JP4406834B2 - Method for producing composite of organic polymer and glass and composite - Google Patents

Description

The present invention relates to a method for producing an organic-inorganic composite having glass in an organic polymer, and an organic-inorganic composite obtained by the production method.

  Compounding inorganic fine particles in organic polymer for the purpose of imparting properties such as processability and flexibility of organic polymer and heat resistance, abrasion resistance and surface hardness of inorganic substances such as glass. To do is widely studied. In order to sufficiently exhibit the effect of the compounding by this method, it is preferable to compound the inorganic fine particles having the smallest possible particle size at a high filling rate. When the particle size of the inorganic fine particles is reduced, the surface area per weight of the inorganic particles is increased, and the interface region between the organic material and the inorganic material is widened, so that a high reinforcing effect can be expected (area effect). In addition, as the filling rate of the inorganic fine particles increases, the compounding effect naturally increases (volume effect).

  However, most of the polyamides are used as the organic polymer component of the organic-inorganic composite, and there are very few examples of using other polymers as the organic component. There are few prior arts for composites using polyurethane, and only Patent Documents 1 and 2 are known. These methods according to the patent literature are methods in which a metal alkoxide is hydrolyzed and polycondensed to form a metal oxide, using a so-called sol-gel method, and a glass or the like is combined with an organic polymer. In addition, since the polycondensation reaction requires a long time, the production efficiency is extremely low. For example, in Example 1 of Patent Document 1, a reaction time of 1 to 2 days at room temperature is required to obtain the target complex. Moreover, in the manufacture example 1 in the Example of patent document 2, after reaction for 5 hours at 80 degreeC, reaction for 1 hour is further required at 50 degreeC.

In addition, in any of these methods, since an organic-inorganic composite is obtained in a state dissolved in a solvent, it is necessary to further remove the solvent by a method such as casting in order to obtain a solid composite. Therefore, it is suitable as a coating material used for coating the surface, but is very inefficient for use in other applications. In addition, in order to obtain an organic-inorganic composite by the sol-gel method, a metal alkoxide capable of causing a sol-gel reaction is essential, but metal alkoxides are generally expensive materials, so that the price of the composite is high. Conversion is inevitable. Moreover, an organic-inorganic composite using polyurea as an organic polymer component has not been provided so far.

  In order to avoid the above problem, a method of manufacturing a composite by forcibly mixing an inorganic material with an organic polymer by a so-called melt-kneading method is known. However, since the inorganic material and the organic polymer are essentially different in terms of surface characteristics, specific gravity, heat insolubility, and chemical insolubility, it is extremely difficult to make the inorganic material in a finely dispersed state with a uniform and high filling rate. In addition, nanometer-order inorganic fine particles are usually expensive and may be scattered, resulting in poor handling.

JP-A-9-291131 JP 2000-63661 A

  An object of the present invention is to provide an organic / inorganic composite of glass and at least one organic polymer selected from the group consisting of polyurethane and polyurea, a glass raw material that is an inorganic component, not an expensive alkoxide, but an inexpensive alkali silicate Another object of the present invention is to provide a production method capable of easily obtaining a solid-state complex by a short-time reaction at normal pressure and room temperature.

Namely, an organic solution (A) in which one compound selected from the group consisting of a dichloroformate compound and a phosgene compound is dissolved in an organic solvent and an aqueous solution (B) in which an alkali silicate and a diamine are dissolved in water are brought into contact with each other. A method for producing an inorganic composite is provided.

Further, the present invention is a composite of at least one organic polymer selected from the group consisting of polyurethane and polyurea obtained by the above production method and glass, wherein the glass content is 10 to 80% by mass. An organic-inorganic composite having an average particle size of glass of 500 nm or less is provided.

