CN100348645C - Cage type sesquialter oxosilane resin with functional group and its preparation method - Google Patents

Abstract

Provided is a cage-type silsesquioxan resin eliminating conventional defects, with regulated molecular weight distribution and molecular structure, and having a (meth)acryloyl group, a glycidyl group or a vinyl group, and to provide a method for producing the cage-type silsesquioxan resin in high yield. The cage-type silsesquioxan resin expressed by [RSiO<SB>3/2</SB>]<SB>n</SB>(R is the (meth)acryloyl group, glycidyl group or vinyl group, n is 8, 10, 12 or 14), is obtained by carrying out a hydrolysis reaction with partial condensation of a silicon compound expressed by RSiX<SB>3</SB>(R is same as prescribed, X is a hydrolyzable group), in the presence of an organic polar solvent and a basic catalyst, and then carrying out a recondensation of the hydrolysis product in the presence of a non-polar solvent and a basic catalyst. The cage-type silsesquioxan resin has compatibility with a (meth)acrylate resin and an epoxy resin and widely used as a material for radically polymerizable resin composition.

Description

Cage-type silsesquioxane-based resin having functional groups and method for producing the same

technical field

The present invention relates to a cage-type silsesquioxane resin and a method for producing the same. Specifically, it relates to a reaction in which all silicon atoms are composed of organic functional groups having (meth)acryloyl, glycidyl, or vinyl groups. A method for producing a cage-type silsesquioxane-based resin with sexual functional groups.

current technology

The silsesquioxane resin represented by the general formula [RSiO _3/2 ] _n can be roughly divided into three types of polyorganosilsesquioxane (polyorganosilsesquioxane) of cage type, ladder type and random type. Among them, the cage-type silsesquioxane resin has a clear molecular structure and a rigid skeleton. In addition, since the molecular structure is already controlled, it is possible to control the molecular structure by using it as a building block of a polymer. If the structure can be controlled, completely different performances can be expected. In other words, even if they are both represented by the general formula [RSiO _3/2 ] _n , there may be considerable differences in performance depending on the molecular structure of the silsesquioxane resin.

Synthesis of silsesquioxane compounds is known, for example, by hydrolyzing phenyltrichlorosilane and then performing an equilibrium reaction using KOH (J.Am.Chem.Soc, 82, 6194-6195, 1960) as a representative of many methods. In the synthetic method of cage silsesquioxane resin, the synthetic method of cage silsesquioxane resin with reactive functional groups is in Zh.Obshch.Khim.1552-1555.49.1997 (Non-Patent Document 1) A synthetic method with a vinyl group has been disclosed. Moreover, the manufacturing method etc. of the silsesquioxane which have a glycidyl group are also disclosed by Unexamined-Japanese-Patent No. 11-29640 (patent document 1).

However, even with reference to the manufacturing method disclosed in Japanese Patent Laid-Open Publication No. 11-29640, the synthesis of silsesquioxane resins having (meth)acryl groups will be difficult to fully control the molecular weight distribution and structure, resulting in A silsesquioxane resin having a clear molecular structure such as a cage structure could not be produced in good yield.

[Patent Document 1] Japanese Patent Laid-Open No. 11-29640

[Non-Patent Document 1] Zh.Obshch.Khim.1552-1555.49.(1997)

Contents of the invention

The object of the present invention is to solve the known disadvantages and provide a cage-type silsesquioxane resin with (meth)acryloyl, glycidyl, or vinyl groups with controlled molecular weight distribution and molecular structure. Furthermore, it provides the method which can manufacture the said cage silsesquioxane resin with high yield.

In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive studies and found that these problems can be solved by using specific reaction conditions, thereby completing the present invention.

In other words, the present invention is the manufacture method of cage type silsesquioxane resin, the following general formula (1)

RSiX ₃ (1)

The silicon compound shown, wherein, R is an organic functional group having any one of (meth)acryloyl, glycidyl, or vinyl, X is a hydrolyzable group, and the compound can be dissolved in an organic polar solvent and a basic catalyst In the presence of , the hydrolysis reaction is carried out to produce partial condensation, and the hydrolyzed product obtained is then re-condensed in the presence of a non-polar solvent and a basic catalyst.

