solved by the Invention As a result of extensive research in order to overcome the above problems, the present inventors have discovered that the products obtained by heat treatment of dicyclopentadines can be used alone or in combination with fulbornene. A mixture of these monomers has high polymerization activity, and by ring-opening polymerization of these in a mold with a predetermined shape in the presence of a metathesis catalyst system, it has a high glass transition point. However, the present inventors have discovered that a thermosetting resin with improved flexural modulus can be obtained, and based on this knowledge, they have completed the present invention.

A means for solving the problems, that is, the gist of the present invention is to provide a method for ring-opening polymerization, which is characterized in that dicyclopentadiene is heat-treated at 120 to 250°C, and then, if necessary, a norbornene monomer is mixed therein. It is in the method of manufacturing monomers.

Hereinafter, the constituent elements of the present invention will be explained in detail.

(Dicyclopentadines) The raw material dicyclopentadines used in the present invention usually has a purity of 90% by weight or more, preferably 9% by weight or more.
If it is 5% by weight or more, it is not necessarily necessary to purify it in advance, and the heat-treated product is highly active and yields a good ring-opened polymer.

Dicyclopentadines usually contain low-boiling point impurities and high-boiling point impurities as impurities, and specific examples of the former include hydrocarbons having 4 to 6 carbon atoms, chains such as cyclopentadiene and butadiene, isoprene, piperylene, etc. Examples of the latter include co-dimers with conjugated diolefins (vinylnorbornene, isopropenylnorbornene, propenylnorbornene, etc.); Codimerized product (methylbicyclononadene)
Examples include. Among these, hydrocarbons having 4 to 6 carbon atoms cause molding defects in reaction injection molding, so conventionally they had to be sufficiently removed, but in the present invention,
Even if the purity is 98% or less, it has sufficient polymerization activity.

The dicyclopentadiene used in the present invention is an alkyl substituted analyte such as dicyclopentadiene (DCP) or its methyl substituted product or ethyl substituted product. The starting DCP is an endo isomer, an exo isomer or a mixture thereof.

(Heat treatment of dicyclopentadines) The conditions for heat treatment are that dicyclopentadines are treated in an atmosphere of an inert gas such as nitrogen gas at a temperature of 120 to 250°C, preferably 150 to 220°C, and a temperature of 0.5 to A method of heating for 20 hours, preferably 1 to 10 hours is mentioned.

The reaction format of the treatment may be either batch or continuous.Also, during the treatment, a solvent inert to the reaction such as benzene, toluene, xylene, etc. may be coexisting, but in this case, the solvent may be removed after the treatment. Since this requires an operation to remove , it is preferable to perform the treatment without using a solvent as much as possible.

In addition, it is preferable that the S treatment be carried out in the presence of an antioxidant, and phenolic antioxidants are preferred.
For example, 4,4-dioxydiphenyl, hydroquinone monobenzyl ether 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2
．． 6-di-7milhydroquinone, 2,6-di-t-butyl-P-cresol, 4-hydroxymethyl-2.

6-di-t-butylphenol, 4,4'-methylene-
Examples include bis-(6-t-butyl-O-cresol), butylated hydroxy 7-nisole, phenol condensates, butylenated phenols, dialkyl phenol sulfides, high molecular weight polyhydric phenols, and bisphenols. Quinones such as t-butylcatechol, hydroquinone, resorcinol, and pyrogallol can also be used. The amount of antioxidant used is usually 10% for DCPs.
N10, OOOppm, preferably 100~l・OO
It is OPPm.

The obtained product can be used as it is as a raw material for producing a thermosetting resin by ring-opening polymerization, but if necessary, unreacted DCPs or low-boiling impurities may be removed by distillation.

