JP2716515B2 - New silane compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention is used as a silane coupling agent having excellent performance as a surface treatment agent for reinforcing materials such as glass fibers when a specific polymer is used as a matrix resin. It relates to a novel silane compound. More specifically, in the presence of a metathesis polymerization catalyst,
The present invention relates to a novel silane compound which can be used as a silane coupling agent having excellent performance as a surface treating agent such as glass fiber as a reinforcing material for a resin which simultaneously performs polymerization and molding.

b. Prior Art When an inorganic reinforcing material such as glass fiber is used as a reinforcing material for an organic resin, the inorganic reinforcing material is treated with a silane coupling agent in order to improve the adhesiveness. Such a silane coupling agent is a compound having both a portion that contributes to adhesion to an inorganic reinforcing material through a silanol-based group and an organic group portion that has strong interaction with a resin used. As for the organic group portion, an appropriate one naturally depends on the structure of the resin used.

Silane cups that provide good adhesion to polyester resins (both saturated and unsaturated types), epoxy resins, phenolic resins, polyurethane resins, polyamide resins, etc., which have been often used together with inorganic reinforcing materials, have been used. Ring agents are already commercially available. However, for a new resin, particularly a resin utilizing a new chemical reaction, it is necessary to try a silane coupling agent suitable for it.

In recent years, as such a new resin, a resin that simultaneously performs polymerization and molding of such a monomer using a cyclic olefin as a monomer in the presence of a metathesis polymerization catalyst has been receiving attention.

It is known that cyclic olefins provide ring-opened polymers with metathesis polymerization catalyst systems. Thus, a method has been proposed in which a metathesis-polymerizable cyclic olefin, such as dicyclopentadiene (DCP), which is inexpensively obtained, is polymerized and molded in one step in a mold using a metathesis polymerization catalyst system to obtain a polymer molded product. That is, utilizing the fact that the metathesis polymerization catalyst system is composed of two components, a catalyst component such as tungsten chloride and an activator component such as alkylaluminum, two types of liquids comprising each two components and a monomer are used. Thus, a method has been proposed in which, after rapid mixing at the time of polymerization, the mixture is poured into a mold to obtain a polymer molded product (see, for example, JP-A-58-1290).
No. 13).

According to this method, a large molded product can be obtained using an inexpensive low-pressure mold. Moreover, such a molded product has a good balance between rigidity and impact resistance, and can be said to be a very industrially attractive method.

However, it has been found that for some applications, higher stiffness, higher dimensional stability, and even improved heat distortion temperatures are often required.

The use of an inorganic filler as a solution for simultaneously achieving the three important improvements in performance of such a molded product, particularly, a method using an inexpensive and effective glass reinforcing material and other inorganic reinforcing materials is given. Thus, a silane coupling agent that is useful for bonding such a resin to an inorganic reinforcing material such as glass fiber has become necessary.

A silane coupling agent for a resin that is molded simultaneously with such metathesis polymerization is not well known in the past, but considering the principle for obtaining a silane coupling agent having good adhesion to conventional various resins. Thus, it is considered that a silane coupling agent having a metathesis-polymerizable organic group should be designed because the resin is cured by metathesis polymerization and comes into contact with glass fibers. As such a metathesis polymerizable group, good polymerizability,
A norbornene structure can be considered as a group that can be easily synthesized. As the silane compound having a norbornene group, a vinylsilane compound is generally derived.
For example, triethoxynorbornenyl silane is known. However, the norbornene ring of such a silane compound is directly connected to the silicon atom, and is easily obtained from a place where it is considered that the norbornene ring should be located farther from the silicon atom in order to participate in the resin formation reaction. As a result of intensive studies to obtain a novel silane compound derived from a possible raw material and having a norbornene ring at least not directly bonded to a silicon atom, the present invention has been achieved.

c. Configuration of the Invention In other words, the present invention focuses on a methacrylsilane-based coupling agent which is currently most commonly used as a silane coupling agent for an unsaturated polyester resin used together with an inorganic reinforcing material. By reacting the methacryl group of such a coupling agent with cyclopentadiene, a novel silane compound containing a norbornene ring has been successfully obtained.