The cage type silsesquioxane resin obtained according to the manufacturing method is preferably the following general formula (2)

[RSiO _3/2 ] _n (2)

, wherein R is an organic functional group having any one of (meth)acryl, glycidyl, or vinyl, and n is 8, 10, 12, or 14. In addition, in the general formula (1), R is preferably the following general formulas (3), (4), (5)

【Chemical 1】

The organic functional group shown, wherein m is an integer from 1 to 3, and R ₁ is a hydrogen atom or a methyl group. Furthermore, the number average molecular weight of the above hydrolyzate is preferably in the range of 500 to 7000. In addition, the hydrolyzed product is a cage-type silsesquioxane resin obtained by recondensing a mixture of cage-type, ladder-type and random-type silsesquioxanes, which is shown by the above general formula (2), n 3 or more cage silsesquioxane resin mixtures selected from 8, 10, 12 and 14, preferably n is the total amount of cage silsesquioxanes of 8, 10, 12 and 14, the total times More than 50wt% of semisiloxane.

In other words, one solution of the present invention is a cage silsesquioxane resin with functional groups produced by the method of the present invention, which has a cage silsesquioxane resin with functional groups, and in the mixture, the following general formula (2) The ratio of the cage-type silsesquioxane resin shown in (2) is more than 50wt%,

[R8iO _3/2 ] _n (2)

Wherein, R is an organic functional group having any one of a (meth)acryloyl group, a glycidyl group, or a vinyl group, and n is 8, 10, 12 or 14.

Furthermore, the present invention is a cage-type silsesquioxane resin with functional groups. In the mixture, the proportion of the cage-type silsesquioxane resin represented by the above general formula (2) accounts for more than 50 wt % of the cage-type silsesquioxane resins with functional groups. Cage silsesquioxane resin. Among them, the molecular weight distribution (Mw/Mn) of the cage silsesquioxane resin is preferably in the range of 1.03 to 1.10.

Brief description of the drawings

Fig. 1 is the GPC of the hydrolyzate of embodiment 1

Fig. 2 is the LC-MS of the hydrolyzate of embodiment 1

Fig. 3 is the GPC of the recondensation reaction product of Example 1

Fig. 4 is the LC-MS of the recondensation reaction product of embodiment 1

Fig. 5 is the GPC of the recondensation reaction product of Example 2

Fig. 6 is the GPC of the recondensation reaction product of Example 3

Fig. 7 is the LC-MS of the recondensation reaction product of embodiment 3

Fig. 8 is the GPC of the recondensation reaction product of Example 4

Fig. 9 is the LC-MS of the recondensation reaction product of embodiment 4

Figure 10 is the GPC of Comparative Example 1

Figure 11 is the GPC of Comparative Example 2

Detailed ways

Hereinafter, embodiments of the present invention will be specifically described.

In addition, in the following description, among the cage silsesquioxane resins represented by the general formula (2), the compound with n=8 is called T8, the compound with n=10 is called T10, and the compound with n=12 is called T8. It is called T12, and the compound of n=14 is called T14. The cage silsesquioxane resin of the present invention is a cage silsesquioxane resin represented by general formula (2), or a resin containing it as a main component, and may contain other components such as components with different n numbers. Also, when referred to as "cage silsesquioxane resin", the meaning can be construed to include oligomers.

The structural formulas of T8, T10, T12 and T14 are shown in the following formulas (6), (7), (8) and (9), respectively. In addition, in the following formulas (6) to (9), R means an organic functional group having any one of a (meth)acryloyl group, a glycidyl group, or a vinyl group.

【Chemical 2】

【Chemical 3】

【Chemical 4】

【Chemical 5】

According to the present invention, any one of the above-mentioned T8, T10, T12 and T14, or a mixture of two or more, preferably 3 or 4, can be obtained as the main component, and preferably contain more than 50 wt% of silsesquisilicon oxane resin.

Especially when the organic functional group R is an organic functional group having a (meth)acryloyl group or a glycidyl group, the cage-type silsesquioxane resin composed of T8, T10, and T12 accounts for more than 50 wt% of the total, Preferably it accounts for more than 70wt%. In this case, T8 can be set in the range of 20 to 40 wt%, T10 in 40 to 50 wt%, and T12 in the range of 5 to 20 wt%.

Furthermore, when the organic functional group belongs to the case of a vinyl functional group, the cage silsesquioxane resin composed of T10, T12, and T14 accounts for more than 50 wt% of the total, preferably more than 70 wt%. In this case, T10 can be set in the range of 10 to 40 wt%, T12 in 20 to 60 wt%, and T14 in the range of 5 to 20 wt%.