According to the method for producing an organic-inorganic composite of the present invention, an organic-inorganic composite of glass and at least one organic polymer selected from the group consisting of polyurethane and polyurea, and a very inexpensive sodium silicate as an inorganic component raw material, In addition, a solid form can be easily obtained by a reaction of only one short stirring operation for 30 minutes or less at normal pressure and room temperature.
In addition, the organic-inorganic composite obtained by the production method of the present invention may contain glass as an inorganic component uniformly in a fine particle state with a high content of 10 to 80% by mass and an average particle size of 500 nm or less. it can.

Hereinafter, the present invention will be described in detail.
<Method for producing organic-inorganic composite>
The organic-inorganic composite manufacturing method of the present invention includes an organic solution (A) in which one compound selected from the group consisting of a dichloroformate compound and a phosgene compound is dissolved in an organic solvent, and an alkali silicate and a diamine in water. The dissolved aqueous solution (B) is mixed and stirred and reacted to produce a composite of at least one organic polymer selected from polyurethane and polyurea and glass.

(Composite synthesis process)
In the complex synthesis step, for example, the monomer in the organic solution (A) and the diamine in the aqueous solution (B) are rapidly polycondensed by an agitation operation at room temperature and normal pressure for several minutes to 30 minutes, and organic A polymer is obtained with good yield. Under the present circumstances, the production | generation of an organic polymer is accelerated | stimulated because the alkali metal in an alkali silicate acts as a removal agent of the hydrogen halide generate | occur | produced in the case of the polycondensation of a monomer and diamine. Simultaneously with this reaction, the alkali silicate is insolubilized in an organic solution or water by being converted into glass and precipitated as a solid. Furthermore, at this time, the formation of organic polymer by polycondensation of monomer and diamine and the precipitation of glass do not occur either, but occur in parallel, so nanometer order glass is finely dispersed in organic polymer. The resulting composite is obtained. Moreover, the glass solidified by this reaction exists in the composite as silica (silicon oxide) glass from which most of the alkali metal has been removed from the alkali silicate which is the raw material. Thus, the composite obtained by the present invention is essentially different from a mixture obtained by simply mixing an organic polymer and glass powder. It is also different from a composite of an organic material and an inorganic compound gel obtained by a so-called sol-gel method.
According to the production method of the present invention, an organic-inorganic composite having a glass content of 10 to 80% by mass and an average particle size of glass of 500 nm or less can be produced.
The glass content is preferably 15 to 70% by mass, more preferably 20 to 60% by mass. The average particle size of the glass is preferably 250 nm or less, more preferably 100 nm or less, and particularly preferably 50 nm or less.

  Examples of the dichloroformate compound in the organic solution (A) include 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol. All the hydroxyl groups of aliphatic diols such as chlorogenated by phosgenation treatment; resorcin (1,3-dihydroxybenzene), hydroquinone (1,4-dihydroxybenzene), 1,6-dihydroxynaphthalene, 2, 2'-biphenol, bisphenol S, bisphenol A, tetramethylbiphenol, etc., all of the hydroxyl groups of dihydric phenols having two hydroxyl groups on one or more aromatic rings are chlorogenated by phosgenation treatment Can be mentioned. These can be used alone or in combination of two or more.

Examples of the phosgene compound in the organic solution (A) include phosgene, diphosgene and triphosgene. These may be used alone or in combination of both species.
In the present invention, by selecting a monomer in the organic solution (A), the type of the organic polymer that is the matrix of the complex can be changed. When a dichloroformate compound is used as a monomer, polyurethane can be obtained, and when a phosgene compound is used, polyurea can be obtained by reaction with a diamine in the aqueous solution (B).

  The organic solvent used in the organic solution (A) can be used without particular limitation as long as it does not react with the various monomers and diamines and dissolves the various monomers in the organic solution (A). Among these, those incompatible with water include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, halogenated hydrocarbons such as chloroform and methylene chloride, and fats such as cyclohexane. Typical examples of the cyclic hydrocarbons that are compatible with water include ethers such as tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, and alkyl acetates such as ethyl acetate and propyl acetate. .