 That is, the present invention includes the following inventions.

Formula (I) A novel silane compound represented by the formula:

As a method for producing such a novel silane compound, a method of obtaining the silane compound by a reaction between (meth) acrylsilanes and cyclopentadiene which are easily available as described above is most preferable.

Such a reaction may be carried out in the presence of an inert solvent, but since both components are liquid, they can be easily carried out without a solvent.In general, under an inert atmosphere, since cyclopentadiene has a low boiling point, the reaction is carried out in an autoclave. The reaction may be carried out at a temperature of 60 to 200 ° C, particularly preferably 100 to 140 ° C, and a reaction time of 0.5 to 10 hours, particularly preferably 1 to 4 hours. The molar ratio of the two raw materials should theoretically be 1: 1. However, since cyclopentadiene itself causes a self-Diels-under addition reaction and produces dicyclopentadiene and tricyclopentadiene as by-products, it was added (meta- If it is desired to react acrylsilanes as much as possible, it is preferable to use cyclopentadiene in excess. However, in this case, a considerable portion of the cyclopentadiene is to be a by-product, and conversely, it is also possible to use (meth) acrylsilanes in excess, to recover and reuse them. The decision should be made in consideration of the above advantages and disadvantages.

After completion of the reaction, unreacted raw materials and by-products as described above are distilled off from the reaction mixture, and in principle, the novel silane compound of the present invention may be further distilled. In general, such a silane compound should be able to be distilled.However, this novel silane compound has a possibility that the norbornene ring in its structure may be dissociated into the original raw material by a reverse Diels-Under reaction. Selection is difficult, and for use as a general silane coupling agent, it is possible to use unreacted raw materials and by-products sufficiently distilled without such purification. Further, when it is desired to purify, for example, by selectively extracting with an immiscible solvent having a different polarity, such as methanol and heptane, it can be separated from impurities to obtain a product of good purity.

The most preferable method for producing the novel silane compound of the present invention is described above, but it can also be obtained by other methods.

The (meth) acrylsilane-based compound as the raw material is generally obtained by the following reaction.

Similarly to this reaction, a method of synthesizing allyl norbornene carboxylate in which allyl (meth) acrylate is first reacted with cyclopentadiene and subjecting it to an addition reaction with trialkoxysilane can be considered, but in this case, Si-H is added. Although there are two possible double bonds and the by-product is generated as shown in the following formula, the target product can be obtained, but it is hard to say that it is an excellent production method.

When using norbornene carboxylic acids as a raw material, a method based on a reaction with chloropropylsilanes which are commercially available as a silane coupling agent can be used.

In addition, it is possible to obtain a novel silane compound of the present invention by utilizing a known chemical reaction of a silane compound, and the silane compound can be effectively used as a silane coupling agent or the like regardless of the production method. However, considering the conditions such as the raw material and post-treatment, the method according to the formula (II) is most preferable as described above.

The structure of the novel silane compound of the present invention can be confirmed by NMR, IR and the like.

The actual application of such a novel silane compound as a silane coupling agent is generally carried out by using an inorganic filler previously treated with a silane coupling agent, or conversely, adding the silane coupling agent to a polymerizable solution. And a method in which silane treatment of the inorganic filler is performed simultaneously with curing.

The latter method has the advantage that the step of silane treatment of the inorganic filler can be omitted, but the silane treatment of the inorganic filler is
Contact with the polymerizable solution also occurs at the same time, and silane treatment must be performed under the same conditions, the silane coupling agent needs to be added in a considerably larger amount than the theoretically required amount, and It is necessary that the silane coupling agent added in this way does not affect the polymerization reaction, but in the case of a metathesis polymer to which the silane compound of the present invention is applied, as described above, the metathesis polymerization reaction It is sensitive to the coexistence of polar compounds, and the progress of polymerization is fast, so there is no difficulty in proceeding simultaneously with the silane treatment,
The application of the former method is preferred.