Other components are mainly compounds other than T8, T10, T12 and T14 with different n values, compounds other than cages, and the like.

The molecular weight distribution (measured using GPC measurements) of T8, T10, T12 and T14 may be in the range of 1.00 to 1.01. The molecular weight distribution (Mw/Mn) of the cage silsesquioxane resin of the present invention is below 1.1, preferably in the range of 1.03 to 1.10. The molecular weight ranges from 600 to 2500, preferably from 1000 to 2000, as the number average molecular weight.

Furthermore, if an operation of separating one of T8 to T14 from the resin containing T8 to T14 is added, a silsesquioxane resin composed of any one of T8 to T14 and a silsesquioxane resin composed of any of T8 to T14 can also be obtained. One of the silsesquioxane resins was isolated. The silsesquioxane resin thus separated is also included in the silsesquioxane resin of the present invention.

In the production method of the silsesquioxane of the present invention, first, the silicon compound represented by the general formula (1) is hydrolyzed in the presence of an organic polar solvent and a basic catalyst. In the general formula (1), R is an organic functional group with (meth)acryloyl, glycidyl, or vinyl, and the (meth)acryloyl or glycidyl can be directly bonded to Si. It is better to add hydrocarbon groups such as alkylene or phenylene, or other divalent groups.

The best organic functional group R is shown in general formula (3). In the general formula (3), R ₁ is H or methyl, and m is 1 to 3. When specific examples of preferable R are illustrated, 3-methacryloyloxypropyl, methacryloyloxymethyl, and 3-acryloyloxypropyl are illustrated.

In the general formula (1), X is a hydrolyzable group, for example: alkoxy group, acetoxy group, etc., preferably alkoxy group. Examples of alkoxy include: methoxy, ethoxy, n- and i-propoxy, n-, i-, and tert-butoxy, and the like. Among them, the highly reactive methoxy group is preferable.

Among the silicon compounds represented by the general formula (1), if preferred compounds are exemplified, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-epoxypropyl Oxypropyltrimethoxysilane, 3-Glycidoxypropyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane. Among them, 3-methacryloxypropyltrimethoxysilane, which can be easily obtained as a raw material, is preferably used.

The basic catalyst used in the hydrolysis reaction is, for example, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. , benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide and other ammonium hydroxide salts. Among these, tetramethylammonium hydroxide is preferably used from the viewpoint of high catalyst activity. Basic catalysts are usually used in aqueous solution.

Regarding the hydrolysis reaction conditions, the reaction temperature is preferably 0 to 60°C, especially 20 to 40°C. If the reaction temperature is lower than 0°C, the reaction rate will slow down, and the hydrolyzable group will exist in an unreacted state, resulting in a longer reaction time; on the contrary, if it is higher than 60°C, because the reaction rate is too fast , and a complicated condensation reaction is carried out, and as a result, the high molecular weight of the hydrolyzed product is promoted. In addition, the reaction time is preferably more than 2 hours. If the reaction time is less than 2 hours, the hydrolysis reaction will not proceed sufficiently, and the hydrolyzable group will remain in an unreacted state.

Although the presence of water is necessary for the hydrolysis reaction, it can be supplied by an aqueous solution of a basic catalyst, or by adding additional water. The amount of water is a sufficient amount to hydrolyze the hydrolyzable groups, preferably less than 1.0 to 1.5 times the theoretical amount. In addition, it is preferable to use an organic solvent during hydrolysis, and the organic solvent can be alcohols such as methanol, ethanol, 2-propanol, or other polar solvents. Preferably, it is a lower alcohol with a carbon number of 1 to 6 having solubility in water, especially 2-propanol. If a non-polar solvent is used, the reaction system will not be uniform, the hydrolysis reaction will not be fully carried out, and unreacted alkoxy groups will remain, so it is not suitable.

After the hydrolysis reaction is complete, the water or aqueous reaction solvent is separated. The separation of water or the aqueous reaction solvent can be carried out by evaporation under reduced pressure and the like. In order to fully remove water and other impurities, it is possible to add a non-polar solvent to dissolve the hydrolyzate, wash the solution with salt water, etc., and then dry it with a desiccant such as anhydrous magnesium sulfate. If the non-polar solvent is separated by evaporation or the like, the hydrolyzate can be recovered, but if the non-polar solvent can be used as the non-polar solvent in the next reaction, it does not need to be separated.