  The diamine in the aqueous solution (B) can be used without particular limitation as long as it reacts with each monomer in the organic solution (A) to produce an organic polymer. Specifically, aliphatic diamines such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane; m-xylylenediamine , P-xylylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, and other aromatic diamines; Examples include aromatic diamines substituted with atoms, nitro groups, alkyl groups, and the like. These may be used alone or in combination of two or more.

  The monomer concentration in the organic solution (A) and the diamine concentration in the aqueous solution (B) are not particularly limited as long as the polycondensation reaction proceeds sufficiently, but from the viewpoint of bringing each monomer into good contact, 0.01 A concentration range of ˜3 mol / L, particularly 0.05 to 1 mol / L is preferred.

Examples of the alkali silicate in the aqueous solution (B) include those represented by the composition formula of A ₂ O · nSiO ₂ such as water glass No. 1, No. 2, No. 3, etc. described in JIS K 1408. Here, A is an alkali metal, and the average value of n is 1.8-4. Moreover, an alkali metal silicate etc. (for example, sodium metasilicate 1 type, 2 types) whose average value of n is 0.8-1.1 can also be used. Water glass (alkali silicate) by acting as a remover of the acid generated when the alkali metal compound contained in the alkali silicate is polycondensed between the monomer in the organic solution (A) and the diamine in the aqueous solution (B) Promotes the polycondensation of the monomer and the diamine, and at the same time becomes a raw material for the inorganic compound constituting the composite by being converted to solid glass (silica) insoluble in the polar solvent.

In the present invention, the reaction of the monomer (dichloroformate compound, phosgene compound) in the organic solution (A) and the diamine in the aqueous solution (B) is a reaction for synthesizing polyamide by mixing a dicarboxylic acid halide and a diamine. Reactivity is slightly lower than. Therefore, by using an alkali silicate having a high pH as a component of the aqueous solution (B) when dissolved in water, the reaction according to the present invention can be promoted and a complex can be obtained in a high yield. As such a material, water glass No. 1 or alkali metasilicate, which is an alkali silicate having an average value of n of 2 or less, is particularly preferably used.

  The concentration of the alkali silicate in the aqueous solution (B) is determined to some extent by the monomer concentration in the organic solution (A) and the diamine concentration in the aqueous solution (B), but maintains a high yield of the complex and is heavy. 1-200 g / L is desirable for the reason of preventing the side reaction of the monomer and water in the organic solution (A) that may be generated due to excessive heat generation during the condensation.

  Alkali silicate has the effect of accelerating the polycondensation reaction by neutralizing the hydrogen halide produced during the polycondensation reaction of polyurethane or polyurea, so the amount of these compounds is small, and the resulting hydrogen halide proceeds in the polycondensation reaction. In the case of inhibiting the acid acceptor, an acid acceptor such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate may be added to the aqueous solution (B), and the acid acceptor solution is added to the synthesis system after the addition. May be.

  The production apparatus used for production of the composite is not particularly limited as long as it is an apparatus that can satisfactorily contact the organic solution (A) and the aqueous solution (B). Is possible. However, since the polycondensation reaction takes several minutes to 30 minutes, it is preferable to use a batch type stirring device in order to ensure a sufficient reaction time. As a batch-type device, it is necessary to make good contact between the organic solution (A) and the aqueous solution (B). Therefore, a general-purpose stirring device having a propeller blade, a Max blend blade, a Faudler blade, etc. Can be used.

  The polycondensation reaction between the monomer in the organic solution (A) and the diamine in the aqueous solution (B) proceeds sufficiently in a temperature range of, for example, −10 to 50 ° C. near room temperature. Therefore, the temperature at which the organic solution (A) and the aqueous solution (B) are brought into contact with each other is set to a temperature range of about −10 to 50 ° C. near room temperature. At this time, neither pressurization nor decompression is required. The polycondensation reaction is usually completed in 30 minutes or less, depending on the type of monomer used and the reaction apparatus.