In the former case, the silane coupling agent diluted with a solvent is generally brought into contact with the inorganic filler during the silane treatment of the inorganic filler, and the silane coupling agent is fixed to the surface of the inorganic reinforcing material by drying and heat treatment. Will be. As such a solvent, water is most preferable from an industrial point of view, and then, a mixture of water and a polar organic solvent such as alcohol or acetone is used, which is suitable in terms of miscibility with the solvent and processing speed. Will be selected.

As the inorganic filler, a glass reinforcing material can be cited as the most commonly used one.

As the glass reinforcing material, any material such as a fibrous material and a powdery material can be used.

As described above, the treatment for applying the novel silane compound of the present invention to a glass reinforcing material as a silane coupling agent can be performed using a method established as a method for applying a general silane coupling agent to a glass reinforcing material as it is. Come.
In particular, in the case of glass fiber reinforcement based on chopped or continuous strand, a silane coupling agent is added to one component of the oil agent at the time of spinning, and the silane coupling agent is attached at the same time during the spinning process. You can also take the method of doing it.

In addition to the glass reinforcing material, inorganic fillers having —OH groups capable of bonding to the silane treatment agent on the surface can similarly improve the adhesion to the metathesis polymer by the silane treatment agent. Of these inorganic materials, not only oxide-based inorganic materials, but also nitrides and carbides are often actually oxidized on the surface to have OH groups, and the effect can often be exerted.

Examples of such a fibrous inorganic filler include wollastonite, potassium titanate, and alumina fiber, and various mica as a plate-like material.

Examples of powdered materials include kaolin, calcined clay, quartz powder,
Examples include silica stone powder, feldspar powder, talc, aluminum silicate, alumina, and other various ceramic powders. Specific examples of such inorganic fillers include various inorganic pigments. That is, it can be used for improving the dispersibility of fine powder pigments such as titanium oxide and iron black.

The resin used to reinforce the inorganic reinforcing agent treated with the silane compound according to the present invention is obtained as a molded product by performing the molding simultaneously with the polymerization of a metathesis polymerizable cycloolefin in the presence of a metathesis polymerization catalyst as described above. However, preferred specific examples of the metathesis polymerizable cycloolefin monomer include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, norbornene, norbornadiene, and 5-cyclohexenyl norbornene. , 1,4,5,8
-Dimethano-1,4,4a, 5,6,7,8,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7,8,8,8a-octa Hydronaphthalene, 6-ethylidene-1,4,5,8-dimethano
1,4,4a, 5,7,8,8,8a-Heptahydro-naphthalene, 6-methyl-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a- Heptahydronaphthane, 1,4,5,8-dimethano-1,4,4a, 5,8,8a-
Examples thereof include one or a mixture of two or more kinds of cyclic olefins having 1 to 3 norbornene structures such as hexahydronaphthalene and ethylenebis (5-norbornene). Particularly, dicyclopentadiene or a monomer containing the same as the main component Mixtures are preferably used.

Further, if necessary, a metathesis polymerizable cyclic compound having different elements such as oxygen and nitrogen can be used. Such polar monomers are often used in copolymerization with dicyclopentadiene or the like.

The metathesis polymerization catalyst is composed of a main catalyst component and an activator component.

As the main catalyst component, a compound such as a halide such as tungsten, rhenium, tantalum or molybdenum is used after being solubilized in a monomer.

However, if the monomer is brought into contact with the halide as it is, cationic polymerization may occur. In order to prevent the cationic polymerization, a method of preventing the polymerization with a chelating agent or the like may be used. Thus, one stable reactive solution containing the main catalyst component can be obtained.

On the other hand, as the activator, an organometallic compound such as aluminum or tin is generally used, and the other reaction solution is formed by dissolving these in a monomer. In this case, a Lewis base is added for the purpose of adjusting the reactivity of the activator.