In the hydrolysis reaction of the present invention, the condensation reaction of the hydrolyzate will occur along with the hydrolysis. The hydrolyzate produced by the condensation reaction of the hydrolyzate is usually a colorless viscous liquid with a number average molecular weight of 500 to 7000. The hydrolyzate is different with reaction conditions, and its number average molecular weight is in the resin (or oligomer) of 500 to 3000, the major part (preferably almost all) of the hydrolyzable group X shown in general formula (1) It is substituted with OH groups, and most of the OH groups are preferably condensed by more than 95%.

Regarding the structure of the hydrolyzate, there are multiple cage-type, ladder-type, and random-type silsesquioxanes. Although compounds with cage-type structures are used, the ratio of complete cage-type structures is also relatively small, mainly cage-type. Partially open incomplete cage structure. Therefore, in the present invention, the hydrolyzate obtained by hydrolysis is heated in an organic solvent in the presence of a basic catalyst to condense the siloxane bond (called "recondensation"), and selectively Manufacture of cage-structured silsesquioxanes.

After the water or the aqueous reaction solution is separated, the recondensation reaction is carried out in the presence of a non-polar solvent and a basic catalyst.

Among the reaction conditions of the relevant recondensation reaction, the preferred reaction temperature is in the range of 100 to 200°C, especially 110 to 140°C. In addition, if the reaction temperature is too low, sufficient driving force for the recondensation reaction cannot be obtained, and the reaction cannot proceed. Conversely, if the reaction temperature is too high, since the reactive organic functional groups may initiate self-polymerization, it is necessary to suppress the reaction temperature or add additives such as polymerization inhibitors. The reaction time is preferably 2 to 12 hours. The usage amount of the organic solvent is only enough to dissolve the hydrolyzate, and the usage amount of the basic catalyst is in the range of 0.1 to 10 wt% of the hydrolyzate.

The non-polar solvent only needs to have no (or almost no) solubility in water, and is preferably a hydrocarbon solvent. Related hydrocarbon solvents include non-polar solvents with low boiling points such as toluene, benzene, and xylene. Among them, toluene is preferably used.

The basic catalyst can adopt the basic catalyst used in the hydrolysis reaction, for example: potassium hydroxide, sodium hydroxide, cesium hydroxide and other alkali metal hydroxides, or tetramethylammonium hydroxide, tetraethylammonium hydroxide , tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide and other ammonium hydroxide salts. Catalysts soluble in non-polar solvents such as tetraalkylammonium are preferable.

In addition, the hydrolyzate used in the recondensation is preferably washed with water, dehydrated and concentrated, but it can be used even if it has not been washed with water or dehydrated. During this reaction, although water can exist, it does not need to be added actively, only the degree of water brought in from the alkaline catalyst solution is sufficient. In addition, when the hydrolysis of the hydrolyzate does not proceed sufficiently, although the hydrolysis of the remaining hydrolyzable groups requires more than the necessary theoretical amount of water, the hydrolysis reaction usually proceeds sufficiently.

After the recondensation reaction, the catalyst was washed with water, removed, and concentrated to obtain a silsesquioxane mixture.

Although the silsesquioxane resin obtained according to the present invention varies with the type of functional group, reaction conditions, and the state of the hydrolyzed product, the structural components are multiple cage-type moieties shown in general formulas (6) to (9). Semisiloxane accounts for more than 50wt% of the whole. The abundance ratio of T8 to T14 may be as described above. In the general formula, when R is a 3-methacryloxypropyl group, T8 can be separated by the precipitation of needle crystals by placing the silane mixture below 20°C.

Invention effect

According to the production method of the cage silsesquioxane of the present invention, the structure-controlled cage silsesquioxane can be produced in high yield. The obtained cage silsesquioxane has reactive functional groups on all silicon atoms, so it is compatible with (meth)acrylates, epoxy resins, etc., can be mixed arbitrarily, and can be widely used for photopolymerization Raw materials for permanent resin compositions. In addition, by using cage silsesquioxane in the photopolymerizable resin composition, the crosslinking density of the resin can be increased, and the heat resistance, thermal stability, chemical resistance, and mechanical properties of the cured resin can also be effectively improved. performance.

