JP2005272632A - Silyl group-containing iodized epoxy compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a silyl group-containing iodized epoxy compound which is an iodine-containing compound having little change in hue and suitable as a flame retardant capable of replacing a bromine-based flame retardant, and to provide a method for producing the epoxy compound. <P>SOLUTION: The silyl group-containing iodized epoxy compound has a structure represented by formula (1) [wherein A is a divalent group represented by formula (2) (wherein 1≤p+q≤12 and I is an iodine atom and (m) and (n) are each independently an integer of 1 or 2); R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each independently a 1-4C alkyl group or alkoxy group which may have a substituent group; (p) is an integer of 0-12 and (q) is an integer of 1-12]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel silyl group-containing iodinated epoxy compound and a method for producing the same.

  Many compounds are already known as flame retardants for flame-retarding resins. For example, brominated flame retardants containing bromine atoms include aliphatic, bisphenol, phenol, aromatic, biphenyl, carboxylic acid, epoxy, imide, and acrylic types. Brominated flame retardants are widely used in electrical and electronic equipment (see, for example, Patent Document 1 or 2).

However, although brominated flame retardants are considered to have a lower environmental impact than chlorinated flame retardants, their use has been tended to be regulated in recent years, and the development of new flame retardants to replace brominated flame retardants Is desired.
Japanese Patent Laid-Open No. 54-15594 JP-A-4-11652

  Iodine-containing compounds are expected to have a flame-retarding effect by the same action as conventional halogen-based flame retardants such as brominated flame retardants, and are considered to be able to replace brominated flame retardants. However, in the case of conventionally known iodine-containing compounds, the present inventors have found that the resin is easy to be colored when mixed with the resin and heated and kneaded, and that the hue change in the resin molded body is large. Yes. Because of this problem, it was considered extremely difficult to put iodine-containing compounds into practical use as flame retardants.

  On the other hand, as other flame retardants that replace brominated flame retardants, for example, non-halogen flame retardants such as phosphorus flame retardants are known, but depending on the application, brominated flame retardants may be used as non-halogen flame retardants. It may be difficult to just substitute.

  Accordingly, an object of the present invention is to provide a silyl group-containing iodinated epoxy compound and a method for producing the same, which are iodine-containing compounds that are suitable as flame retardants that have little hue change and can replace brominated flame retardants.

  In order to solve the above problems, the present invention provides a silyl group-containing iodinated epoxy compound having a structure represented by the following general formula (1).

［式中、Ａは下記一般式（２）で表される２価の基、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に置換基を有していてもよい炭素数１〜４のアルキル基又はアルコキシ基、ｐは０〜１２の整数、ｑは１〜１２の整数、をそれぞれ示す。

但し、１≦ｐ＋ｑ≦１２であり、Ｉはヨウ素原子を示し、ｍ及びｎはそれぞれ独立に１又は２の整数を示す。］

[Wherein, A is a divalent group represented by the following general formula (2), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 4 carbon atoms which may have a substituent. Or an alkoxy group, p represents an integer of 0 to 12, and q represents an integer of 1 to 12, respectively.

However, it is 1 <= p + q <= 12, I shows an iodine atom, m and n show the integer of 1 or 2 each independently. ]

  This silyl group-containing iodinated epoxy compound exhibits a flame-retarding effect by containing iodine atoms. In addition, due to the relatively large molecular weight and the structure with a reduced content of hydroxyl groups, the decomposition temperature was increased, and the effect of suppressing hue change when mixed with other resins was obtained. Conceivable. Moreover, by using a silyl group as the group for protecting the hydroxyl group, the above-described effect of suppressing hue change can be obtained without significantly impairing the effect of improving the flame retardancy by the iodinated epoxy compound.

  As an iodine-containing compound, an iodinated bisphenol compound having a structure represented by the following general formula (5) has been conventionally known. However, this compound has a large change in hue of a resin and is practically used as a flame retardant. The application of was difficult.

［式中、Ｉはヨウ素原子を示し、ｍ及びｎはそれぞれ独立に１又は２の整数を示す。］

[Wherein, I represents an iodine atom, and m and n each independently represents an integer of 1 or 2. ]

  The present inventor believes that this hue change is caused by a part of the iodinated bisphenol compound being decomposed when heated, and the iodine atoms are liberated as hydrogen iodide, etc. In order to do this, this was reacted with epihalohydrin, and the use of an iodinated epoxy compound having a structure represented by the following general formula (3) as a flame retardant was examined.

［式中、Ａは上記一般式（２）で表される２価の基、ｒは１〜１２の整数、をそれぞれ示す。］

[Wherein, A represents a divalent group represented by the general formula (2), and r represents an integer of 1 to 12, respectively. ]

  However, although the above-mentioned iodinated epoxy compound is improved in hue change, it is still not sufficient, and it has become clear that further improvement is necessary. Therefore, as a result of repeated studies based on this knowledge, a silyl group-containing epoxy compound having a structure represented by the above general formula (1) having a structure in which a silyl group is further introduced into the iodinated epoxy compound, The present inventor has found that the change in hue when added to various resins is sufficiently suppressed, and the present invention has been completed.

  The silyl group-containing iodinated compound has a structure in which many of the hydroxyl groups in the iodinated epoxy compound are protected by introduction of a silyl group. The hydroxyl group of the iodinated epoxy compound is an aliphatic hydroxyl group, and its reactivity is low compared to an aromatic hydroxyl group (phenolic hydroxyl group). In addition, this hydroxyl group is generally considered to be hardly involved in a decomposition reaction or the like from the viewpoint of steric hindrance. However, the silyl group-containing epoxy compound has a significantly improved hue change compared to the iodinated epoxy compound, and contrary to expectations, this aliphatic hydroxyl group is greatly involved in the hue change. The inventor has inferred. From this point, it is preferable that the silyl group-containing epoxy compound contains fewer hydroxyl groups, and the value of q / (p + q) in the general formula (1) (hereinafter referred to as “silylation rate”) is 0.9. It is preferable to be within the range of ˜1.

In the general formula (1), R ¹ , R ^2, and R ³ are preferably methyl groups from the viewpoint of flame retardancy and dispersibility in the resin.

  The flame retardant of the present invention is composed of the silyl group-containing epoxy compound of the present invention, exhibits an excellent flame retarding effect, and is less colored when kneaded with a resin.

  The present invention also provides an iodinated epoxy compound having a structure represented by the general formula (3). This iodinated epoxy compound is a useful compound as an intermediate for synthesizing a silyl group-containing epoxy compound by employing the following production method of the present invention.

［式中、Ｘは加水分解性基、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に置換基を有していてもよい炭素数１〜４のアルキル基又はアルコキシ基、をそれぞれ示す。］ In the method for producing a silyl group-containing iodinated epoxy compound of the present invention, a silicon compound having a structure represented by the following general formula (4) is added to the iodinated epoxy compound having a structure represented by the above general formula (3). It has the process made to react, It is characterized by the above-mentioned. By this method, a silyl group is efficiently introduced into the hydroxyl portion, and the silyl group-containing iodinated epoxy compound of the present invention having the structure represented by the general formula (1) is obtained.

[Wherein, X represents a hydrolyzable group, and R ¹ , R ^2, and R ³ each independently represent a C 1-4 alkyl group or alkoxy group that may have a substituent. ]

  Moreover, this invention comprises the process of making an epihalohydrin react with the iodinated bisphenol compound which has a structure represented by the said General formula (5), The structure represented by the said General formula (3) characterized by the above-mentioned. A method for producing an iodinated epoxy compound is provided. By this method, an iodinated epoxy compound having a structure represented by the above general formula (3) can be obtained efficiently and reliably, and by reacting it with a silicon compound having a hydrolyzable group, etc. An iodinated epoxy compound can be obtained.

  According to the present invention, there are provided a silyl group-containing iodinated epoxy compound and a method for producing the same, which is an iodine-containing compound that is suitable as a flame retardant capable of substituting for a brominated flame retardant with little hue change.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The silyl group-containing iodinated epoxy compound of the present invention has a structure represented by the general formula (1). In the general formula (1), the repeating unit having a hydroxyl group and the repeating unit having a silyl group are usually randomly copolymerized, but each repeating unit forms a block in which the repeating units are continuously bonded to each other. It may be.

  Although the sum (degree of polymerization) of p and q should just be 12 or less, it is more preferable that it is 9-12. When the degree of polymerization exceeds 12, the solubility or dispersibility in other resins tends to decrease. On the other hand, when the degree of polymerization is less than 9, the decomposition temperature tends to decrease.

  It is preferable that the silylation rate which is the ratio containing the repeating unit which has a silyl group is 0.9-1. If the silylation rate is less than 0.9, the hue change tends to increase when added to a resin or the like.

  The values of m and n, which are the number of iodine groups substituting the bisphenol skeleton of the silyl group-containing iodinated epoxy compound, may be each independently an integer of 1 or 2, but it is preferable that both of them are 2. In particular, m and n are 2, and A in the general formula (1) is a divalent group represented by the following chemical formula (6) having iodine groups at the 3, 3 and 3 ′ and 3 ′ positions. It is preferable from the viewpoint that the synthesis is easy.

  The silyl group-containing iodinated epoxy compound contains a plurality of divalent groups represented by A in the above general formula (1), but they may have different numbers of iodine groups and different substitution positions. However, from the viewpoint of the flame retarding effect, the iodine content relative to the entire silyl group-containing iodinated epoxy compound is preferably 52 to 60% by weight, and more preferably 55 to 60% by weight.

In the general formula (1), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 4 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 2 carbon atoms). Or an alkoxy group, and may have a substituent such as a halogen group or a silyl group. In particular, R ¹ , R ² and R ³ are preferably methyl groups from the viewpoint of flame retardancy, dispersibility in resin, and the like.

  The flame retardant of the present invention is composed of the silyl group-containing iodinated epoxy compound of the present invention, and may be composed of a single compound, but usually a plurality of silyl group-containing iodines having different degrees of polymerization, etc. It is used as a mixture composed of an epoxy compound. In this mixture, those in which at least one of p, q, p + q, m and n in the above general formula is not within the above range may coexist. However, it is preferable that the values of p, q, p + q, m, and n as average values of the entire mixture are within the above ranges. Moreover, the flame retardant of this invention can also be used in the state which made another component coexist as needed.

  The flame retardant of the present invention can be added and used by dissolving or dispersing in other thermoplastic resins or thermosetting resins. In particular, the flame retardant of ABS resin, polycarbonate resin, polyester resin, polyamide resin, etc. It can be suitably used for flame retardancy. The amount added to the resin may be determined as appropriate so as to obtain the desired flame retardancy, but it is usually sufficient to add 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin. Is obtained.

  The silyl group-containing iodinated epoxy compound of the present invention as described above comprises the following method mainly comprising a two-step synthesis reaction through an iodinated epoxy compound having a structure represented by the general formula (3) as an intermediate. It can manufacture more suitably.

  As the first step, first, an iodinated epoxy containing, as a main component, a component having a structure represented by the above general formula (3) by reacting the iodinated bisphenol compound represented by the above general formula (5) with an epihalohydrin. A compound is obtained.

Examples of the iodinated bisphenol compound used as a raw material include bisphenol A, iodine (I ₂ ), potassium iodate (KIO ₃ ), potassium periodate (KIO ₄ ), periodate (HIO ₄ ), and iodate (HIO). ₃ ), and can be obtained by reacting an iodinating agent such as iodine monochloride (ICl). At this time, the values of m and n, which are the number of iodine groups, can be controlled within a range of 1 or 2 by appropriately adjusting the equivalent ratio of the raw material bisphenol A and the iodinating agent. For example, by reacting iodine monochloride as a ratio in the range of 4.0 to 6.5 mol with respect to 1.0 mol of bisphenol A, a component (tetraiodide) in which m and n are 2 is a main component. An iodinated bisphenol compound is obtained. The tetraiodide obtained at this time usually has a structure represented by the following chemical formula (7) in which the 3,3 and 3 ′, 3 ′ positions are substituted with iodine.

  The reaction between the iodinated bisphenol compound and epihalohydrin can be carried out by heating in the presence of an alkaline compound such as sodium hydroxide in a reaction solvent, for example. At this time, it is preferable that the preparation amount of the epihalohydrin with respect to 1.0 mol of iodinated bisphenol compounds exists in the range of 1.0-2.0 mol. A single compound may be sufficient as the iodinated bisphenol compound used as a raw material of reaction, and the mixture of the multiple types of compound from which iodine content and the position of substitution differ may be sufficient.

  As the epihalohydrin, epichlorohydrin, epibromohydrin, methyl epichlorohydrin, methyl epibromohydrin, or the like can be used. Among these, it is preferable to use epichlorohydrin from the viewpoints of good reactivity and easy removal of by-products.

  When synthesizing an iodinated epoxy compound by the above reaction, it is particularly preferable to use acetone or the like as a reaction solvent because it is easy to remove the solvent after the reaction.

  The degree of polymerization (value of r) of the resulting iodinated epoxy compound can be appropriately controlled in the above reaction by the charging ratio (equivalent ratio) of the iodinated bisphenol compound and epihalohydrin, the charging order, and the like. The degree of polymerization tends to increase as the equivalent ratio of epihalohydrin to iodinated bisphenol compound decreases. In addition, as for the order of preparation, adding the epihalohydrin to the solution in which the iodinated bisphenol compound is dissolved little by little, on the contrary, the degree of polymerization is higher than adding the solution in which the iodinated bisphenol compound is dissolved to the epihalohydrin in small amounts. An iodinated epoxy compound is obtained.

  More specifically, for example, the amount of the epihalohydrin relative to 1.0 mol of the iodinated bisphenol compound is 0.9 to 1.1 mol, and the epihalohydrin is usually added little by little to the solution in which the iodinated bisphenol compound is dissolved. An iodinated epoxy compound having a component having a polymerization degree of 9 to 12 as a main component is obtained.

  Next, as a second step, by reacting an iodinated epoxy compound with a silicon compound represented by the following general formula (4), a silyl group containing the component represented by the above general formula (1) as a main component is contained. An epoxy compound is obtained. For example, this reaction can be allowed to proceed by introducing an iodinated epoxy compound and a silicon compound into a solvent such as tetrahydrofuran and stirring at 20 to 80 ° C. preferably under inert gas substitution.

［式中、Ｘは加水分解性基、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に置換基を有していてもよい炭素数１〜４のアルキル基又はアルコキシ基、をそれぞれ示す。］

[Wherein, X represents a hydrolyzable group, and R ¹ , R ^2, and R ³ each independently represent a C 1-4 alkyl group or alkoxy group that may have a substituent. ]

  Examples of the hydrolyzable group X possessed by the silicon compound include a halogen atom, an alkoxy group, an acyloxy group, an alkenyloxy group, an amino group, a ketoximate group, an aminooxy group, a carbamoyl group, and a mercapto group. Among these, an alkoxy group is particularly preferable. 1-6 are preferable and, as for carbon number of an alkoxy group, 1-4 are still more preferable. As the alkoxy group, a methoxy group is particularly preferable.

When R ¹ , R ² and R ^{3 of the} silicon compound are alkyl groups, the carbon number is preferably 1 to 3, and more preferably 1 or 2. R ¹ , R ² and R ³ are alkyl groups or alkoxy groups, and may have a substituent such as a halogen group or a silyl group. In particular, it is preferable that R ¹ , R ^2, and R ³ are methyl groups from the viewpoint of flame retardancy, dispersibility in resin, and the like.

  Specific examples of the silicon compound include trimethylmethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane and the like. Among these, trimethylmethoxysilane is preferable from the viewpoint of flame retardancy and dispersibility of the resulting silyl group-containing iodinated epoxy compound.

  The silylation rate of the resulting silyl group-containing iodinated epoxy compound can be controlled by the reaction temperature, the equivalent ratio of the silicon compound to the hydroxyl group of the iodinated epoxy compound, and the like. As the reaction temperature is increased and the equivalent ratio of the silicon compound is increased, the silylation rate tends to increase. More specifically, for example, the amount of the silicon compound with respect to 1 mol of hydroxyl group of the iodinated epoxy compound is 1.0 to 2.0 mol, and the reaction is usually performed at 20 to 80 ° C. A silyl group-containing epoxy compound having a component of 0.9 to 1 as a main component is obtained.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
<Synthesis of iodinated bisphenol compound 1>
Bisphenol A (850 g, 3.72 mol), acetic acid (9.10 kg) and water (1.73 kg) were charged into a 20 L flask, and 2N-ICl (11.6 kg, 16.4 mol) while being heated to 80 ° C. ) Was added dropwise over 3 hours, and the mixture was further stirred for 7 hours while maintaining the temperature at 80 ° C. Thereafter, the reaction solution was cooled, the precipitated solid was filtered off, and washed with water.
Next, the obtained solid, acetic acid (12.8 kg), and water (2.42 kg) were charged into a 20 L flask, and 2N-ICl (2.80 kg, 3.96 mol) was heated to 80 ° C. while being heated to 30 ° C. The solution was added dropwise over a period of time, and the mixture was kept at 80 ° C and further stirred for 7 hours. Thereafter, the reaction solution was cooled, and the precipitated solid was filtered off and washed with water. The solid obtained at this time was further reacted with 2N-ICl in the same manner as described above to obtain a solid reaction product. The reaction product was washed with ethyl acetate and acetone and then dried to obtain iodinated bisphenol compound 1 (1.71 kg, 2.33 mol) (yield 62.6%).

The iodine content of the iodinated bisphenol compound 1 was 69.3% by weight, and TLC analysis showed a single spot at Rf 0.62. The following signals were observed in its ¹ H-NMR spectrum, absorption derived from C-I bonds to 875.6Cm ^-1 and 704.1Cm ^-1 in the IR spectrum (Figure 1) was observed. From these data, the iodinated bisphenol compound 1 was identified as a tetraiodinated product represented by the general formula (7).
¹ H-NMR (300 MHz); (DMSO-d ₆ , δ ppm) 1.50 (s, 6H), 7.48 (s, 4H), 9.41 (s, 2H).
In this example, the iodine content was measured by the combustion method, and the IR spectrum was measured by the KBr method. In addition, TLC analysis was performed by using a mixed solvent of ethyl acetate / n-hexane (volume ratio: 3/7) using SilicaGel 60 (Merck Japan Co., Ltd.) fixed on an F254 glass plate as a developing solvent. Went as.

(Synthesis Example 2)
<Synthesis of iodinated bisphenol compound 2>
Bisphenol A (400 g, 1.75 mol), acetic acid (4.28 kg) and water (816 kg) were charged into a 20 L flask, and 2N-ICl (4.96 kg, 7.01 mol) was added while heating to 80 ° C. The solution was added dropwise over 2 hours, kept at 80 ° C., and further stirred for 7 hours. Thereafter, the reaction solution was cooled, and the precipitated solid reaction product was filtered off and washed with water. This reaction product was washed with ethyl acetate and acetone and then dried to obtain iodinated bisphenol compound 2 (275 g) (yield 21.4%).

The iodine content of iodinated bisphenol compound 2 was 68.0% by weight, and TLC analysis showed two spots of Rf 0.62 and 0.49. Further, in the ¹ H-NMR spectrum, signals derived from a tetraiodide similar to Synthesis Example 1 and a triiodide represented by the following chemical formula (8) were observed, respectively, and 875.6 cm ^{− in} the IR spectrum. Absorption due to C—I bonds was observed at ¹ and 704.1 cm ⁻¹ . Based on these data, it was confirmed that the iodinated bisphenol compound 2 is a mixture of a tetraiodide and a triiodide.
¹ H-NMR (300 MHz); (DMSO-d ₆ , δ ppm)
Tetraiodide: 1.50 (s, 6H), 7.48 (s, 4H), 9.41 (s, 2H)
Triiodide: 1.50 (s, 6H), 6.80 (d, 1H), 6.98-7.01 (dd, 1H), 7.44 (s, 1H), 7.46 (s, 1H), 9.43 (s, 1H).

(Example 1)
<Synthesis of iodinated epoxy compound 1>
A 10-liter flask purged with nitrogen was charged with the iodinated bisphenol compound 1 (1.71 kg, 2.33 mol), acetone (3 L), and 10% NaOH solution (1.03 kg) obtained in Example 1, and the mixture was heated to 65 ° C. While heating, epichlorohydrin (237 g, 2.56 mol) was added dropwise over 6 hours, followed by further stirring at 65 ° C. for 15 hours. Thereafter, the reaction solution is cooled, the solvent is distilled off, and the resulting viscous reaction product is washed with water and dried under reduced pressure at 80 ° C. to obtain iodinated epoxy compound 1 (1.79 kg). It was. The iodine content of the iodinated epoxy compound 1 was 60.2% by weight, and the epoxy equivalent was 4215 g / eq. Met. From the value of iodine content and epoxy equivalent, the average molecular weight was calculated to be 8430, and the average degree of polymerization was calculated to be 9.6.

The epoxy equivalent was measured by the hydrochloric acid-dioxane method in the following operations 1) to 3).
1) A sample obtained by precisely weighing about 0.5 g to obtain a precisely weighed value (g) is dissolved in 25 mL of 0.2N-dioxane hydrochloride solution (concentrated hydrochloric acid 1.6 mL / purified dioxane 100 mL) to obtain a sample solution. .
2) After leaving the sample solution at room temperature for 15 minutes, add 25 mL of alcohol and titrate with 0.1N NaOH normal solution to measure titration (mL) (indicator: cresol red).
3) The blank test is performed in the same manner, and the epoxy equivalent is calculated by the following formula (1).
Epoxy equivalent = 10000 × (precisely measured value) / [(factor of 0.1N NaOH normal solution) × {(blank test titration) − (sample droplet quantification)}] (1)

The hydroxyl equivalent was measured by the acetyl chloride method in the following operations 1) to 6).
1) A sample obtained by precisely weighing about 1 g to obtain a precisely weighed value is dissolved in 10 mL of dioxane to obtain a sample solution.
2) Add 10 mL of acetyl chloride solution (acetyl chloride 11.8 mL / toluene 100 mL) to the sample solution.
3) Further, add 2 mL of pyridine and heat-treat at 60 ° C. for 1 hour with vigorous stirring.
4) Add 2 mL of distilled water and cool in an ice bath for 30 minutes, and then add 25 mL of acetone.
5) Titrate the sample solution with 0.5N NaOH normal solution and measure the titration amount (mL).
6) The blank test is performed in the same manner, and the hydroxyl equivalent is calculated by the following formula (2).
Hydroxyl equivalent = 2000 × (exactly measured value) / [(factor of 0.5N NaOH normal solution) × {(blank test titration) − (sample droplet quantification)}] (2)

  When TG / DTA was measured for the iodinated epoxy compound 1, the endothermic peak at 281.7 ° C. observed in the raw material iodinated bisphenol compound 1 disappeared, and at 350.7 ° C., A new exothermic peak believed to be derived from decomposition was seen. In addition, TG / DTA was measured in the range of 0-500 degreeC by the temperature increase rate of 20 degree-C / min in nitrogen atmosphere.

(Example 2)
<Synthesis of iodinated epoxy compound 2>

  Into a 100 mL flask, epichlorohydrin (2.5 g, 0.027 mol) was added and heated to 120 ° C., and the iodinated bisphenol compound 1 (10 g, 0.014 mol) and 10% obtained in Example 1 were used. A mixture of NaOH solution (10.9 g) was added dropwise over 30 minutes, and the mixture was further stirred at 120 ° C. for 4 hours. Thereafter, the reaction solution was cooled, the precipitated solid was dissolved in acetone, and insoluble matters were removed by filtration. Subsequently, the solvent was distilled off from the filtrate to obtain a solid iodinated epoxy compound 2 (9.9 g). The iodine content of the iodinated epoxy compound 2 was 60.1% by weight, and the epoxy equivalent was 724. From the value of iodine content and epoxy equivalent, the average molecular weight was calculated to be 1451, and the average degree of polymerization was calculated to be 0.77. Moreover, when TG / DTA was measured about this, the exothermic peak considered to originate mainly in decomposition | disassembly of an epoxy group was observed at 323.1 degreeC. From these data, the iodinated epoxy compound 2 is a mixture containing at least a component represented by the above general formula (3), where r is 1, and an intermediate for obtaining the silyl group-containing iodinated epoxy compound of the present invention. It was confirmed that it could be used as a body.

(Example 3)
<Synthesis of silyl group-containing iodinated epoxy compound 1>
A 10-liter flask purged with nitrogen was charged with the iodinated epoxy compound 1 (1.79 kg) obtained in Example 1, tetrahydrofuran (3.58 L), and trimethylmethoxysilane (426 g, 4.09 mol), and the mixture was stirred at 80 ° C. for 15 minutes. Stir for hours. Thereafter, the reaction solution was cooled, and the viscous reaction product obtained by distilling off the solvent was washed with n-hexane, dried under reduced pressure at 80 ° C., and silyl group-containing iodinated epoxy compound 1 (1.63 kg). ) The iodine content of the silyl group-containing iodinated epoxy compound 1 is 60.6% by weight, and the epoxy equivalent is 4215 g / eq. The hydroxyl group equivalent is 9429 g / eq. Met. From the values of epoxy equivalent and hydroxyl equivalent, the average molecular weight was calculated to be 9429, and the average silylation rate was calculated to be 0.99.

When the TG / DTA of the silyl group-containing iodinated epoxy compound 1 was measured, an exothermic peak considered to be mainly due to the decomposition of the epoxy group was observed at 360.9 ° C. Further, in the IR spectrum, the broad absorption around 3400 cm ⁻¹ derived from the hydroxyl group observed in the iodinated epoxy compound as the raw material has almost disappeared (FIG. 1), and the hydroxyl group is silylated. Was confirmed.

Example 4
<Synthesis of silyl group-containing iodinated epoxy compound 2>
A 50 mL flask substituted with nitrogen was charged with the iodinated epoxy compound 1 (10 g) obtained in Example 1, tetrahydrofuran (20 mL), and trimethylmethoxysilane (1.8 g, 0.0017 mol), and stirred at room temperature for 8 hours. . Thereafter, the viscous reaction product obtained by distilling off the solvent was washed with n-hexane and dried under reduced pressure at 80 ° C. to obtain a silyl group-containing iodinated epoxy compound 2 (8.2 g). The iodine content of the silyl group-containing iodinated epoxy compound 2 is 59.9% by weight, and the epoxy equivalent is 4225 g / eq. The hydroxyl group equivalent is 1145 g / eq. Met. From the values of the epoxy equivalent and the hydroxyl equivalent, the average silylation rate was calculated to be 0.755.

(Example 5)
<Evaluation of flame retardancy>
The silyl group-containing iodinated epoxy compound 1 (10 parts by weight) obtained in Example 3 was added to 100 parts by weight of an acrylonitrile-butadiene-styrene copolymer (Toyolac (trade name), manufactured by Toray Industries, Inc.). The mixture was melt-kneaded using a twin-screw extruder (cylinder setting temperature 220 ° C.) to obtain a pellet-shaped thermoplastic resin composition. In this melt-kneading, coloring of the resin composition was not particularly recognized. The obtained thermoplastic resin composition was dried at 80 ° C. for 4 hours, and then molded using an injection molding machine at a cylinder temperature of 210 ° C. and a mold temperature of 60 ° C. to obtain a test piece.

  About the obtained test piece, the flame retardance was evaluated according to UL94 specification. The size of the test piece was 12.7 mm in width, 127 mm in length, and 1.6 mm in thickness, and five combustion tests were performed. The total of the five combustion times was defined as the total combustion time (seconds), and when this exceeded 250 seconds, measurement was impossible. Based on the results such as the presence or absence of dripping from the test piece and the total combustion time, the flame retardance rank was determined as V-2 according to the UL94 standard.

(Comparative Example 1)
<Evaluation of flame retardancy>
A test piece was molded and its flame retardancy was evaluated in the same manner as in Example 5, except that the silyl group-containing iodinated epoxy compound 1 was not mixed. The total combustion time was not measurable, and the flame retardancy was out of specification (not applicable to any of V-0 to V-2).

FIG. 1 is an IR spectrum of the iodinated bisphenol compound 1 obtained in Synthesis Example 1, the iodinated epoxy compound 1 obtained in Example 1, and the silyl group-containing iodinated epoxy compound 1 obtained in Example 3.

Claims (7)

A silyl group-containing iodinated epoxy compound having a structure represented by the following general formula (1).

[Wherein, A is a divalent group represented by the following general formula (2), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 4 carbon atoms which may have a substituent. Or an alkoxy group, p represents an integer of 0 to 12, and q represents an integer of 1 to 12, respectively.

However, it is 1 <= p + q <= 12, I shows an iodine atom, m and n show the integer of 1 or 2 each independently. ]   The silyl group-containing iodinated epoxy compound according to claim 1, wherein the value of q / (p + q) is 0.9 to 1. The silyl group-containing iodinated epoxy compound according to claim ¹ , wherein R ¹ , R ^2, and R ³ are methyl groups.   The flame retardant which consists of a silyl group containing iodinated epoxy compound as described in any one of Claims 1-3. An iodinated epoxy compound having a structure represented by the following general formula (3).

[Wherein, A represents a divalent group represented by the following general formula (2), and r represents an integer of 1 to 12, respectively.

However, I shows an iodine atom, m and n show the integer of 1 or 2 each independently. ] A silyl group having a structure represented by the following general formula (1), comprising the step of reacting the iodinated epoxy compound according to claim 5 with a silicon compound having a structure represented by the following general formula (4): A method for producing an iodinated epoxy compound.

[Wherein, X is a hydrolyzable group, R ¹ , R ² and R ³ are each independently an optionally substituted alkyl group or alkoxy group having 1 to 4 carbon atoms, and A is the following general formula ( 2), p is an integer of 0 to 12, and q is an integer of 1 to 12, respectively.

However, it is 1 <= p + q <= 12, I shows an iodine atom, m and n show the integer of 1 or 2 each independently. ] The manufacturing method of the iodinated epoxy compound which has the process of making an epihalohydrin react with the iodinated bisphenol compound which has a structure represented by following General formula (5).

[Wherein, I is an iodine atom, m and n are each independently an integer of 1 or 2, A is a divalent group represented by the following general formula (2), and r is an integer of 1 to 12, respectively. .

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