Further, in such a reactive solution, in practical use, to improve or maintain the properties of the obtained polymer,
Further, various additives are blended. Such additives include fillers, pigments, antioxidants, light stabilizers,
Flame retardants, polymer modifiers, etc. Even in such an additive, a molded product is obtained at the same time as polymerization as in the case of the inorganic filler in the present invention, and it is impossible to add the additive. Need to be kept.

As such additives, those which are inactive with respect to the metathesis polymerization catalyst component in a practically acceptable degree are selected and used.

A polymer molded product using the novel silane coupling compound inorganic filler of the present invention is produced by simultaneously performing polymerization and molding as described above.

As such a molding method, as described above, a catalyst and a raw material monomer are mixed by a simple mixer such as a static mixer, or a resin injection method in which a premix mixed in advance is poured into a mold, and a catalyst system. It is possible to adopt a RIM method in which the reaction solution A and the reaction solution B which are divided into two are colliding and mixed in a head portion, and are directly poured into a mold. In particular, the RIM method is generally used.

In either case, the injection pressure into the mold can be relatively low, so that inexpensive molds can be used. Further, when the polymerization reaction in the mold is started, the temperature in the mold is rapidly increased by the reaction heat, and the polymerization reaction is completed in a short time. Unlike polyurethane-RIM, release from the mold is easy and often does not require a special release agent.

As described above, the application of an inorganic filler such as a glass reinforcing material is performed by previously filling a mold in the case of a fiber form having a certain length or more, and in the case of a powder form, by adding the reactive solutions A and B to each other. A method of dispersing at least one of them and injecting it into a mold is adopted.

The reinforcing effect of such an inorganic filler is generally attributable to the good use of the novel silane compound according to the present invention as a silane coupling agent, whereby good adhesion is realized.
The improved physical properties increase in proportion to the amount of the reinforcing material added.
Therefore, the amount of addition may be determined according to the required physical properties depending on the application. In general, when higher rigidity is desired, a higher addition amount of the inorganic filler is required, but as the addition amount increases, in the case of the fiber form, the reactive solution does not form voids, and the single fiber In the case of powders, it becomes difficult to sufficiently penetrate the reaction solution, and in the case of powders, the fluidity of the reaction solution in which the powders are suspended becomes poor, and a technical limit is generated by itself. However, even if the fiber is the same, the limit varies depending on the size of the single fiber, the form of the aggregate, and the like, and optimization in that aspect is also necessary to obtain a good reinforcing body.

In general, the filling rate of the inorganic filler is generally preferably in the range of 0.03 to 0.5, more preferably 0.05 to 0.4 in terms of volume fraction.

In addition, it is not necessary to uniformly distribute the inorganic filler in the molded product when applying such an inorganic filler, and it is only necessary to consider an optimal arrangement that further satisfies the required performance.

For example, when it is desired to increase the rigidity or the like of a specific portion in the same molded product, the fiber assembly reinforcing material may be provided only at the corresponding location or at a higher priority rate at that portion. In addition, when it is desired to efficiently increase the bending rigidity of the plate-like object, the reinforcing material may be provided on both sides at a higher filling rate. On the other hand, when the surface is required to have a smooth surface with little unevenness, a method called a glass veil in which fine dendil glass fibers are entangled, for example, only at the surface portion, even if the reinforcing effect is somewhat sacrificed. Can also be taken. Further, an organic fiber veil, paper, or the like can be used only on the surface.

In addition, a method of reducing the weight while maintaining the bending strength by filling a portion having a sufficient strength by the use of the reinforcing material with a foam-like material can be applied.

d. Effect of the Invention Thus, the novel silane compound of the present invention can be easily derived from existing silane compounds, and the inorganic material-filled metathesis polymer molded article treated with applying such a silane compound as a silane coupling agent Has improved mechanical and thermal properties and can be favorably used in applications requiring higher rigidity, dimensional stability, heat distortion temperature, etc. than conventional metathesis polymer moldings. That is, members of land, water, and various transportation equipment such as automobiles, motorcycles, boats, snows, and mobiles, and members of industrial, leisure, sports, self-propelled equipment, and mobile equipment such as golf carts and tractors. It can be used for a wide range of applications, such as housings for electronics, machinery, etc.