Example

Hereinafter, the present invention will be described more specifically using examples.

Example 1

120 ml of 2-propanol (IPA) as a solvent, and 9.4 g of 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst were placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. Put 45ml of IPA and 38.07g of 3-methacryloxypropyltrimethoxysilane (MTMS: SZ-6300, manufactured by Toray Taoconic Silicone Co., Ltd.) in the dropping funnel, and then react while stirring While the container was at room temperature, the IPA solution of MTMS was added dropwise within 30 minutes. After the addition of MTMS was completed, the mixture was stirred for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure, and then dissolved in 250 ml of toluene. The reaction solution was washed with saturated brine until it became neutral, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 25.8 g of a hydrolyzate (silsesquioxane) at a yield of 94%. This silsesquioxane is a colorless viscous liquid soluble in various organic solvents.

The GPC of this silsesquioxane was measured, and the results are shown in Figure 1. From Fig. 1, the molecular weight distribution and abundance ratio of silsesquioxanes are calculated as in Table 1. The molecular weight distribution (Mw/Mn) of the hydrolyzate at this stage was 1.26.

Furthermore, mass analysis (LC-MS) after separation by high-speed liquid chromatography was carried out, and the results are shown in FIG. 2 . From Fig. 2, T9 (OH) and T11 (OH) of the incomplete cage structure of the cages shown in the following (10) and (11) are partially opened, and T8, T10, T12 of the complete cage structure Molecular ions attached to ammonium ions. In the following formulae, R is a 3-methacryloyloxypropyl group.

【Chemical 7】

【chemical 8】

As a result of 1H-NMR measurement, a broad signal derived from the methacryloxypropyl group was observed. In addition, no signal (3.58 ppm) originating from methoxy was observed. The integral ratio of -C=CH ₂ and -O-CH ₂ - was compared, and the result was 1.999:2.002. From this, it was confirmed that the reaction to the double bond of the methacryloxypropyl group was not initiated. In particular, from the above results, it was confirmed that peak 1, peak 2 and peak 3 are random compounds (R type) or ladder type compounds (L type) of silsesquioxane structure. Peak 4 was identified as a cage or partially opened cage compound (type C). If calculated from the results of GPC and LC-MS, it is calculated from GPC that the compound (type C) is composed of T8, T10, T12, and incomplete cage T9OH, T11OH, and the total amount is 24.6%. The results of LC-MS, the amount of T8, T10, T12, T9OH, T11OH are calculated as shown in Table 1.

Next, put 20.65 g of the silsesquioxane obtained above, 82 ml of toluene, and 10% TMAH aqueous solution into a reaction vessel equipped with a stirrer, a water-dividing distillation receiving tube (Dean-Stark) with a small nozzle interface, and a cooling tube. 3.0g, and gradually heated to distill off the water. It was further heated to 130° C., and the toluene was recondensed at reflux temperature. The temperature of the reaction solution at this time was 108°C. After toluene was refluxed and stirred for 2 hours, the reaction was terminated. The reaction solution was washed with saturated brine until it became neutral, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 18.77 g of the desired cage silsesquioxane (mixture). The obtained cage silsesquioxane is a colorless viscous liquid soluble in various organic solvents.

The GPC of the reactant after the recondensation reaction was measured, and the results are shown in FIG. 3 . From Figure 3, Mn2018 (peak 5), Mn1570 (peak 6), Mn1387 (peak 7), and Mn1192 (peak 8) were found. The molecular weight, molecular weight distribution, and amount of each peak are shown in Table 1. The molecular weight distribution (Mw/Mn) of the reactant after the recondensation reaction was 1.04.

Furthermore, the mass analysis after separation by high-speed liquid chromatography was carried out, and the results are shown in FIG. 4 . It was confirmed from FIG. 4 that molecular ions of ammonium ions were attached to T8, T10, and T12.

From the above results, the structure of silsesquioxane in peak 5 is a random or ladder compound. Peak 6 can be identified as T12, peak 7 can be identified as T10, and peak 8 can be identified as T8.

