KR101736086B1 - Bisphenol-based epoxy compound having alkoxysilyl group and method for preparing the same, and composite of organic-inorganic materials comprising a cured product thereof and method for preparing the composite - Google Patents

Abstract

The present invention relates to a bisphenol-based epoxy compound having an alkoxysilyl group, a process for producing the same, and an organic-inorganic composite including the cured product and a process for producing the complex. More particularly, And a novel bisphenol-based epoxy compound which exhibits improved heat resistance and thermal expansion characteristics when used for the production of high-performance electronic parts and also has excellent curing property, a process for producing the same, and an organic- Lt; / RTI >

Description

TECHNICAL FIELD The present invention relates to a bisphenol-based epoxy compound having an alkoxysilyl group, a process for producing the bisphenol-based epoxy compound, an organic-inorganic material composite including the cured product and a method for preparing the same -organic materials comprising a cured product and a method for preparing the composite,

The present invention relates to a bisphenol-based epoxy compound having an alkoxysilyl group, a process for producing the same, and an organic-inorganic composite including the cured product and a process for producing the complex. More particularly, And a novel bisphenol-based epoxy compound which exhibits improved heat resistance and thermal expansion characteristics when used for the production of high-performance electronic parts and also has excellent curing property, a process for producing the same, and an organic- Lt; / RTI >

(CTE) control technology is very important in all fields where materials with different thermal expansion characteristics such as polymer / ceramic, polymer / metal, polymer / polymer, etc. are used as constituent materials of the same parts. A printed circuit board, a packaging, an organic thin film transistor, a flexible display, and the like which require high integration, high miniaturization, flexibility, and high performance. In order to secure the design, processability and reliability of components in the manufacturing industry such as flexible display substrates, CTE control technology of polymer materials has been actively studied. This is because the high thermal expansion characteristics of the polymer material at the component process temperature not only cause defects in the manufacture of the parts but also limit the process and difficulty in securing the design, processability and reliability of parts.

For example, epoxy resin, one of the polymer materials, has a thermal expansion coefficient of about 50 to 80 ppm / ° C and a ceramic material (thermal expansion coefficient of silicon: 3 to 5 ppm / ° C) of inorganic particles and a metallic material (thermal expansion coefficient of copper: 17 ppm / ° C). In this case, when there is a change in the temperature in the process, cracking of the inorganic layer, occurrence of warpage of the substrate, peeling-off of the coating layer and breakage of the substrate due to the difference in the coefficient of thermal expansion (CTE-mismatch) Lt; / RTI >

Korean Patent Laid-Open No. 1998-0030543 discloses a technique for epoxy resin composition for encapsulating semiconductor devices. However, this technique has a problem that CTE (coefficient of thermal expansion) is high even when an inorganic filler is used.

Disclosure of the Invention The present invention has been made to solve the above problems of the prior arts, and it is an object of the present invention to provide a semiconductor device having improved heat resistance and thermal expansion characteristics (i.e., low thermal expansion coefficient (Low CTE) and high glass transition temperature (Tg-less) or a high glass transition temperature (Tg) characteristic) and exhibits excellent curing, and a novel bisphenol-based epoxy compound capable of producing such a composite. .

In order to solve the above technical problems, the present invention provides an epoxy compound having an alkoxysilyl group selected from the group consisting of the following chemical formulas (A) to (F) and polymerization products thereof:

In each of the above Formulas A to F,

The substituent Q is independently selected from the group consisting of an alkoxysilyl-alkylene group, hydrogen, and an alkylene group having a terminal unsaturated carbon-carbon double bond,

With the proviso that at least one of the substituents Q is an alkoxysilyl-alkylene group.

According to another aspect of the present invention, there is provided a process for preparing a compound of formula (I), comprising the steps of: (1) reacting a compound of any one of the following formulas 1 to 6 with an alkyl halide having a terminal unsaturated carbon- (2) rearranging the alkyl group having an unsaturated carbon-carbon double bond in the reaction product of the step (1) in the molecule; (3) reacting the reaction product of step (2) with an alkyl halide having an epoxy group; And (4) reacting the reaction product of step (3) with a silane having hydrogen and an alkoxy group.

According to another aspect of the present invention, there is provided an organic-inorganic composite material comprising a cured product of a mixture comprising an epoxy compound having an alkoxysilyl group of the present invention and silica.

According to still another aspect of the present invention, there is provided a method for producing an organic-inorganic composite material characterized in that an epoxy compound having an alkoxysilyl group of the present invention is mixed with silica to condense and cure the epoxy compound.

The organic-inorganic composite material produced by using the epoxy compound of the novel structure according to the present invention is a composite material in which an alkoxysilyl group in an epoxy compound forms an effective intermolecular bond with an inorganic material such as silica and glass fiber, (I.e., a low CTE and a glass transition temperature do not appear (Tg-less) and a high glass transition temperature (High Tg) characteristic) due to the bonding and bonding between the alkoxysilyl group and the curing agent And is excellent in the degree of curing and can be suitably used for high integration of next generation semiconductor substrates, PCBs, and the like and for manufacturing high-performance electronic parts. In addition, when the epoxy compound having a novel structure according to the present invention is applied to a metal film, excellent adhesion to the metal film can be exhibited by chemical bonding between the surface of the metal film and the alkoxysilyl group, can do.

FIG. 1 is a graph showing the dimensional change of the organic-inorganic composite prepared in Example 2 according to the temperature change. FIG.
FIG. 2 is a graph showing the dimensional change of the organic-inorganic composite prepared in Comparative Example 1 according to the temperature change. FIG.
FIG. 3 is a graph illustrating the dimensional change of the organic-inorganic composite material produced in Example 9 according to the temperature change. FIG.
FIG. 4 is a graph showing the dimensional change of the organic-inorganic composite prepared in Comparative Example 2 according to the temperature change. FIG.
5 is a graph showing the dimensional change of the organic-inorganic composite prepared in Example 22 according to the temperature change.
FIG. 6 is a graph showing the dimensional change of the organic-inorganic composite prepared in Example 23 according to the temperature change. FIG.
FIG. 7 is a graph illustrating the dimensional change of the organic-inorganic composite material produced in Comparative Example 3 according to the temperature change. FIG.