e. Example [Production and confirmation of (methylnorbornenylcarboxypropyl) trimethoxysilane (MNCSi)] 400 g of commercially available (methacryloxypropyl) trimethoxysilane and commercially available dicyclopentadiene are thermally dissociated and stored in a refrigerator. The obtained cyclopentadiene (105 g) was reacted in a 2 autoclave under a nitrogen atmosphere at 120 ° C. for 2 hours. The reaction mixture is heated in a rotary evaporator under hot water heating and reduced pressure, and unreacted raw materials such as methacryloxypropyl-trimethoxysilane, cyclopentadiene, and subcomponents such as dicyclopentadiene and tricyclopentadiene.
After distilling off volatile compounds, dilute with methanol 1
Then extraction was carried out with heptane 1.

After heptane extraction was performed three times, heptane was distilled off to obtain 440 g of a residue. 90MHZ N of such residue
When MR and IR were measured, it was confirmed that (methylnorbornenecarboxypropyl) trimethoxysilane having good purity was obtained as shown in FIGS.

That is, as shown in FIG. 1, the proton of the norbornene ring, the proton of —O—CH ₂ —, the proton of —OCH _{3, the} proton of —CH ₃ , the proton of Si—CH ₂ —proton can be assigned and the 5-position methyl From the chemical shift of the group,
It was confirmed that the production ratio of o and endo was about 2: 1. Each peak integrated value is in good agreement with the theoretical value, which indicates that the product is obtained with high purity.

In addition, as shown in FIG. 2, the presence of —SiOCH ₃ and the ester group can be confirmed from the IR, and it can be confirmed that the target product is formed.

As described above, it was confirmed that a novel silane coupling agent (methylnorbornenylcarboxypropyl) trimethoxysilane was obtained.

Reference Example [Confirmation of Adhesion of Glass Treated with New Silane Coupling Agent (MNCSi) with Metathesis Polymer] Table 1 shows the examination of the adhesion of the glass treated with the new silane coupling agent MNCSi obtained in the above example with the metathesis polymer. The comparison was made with a commercially available silane coupling agent such as shimezu.

The medium for glass treatment with the silane coupling agent is also shown in the table. The silane treatment agent for the medium was used at 1 wt%.

[Preparation of Main Catalyst Concentrate] 19.80 g (0.05 mol) of high-purity tungsten hexachloride was added to 90 ml of dry toluene under a nitrogen stream, and t-butanol was added in an amount of 0.1 g.
A solution of 925 g in 5 ml of toluene was added and stirred for 1 hour. Then, a solution consisting of 11.05 g (0.05 mol) of nonylphenol and 5 ml of toluene was added, and the mixture was stirred for 1 hour under a nitrogen purge. 10 g of acetylacetone was added to the mixture, and stirring was continued overnight under a nitrogen purge while purging out hydrogen chloride gas produced as a by-product.
A 0.5 M tungsten-containing catalyst concentrate was prepared.

[Preparation of activator concentrate] Di-n-octyl aluminum iodide 5.70 g, tri-n-octyl aluminum 31.17 g, diglyme 13.42
g under a nitrogen stream, then add DCP and add a total of 100 m
This was diluted to 1 to obtain a 1.0 M aluminum-containing activator concentrate.

[Metathesis Polymerization Inhibition and Adhesion Test of Each Silane Coupling Agent] The inner surface of a jar type glass container was treated with a medium solution of the silane coupling agent shown in Table 1 above, and heat-treated at 120 ° C. for 10 minutes. Glass containers treated with each silane coupling agent were prepared.

On the other hand, each of the main catalyst concentrate and the activator concentrate is
A reactive solution A having a tungsten content of 0.001M and a reactive solution B having an aluminum content of 0.003M were prepared by adding to a monomer mixture of 96.5% by weight of DCP and 3.5% by weight of ethylidene norbornene.