The above-mentioned cage-type silsesquioxane mixture after recondensation is placed below 20° C., and needle crystals are precipitated. The needle-like crystals were 5.89 g after filtration. In addition, when GPC measurement was performed on the needle-like crystals, only peak 8 was detected, and it was confirmed that the crystals were T8. As a result of 1H-NMR measurement, a signal derived from the methacryloxypropyl group was observed, which was a broad signal before recondensation and separated into a sharp signal. From this, it can be inferred that a compound having excellent objectivity (that is, a compound having a cage structure) was produced. In addition, no signal (3.58 ppm) derived from methoxy was observed. The integral ratio of -C=CH ₂ and -O-CH ₂ - was compared, and the result was 1.999:1.984. The GPC arrangement before and after the recondensation reaction is shown in Table 1.

Table 1

before recondensation After recondensation Mn (area%) peak (Mw/Mn) type   4291 (32.7%) 1 (1.07) random trapezoid   2018 (6.3%) 5 (1.00) random trapezoid Mn (area%) peak (Mw/Mn) type   2826 (19.6%) 2 (1.00) random trapezoid   1570(9%)6(1.00)(T12) cage Mn (area%) peak (Mw/Mn) type   2187 (23.1%) 3 (1.0) random trapezoid   1387(47.5%)7(1.00)(T10) cage Mn (area%) peak (Mw/Mn) type   1483 (24.6%) 4-cage (including incomplete)   1192 (37.2%) 8 (1.00) (T8) cage

It can be seen from Table 1 that before the recondensation reaction, the silsesquioxane structures of peak 1, peak 2 and peak 3 are random or ladder, and account for 75.4% of the total; in contrast, after the recondensation reaction, These peaks disappeared, and the silsesquioxane structure of peak 6, peak 7 and peak 8 was a clear cage type, and accounted for 93.7% of the total. In other words, it was shown that silsesquioxanes having a random, ladder-like structure were converted into a cage-like structure by performing a recondensation reaction.

Example 2

As in Example 1, the synthesis of the silsesquioxane composition was carried out with the following loadings. 40ml of IPA, 2.2g of 5% TMAH aqueous solution, and 8.46g of MTMS were added dropwise, stirred at room temperature (20 to 25°C, heat dissipation during hydrolysis reaction) for 2 hours, and then IPA was distilled off under reduced pressure. Dissolved with 30 ml of toluene. The recondensation reaction was carried out as in Example 1 to obtain 5.65 g of a silsesquioxane mixture with a yield of 92%. The GPC measurement results of this cage silsesquioxane mixture are shown in FIG. 5 . Table 2 shows the results of calculating the molecular weight Mn, molecular weight distribution Mw/Mn, type and amount of each peak from FIG. 5 . In Example 2, the water-washing step of the silsesquioxane composition was omitted. Even without the water-washing step, it was confirmed that the cage-type silsesquioxane mixture could be synthesized although the ratio of the cage-type structure decreased.

Example 3

Into a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 200 ml of IPA as a solvent and 15.6 g of a 5% TMAH aqueous solution of a basic catalyst were charged. Put 30ml of IPA and 60.38g of 3-glycidoxypropyltrimethoxysilane into the dropping funnel, and then dissolve the 3-glycidoxypropyltrimethoxysilane at room temperature while stirring the reaction vessel. The IPA solution of silane was added dropwise within 60 minutes. After completion of the dropwise addition, stirring was performed for 6 hours without heating. After stirring for 6 hours, the IPA was removed from the solvent under reduced pressure, and then dissolved with 200 ml of toluene.

The recondensation reaction was carried out as in Example 1 to obtain a silsesquioxane mixture. The GPC measurement result of this cage-type silsesquioxane mixture is shown in FIG. 6 , and the measurement result of LC-MS is shown in FIG. 7 . Table 2 shows the results of calculating the molecular weight Mn, molecular weight distribution Mw/Mn, type and amount of each peak from FIG. 6 and FIG. 7 . From the above results, peak 9 and peak 10 are random or ladder compounds with silsesquioxane structure, and it can be identified that peak 11 is T12, peak 12 is T10, and peak 13 is T8. In other words, it was confirmed in Example 3 that the synthesis of the cage silsesquioxane mixture having the functional group R being a glycidyl group was possible.

Example 4

Into a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 120 ml of IPA as a solvent and 4.0 g of a 5% TMAH aqueous solution of a basic catalyst were charged. 30 ml of IPA and 10.2 g of vinyltrimethoxysilane were placed in the dropping funnel, and the IPA solution of vinyltrimethoxysilane was dripped at 0° C. over 60 minutes while stirring the reaction vessel. After the dripping was finished, it was gradually returned to room temperature, and stirred for 6 hours without heating. After stirring for 6 hours, the IPA was removed from the solvent under reduced pressure, and then dissolved with 200 ml of toluene.