(Use of organic-inorganic composite)
Since the organic-inorganic composite obtained by the present invention has a high inorganic fraction, it can be used as a polymer reinforcing agent by kneading and dispersing in a polymer corresponding to the organic component of each composite. Can be used. Further, since the composite has processability due to organic components, it can be pressure-molded and can be used as various structural materials. Further, the composite can also be used as a polar solvent absorber that holds a large amount of polar solvent (10 times or more with respect to the weight of the composite) due to the high inorganic fraction and the polar group of the organic component. In particular, when the polar solvent is an electrolytic solution, it can also be used as an electrochemical device such as a battery separator holding the electrolytic solution, a capacitor separator, or a separator of an electrochromic display element.

  In particular, when the organic polymer component is polyurea, it can be synthesized using phosgene, which is used in a very wide range as various raw materials. . In addition, among the above uses, particularly when used as a polar solvent absorber or an electrolyte solution holder, a large amount of the urea bond, which is a polar group, is present with respect to the total complex weight. It can be made particularly high and can be used suitably.

  Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “part” means “part by mass”.

(Example 1: Synthesis of glass / polyurea composite)
1.56 parts of 1,6-diaminohexane and 5.37 parts of water glass No. 1 were added to 38.5 parts of ion-exchanged water, and the mixture was stirred at 25 ° C. for 15 minutes to obtain a homogeneous transparent aqueous solution (B). An organic solution (A) in which 1.34 parts of triphosgene was dissolved in 44.4 parts of toluene while the aqueous solution (B) was charged into a 300 ml Separa flask at room temperature and stirred at 300 revolutions per minute using an anchor blade. Was added dropwise over 20 seconds. A white polymer started to gradually precipitate from 5 minutes after the start of stirring. Since no increase was observed in the amount of precipitated polymer after 15 minutes, the synthesis operation was completed 25 minutes after the start of stirring. The liquid in which the white product obtained by this operation was dispersed was filtered under reduced pressure on a filter paper having an opening of 4 μm using a Nutsche having a diameter of 90 mm. The product on Nutsche was dispersed in 100 parts of methanol, stirred for 30 minutes with a stirrer, and filtered under reduced pressure for washing treatment. Subsequently, the same washing operation was performed using 100 parts of distilled water, followed by filtration under reduced pressure to obtain a wet cake of pure white glass / polyurea composite.

(Example 2: Synthesis of glass / polyurethane composite)
(Synthesis of dichloroformate compound)
Triphosgene 2.835 parts was added to 2.583 parts of 1.4-butanediol and stirred for 30 minutes at room temperature to completely dissolve the triphosgene. Further, 3.000 g of triphosgene was added and stirred at room temperature for 30 minutes to obtain a viscous light yellow transparent liquid. The liquid was subjected to reduced pressure treatment at 0.02 MPa for 3 hours while stirring to remove the remaining excess triphosgene and hydrochloric acid generated when the diol was chloroformated with the phosgene compound. By the above operation, butane-bis-chloroformate ester in which both ends of 1.4 butanediol were chloroformated was obtained.
(Synthesis of glass / polyurethane composite)
As the organic solution (A), a pure white solution was used in the same manner as in Example 1 except that 2.924 parts of butane-bis-chloroformate was dissolved in 44.4 parts of toluene. A wet cake of a glass / polyurethane composite was obtained.

(Comparative Example 1)
(Comparative Example 1: Glass / polyurea composite prepared by melt kneading method)
(Synthesis of glass-free polyurea)
A polyurea wet cake containing no inorganic components was prepared by synthesizing in the same manner as in Example 1 except that 1.247 parts of sodium hydroxide was used instead of water glass No. 1 in the aqueous solution (B). Obtained. The obtained polyurea wet cake was dried at 120 ° C. for 2 hours to obtain a dried polyurea. 10 parts of polyurea thus obtained and 5.0 parts of silicon oxide (silica) powder having an average particle diameter of 100 nm are melt-kneaded at 200 ° C. in a small twin screw extruder MP2015 made by Tsubako, thereby producing pellets. An organic-inorganic composite was obtained. The raw material charging operation prior to the kneading operation is extremely difficult because the powder is likely to be scattered due to the extremely small particle size of silicon oxide.
<Evaluation of material properties of various composites>
The composite obtained by the above operation was measured for the following items, and the results obtained are shown in Table 1.

(1) Measuring method of inorganic compound content (ash content):
The measuring method of the content rate of the inorganic compound contained in each material is as follows.
Each material was completely dried in air at 120 ° C. for 2 hours to obtain a dry composite. This was precisely weighed (composite mass) and then calcined in air at 600 ° C. for 3 hours to completely burn off the organic polymer component, and the mass after firing was measured to obtain the ash mass (= glass mass). The glass content was calculated from the following formula.
Glass content (mass%) = (mass ash / composite mass) × 100
In the composites obtained in Examples 1 and 2, even when the organic polymer was removed by firing, the shape before firing was maintained, whereas in the composite obtained in Comparative Example 1, the prototype was not retained. .

(2) Measurement of particle size of inorganic compound in composite and observation of dispersion state:
The composite was hot-pressed for 2 hours under conditions of 170 ° C. and 20 MPa / cm ² to obtain a flake made of the composite having a thickness of about 1 mm. This was made into an ultrathin section having a thickness of 75 nm using a microtome. The obtained section was observed with a transmission electron microscope “JEM-200CX” manufactured by JEOL Ltd. at a magnification of 100,000. In Examples 1 and 2, it was observed that the glass was finely dispersed in a bright organic polymer as a dark image. On the other hand, in Comparative Example 1, it was observed that most particles formed aggregates in the glass and existed in the polymer as coarse particles of 1 μm or more. FIG. 1 is a transmission electron micrograph of a glass / polyurea composite, and FIG. 2 is a transmission electron micrograph of the glass / polyurethane composite.

  Subsequently, the particle size of 100 glass particles was measured, and the average value was defined as the average particle size of the inorganic compound. In this observation, it is observed that in the composites of Examples 1 and 2, the inorganic compound (silica) having a particle size of 100 nm or less is network-like, that is, a three-dimensional network is formed and finely dispersed in the organic polymer. It was done.

表１で示された通り、比較例１では平均粒径１００ｎｍの酸化ケイ素粉末を使用したにもかかわらず、混練の工程でガラス成分の凝集が生じ、ナノメートルオーダーの複合を行うことができなかった。一方、実施例１及び実施例２に示されたとおり、本発明によってナノメートルオーダーであるガラス微粒子を、５０ｗｔ％以上の高い含有率で有する有機無機複合体を得ることができた。また本発明では、以上の特徴を持つ有機無機複合体を、常温常圧下で３０分以下の短時間の操作で得ることができた。

As shown in Table 1, in Comparative Example 1, although silicon oxide powder having an average particle diameter of 100 nm was used, aggregation of glass components occurred in the kneading process, and nanometer order composite could not be performed. It was. On the other hand, as shown in Example 1 and Example 2, according to the present invention, an organic-inorganic composite having glass fine particles of nanometer order at a high content of 50 wt% or more could be obtained. Further, in the present invention, an organic-inorganic composite having the above characteristics could be obtained by a short time operation of 30 minutes or less under normal temperature and pressure.

2 is a transmission electron micrograph of a glass / polyurea composite. It is a transmission electron micrograph of a glass / polyurethane composite.

Claims (2)

An organic solution (A) obtained by dissolving one compound selected from the group consisting of a dichloroformate compound and a phosgene compound in an organic solvent and an aqueous solution (B) obtained by dissolving alkali silicate and diamine in water are mixed and stirred, A composite of at least one organic polymer selected from the group consisting of polyurethane and polyurea obtained by reacting with glass, wherein the glass content is 10 to 80% by mass, and the average of the glass An organic-inorganic composite having a particle size of 500 nm or less. The organic-inorganic composite according to claim 1, wherein the average particle size of the glass is 100nm or less.

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