The products obtained by heat treatment of DCPs are:

It is waxy or oily. The waxy type usually has a freezing point of 100°C or lower, preferably 60°C or lower, and the oily type usually has a viscosity of 200 centipoise (c p s) or lower at 30°C, #? Preferably, the power is less than 100 cps. These products contain unreacted DCPs and thermally reacted products of DCPs, but in the present invention, the thermally reacted products of DCPs are contained in an amount of 5% by weight.
Those containing 10% by weight or more are preferable.

(Norbornene No. 7) In the present invention, norbornene No. 7, which is used in combination with the heat-treated product of DCPs as needed, is substituted or unsubstituted norbornene.

Dicyclopentadiene, dihydrodicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, tetracyclododecene, etc. Specific examples include dicyclopentadiene, methyltetracyclododecene, 2
-norbornene, 5-methyl-2-norbornene, 5,
Examples include 6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-dodecyl-2-norbornene, etc. It will be done.

(Mixing the heat-treated product of DCPs and norbornene monomer) The waxy or oily product obtained by heat-treating DCPs can be used alone as a monomer for ring-opening polymerization, but if necessary, it may be mixed with a norbornene monomer. It is possible to use them in combination. In that case, the mixing ratio of the heat-treated product and the norbornene monomer may be appropriately selected depending on the purpose, but usually the former is 100 to 10% by weight, preferably 100 to 20% by weight, and the latter is O to 90% by weight.
% by weight, preferably 0 to 80% by weight, and it is preferable that the thermally reacted product of DCPs contained in the heat-treated product is present in the mixture at 5% by weight or more, more preferably 10% by weight or more. As the proportion of the product decreases, the glass transition temperature and flexural modulus of the resulting thermosetting 4# resin decrease.

Although there are no particular limitations on the properties of the mixture, it is advantageous for operations such as injection into a mold to be liquid at 30°C, preferably 10°C.

The viscosity of the liquid at 30° C. is usually 500 cps or less, preferably 200 cps or less, particularly 100 cps or less.

In addition, it is possible to lower the freezing point by adding a polymer modifier such as an elastomer or DCPII resin, or a filler to the heat-treated product or mixture. It is sufficient if the mixture containing the above is liquid at the above temperature.

The heat-treated product and the norbornene monomer can be easily mixed using a mixer such as a power mixer, static mixer, or collision mixer. However, if the heat-treated product is wax-like, the heat-treated An efficient method is to mix the molten state with the norbornene monomer after completion of the process.

(Other optional components) Various additives such as fillers, antioxidants, pigments, colorants, and polymer modifiers can be blended into the monomer for ring-opening polymerization of the present invention, and the resulting The properties of ring-opened polymers can be modified.

Fillers include inorganic fillers such as glass, carbon black, talc, calcium carbonate, and mica.

Polymer modifiers include elastomers and thermopolymerized DCP resins.For example, blending an elastomer can increase the impact strength of a thermosetting resin, and blending a thermopolymerized DCP resin can further improve the flexural modulus. can do. The polymer modifier is dissolved and blended into the seven-mer reaction solution.

Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block combination, ethylene nia tr-pyrene terpolymer, and the like. The proportion of these used is usually 0.1 to 20% by weight.

(Polymerization method of monomer for ring-opening polymerization) The monomer for ring-opening polymerization of the present invention can be polymerized using a known metathesis catalyst and activator.

That is, by a polymerization method in which the heat-treated product of the present invention or a mixture of the product and a norbornene monomer is introduced into a mold of a predetermined shape and bulk polymerized in the mold in the presence of a metathesis catalyst system, Thermosetting S+ can be manufactured. Substantially bulk polymerization is sufficient, and the presence of a small amount of inert solvent is acceptable.It is preferable to use the metathesis catalyst system by dissolving it in a 7-mer solution. It may be used by suspending or dissolving it in a small amount of solvent as long as it does not adversely affect the product's performance.

In a preferred method for producing a thermosetting resin, the heat-treated product or a mixture of the product and a norbornene monomer is divided into two liquids and placed in separate containers, one containing a metathesis catalyst and the other containing an activator. to prepare two stable reaction solutions. These two types of reaction solutions are mixed and then poured into a mold kept at a high temperature, where open tetrapolymerization in bulk is initiated to obtain a thermosetting resin.