Next, a recondensation reaction was carried out as in Example 1 to obtain a silsesquioxane mixture. The GPC and LC-MS measurement results of the cage silsesquioxane mixture are shown in Figure 8 and Figure 9 . Table 2 shows the results of calculating the molecular weight Mn, molecular weight distribution Mw/Mn, type and amount of each peak from FIG. 8 and FIG. 9 . From the above results, the silsesquioxane structures of peaks 14, 15 and 16 are random or ladder compounds, and it can be identified that peak 17 is T14, peak 18 is T12, and peak 19 is T10. In other words, it was confirmed in Example 4 that the synthesis of the cage silsesquioxane mixture having the functional group R being a vinyl group was possible.

Comparative example 1

Into a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 160 ml of IPA as a solvent and 6.5 g of a 5% TMAH aqueous solution were charged. Put 18ml of IPA and 27.54g of MTMS into the dropping funnel, and then add the IPA solution of MTMS dropwise within 30 minutes at room temperature while stirring the reaction vessel. After the addition of MTMS was completed, it was stirred at room temperature for 2 hours. After stirring for 2 hours, it was heated to 95°C. Stir for an additional 4 hours under IPA reflux. The solvent was distilled off under reduced pressure, and then dissolved in 377 ml of toluene. The reaction solution dissolved in toluene was washed with saturated brine until it became neutral, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate is filtered, the concentrated reaction solution is washed in saturated brine until it becomes neutral, and then anhydrous magnesium sulfate is dehydrated. The filtered anhydrous magnesium sulfate was removed and concentrated to obtain 19.59 g of a hydrolyzate (silsesquioxane). The obtained silsesquioxane is a colorless viscous liquid soluble in various organic solvents.

The GPC measurement results of this silsesquioxane are shown in FIG. 10 . As can be seen from FIG. 10 , the same waveform as observed in Example 1 could not be obtained, and impurities other than the cage type were contained. In other words, Comparative Example 1 shows that the recondensation reaction does not proceed in the presence of a polar solvent such as IPA. In addition, the molecular weight distribution (Mw/Mn) of this silsesquioxane was 1.15.

Comparative example 2

Into a reaction container equipped with a stirrer, a dropping funnel, and a thermometer, 50 ml of toluene as a solvent and 3.0 g of a 5% TMAH aqueous solution were charged. A solution consisting of 10 ml of toluene and 12.64 g of MTMS was placed in the dropping funnel, and the toluene solution of MTMS was added dropwise at room temperature while stirring the reaction vessel within 10 minutes. After the dropwise addition was completed, it was stirred at room temperature for 2 hours. After stirring for 2 hours, it was heated to 135°C. At the temperature of toluene reflux (solution temperature 108° C.), stirring was continued for 4 hours. The reaction solution was washed with saturated brine until it became neutral, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate is filtered, the concentrated reaction solution is washed in saturated brine until it becomes neutral, and then anhydrous magnesium sulfate is dehydrated. The filtered anhydrous magnesium sulfate was removed and concentrated to obtain 10.78 g of a hydrolysis product. The GPC measurement results of the obtained silsesquioxane silicon composition are shown in FIG. 11 . From Figure 11 a sharp MTMS peak of the starting material was observed. In other words, Comparative Example 2 shows that the reaction system does not form a homogeneous state. If toluene, a non-polar organic solvent, is used for the hydrolysis reaction, the hydrolysis reaction cannot be sufficiently performed, and condensation is difficult to proceed.

Table 2 summarizes the GPC measurement results of Examples 1, 2, 3 and 4, and Comparative Examples 1 and 2. In Table 2, 3-MAP refers to 3-methacryloxypropyl, and 3-GOP refers to 3-epoxypropylpropyl. In addition, L refers to a ladder type, R refers to a random type, and C refers to an incomplete cage type. T8 to T14 refer to cage type.