Hereinafter, the present invention will be described in detail.

The epoxy compound having an alkoxysilyl group of the present invention is selected from the group consisting of the following structural formulas A to F and polymerization products thereof:

In each of the above Formulas A to F,

The substituent Q is independently selected from the group consisting of an alkoxysilyl-alkylene group, hydrogen, and an alkylene group having a terminal unsaturated carbon-carbon double bond,

With the proviso that at least one of the substituents Q is an alkoxysilyl-alkylene group.

The alkoxysilyl-alkylene group may have 1 to 3 (mono-, di- or trialkoxy) alkoxyl groups bonded to the silane atom, preferably 2 to 3 (di- or trialkoxy), and most preferably 3 Trialkoxy), wherein the alkoxy group is preferably a (C ₁ -C ₁₀ ) alkoxy group, more preferably a (C ₁ -C ₆ ) alkoxy group, even more preferably a (C ₁ -C ₃ ) Preferably an ethoxy group. The alkoxysilyl-alkylene group may further have an alkyl group such as a (C ₁ -C ₁₀ ) alkyl group as a substituent bonded to a silane atom in addition to the alkoxy group. The alkoxysilyl-alkylene group is preferably an alkoxysilyl- (C ₁ -C ₁₀ ) alkylene group, more preferably an alkoxysilyl- (C ₃ -C ₁₀ ) alkylene group, still more preferably an alkoxysilyl- (C _3- C ₆ ) alkylene group, and most preferably an alkoxysilyl-propylene group (i.e., alkoxysilyl- (CH ₂ ) ₃ -).

The alkylene group having a terminal unsaturated carbon-carbon double bond is preferably a CH ₂ ═CH- (C ₁ -C ₁₀ ) alkylene group, more preferably a CH ₂ ═CH- (C ₁ -C ₆ ) alkylene group, More preferably a CH ₂ ═CH- (C ₁ -C ₃ ) alkylene group, and most preferably an allyl group (ie, CH ₂ ═CH-CH ₂ -).

In the above, each of the alkylene group, alkoxy group and alkyl group may be independently linear or branched, and may be substituted or unsubstituted. When the alkylene group, the alkoxy group or the alkyl group is a substituted form, the substituent is, for example, one selected from a (C ₁ -C ₁₀ ) alkyl group, a (C ₁ -C ₁₀ ) alkoxy group and a (C ₆ -C ₁₂ ) Or more.

In each of Formulas A to F, at least one (e.g., 1 to 3) of substituents Q is an alkoxysilyl-alkylene group, and more preferably two of substituents Q are alkoxysilyl-alkylene groups. The remaining Q, which is not an alkoxysilyl-alkylene group, is hydrogen or an alkylene group having a terminal unsaturated carbon-carbon double bond. According to one preferred embodiment of the present invention, two of the substituents Q in the above formulas (A) to (F) are alkoxysilyl-alkylene groups and the remaining two are hydrogen. When two of the substituents Q in the formulas (A) to (F) are alkoxysilyl-alkylene groups, it is preferable that these two alkoxysilyl-alkylene groups are each bonded to two phenyl groups one by one.

Specific examples of the compounds corresponding to the above formulas (A) to (F) include, but are not limited to, the following compounds.

Exemplary specific compounds of each of the above Formulas A to F may be prepared by repeating the specific step (s), for example, according to the method described in the examples of this specification.

Further, the epoxy compound having an alkoxysilyl group of the present invention may be selected from the group consisting of the following formulas AA to FF:

In each of the above formulas AA to FF,

Substituent Q is as defined in formulas A to F above,

n is an integer of 2 to 10;

(1) reacting a compound of any one of the following formulas (1) to (6) with an alkyl halide having a terminal unsaturated carbon-carbon double bond; (2) rearranging the alkyl group having an unsaturated carbon-carbon double bond in the reaction product of the step (1) in the molecule; (3) reacting the reaction product of step (2) with an alkyl halide having an epoxy group; And (4) reacting the reaction product of step (3) with a silane having hydrogen and an alkoxy group.

The alkyl halide having a terminal unsaturated carbon-carbon double bond used in the step (1) is preferably a CH ₂ CH- (C ₁ -C ₁₀ ) alkyl halide (for example, chloride, bromide or iodide) Is more preferably CH ₂ ═CH- (C ₁ -C ₆ ) alkyl halide, even more preferably CH ₂ ═CH- (C ₁ -C ₃ ) alkyl halide, most preferably allyl halide such as allyl bromide.

An alkyl halide having an epoxy group used in the above (3) is preferably an epoxy - (C ₁ -C ₁₀₎ alkyl halide (e.g., chloride, bromide or iodide), more preferably an epoxy - (C ₁ -C ₆ ) alkyl halide, even more preferably an epoxy- (C ₁ -C ₃ ) alkyl halide, most preferably an epoxy-methyl halide, such as epichlorohydrin.

The (4) a silane having a hydrogen and alkoxy used in the step is preferably (C ₁ -C ₁₀₎ alkoxy group, more preferably a (C ₁ -C ₆₎ alkoxy group, even more preferably (C ₁ - C ₃ ) alkoxy group, most preferably ethoxy group having 1 to 3, preferably 2 to 3, most preferably 3, and further preferably 1 to 3, preferably 1 to 2, And most preferably one silane compound is, for example, triethoxysilane (HSi (OEt) ₃ ).