In the polymerization of the monomer for ring-opening polymerization of the present invention, an impingement mixer conventionally known as a RIM molding device can be used to mix the two reaction solutions. In this case, the vessels containing the two reaction solutions become sources of separate streams. The two streams are instantaneously mixed in a RIMa& mixing head and then injected into a hot mold where they undergo instant bulk polymerization to obtain a thermoset resin.

As described above, an impingement mixing device can be used, but is not limited to such a mixing means, and when the pot life at room temperature is as long as 1 hour, mixing of two reaction solutions in a mixer is possible. After completion of the injection, injection or injection into the preheated mold may be performed once or several times (see, for example, Japanese Patent Application Laid-Open No. 59-51911).
This method has the advantage that the device can be made smaller and can be operated at lower pressure than an impingement mixing device.

In addition, the polymerization method is not limited to the case where the above two types of reaction solutions are used, but as can be easily understood by those skilled in the art, for example, the reaction solution and additives are placed in a third container and the Various modifications are possible, such as using it as a third flow.

The mold temperature is 50°C or higher, preferably 60-200°C, particularly preferably 90-130°C. Mold pressure is usually 0
．． It is within the range of 1 to 100 Kg/Cm''.

The polymerization time may be selected as appropriate, but is usually shorter than about 20 minutes, preferably 5 minutes or less.

It may be longer.

Note that the bipolymerization reaction components must be stored and operated under an inert gas atmosphere such as nitrogen gas, and the mold may or may not be sealed with an inert gas.

In this way, the seven-spot produced by the production method of the present invention is a normal R
Since it is possible to polymerize by the IM method and it is not necessarily necessary to highly purify DCPs, there is an advantage that the monomer cost can be kept low.

(Properties of Thermosetting Resin) The bulk polymer obtained using the seven polymers of the present invention is a thermosetting resin that becomes a hard solid when cooled. The glass transition point (Tg) is 95°C or higher, preferably 100°C or higher, and has a high heat distortion temperature.

EXAMPLES The present invention will be described in more detail with reference to examples and reference examples below, but the present invention is not limited to these examples only. All parts, ratios, and percentages are based on total weight. be.

Example 1 700 g of 98.5% pure dicyclopentadiene (D CP) containing 500 ppm of 2,6-di-tert-butylphenol (BIT) was placed in a large autoclave.
After the preparation and sufficient nitrogen replacement, the temperature was raised to 170℃, and
An oily substance was obtained after reacting for a period of time. The viscosity of this oil is 30
10 cps at °C and one composition has 75% unreacted DCP.
, the trimer or higher component of cyclopentadiene (cp) was 25%.Example 2 A waxy product was produced in the same manner as in Reference Example 1, except that the reaction conditions were 180°C for 4 hours. I got something. This waxy product has a freezing point of 50°C (viscosity at 55°C is 30 cps), 40% unreacted DCP, CP
The composition was 60% composed of Sankeitai or higher components.

Table 1 shows the solidification points obtained when DCP was roughly added and mixed to the waxy product thus obtained and the mixing ratio was varied.

Table 1 Example 3 94.5% pure DCP containing 500 ppm BHT (
CP dimer, containing 3.2% penylnorborneso and impropenylturbo as impurities, A-0
, 7%, heel norbornene O 82%, other 1.4%
Example 1 except that 1 containing Nippon Zeon Co., Ltd.) was used.
Heat treatment was performed in the same manner as above, and the viscosity at 30°C was 10c.
An oil of ps was obtained. The composition of this oil is the unreacted DC
P was 76%, and components of CP trimer or higher were 24%.

Reference Example 1 The oil obtained in Example 1 was placed in two containers, and one contained:
Diethylaluminum chloride (D E
A C) at 33 mmolar concentration and n-propatool at 4.
Each was added to a concentration of 95 mmol (solution A).