Take 10 ml of each of the solutions A and B into another syringe 3
After the temperature reached 0 ° C, both were simultaneously extruded into the above treated glass container under a nitrogen stream under rapid stirring, and when mixing of the two liquids was completed, the stirrer was raised, and a thermocouple was inserted instead, and both liquids were pushed in. The time (polymerization time) at which the temperature reached 100 ° C. from the end of the injection from the syringe was measured.

Table 2 shows the results. By comparing the polymerization times, the effect of the silane coupling agent on metathesis polymerization can be understood, but it is understood that MNC-Si has a small effect on the polymerizability. Furthermore, it was observed whether the resulting polymer solid silane-treated glass container adhered well or separated easily. The results are also shown in Table 2. As can be seen, only the MNC-Si adhered well to the silane-treated glass container, and did not readily separate. Due to shrinkage during other polymerizations, it is qualitative that it is separated from the glass container or easily separated, but the MNC-Si silane-coupling agent treated glass has good adhesion with the metathesis polymer. Was confirmed.

[Adhesion Test Using Glass Plate] Instead of the glass container of Example 1, silane coupling treatment was similarly performed on a prepared glass plate for a microscope.

On the other hand, each of the reaction solutions A and B prepared as described above was 10 m
Each of the syringes was mechanically extruded at the same ratio, and both liquids were blown out from a nozzle to collide with each other and flow into a small mold to form a molded plate. At that time, the above-mentioned silane-treated glass plate was attached to one surface of a molding die, and the molded plate was adhered to glass so as to be formed. As a result of such polymerization, when the resin was treated with MNC-Si, the glass plate was broken into many pieces due to shrinkage of the formed resin, but each one was well fixed to the resin. On the other hand, those treated with the silane treatment agents for comparison 1 to 4 and the glass plate without any silane treatment are separated from the resin produced only by being split into two pieces, and have good adhesion. Did not show sex.

[Composite strength test with glass woven cloth] Glass woven cloth (basis weight: 215 g / m ² , plain woven, 0.22 m thick) which has been burned and volatilized by spinning oil etc. to clean the surface
m) was immersed in each silane coupling agent solution shown in Table 1, pulled up, squeezed with a roller, air-dried for one day, and then placed in a hot air oven.
Heat treated at 120 ° C for 10 minutes.

10 pieces of glass woven fabric treated in this way are stacked in a flat mold of 30 mm × 30 cm with a thickness of 3.5 mm length,
In the mold, the same monomer composition as above is used with Firestone SBR
Reactive solution A and aluminum content in which the main catalyst concentrate and the activator concentrate were each dissolved in a 2% by weight solution of Steron 720 to a tungsten content of 0.001M.
A reactive solution B having a concentration of 0.003M was prepared, and this was subjected to collision mixing and injection using a practical RIM molding machine, and a glass woven fabric reinforced metathesis polymer molded plate having a glass fiber content (Vol-content) of 22% was prepared. I got

A sample was cut out from the molded plate according to a conventional method, and the bending strength and the bending modulus were measured. Table 3 shows the results. Compared to composite plates using woven fabrics treated with other silane coupling agents and composite plates using woven fabrics without silane treatment, composite plates using glass woven fabric treated with MNC-Si High bending strength,
It turns out that it shows a bending modulus. Such bending strength and bending modulus are as follows in the case of glass fiber reinforced resin material.
It is said that the quality of the adhesiveness between the glass fiber and the resin is most sensitively affected, indicating that MNC-Si gives good adhesiveness.

Further, it can be seen that when an inappropriate silane coupling agent is used, only a bending strength and a bending modulus which are worse than in the case of no treatment are obtained.

[Brief description of the drawings]

Figure 1 shows (methylnorbornenylcarboxypropyl)
FIG. 3 shows a NMR spectrum of trimethoxysilane at 90 MHz. Figure 2 shows (methylnorbornenylcarboxypropyl)
FIG. 3 shows an infrared spectrum diagram of trimethoxysilane.

Claims (1)

(57) [Claims] (1) Expression A novel silane compound represented by the formula: