JPH06200034A - Layered organosilicon polymer, its molding and their preparation - Google Patents

Abstract

PURPOSE:To obtain a polymer having both the feature of an inorganic material and the feature of an organic material by reacting an organoalkoxysilane having an alkoxyl group and an organic group with a salt of a metal or the like in a weakly alkaline liquid. CONSTITUTION:An organoalkoxysilane having an alkoxyl group and an organic group and an inorganic salt, organic salt or alkoxide of a metal selected from among Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V and Zr and optionally a silicon alkoxide are dissolved or dispersed in an inorganic polar solvent, an organic polar solvent or a mixture thereof, and an alkali is further added to the mixture to make it weakly alkaline. Thus, optionally after aging, a layered organosilicon polymer which is a laminate of a tetrahedral sheet 4 having silicon or a metal as the central metal with an octahedral sheet 2 having a metal as the central atom, wherein part or all of the silicon or metal atoms as the central atoms of the tetrahedral sheet 4 are covalently bonded with an organic group can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a layered organic silicon-based polymer, a molded product thereof and a method for producing the same, and more specifically, it can be used as a coating material, a filler for a resin or various functional materials. A layered organosilicon polymer, a molded article formed by reacting and binding the organic part of the polymer and formed into a layered coating material and various shapes according to other purposes, and these layered organosilicon polymers and molded articles thereof Manufacturing method.

[0002]

2. Description of the Related Art Generally, a main component material such as a coating material or a molded body or an inorganic material as a filler has characteristics such as high hardness and heat resistance, but it rapidly forms a dense solid phase from a liquid phase or a solution. Requires heating and firing. Further, the affinity with the organic solvent or the organic phase is not good. On the other hand, organic materials have characteristics such as flexibility and rapid film formation at room temperature, but have the drawback of poor hardness and heat resistance. For this reason, conventionally, an inorganic-organic hybrid material having the above-mentioned characteristics of an inorganic material and an organic material in combination and further limiting the above-mentioned drawbacks as much as possible, and such a material can be easily prepared, for example, at a temperature near room temperature. There is a demand for the development of an effective manufacturing method that can be rapidly manufactured under the conditions.

As one of the techniques to meet such demands, Japanese Patent Laid-Open No. 1-108272 discloses an inorganic-organic hybrid paint. This paint is an abrasion resistant coating material consisting of a partial hydrolyzate of epoxysilane, a carbonyl group containing compound and the reaction product of a non-silane based aliphatic polyamine.

However, in this case, the inorganic structure in the coating film is limited to a part introduced into the organic polymer, and further, the inorganic structure portion grows or forms a film during the formation of the coating film by the organic reaction at around room temperature. Since it does not occur, the characteristics of the inorganic material cannot be sufficiently expressed, and a dramatic improvement in performance as compared with the organic polymer cannot be expected.

Next, for example, Japanese Patent Application Laid-Open No. 62-74957 filed by the applicant of the present invention has a field of application which is not in agreement with that of the present invention, but it is an inorganic-organic hybrid material (organized clay (layered). An interlayer compound in which an organic compound is introduced between layers of a clay mineral by an ion exchange reaction is disclosed. Such organized clay is extremely effective in achieving the object of the invention according to the above-mentioned application, but is not always sufficient in the following points (1) to (4) when applied to the fields intended by the present invention.

Organic substances that are difficult to ionize, such as those containing an epoxy moiety and those having an amino group at the end,
Cannot be introduced. Organic matter can be introduced only up to the ion exchange capacity specific to clay. For example, in the case of sodium-type montmorillonite, which is a typical layered clay mineral, the theoretical amount of organic ions that can be introduced is 0.0825 per silicon atom. The upper limit is about 3 times the amount. Furthermore, it is necessary to consider that it is actually difficult to completely disperse the layered clay mineral (complete separation between layers). Since the organic matter and the layered clay mineral are bound by ionic bonds, the organic matter undergoes an ion exchange reaction in various operations during practical use (for example, mixing with other components when used as a coating material or filler). May be liberated from layered clay minerals.

[0007]

SUMMARY OF THE INVENTION Therefore, the present invention has the following points as problems to be solved.

(First Problem) First, a structure in which an inorganic structural portion is sufficiently grown, and a sufficient amount of organic matter is introduced into the inorganic structural portion, and a strong bond is formed between them. To provide an inorganic-organic hybrid material.

(Second Problem) Secondly, to provide an effective production method capable of rapidly producing the above-mentioned inorganic-organic hybrid material under such easy conditions that organic substances are not damaged. More desirably, there are no significant restrictions on the type of organic material introduced in such a method. For example, it should be possible to easily introduce organic substances that are difficult to ionize.

(Third Problem) Thirdly, in consideration of practical use of the above-mentioned inorganic-organic hybrid material as a coating material, a filler, etc., in the inorganic-organic hybrid material, the grown inorganic structure portion and a sufficient amount thereof are provided. To provide a molded article in which a solid and dense solid phase is formed by effectively utilizing the organic part of

(Fourth Problem) Fourthly, the above-mentioned molded body is
To provide a production method capable of rapid production under easy conditions such that an organic substance portion is not damaged.

[0012]

[Points of Interest] In order to solve the above-mentioned problems, the present inventor has found that the inorganic structure of the inorganic-organic hybrid material has many advantages such as crystallinity, high heat resistance, and good moldability. Focusing on clay minerals, we tried to realize a structure in which organic groups were introduced by Si—C covalent bonds.

By the way, it is difficult to introduce an organic group covalently bonded to Si in the structure of the already completed layered clay mineral.

On the other hand, the introduction of such an organic group in the process of synthesizing the layered clay mineral means that the organic group is directly bonded to a part of the tetrahedron of silicon. Then, it is usual to think that a silicon tetrahedral sheet cannot be formed due to a lack of the number of bonds of silicon, and thus a structure of a layered clay mineral cannot be formed. However, the present inventor has confirmed for the first time that this is actually possible, and completed the present invention.

[0015]

[Means for Solving the Problems]

(Means for Solving the First Problem) The structure of the first invention (the invention according to claim 1) for solving the first problem is a tetrahedral sheet having silicon or a metal as a central atom and a metal. A crystalline layered polymer composed of a laminate with an octahedral sheet having as a central atom, wherein some or all of the atoms of silicon or metal, which is the central atom of the tetrahedral sheet, are bonded to an organic group by covalent bonds. Is a layered organosilicon polymer.

(Means for Solving the Second Problem) The configuration of the second invention (the invention according to claim 2) for solving the second problem is as follows: a) and b) Accordingly, c) is dissolved or dispersed in the liquid of d), and alkali is added to adjust the pH to weakly alkaline, and the layered organosilicon polymer described in the first invention is obtained immediately or after aging. It is a method for producing a layered organosilicon polymer. a) An organoalkoxysilane having at least one alkoxy group and at least one organic group. b) Mg, Al, Ni, Co, Cu, Mn, Fe, L
An inorganic salt, organic salt or alkoxide of at least one metal selected from i, V and Zr. c) Silicon alkoxide having at least one alkoxy group. d) One type of inorganic or organic polar solvent, or 2
Mixed solvent of more than one polar solvent.

(Means for Solving the Third Problem) The constitution of the third invention (the invention according to claim 3) for solving the third problem is the layered organosilicon system according to the first invention. A polymer having a polymerizable functional group in its organic group is formed into any specific shape, and the organic group is bonded to each other by a polymerization reaction of the functional group It is a molded body.

(Means for Solving the Fourth Problem) The constitution of the fourth invention (the invention according to claim 4) for solving the fourth problem is as follows: Accordingly, c) is dissolved or dispersed in the liquid of d), and an alkali is further added to adjust the pH to be weakly alkaline, and the layered organosilicon polymer described in the first invention is obtained immediately or after aging. After that, the molded product of the layered organosilicon-based polymer is formed by giving an arbitrary specific shape to this and causing a functional group of the organic group to undergo a polymerization reaction to bond the organic groups to each other. a) An organoalkoxysilane having at least one alkoxy group and at least one organic group containing a polymerizable functional group. b) Mg, Al, Ni, Co, Cu, Mn, Fe, L
An inorganic salt, organic salt or alkoxide of at least one metal selected from i, V and Zr. c) Silicon alkoxide having at least one alkoxy group. d) One type of inorganic or organic polar solvent, or 2
Mixed solvent of more than one polar solvent.

[0019]

[Action / effect]

(Operation and Effect of First Invention) The layered organic silicon-based polymer has a crystal structure in which the inorganic structural portion is a laminate of a tetrahedral sheet having silicon or a metal as a central atom and an octahedral sheet having a metal as a central atom. Since it has a highly developed structure as a functional layered polymer, the characteristics of the inorganic material such as high hardness and high heat resistance can be well expressed.

With respect to silicon or metal, which is the central atom of the tetrahedral sheet, some or all of the atoms are bonded to organic groups to the extent necessary, so that the amount of organic groups that can be introduced is limited. Can introduce a sufficient amount of 1 to 3 organic moieties per central atom of a tetrahedron. Therefore, it is possible to secure the characteristics of the organic material such as flexibility when used as a coating material or the like and rapid film formation at room temperature, and, for example, when it is used as a filler or the like, an organic solvent or an organic phase is used. Affinity is also secured.

Furthermore, since the organic side chain is bonded to the central atom of the tetrahedral sheet by a covalent bond, the bond between the two is robust and, for example, it is mixed with other components when used as a coating material or a filler. For example, even if various operations are performed in practical use, the bond between the two is not impaired.

(Operation and Effect of the Second Invention) As described above, the second invention is the first to have a structure in which an organic group is introduced into silicon constituting a silicon tetrahedron of a layered clay mineral by a Si—C covalent bond. This is the method that made it possible.

In the present invention, the mechanism by which the layered organosilicon polymer is synthesized is not necessarily clear, but the above a), b) or c) is dissolved or dispersed in the liquid d) to adjust the pH to weakly alkaline. Then, while the crystal structure of the octahedral sheet having the metal as the central atom grows in advance, the silicon of the organoalkoxysilane is bonded to the octahedral sheet by dehydration condensation after hydrolysis of the alkoxy group, following this. It is estimated that the crystal structure of the tetrahedral sheet will grow centering on this silicon. Therefore, even when the organic group is directly bonded to a part of the silicon tetrahedron, the silicon tetrahedron sheet is formed following the octahedron sheet,
In the end, we believe that a layered organosilicon polymer will be formed.

Silicon alkoxide is also incorporated into the layered organosilicon-based polymer in the same manner as organoalkoxysilane, but since it has no organic group, silicon alkoxide should be used in a predetermined ratio with respect to the organoalkoxysilane. Thereby, the ratio of the organic group in the layered organosilicon polymer can be adjusted.

Since the ion exchange reaction is not used for the introduction of the organic group, it is possible to introduce an organic material which is difficult to be ionized, for example, an epoxy-containing organic material or an amino-terminal one as an organic group. . The method of the second invention employs a process according to the method for producing a phyllosilicate described in JP-A-3-199118, which is characterized by the synthesis of a layered clay mineral under easy and mild conditions. The organic groups are not damaged by high temperature or extreme pH.

Further, by adjusting the amount of the organoalkoxysilane or silicon alkoxide used in the raw material system, the proportion of organic groups in the layered organosilicon polymer, and by extension, the degree of expression of the characteristics of the organic material and the affinity as a filler. The degree of can be controlled arbitrarily.

(Operation and Effect of Third Invention) The molded product of the third invention maintains all the characteristics of the layered organosilicon polymer of the first invention, and further, the organic group is a polymerization reaction of its functional group. Since they are bonded to each other, hardness, heat resistance, etc. are further improved. Also, when the molded body is formed into a film as a coating material, a large number of inorganic layered polymers are densely laminated and organic groups are bonded to each other to strengthen the laminated structure. Become.

(Operation / Effect of Fourth Invention) In the present invention, the operation / effect in the process until the layered organosilicon polymer is obtained is the same as that of the second invention. After that, the process of causing the functional group to carry out the polymerization reaction is a bonding reaction between the organic groups and can be carried out rapidly under easy conditions without damaging the organic groups.

[0029]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the first to fourth inventions of the present application will be described. (Embodiment of the first invention) The layered organosilicon-based polymer of the first invention has a so-called 2: 1 type structure in which tetrahedral sheets are formed on both sides of an octahedral sheet and 4 on one side of the octahedral sheet. There is a so-called 1: 1 type structure in which a face sheet is formed. If you want to include at least a large amount of organic groups, or if you want to improve the bond strength between organic groups,
A 2: 1 type structure is more preferable.

FIG. 1 is a part of an example of a layered organosilicon polymer having a 2: 1 type structure (a tetrahedral sheet having a central atom of silicon and one organic group bonded to each silicon atom). A tetrahedral sheet 4 having a silicon atom 3 as a center is formed on both sides of an octahedral sheet 2 having a metal atom 1 as a center. And the above silicon atom 3
The organic groups R are bound to each other by a covalent bond as a part of the tetrahedral sheet 4.

In addition to the case where the central atom of the tetrahedral sheet is silicon, a part or all of it may be Al, Fe, Ge, P or the like. The central atoms of the tetrahedral sheet are Fe and G
e, P, etc. are due to the central atom substitution with silicon.
The central atom of the octahedral sheet is Mg, Al, Ni, Co, C
One or two of u, Mn, Fe, Li, V, and Zr
It consists of more than one kind of metal atom.

In this specification, the organic group is a concept that does not include an alkoxy group. As the organic group, any group that can be introduced into the layered organosilicon polymer and can impart the characteristics of the organic material to the polymer can be used.
These organic groups may or may not contain a polymerizable functional group. One to three organic groups are covalently bonded to some or all of the central atoms of the tetrahedral sheet.

(Embodiment of the Second Invention) The organoalkoxysilane of a) supplies the central atom and the organic group of the tetrahedral sheet in the layered organosilicon polymer, and contains at least one alkoxy group (4
Silicon, which is the central atom of the face sheet, is necessary for bonding with the octahedron sheet. ) And at least one organic group. Therefore, those having a ratio of alkoxy group 3: organic group 1 to those having a ratio of alkoxy group 1: organic group 3 can be used.

The metal inorganic salt or organic salt b) supplies the central atom of the octahedral sheet in the layered organosilicon polymer, and the types of metal are Mg and A.
One or two or more of 1, Ni, Co, Cu, Mn, Fe, Li, V and Zr are used. The type of inorganic acid or organic acid that should form a salt with these metals is not limited. Some of these metals may replace silicon, which is the central atom of the tetrahedral sheet, in the process of carrying out the present invention.

The silicon alkoxide of c) is used in combination with an organoalkoxysilane, if necessary, in order to adjust the content of the organic group in the layered organosilicon polymer, and has at least one alkoxy group, In addition, it means one having no organic group. Therefore, those having one alkoxy group to those having four alkoxy groups can be used.

The above-mentioned 2: 1 type or 1: 1 type layered organosilicon polymer is selectively produced by selecting the ratio of the amounts of a) [or a) and c)] and b) used. can do. In short, there is a problem of the equivalence ratio between the metal atom that becomes the central atom of the octahedral sheet and the silicon atom that becomes the central atom of the tetrahedral sheet.

For example, metal atom: silicon atom is 1: 0.
At a ratio of about 5 to 1: 1 a 1: 1 type layered organosilicon polymer is used, and a metal atom: silicon atom ratio is 1: 2.
At a ratio of about 3: 4, a 2: 1 type layered organosilicon polymer is produced.

The solvent of d) is water as an inorganic polar solvent,
Or alcohol as organic polar solvent, acetone,
It is one kind of an organic acid, an inorganic acid or the like, or a mixed solvent of two or more kinds thereof.

A) and b), and optionally c),
It does not necessarily have to be completely dissolved in the solvent of d), and a dispersed state to some extent is sufficient. The alkali added to the solution or dispersion may be of any type.

The weakly alkaline pH adjusted by the addition of alkali cannot be uniformly defined due to factors such as the selection of the raw material system, but is, for example, about pH 8 to 10. In short, the pH is such that crystallization as a layered organosilicon polymer, that is, gelation occurs at a rate higher than a desired rate, and the organic group is not strongly alkaline. The above-mentioned gelation process sufficiently occurs even at a temperature of about room temperature, but the gelation may be performed under a constant high temperature condition that does not damage the organic group.