Table 2

Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Functional group 3-MAP 3-MAP 3-GOP Vinyl 3-MAP 3-MAP Hydrolysis reaction solvent Recondensation reaction solvent IPA toluene IPA toluene IPA toluene IPA toluene IPAIPA Toluene Toluene Mn; Mn/Mw (area%) 2717; 1.01 (3.8%) L.R. 3216; 1.02 (9.4%) L.R. 3081; 1.04 (12.3%) L.R. 2873 (10.4%) L.R. 2399 (8.5%) Mn; Mn/Mw (area%) type 2018; 1.00 (6.3%) L.R. 1994; 1.00 (15%) L.R. 2370; 1.00 (18.2%) L.R. 2156; 1.00 (9.5%) L.R. 2086 (20.6%) L.R. Mn; Mn/Mw (area%) type 1558; 1.00 (18.1%) L.R. Mn; Mn/Mw (area%) type 1570; 1.00 (9%) T12 1538; 1.00 (9.5%) T12 1839; 1.00 (14.2%) T12 977; 1.00 (6.9%) T14 1568 (50.8%) Mn; Mn/Mw (area%) type 1387; 1.00 (47.5%) T10 1351; 1.00 (45.5%) T10 1633; 1.00 (38.2%) T10 795; 1.00 (31.5%) T12 1341 (69%) C Mn; Mn/Mw (area%) type 1192; 1.00 (37.2%) T8 1159; 1.00 (26.2%) T8 1396; 1.00 (20.0%)T8 637; 1.00 (21.7%) T10 Mn; Mn/Mw (area%) type 547 (40.7%) MTMS

Claims (7)

1. a manufacture method of cage type silsesquioxane resin, it is characterized in that following general formula (1) RSiX ₃ (1) The silicon compound shown, wherein R is an organic functional group having any one of (meth)acryloyl, glycidyl, or vinyl, and X is a hydrolyzable group. In the presence of the present invention, the hydrolysis reaction is carried out to produce partial condensation, and the obtained hydrolyzed product is then re-condensed in the presence of a non-polar solvent and a basic catalyst. 2. the manufacture method of cage type silsesquioxane resin according to claim 1, wherein said cage type silsesquioxane resin is represented by following general formula (2) [RSiO _3/2 ] _n (2) Wherein, R is an organic functional group having any one of (meth)acryloyl, glycidyl, or vinyl, and n is 8, 10, 12 or 14. 3. the manufacture method of cage type silsesquioxane resin according to claim 1 or 2, wherein in general formula (1), R is shown in following general formula (3), (4), (5) organic functional group 【Chemical 1】

_CH2 =CH- (5) Wherein, m is an integer from 1 to 3, and R ₁ is a hydrogen atom or a methyl group. 4. a manufacture method of cage type silsesquioxane resin, it is characterized in that following general formula (1) RSiX ₃ (1) The silicon compound shown, wherein R is an organic functional group having any one of (meth)acryloyl, glycidyl, or vinyl, X is a hydrolyzable group, and the compound is in the presence of an organic polar solvent and a basic catalyst , carry out a hydrolysis reaction to generate partial condensation, and obtain a hydrolyzate with a number average molecular weight of 500 to 7000, and then re-condense the obtained hydrolyzate in the presence of a non-polar solvent and a basic catalyst. 5. The manufacture method of the cage-type silsesquioxane resin according to claim 4, wherein the hydrolyzate is a mixture of cage-type, ladder-type and random-type silsesquioxanes, which is obtained through recondensation Obtain cage type silsesquioxane resin, it is represented by following general formula (2) [RSiO _3/2 ] _n (2) Wherein R is an organic functional group having any one of (meth)acryloyl, glycidyl, or vinyl, n is 8, 10, 12 or 14, and 3 is selected from n being 8, 10, 12 and 14 More than one cage silsesquioxane resin mixture, and the total amount of cage silsesquioxanes where n is 8, 10, 12 and 14 accounts for more than 50wt% of the total silsesquioxanes. 6. A cage-type silsesquioxane resin with functional groups manufactured by the method of any one of claims 1 to 5, which has a cage-type silsesquioxane resin with functional groups, and in the mixture, The proportion of the cage silsesquioxane resin represented by the following general formula (2) is more than 50 wt%, [RSiO _3/2 ] _n (2) Wherein, R is an organic functional group having any one of a (meth)acryloyl group, a glycidyl group, or a vinyl group, and n is 8, 10, 12 or 14. 7. The cage silsesquioxane resin having functional groups according to claim 6, wherein the cage silsesquioxane resin has an average molecular weight distribution (Mw/Mn) in the range of 1.03 to 1.10.

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