In the above step (1), the molar ratio of the compound of any one of formulas (1) to (6): alkyl halide having a terminal unsaturated carbon-carbon double bond is preferably 1: 2 to 1: 6, more preferably 1: To 1: 3. If the amount of the alkyl halide having a terminal unsaturated carbon-carbon double bond is too small relative to one of the compounds of the formulas (1) to (6), there may be a problem that the conversion rate is lowered. On the contrary, if the amount is too large, Can be.

In step (3), the reaction product of step (2): the molar ratio of the alkyl halide having an epoxy group is preferably from 1: 2 to 1:15, more preferably from 1: 5 to 1:12. If the amount of the alkyl halide having an epoxy group is too small as compared with the reaction product of the step (2), the molecular weight may be increased. On the other hand, if the amount is too large, there may be a problem of generation of impurities due to side reactions.

In step (4), the reaction product of step (3): the molar ratio of the hydrogen and the silane having an alkoxy group is preferably 1: 1 to 1: 4, more preferably 1: 1 to 1: 3. If the amount of the hydrogen and alkoxy group-containing silane to be used is too small as compared with the reaction product of the step (3), there may be a problem that the conversion is lowered, and if too large, the removal of the unreacted materials may become difficult.

The reaction of step (1) may be carried out in the presence of a base (for example, but not limited to) in an organic solvent (e.g. acetone, tetrahydrofuran, acetonitrile, methyl ethyl ketone, DMF, DMSO, (E.g., potassium carbonate) at room temperature to 150 캜 (e.g., 80 캜) under reflux.

The intramolecular rearrangement reaction of the terminal -unsaturated alkyl substituent in the step (2) may be carried out in an organic solvent (for example, 1,2-dichlorobenzene, acetone, tetrahydrofuran, acetonitrile, methyl ethyl ketone, DMF, DMSO, etc.) at 100-250 占 폚 (e.g., 190 占 폚) under reflux.

The reaction of step (3) may be carried out in the presence of a base (for example, sodium hydroxide) in a hydrophilic solvent (e.g., isopropyl alcohol, water, N-methylpyrrolidone, At room temperature to 80 캜 (e.g., 60 캜) under reflux.

The reaction of step (4) may be carried out in the presence of a catalyst (for example, platinum (Pt), triethylamine (For example, 80 占 폚) in the presence of an acid catalyst, nickel (Ni), cobalt (Co), palladium (Pd), iridium (Ir), ruthenium (Ru), rhodium ≪ / RTI >

Another aspect of the present invention provides an organic-inorganic composite material comprising a cured product of a mixture comprising an epoxy compound having an alkoxysilyl group of the present invention and silica.

As the silica, there can be used silica which is usually used in the production of the organic-inorganic material composite without limitation, but its average particle size may be in the range of 10 nm to 10 μm. The silica content in the composite may be, for example, 2 to 20 parts by weight, more specifically 3 to 15 parts by weight, and more specifically 5 to 10 parts by weight, based on 1 part by weight of the epoxy compound, but is not limited thereto .

The mixture containing the alkoxysilyl group-containing epoxy compound and silica may be mixed with a curing agent such as an aminotriazine type novolak curing agent, an amine curing agent, a phenol curing agent, a non-hydroxide curing agent, A tertiary amine type, a quaternary ammonium type, an organic acid salt type, a phosphorus type, etc.), or a combination thereof. If necessary, it acts as a toughness to complement the brittle characteristic after curing, Polyvinyl butyral, which serves to give a uniform surface, and additives for surface improvement used to make a uniform surface in film production.

The curing of the mixture comprising the alkoxysilyl group-containing epoxy compound and silica can be carried out, for example, at room temperature to 250 ° C, but is not limited thereto.

The organic-inorganic composite material of the present invention may further contain inorganic materials such as glass fiber, zirconia, titania, alumina, T-10 type silsesquioxane, ladder type silsesquioxane, And the like. The amount of additional inorganic material (e.g., glass fiber) in the composite is, for example, 20 to 80 wt%, more specifically 30 to 70 wt%, and even more specifically 40 to 60 wt%, based on 100 wt% But is not limited thereto.

Another aspect of the present invention provides a method for producing an organic-inorganic composite material, which comprises mixing and curing the epoxy compound having an alkoxysilyl group of the present invention with silica.

In the method for producing an organic-inorganic composite, if necessary, one or more of the above-mentioned curing agent, curing catalyst, polyvinyl butyral, surface improving additive and the like may be mixed together with the epoxy compound and silica.

According to one embodiment of the present invention, in the production of the organic-inorganic composite material, a combination of (a) an epoxy group and a curing agent, (b) a combination of an alkoxysilyl group and silica and glass fiber, (c) And (d) the bonding between the alkoxysilyl group and the curing agent occurs at the same time.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention, but the present invention is not limited thereto.

[ Example ]

Synthetic example  A: Di-tert- Alkoxysilylated  Synthesis of epoxy compounds

(1) Step 1: Aleration

30.00 g of bisphenol B (Sigma Aldrich), 26.79 ml of allyl bromide (Sigma Aldrich), 102.67 g of K ₂ CO ₃ and 500 ml of acetone were added to a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector. Respectively. The homogeneously mixed solution was reacted at a set temperature of 80 ° C overnight (reflux). After the reaction, the reaction mixture cooled to room temperature was filtered through celite and evaporated to obtain a reaction mixture. The resultant mixture was extracted with ethyl acetate and washed three times with water. After washing, drying was performed using MgSO ₄ , and then MgSO ₄ was removed using a paper filter. The solvent was removed using a rotary evaporator to obtain an allylated intermediate product (A-1). ^{Using 1} H NMR, the intermediate product (A-1) was identified by the peak of the allyl group adjacent to the oxygen of the allyloxybenzene observed at 4.61 ppm.

(2) Step 2: Aryl rearrangement

30.00 g of the intermediate product (A-1) obtained in the above Step 1 and 300 ml of 1,2-dichlorobenzene (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen injector. The well mixed solution was reacted for 8 hours while refluxing at a set temperature of 190 ° C. After the reaction, the reaction mixture was cooled to room temperature, and the solvent was removed using a vacuum oven to obtain an intermediate product (A-2) having allyl rearranged. ^{Using the 1} H NMR, the intermediate (A-2) was identified with a peak of the allyl group attached to the phenol group observed at 3.2 ppm, 4.93 to 4.96 ppm, and 6.30 ppm.

(3) Step 3: Epoxidation

30 g of the intermediate product (A-2) obtained in the above Step 2, 86.12 g of epichlorohydrin (Sigma Aldrich), 43.06 g of isopropyl alcohol (Sigma Aldrich) and 50 g of distilled water were added to a 1000 ml three- 14.35 g of distilled water was added and mixed at room temperature under a nitrogen stream. The well mixed solution was reacted with 50% sodium hydroxide solution for 3 hours while refluxing to a set temperature of 60 ° C. After the reaction, the layer separation was carried out to remove the lower brine and the upper portion of the solvent was removed by vacuum distillation. The solvent-removed product was washed three times with water and toluene, and neutralized once with phosphoric acid. The water was removed through layer separation, and the remaining toluene solution was filtered through celite, followed by vacuum distillation to obtain an intermediate product (A-3) which was subjected to epoxidation. ^{Using 1} H NMR, the intermediate product (A-3) was identified with a peak of the epoxy group observed at 2.92 and 4.74 ppm.

(4) Step 4: Hydroxylation

30 g of the intermediate product (A-3) obtained in the above Step 3, 22.70 g of triethoxysilane (Sigma Aldrich) and 0.81 g of a chloroplatinic acid (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, g and 200 ml of toluene, and the mixture was stirred at room temperature under a nitrogen stream. The well mixed solution was reacted for 8 hours while refluxing to a set temperature of 80 ° C. After the reaction, the obtained product was filtered with celite and activated carbon, and the solvent was removed by using a rotary evaporator to obtain a bisphenol-B epoxy compound having an alkoxysilyl group as the final object (A). ^{Using 1} H NMR, the final object (A) was identified with triethoxysilane groups observed at 0.91, 1.22, and 3.83 ppm and peaks of epoxy groups observed at 2.50, 3.04, and 4.07 ppm.

Synthetic example  B: Di-tert- Alkoxysilylated  Synthesis of epoxy compounds

(1) Step 1: Aleration

30.00 g of bisphenol E (Fluka), 30.29 ml of allyl bromide (Sigma Aldrich), 116.11 g of K ₂ CO ₃ and 500 ml of acetone were added to a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector. Respectively. The homogeneously mixed solution was reacted at a set temperature of 80 ° C overnight (reflux). After the reaction, the reaction mixture cooled to room temperature was filtered through celite and evaporated to obtain a reaction mixture. The resultant mixture was extracted with ethyl acetate and washed three times with water. After washing, drying was performed using MgSO ₄ , and then MgSO ₄ was removed using a paper filter. The solvent was removed using a rotary evaporator to obtain an allylated intermediate product (B-1). ^{Using 1} H NMR, the intermediate (B-1) was identified with a peak of the allyl group adjacent to the oxygen of the allyloxybenzene observed at 4.61 ppm.

(2) Step 2: Aryl rearrangement

30.00 g of the intermediate product (B-1) obtained in the above Step 1 and 300 ml of 1,2-dichlorobenzene (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector. The well mixed solution was reacted for 8 hours while refluxing at a set temperature of 190 ° C. After the reaction, the reaction mixture was cooled to room temperature, and the solvent was removed using a vacuum oven to obtain an intermediate product (B-2) in which the allyl rearrangement was carried out. ¹ > H NMR was used to identify the intermediate (B-2) with a peak of the allyl group attached to the phenol group observed at 3.22 ppm, 4.93-4.96 ppm, 6.30 ppm.

(3) Step 3: Epoxidation

30 g of the intermediate product (B-2) obtained in the above Step 2, 94.31 g of epichlorohydrin (Sigma Aldrich), 47.15 g of isopropyl alcohol (Sigma Aldrich) and 50 ml of distilled water were added to a 1000 ml three-necked flask equipped with a reflux condenser, 15.72 g of distilled water was added and mixed at room temperature under a nitrogen stream. The well mixed solution was reacted with 50% sodium hydroxide solution for 3 hours while refluxing to a set temperature of 60 ° C. After the reaction, the layer separation was carried out to remove the lower brine and the upper portion of the solvent was removed by vacuum distillation. The solvent-removed product was washed three times with water and toluene, and neutralized once with phosphoric acid. The water was removed through layer separation, and the remaining toluene solution was filtered through celite and vacuum distillation to obtain an intermediate product (B-3) which was subjected to epoxidation. ¹ > H NMR was used to identify the intermediate product (B-3) with a peak of the epoxy group observed at 2.50, 3.04 and 4.07 ppm.

(4) Step 4: Hydroxylation

30 g of the intermediate product (B-3) obtained in the above Step 3, 24.24 g of triethoxysilane (Sigma Aldrich) and 0.817 g of a chloroplatinic acid (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, g and 200 ml of toluene, and the mixture was stirred at room temperature under a nitrogen stream. The well mixed solution was reacted for 8 hours while refluxing to a set temperature of 80 ° C. After the reaction, the obtained product was filtered through celite and activated carbon, and the solvent was removed using a rotary evaporator to obtain a bisphenol E epoxy compound having an alkoxysilyl group as the final object (B). ^{Using 1} H NMR, the final object (B) was identified with triethoxysilane groups observed at 0.91, 1.22, and 3.83 ppm and peaks of epoxy groups observed at 2.50, 3.04, and 4.07 ppm.

Synthetic example  C: Di-tert- Alkoxysilylated  Synthesis of epoxy compounds

(1) Step 1: Aleration

30.00 g of bisphenol Z (Fluka), 24.19 of allyl bromide (Sigma Aldrich), 138.21 g of K ₂ CO ₃ and 500 ml of acetone were added to a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector and mixed at room temperature under a nitrogen stream . The homogeneously mixed solution was reacted at a set temperature of 80 ° C overnight (reflux). After the reaction, the reaction mixture cooled to room temperature was filtered through celite and evaporated to obtain a reaction mixture. The resultant mixture was extracted with ethyl acetate and washed three times with water. After washing, drying was performed using MgSO ₄ , and then MgSO ₄ was removed using a paper filter. The solvent was removed using a rotary evaporator to obtain an allylated intermediate (C-1). ^{Using 1} H NMR, the intermediate (C-1) was identified with a peak of the allyl group adjacent to the oxygen of the allyloxybenzene observed at 4.61, 5.23 to 5.24, and 5.89 ppm.

(2) Step 2: Aryl rearrangement

30.00 g of the intermediate product (C-1) obtained in the above Step 1 and 300 ml of 1,2-dichlorobenzene (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen injector. The well mixed solution was reacted for 8 hours while refluxing at a set temperature of 190 ° C. After the reaction, the reaction mixture was cooled to room temperature, and the solvent was removed using a vacuum oven to obtain an intermediate product (C-2) in which the allyl rearrangement was carried out. ^{Using 1} H NMR, the intermediate (C-2) was identified with a peak of the allyl group attached to the phenol group observed at 3.22 ppm, 4.93 to 4.96 ppm, and 6.30 ppm.

(3) Step 3: Epoxidation

30 g of the intermediate product (C-2) obtained in the above Step 2, 79.691 g of epichlorohydrin (Sigma Aldrich), 39.84 g of isopropyl alcohol (Sigma Aldrich) 13.28 g of distilled water was added and mixed at room temperature under a nitrogen stream. The well mixed solution was reacted with 50% sodium hydroxide solution for 3 hours while refluxing to a set temperature of 60 ° C. After the reaction, the layer separation was carried out to remove the lower brine and the upper portion of the solvent was removed by vacuum distillation. The solvent-removed product was washed three times with water and toluene, and neutralized once with phosphoric acid. The water was removed through layer separation, and the remaining toluene solution was filtered through celite and vacuum distillation to obtain an intermediate product (C-3) which was subjected to epoxidation. ^{Using 1} H NMR, the intermediate product (C-3) was identified with a peak of the epoxy group observed at 2.50, 3.04, and 6.30 ppm.

(4) Step 4: Hydroxylation

30 g of the intermediate product (C-3) obtained in the above Step 3, 21.40 g of triethoxysilane (Sigma Aldrich) and 0.8175 g of a spiro catalyst (Chloroplatinic acid, Sigma Aldrich) were placed in a 1000 ml three- g and 200 ml of toluene, and the mixture was stirred at room temperature under a nitrogen stream. The well mixed solution was reacted for 8 hours while refluxing to a set temperature of 80 ° C. After the reaction, the obtained product was filtered with celite and activated carbon, and the solvent was removed using a rotary evaporator to obtain a bisphenol Z epoxy compound having an alkoxysilyl group as the final object (C). ^{Using the 1} H NMR, the final target (C) was identified as the triethoxysilane group observed at 0.91, 1.22, and 3.83 ppm and the peak of the epoxy group observed at 2.50, 3.04, and 4.07 ppm.

Synthetic example  D: Di-tert- Alkoxysilylated  Synthesis of epoxy compounds

(1) Step 1: Aleration

30.00 g of bisphenol AP (AccuStandard), 22.35 g of allyl bromide (Sigma Aldrich), 85.68 g of K ₂ CO ₃ and 500 ml of acetone were added to a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector and mixed at room temperature under a nitrogen stream . The homogeneously mixed solution was reacted at a set temperature of 80 ° C overnight (reflux). After the reaction, the reaction mixture cooled to room temperature was filtered through celite and evaporated to obtain a reaction mixture. The resultant mixture was extracted with ethyl acetate and washed three times with water. After washing, drying was performed using MgSO ₄ , and then MgSO ₄ was removed using a paper filter. The solvent was removed using a rotary evaporator to obtain the allylated intermediate product (D-1). ^{Using 1} H NMR, the intermediate (D-1) was identified with a peak of the allyl group adjacent to the oxygen of the allyloxybenzene observed at 4.61, 5.23 to 5.24 and 5.89 ppm.

(2) Step 2: Aryl rearrangement

30.00 g of the intermediate product (D-1) obtained in the above Step 1 and 300 ml of 1,2-dichlorobenzene (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector. The well mixed solution was reacted for 8 hours while refluxing at a set temperature of 190 ° C. After the reaction, the reaction mixture was cooled to room temperature, and the solvent was removed using a vacuum oven to obtain an intermediate product (D-2) in which the allyl rearrangement was carried out. ¹ H NMR was used to identify the intermediate (D-2) with a peak of the allyl group attached to the phenol group observed at 3.22 ppm, 4.93-4.96 ppm, 6.30 ppm.

(3) Step 3: Epoxidation

30 g of the intermediate product (D-2) obtained in the above Step 2, 75.01 g of epichlorohydrin (Sigma Aldrich), 37.51 g of isopropyl alcohol (Sigma Aldrich) and 10.0 g of distilled water were placed in a 1000 ml three- 12.50 g of distilled water was added and mixed at room temperature under a nitrogen stream. The well mixed solution was reacted with 50% sodium hydroxide solution for 3 hours while refluxing to a set temperature of 60 ° C. After the reaction, the layer separation was carried out to remove the lower brine and the upper portion of the solvent was removed by vacuum distillation. The solvent-removed product was washed three times with water and toluene, and neutralized once with phosphoric acid. Water was removed through layer separation, and the remaining toluene solution was filtered through celite and vacuum distillation to obtain an intermediate product (D-3) which was subjected to epoxidation. ^{Using 1} H NMR, the intermediate product (D-3) was identified with a peak of the epoxy group observed at 2.50, 3.04 and 4.07 ppm.

(4) Step 4: Hydroxylation

30 g of the intermediate product (D-3) obtained in the above step 3, 20.43 g of triethoxysilane (Sigma Aldrich), 0.817 g of a chloroplatinic acid (Sigma Aldrich) g and 200 ml of toluene, and the mixture was stirred at room temperature under a nitrogen stream. The well mixed solution was reacted for 8 hours while refluxing to a set temperature of 80 ° C. After the reaction, the obtained product was filtered with celite and activated carbon, and the solvent was removed using a rotary evaporator to obtain a bisphenol AP epoxy compound having an alkoxysilyl group as a final object (D). ^{Using the 1} H NMR, the final object (D) was identified with triethoxysilane groups observed at 0.91, 1.22, and 3.83 ppm and peaks of epoxy groups observed at 2.50, 3.04, and 4.07 ppm.

Synthetic example  E: Bisphenol TMC And < RTI ID = Alkoxysilylated  Synthesis of epoxy compounds

(1) Step 1: Aleration

30.00 g of bisphenol TMC (Fluka), 20.91 g of allyl bromide (Sigma Aldrich), 80.14 g of K ₂ CO ₃ and 500 ml of acetone were added to a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector. Respectively. The homogeneously mixed solution was reacted at a set temperature of 80 ° C overnight (reflux). After the reaction, the reaction mixture cooled to room temperature was filtered through celite and evaporated to obtain a reaction mixture. The resultant mixture was extracted with ethyl acetate and washed three times with water. After washing, drying was performed using MgSO ₄ , and then MgSO ₄ was removed using a paper filter. The solvent was removed using a rotary evaporator to obtain an allylated intermediate product (E-1). ¹ H NMR was used to identify the intermediate (E-1) with a peak of the allyl group adjacent to the oxygen of the allyloxybenzene observed at 4.61, 5.23 to 5.24 and 5.89 ppm.

(2) Step 2: Aryl rearrangement

30.00 g of the intermediate product (E-1) obtained in the above Step 1 and 300 ml of 1,2-dichlorobenzene (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector. The well mixed solution was reacted for 8 hours while refluxing at a set temperature of 190 ° C. After the reaction, the reaction mixture was cooled to room temperature, and the solvent was removed using a vacuum oven to obtain an intermediate product (E-2) in which the allyl rearranged product was obtained. ¹ > H NMR was used to identify the intermediate (E-2) with a peak of the allyl group attached to the phenol group observed at 3.22 ppm, 4.93-4.96 ppm, 6.30 ppm.

(3) Step 3: Epoxidation

(E-2) obtained in the above Step 2, 71.08 g of epichlorohydrin (Sigma Aldrich), 35.54 g of isopropyl alcohol (Sigma Aldrich), and 10.0 g of isopropyl alcohol (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, 11.85 g of distilled water was added and mixed at room temperature under a nitrogen stream. The well mixed solution was reacted with 50% sodium hydroxide solution for 3 hours while refluxing to a set temperature of 60 ° C. After the reaction, the layer separation was carried out to remove the lower brine and the upper portion of the solvent was removed by vacuum distillation. The solvent-removed product was washed three times with water and toluene, and neutralized once with phosphoric acid. The water was removed by layer separation, and the remaining toluene solution was filtered through celite and vacuum distillation to obtain an intermediate product (E-3) which was subjected to epoxidation. ¹ > H NMR was used to identify the intermediate product (E-3) with a peak of the epoxy group observed at 2.50, 3.04 and 4.07 ppm.

(4) Step 4: Hydroxylation

30 g of the intermediate product (E-3) obtained in the above Step 3, 19.60 g of triethoxysilane (Sigma Aldrich), 0.817 g of a chloroplatinic acid (Sigma Aldrich) g and 200 ml of toluene, and the mixture was stirred at room temperature under a nitrogen stream. The well mixed solution was reacted for 8 hours while refluxing to a set temperature of 80 ° C. After the reaction, the obtained product was filtered through celite and activated carbon, and the solvent was removed by using a rotary evaporator to obtain a bisphenol TMC epoxy compound having an alkoxysilyl group as the final target (E). ^{Using 1} H NMR, the final target (E) was identified with triethoxysilane groups observed at 0.91, 1.22, and 3.83 ppm and peaks of epoxy groups observed at 2.50, 3.04, and 4.07 ppm.

Synthetic example  F: Di-ethyl stearate with diethylstilbestrol (DES) Alkoxysilylated  Synthesis of epoxy compounds

(1) Step 1: Aleration

30.00 g of diethylstilbestrol (DES) (Sigma Aldrich), 24.19 g of allyl bromide (Sigma Aldrich), 92.71 g of K ₂ CO ₃ and 500 ml of acetone were added to a 1000 ml three-necked flask equipped with a reflux condenser, And mixed at room temperature in a nitrogen stream. The homogeneously mixed solution was reacted at a set temperature of 80 ° C overnight (reflux). After the reaction, the reaction mixture cooled to room temperature was filtered through celite and evaporated to obtain a reaction mixture. The resultant mixture was extracted with ethyl acetate and washed three times with water. After washing, drying was performed using MgSO ₄ , and then MgSO ₄ was removed using a paper filter. The solvent was removed using a rotary evaporator to obtain an allylated intermediate product (F-1). ¹ H NMR was used to identify the intermediate (F-1) with a peak of the allyl group adjacent to the oxygen of the allyloxybenzene observed at 4.61, 5.23 to 5.24 and 5.89 ppm.

(2) Step 2: Aryl rearrangement

30.00 g of the intermediate product (F-1) obtained in the above step 1 and 300 ml of 1,2-dichlorobenzene (Sigma Aldrich) were placed in a 1000 ml three-necked flask equipped with a reflux condenser, a temperature sensor and a nitrogen gas injector. The well mixed solution was reacted for 8 hours while refluxing at a set temperature of 190 ° C. After the reaction, the reaction mixture was cooled to room temperature, and the solvent was removed using a vacuum oven to obtain an intermediate product (F-2) having allyl rearranged. ¹ > H NMR was used to identify the intermediate (F-2) with a peak of the allyl group attached to the phenol group observed at 3.22 ppm, 4.93-4.96 ppm, 6.30 ppm.

(3) Step 3: Epoxidation

30 g of the intermediate product (F-2) obtained in the above Step 2, 79.69 g of epichlorohydrin (Sigma Aldrich), 39.84 g of isopropyl alcohol (Sigma Aldrich) and 100 ml of distilled water were added to a 1000 ml three- 13.28 g of distilled water was added and mixed at room temperature under a nitrogen stream. The well mixed solution was reacted with 50% sodium hydroxide solution for 3 hours while refluxing to a set temperature of 60 ° C. After the reaction, the layer separation was carried out to remove the lower brine and the upper portion of the solvent was removed by vacuum distillation. The solvent-removed product was washed three times with water and toluene, and neutralized once with phosphoric acid. The water was removed through layer separation, and the remaining toluene solution was filtered through celite and subjected to vacuum distillation to obtain an intermediate product (F-3) which had been subjected to epoxidation. ^{Using 1} H NMR, the intermediate product (F-3) was identified with a peak of the epoxy group observed at 2.50, 3.04, and 6.30 ppm.

(4) Step 4: Hydroxylation

30 g of the intermediate product (F-3) obtained in the above Step 3, 21.40 g of triethoxysilane (Sigma Aldrich) and 0.8175 g of a spiro catalyst (Chloroplatinic acid, Sigma Aldrich) were placed in a 1000 ml three- g and 200 ml of toluene, and the mixture was stirred at room temperature under a nitrogen stream. The well mixed solution was reacted for 8 hours while refluxing to a set temperature of 80 ° C. After the reaction, the resulting product was filtered through celite and activated carbon, and the solvent was removed using a rotary evaporator to obtain a diethylstilbestrol (DES) epoxy compound having an alkoxysilyl group as a final object (F). ¹ H NMR was used to identify the final target (F) with triethoxysilane groups observed at 0.91, 1.22, and 3.83 ppm and peaks of epoxy groups observed at 2.50, 3.04, and 4.07 ppm.

Cured goods  Manufacturing and evaluation of heat resistance characteristics

1. Epoxy Hardened  Produce

Methyl ethyl ketone was added to an epoxy compound and a curing agent (PS-6313, aminotriazine type novolak curing agent, GUN EI CHEMICAL INDUSTRY CO., LTD., Equivalent: 148 g / eq) Followed by mixing at a speed of 1200 rpm for 30 minutes. After the 2-ethyl-4-methylimidazole (Sigma Aldrich) curing catalyst was dissolved to a solid content of 10%, the mixture was added to a mixture of the epoxy compound and the curing agent at a speed of 1200 rpm for 5 minutes to prepare a mixed solution , And the solid content refers to the content of the solid matter in the mixed liquid). The prepared mixed solution was film-cast on a PET film to a thickness of 200 mu m, and then the solvent was removed in an oven heated to 60 DEG C for 30 minutes. After removing the solvent, a cured product was obtained by curing in an oven at 100 ° C for 30 minutes, an oven at 180 ° C for 30 minutes, and an oven at 230 ° C for 30 minutes.

2. Composites comprising epoxy compounds and silica ( Cured goods )

(Solid content: 70%, solvent: methyl ethyl ketone, silica average size: 1 占 퐉, Admatech), polyvinyl butyral, and a surface of a hardener (PS-6313) were added to the epoxy compound and the curing agent (BYK-337, polyether-modified polydimethylsiloxane, Altana) was added, followed by mixing at a speed of 1200 rpm for 30 minutes. After dissolving the 2-ethyl-4-methylimidazole (Sigma Aldrich) curing catalyst to a solid content of 10%, the mixture was added to the mixture of the epoxy compound, the curing agent and the silica slurry at a speed of 1200 rpm for 5 minutes, . The resulting final mixed solution was cast on a PET film to a thickness of 200 mu m, and then the solvent was removed in an oven heated to 60 DEG C for 30 minutes. After removing the solvent, the mixture was cured in an oven at 100 ° C for 30 minutes, at 180 ° C in an oven for 30 minutes, and at 230 ° C in an oven for 30 minutes to obtain a cured composite article.

3. Composites comprising epoxy compounds, silica and glass fibers ( Cured goods )

(Solid content: 70%, solvent: methyl ethyl ketone, silica average size: 1 占 퐉, Admatech), polyvinyl butyral, and a surface of a hardener (PS-6313) were added to the epoxy compound and the curing agent (BYK-337) was added, followed by mixing at a speed of 1200 rpm for 30 minutes. After dissolving the 2-ethyl-4-methylimidazole (Sigma Aldrich) curing catalyst to a solid content of 10%, the mixture was put into a mixture of an epoxy compound, a curing agent and a silica slurry at a speed of 1200 rpm for 5 minutes to prepare a final mixed solution Respectively. The resulting final mixed solution was impregnated with a glass fiber fabric (Nittobo, E-galss 2116 or T-glass 2116) to prepare a glass fiber composite containing an epoxy compound. The glass fiber composite was placed in an oven heated at 60 ° C for 30 minutes to remove the solvent and then molded in a hot press at 100 ° C for 2 hours and at 180 ° C for 2 hours and then cured in an oven at 230 ° C for 2 hours, I got the cargo.

4. Evaluation of physical properties: Evaluation of heat resistance

The dimensional change (CTE) and the glass transition temperature (Tg) according to temperature were measured using a thermo mechanical analyzer (Thermo Mechanical Analyzer, film / fiber mode, Force 0.1N) Respectively. The specimens were prepared with dimensions of ⁴ × 16 × 0.05 (mm ³ ). The measurement results are shown in the following Tables 1 to 3, and the dimensional changes of the cured products produced in Example 2, Comparative Example 1, Example 9, Comparative Example 2, Examples 22 and 23, and Comparative Example 3 were measured A graph is shown in Figs. 1 to 7, respectively.

As shown in Table 1, the cured product of the alkoxysilyl-based epoxy compound having the bisphenol-based core according to the present invention exhibited a significantly higher Tg than the cured product of the bisphenol A epoxy as the comparative example.

In addition, as shown in Table 2, the composite cured product comprising the silica together with the alkoxysilyl-based epoxy compound having the bisphenol-based core of the present invention, which is an example of the present invention, High Tg and low CTE.

Particularly, as shown in Table 3 above, the composite cured product comprising the silica and the glass fiber together with the alkoxysilyl-based epoxy compound having the bisphenol-based core of the present invention, which is an example of the present invention, is a comparative example using bisphenol A epoxy or biphenyl epoxy Exhibited significantly higher Tg (or no glass transition temperature, Tg-less) and significantly lower CTE than the composite cured product.

From the above results, it can be seen that the alkoxysilyl-based epoxy compound having a bisphenol-based core of the present invention has remarkably excellent heat resistance characteristics (i.e., a low CTE and a low CTE) in the organic-inorganic material composite as compared with the conventional bisphenol A epoxy or biphenyl epoxy compound High glass transition temperature or Tg-less). This is presumably because the alkoxysilyl group forms an effective intermolecular bond with the inorganic material, and not only the additional chemical bond of the alkoxysilyl term but also the combination of the alkoxysilyl group and the curing agent appears to increase the crosslinking density of the final composite .

Claims (13)

An epoxy compound having an alkoxysilyl group selected from the group consisting of the following structural formulas B to F and polymerization products thereof:

In each of Formulas (B) to (F) above,
The substituent Q is independently selected from the group consisting of an alkoxysilyl-alkylene group, hydrogen, and an alkylene group having a terminal unsaturated carbon-carbon double bond,
With the proviso that at least one of the substituents Q is an alkoxysilyl-alkylene group. The method according to claim 1, wherein the alkoxysilyl-alkylene group is a mono-, di- or tri (C ₁ -C ₁₀ ) alkoxysilyl- (C ₁ -C ₁₀ ) alkylene group, an alkyl having a terminal unsaturated carbon- Wherein the epoxy group is CH ₂ ═CH- (C ₁ -C ₁₀ ) alkylene group. The epoxy compound according to claim 1, wherein the alkoxysilyl-alkylene group is a triethoxysilyl-propylene group, and the alkylene group having a terminal unsaturated carbon-carbon double bond is an allyl group. The epoxy compound according to claim 1, wherein two of the substituents Q in the formulas (B) to (F) are alkoxysilyl-alkylene groups and the remaining two are hydrogen. The epoxy compound according to claim 4, wherein two alkoxysilyl-alkylene groups are bonded to two phenyl groups one by one. The epoxy compound according to claim 1, which is selected from the group consisting of the following formulas (BB) to (FF):

In each of the above formulas BB to FF,
The substituent Q is as defined in claim 1,
n is an integer of 2 to 10; (1) reacting a compound of any one of the following formulas (2) to (6) with an alkyl halide having a terminal unsaturated carbon-carbon double bond;
(2) rearranging the alkyl group having an unsaturated carbon-carbon double bond in the reaction product of the step (1) in the molecule;
(3) reacting the reaction product of step (2) with an alkyl halide having an epoxy group; And
(4) reacting the reaction product of step (3) with a silane having hydrogen and an alkoxy group,

In each of Formulas (B) to (F) above,
The substituent Q is independently selected from the group consisting of an alkoxysilyl-alkylene group, hydrogen, and an alkylene group having a terminal unsaturated carbon-carbon double bond,
With the proviso that at least one of the substituents Q is an alkoxysilyl-alkylene group. The method of claim 7, wherein the alkyl halide having a terminal unsaturated carbon-carbon double bond used in step (1) is CH ₂ ═CH- (C ₁ -C ₁₀ ) alkyl halide, and the epoxy group used in step (3) alkyl halides having an epoxy - (C ₁ -C ₁₀₎ alkyl halide, and (4) a silane having a hydrogen and alkoxy used in step (C ₁ -C ₁₀₎ characterized in that the alkoxy silane compound having one 1-3 Lt; / RTI > The method according to claim 7, wherein the alkyl halide having an unsaturated carbon-carbon double bond used in step (1) is allyl bromide, the alkyl halide having an epoxy group used in step (3) is epichlorohydrin, Wherein the silane having the hydrogen and alkoxy groups used in the step (a) is triethoxysilane. An organic-inorganic material composite comprising a cured product of a mixture comprising an epoxy compound having an alkoxysilyl group according to any one of claims 1 to 6 and silica. 11. The composite of claim 10, further comprising an additional inorganic material. 12. The composite of claim 11, wherein the additional inorganic material comprises glass fibers in an amount of 20 to 80 weight percent based on 100 weight percent of the composite. A process for producing an organic-inorganic composite material characterized by mixing an epoxy compound having an alkoxysilyl group according to any one of claims 1 to 6 with silica and condensing and curing the mixture.

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