The gelation process may be completed immediately depending on the selection of the raw material system and the reaction conditions, and may require aging to some extent (for example, about 1 to 2 days). The obtained crystalline layered organosilicon-based polymer may be once recovered as a dry powder after removing the solvent, or may be used as a coating material in a gel state.

(Embodiment of the third invention) The polymerizable functional group is typically, for example, a hetero atom or an unsaturated bond, but a compound which is polymerized by two functional groups, for example, an amide bond. A combination of a formable amino group and a carboxyl group may be used, and any kind of functional group may be used as long as it is a functional group capable of causing a polymerization reaction.

Embodiments of the third invention other than those described above are the same as those of the first invention.

(Embodiment of Fourth Invention)

The shape given to the layered organosilicon polymer is, for example, a film shape when the molded body is a coating film, and the shape of the mold when molded with a mold. In any case, the means for molding the molded body, the process, or the shape thereof are completely different depending on the use of the molded body of the third invention and are not limited in any way.

The polymerization reaction of the functional group after molding can be caused by any known means such as heating, and the content of the means is not limited.

Embodiments of the fourth invention other than those described above are the same as those of the second invention.

[0048]

【Example】

(Example 1: Synthesis of acrylic-Ni hybrid clay)
1.96 g of Ni chloride hexahydrate was dissolved in 200 g of ion-exchanged water. 2.73 g of 3-methacryloxypropyltrimethoxysilane diluted with 50 g of methanol was added thereto and well stirred for 1 hour. When 16.5 ml of 1N sodium hydroxide aqueous solution was added thereto at a rate of 2 ml / min, gel was generated. This was left at room temperature for 2 days. After that, filtration, washing with water and vacuum drying were performed to obtain an acrylic-Ni hybrid clay which is a layered organosilicon polymer.

Evaluation of this product by X-ray diffraction revealed a smectite-like pattern having a peak of 001 as shown in FIG. 2, suggesting the formation of a crystal structure. Also,
In the evaluation by infrared absorption analysis (IR), as shown in FIG. 3, 1720 cm ⁻¹ (carbonyl group) or 1640 cm
It was confirmed from the peak of ^-1 (C = C double bond) that an acrylic group was present.

Further, as shown in FIG. 4, the thermal weight reduction (T
In the measurement of G), almost no weight reduction was observed up to about 350 ° C., and it was found that the organic group contained in the layered organosilicon polymer exhibits considerable heat resistance.

(Example 2: Production of acrylic-Si-Mg hybrid resin film) Ni chloride was added to 200 g of ion-exchanged water.
1.96 g of hexahydrate was dissolved. Methanol 50
2.73 g of 3-methacryloxypropyltrimethoxysilane diluted with g was added and well stirred for 1 hour. Here, 16.5 ml of 1N sodium hydroxide aqueous solution was added to 2 ml /
A gel formed when added dropwise at the rate of minutes. After continuing stirring for a while, this was filtered and washed to obtain a gel body which remained wet. After adding 1,000 ml of toluene to this gel body and stirring, and concentrating with a rotary evaporator,
A transparent swollen gel body was obtained.

The above swollen gel body was applied to an acrylic plate,
When dried, a transparent film was obtained. The film was viscous and was easily scratched by the nails. However, when the film was irradiated with ultraviolet rays by a high-pressure ultraviolet lamp for 1 hour, the film was cured. When the pencil hardness of this coating film was measured, it was 9H or more.

Example 3 Synthesis of Acrylic-Mg Hybrid Clay 1.68 g of Mg chloride hexahydrate was dissolved in 200 g of ion-exchanged water. 2.73 g of 3-methacryloxypropyltrimethoxysilane (MPTS) diluted with 50 g of methanol was added thereto and well stirred for 1 hour.
When 16.5 ml of 1N sodium hydroxide aqueous solution was further added thereto at a rate of 2 ml / min, gel was generated. This was left at room temperature for 2 days, and then filtered, washed with water, washed with ethanol and vacuum dried to obtain an acrylic-Mg hybrid clay.

For comparison, clay minerals were synthesized using silicon alkoxide. Deionized water 200g Mg chloride
1.68 g of hexahydrate was dissolved. Methanol 50
Tetramethyl orthosilicate diluted with g (TMO
1.67 g of S) was added and well stirred for 1 hour. To this, 16.5 ml of 1N sodium hydroxide aqueous solution was further added to 2 ml /
A gel was formed when added in minutes. This was left at room temperature for 2 days, then filtered, washed with water, washed with ethanol and vacuum dried to obtain a Mg-containing clay mineral (TMOS clay).

Evaluation of this acrylic-Mg hybrid clay by X-ray diffraction (FIG. 5) revealed a smectite-like pattern having a peak of 001, suggesting the formation of a crystal structure. Further, ²⁹ Si pulse NMR was measured for both of them (FIG. 6). As a result, it was found that neither of them had a broad peak derived from an amorphous material and had relatively good crystallinity.

MP, which is a raw material, is used as a reference in FIG.
The NMR frequency shift of TS is smaller than that of TMOS, but this is because TMOS has four Si—O bonds, whereas one of MPTS has a Si—C bond. Since the NMR frequency shifts of the acrylic-Mg hybrid clay and the TMOS clay have the same relationship, the Si in the acrylic-Mg hybrid clay is
It can be seen that also has a Si-C bond.

¹³ CNMR of the acrylic-Mg hybrid clay was measured (FIG. 7). From the comparison with MPTS given as a reference, it was confirmed that the organic structure bonded to Si in MPTS was present as it was.

[Brief description of drawings]

FIG. 1 is a structural diagram of a layered organosilicon polymer.

FIG. 2 XRD pattern of acrylic-Ni hybrid clay

FIG. 3 Infrared absorption analysis chart of acrylic-Ni hybrid clay

FIG. 4 Thermogravimetric reduction (TG) of acrylic-Ni hybrid clay

FIG. 5: XRD pattern of acrylic-Mg hybrid clay

FIG. 6 Si NMR spectra of acrylic-Mg hybrid clay and TMOS clay

FIG. 7: CNMR spectrum of acrylic-Mg hybrid clay

[Explanation of symbols]

 1 Metal atom 2 Octahedral sheet 3 Silicon atom 4 Tetrahedral sheet

Claims (4)

[Claims] 1. A crystalline layered polymer comprising a laminate of a tetrahedral sheet having silicon or a metal as a central atom and an octahedral sheet having a metal as a central atom, the silicon being a central atom of the tetrahedral sheet. Alternatively, a layered organosilicon-based polymer in which a part or all of the metal atoms are respectively bonded to an organic group by covalent bonds. 2. The following a) and b) and, if necessary, c).
Is dissolved or dispersed in the liquid of d), the pH is adjusted to weak alkaline by further adding an alkali, and the layered organosilicon polymer according to claim 1 is obtained immediately or after aging. A method for producing a layered organosilicon polymer. a) An organoalkoxysilane having at least one alkoxy group and at least one organic group. b) Mg, Al, Ni, Co, Cu, Mn, Fe, L
An inorganic salt, organic salt or alkoxide of at least one metal selected from i, V and Zr. c) Silicon alkoxide having at least one alkoxy group. d) One type of inorganic or organic polar solvent, or 2
Mixed solvent of more than one polar solvent. 3. The layered organosilicon polymer according to claim 1, which has a polymerizable functional group in its organic group, is molded into an arbitrary specific shape, and the organic group has the functional group. A molded article of a layered organosilicon-based polymer, which is bound to each other by the polymerization reaction of 1. 4. The following a) and b) and, if necessary, c).
Is dissolved or dispersed in the liquid of d), the pH is adjusted to weak alkaline by further adding an alkali, and the layered organosilicon polymer according to claim 1 is obtained immediately or after aging to obtain the layered organosilicon polymer. A method for producing a molded article of a layered organosilicon-based polymer, which comprises imparting an arbitrary specific shape to the resin and causing a functional group of the organic group to undergo a polymerization reaction to bond the organic groups to each other. a) An organoalkoxysilane having at least one alkoxy group and at least one organic group containing a polymerizable functional group. b) Mg, Al, Ni, Co, Cu, Mn, Fe, L
An inorganic salt, organic salt or alkoxide of at least one metal selected from i, V and Zr. c) Silicon alkoxide having at least one alkoxy group. d) One type of inorganic or organic polar solvent, or 2
Mixed solvent of more than one polar solvent.