On the other hand, a CB solution in which tri(tridecyl)ammonium molybdate was added to the oil at a concentration of 4 mmol).

Both reaction solutions A and B were mixed at a ratio of 1:1. This mixture maintained a stable state with no viscosity change for 1 hour at 35°C (hereinafter referred to as pot life).

Both reaction solutions were quickly poured into a mold having a spatial coverage of 200×200×2 mm and heated to 90° C. using a gas pump and a power mixer. Injection time was approximately 15 seconds. 30 seconds after the end of the injection, a sudden heat was generated and the reaction started. Then, the reaction was carried out in the mold for a total of 3 minutes. These series of operations were performed under a nitrogen gas atmosphere.

The glass transition point of the molded product thus obtained was measured to be 110°C, and the flexural modulus was 21.000K.
g/crn'.

Reference Example 2 Using a mixture of each composition shown in Table 1 of Example 2, molding was carried out in exactly the same manner as in Reference Example 1 (however, the wax-only mixture was heated to a liquid temperature of 55°C and injected). I got the item. Table 2 shows the pot life, glass transition point, and flexural modulus of these molded products.

(Left below) #! Table 2: Pot life at 5°C - end of crop rotation at 50°C Example 4 A mixture consisting of 50 parts of the waxy product obtained in Example 2, 30 parts of DCP, and 20 parts of methyltetracyclododecene was added to each It was prepared by mixing the ingredients at 55°C. The freezing point of the mixture is below 0℃, and the viscosity at 30℃ is 200P
It was S.

Using this mixture, polymerization was carried out in the same manner as in Reference Example 1, and the resulting molded article had a Tg of 130° C. and a flexural modulus of 27,500 Kg/Cm''.

Reference Example 3 The oil obtained in Example 1 was placed in two containers, and one contained:
DEAC was added to the oil at a concentration of 48 mmolar, and tungsten hexachloride was added to the other vessel at a concentration of 7 mmolar. The two types of reaction solutions prepared in this way were mixed at a mixing ratio of 1:1.
Using a collision mixing type RIM machine, the same mold as in Reference Example 1,
Injection molded under temperature conditions.

The molded article thus obtained had a Tg of 168°C. The pot life of the mixture at 35°C is approximately 1
It was 5 seconds.

Reference Example 3 A molded article was obtained in the same manner as in Reference Example 1 except that the oil obtained in Example 3 was used. The Tg of the obtained molded product is 105
℃, and the flexural modulus was 21,000 K g/Crn'.Example 5 A wax-like product was produced in the same manner as in Example 2 except for using the DCP with a purity of 94.5% used in Example 3. I got something. This waxy product had a freezing point of 45°C and a viscosity of 30 cps at 50°C. Furthermore, the composition was 42% unreacted DCP and 58% CP trimer or more.

50 parts of the waxy product thus obtained.

A molded article was obtained using a mixture containing 50 parts of DCP in the same manner as in Reference Example 1.

The freezing point of the mixture is 3℃, the Tg of the obtained molded product is 115℃, and the flexural modulus is 23.500K g/c
It was m''.

Effects of the Invention According to the present invention, it is possible to produce a hexamer for ring-opening polymerization having a high degree of polymerization activity by simply heat-treating dicyclopentadiene or by mixing the heat-treated product with a norbornene monomer. Crude D that can be obtained and contains impurities
Even in the case of CP, it is not necessary to carry out special purification such as distillation, so the cost can be reduced.

Moreover, by using this 7-mer, it is possible to economically obtain a thermosetting resin that has superior heat deformation temperature and flexural modulus compared to conventional polyDCP polymers. This resin has the excellent effect of being applicable to various fields requiring heat resistance.

Claims (1)

[Claims] A method for producing a monomer for ring-opening polymerization, which comprises heat-treating dicyclopentadiene at 120 to 250°C, and then mixing a norbornene monomer as necessary.