KR102246743B1 - Method for polymerizating alpha-olefin - Google Patents

Abstract

The present invention relates to a prepolymer for blending an epoxy resin represented by the following structural formula 1. Accordingly, when such a prepolymer is blended with an epoxy resin, thermal stability, impact strength, tensile strength, and the like can be improved.
[Structural Formula 1]

Description

Prepolymer for epoxy resin blend and epoxy resin composition comprising the same {METHOD FOR POLYMERIZATING ALPHA-OLEFIN}

The present invention relates to a prepolymer for an epoxy resin blend and an epoxy resin composition comprising the same, and more particularly, to an epoxy resin with improved compatibility, thermal stability, breakthrough toughness, and warpage, including a prepolymer based on POSS (polyhedral oligomeric silsesquioxane) It relates to the composition.

Epoxy is a representative thermosetting resin that is widely used commercially, such as adhesion, paint, aerospace, semiconductors, and composite materials, because of its advantages such as low cost and excellent thermal stability, mechanical properties, and electrical properties. However, since epoxy has a low fracture toughness (impact strength) due to its high crosslinking density during curing, it can cause cracks even with light impacts, which limits its application to areas where repeated impacts are applied. As it continues to grow, there is a problem of poor weatherability.

Therefore, many researchers have done a lot of research to supplement the epoxy fracture toughness, but most of the research results improve the epoxy fracture toughness (impact strength), but mechanical properties such as thermal stability excluding fracture toughness, tensile strength excluding impact strength, and flexural strength. This falling downside appeared.

The first way to solve this problem is to prevent dense curing by making the curing reaction very fast after selecting the epoxy and the curing agent. In other words, when the curing reaction is performed, the activation energy is lowered to make an epoxy resin with a lower density by reacting more quickly.As a substance that lowers the activation energy, a molecule having a thiol group is added as a catalyst to increase the speed of the curing reaction to increase the crosslinking density Epoxy resin with reduced brittleness can be made because it is low. However, as the crosslinking density decreases, the epoxy fracture toughness (impact strength) is improved, but there are disadvantages in that mechanical properties such as thermal stability, tensile strength excluding impact strength, and flexural strength excluding this decrease.

In the second method, in order to increase the toughness of the epoxy, inorganic particles (graphene, graphene oxide), organic particles, organic-inorganic particles, or rubber particles that can absorb external impacts or disperse the impact are used. Methods were studied. However, the degree of dispersion in the epoxy matrix varies depending on the compatibility with the epoxy and the size and quantity of the particles. However, there is a disadvantage that all of the physical properties are degraded. In addition, when used alone, fracture toughness (impact strength) can be increased, but there is a disadvantage that the flexural properties (tensile strength, flexural properties) of the epoxy are inferior.

As a third method, materials that can disperse and absorb strong external impacts and interfere with the path of cracks even when cracks occur due to impact are blended with epoxy in the form of an interpenetrating polymer network. It is a method of curing. This method has the property of being strong, hard, and elastic as it contains materials that can impart stiffness and elasticity, which are characteristic of epoxy, together. At this time, there are urethane-based, urea-based, and polyethylene glycol-based materials that can impart elasticity. All three materials have soft and tough properties, so they can disperse and absorb strong external impacts. Even if a crack occurs due to an impact, it can interfere with the path of the crack. However, despite these advantages, these polymers have poor thermal stability, which reduces the heat resistance of the epoxy, and if the ratio between the epoxy and the polymer does not match, it causes phase separation from the epoxy matrix, resulting in deterioration of not only the impact strength but also the overall chemical and physical properties. There is this.

Accordingly, there is a need to prepare a new urethane resin composition capable of improving the fracture toughness of urethane, preventing deterioration in warpage, and improving thermal stability.

Korean Registered Patent Publication No. 10-1104224 Korean Patent Application Publication No. 10-2013-0131079

An object of the present invention is to solve the above problems, and since organic groups and inorganic groups in their own molecules are mixed, the thermal stability and mechanical properties are good, and the smallest size among silica particles so that the particles can be evenly dispersed in the epoxy matrix.　Based on POSS, it improves the thermal stability of epoxy, improves the impact strength that can disperse and absorb strong external impacts, and secures an elastic region by introducing PEGDMA into the organic functional group of POSS. It is to provide a prepolymer for an epoxy blend that can also improve tensile strength and flexibility, which are the flexural properties of an epoxy, and a hybrid epoxy composition comprising the same.

According to an aspect of the present invention,

A prepolymer for blending an epoxy resin represented by the following Structural Formula 1 is provided.

[Structural Formula 1]

In structural formula 1,

또는

이거나, 또는 R¹ 내지 R⁸ 중 선택된 어느 둘은

의 양단 각각에 결합되어 융합고리를 형성하고, R¹ 내지 R⁸은 동시에 모두

는 아니고,R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,

l, m and p are the number of repetitions, and each independently an integer selected from 0 to 10,

n and q are the number of repetitions, and each independently an integer selected from 5 to 50.

Preferably,

In the above structural formula 1,

또는

이거나, 또는 R¹ 내지 R⁸ 중 선택된 어느 둘은

의 양단 각각에 결합되어 융합고리를 형성하고, R¹ 내지 R⁸은 동시에 모두

는 아니고,R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,

l, m and p are repeating numbers, and each independently an integer selected from 0 to 3,

n and q are the number of repetitions, and each may be an integer independently selected from 10 to 15.

More preferably,

In the above structural formula 1,

또는

로 치환될 수 있다.4 or more of R ¹ to R ^{8 are}

or

Can be substituted with

The prepolymer for blending the epoxy resin may be in a semi-cured state.

According to another aspect of the present invention,

Epoxy resin; And a hybrid epoxy resin composition comprising a; and a prepolymer for the epoxy resin blend represented by the following Structural Formula 1 is provided.

[Structural Formula 1]

In structural formula 1,

또는

이거나, 또는 R¹ 내지 R⁸ 중 선택된 어느 둘은

의 양단 각각에 결합되어 융합고리를 형성하고, R¹ 내지 R⁸은 동시에 모두

는 아니고,R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,

l, m and p are the number of repetitions, and each independently an integer selected from 0 to 10,

n and q are the number of repetitions, and each independently an integer selected from 5 to 50.

The hybrid epoxy resin composition,

Based on 100 parts by weight of the epoxy resin, 3 to 15 parts by weight of the prepolymer for the epoxy resin blend represented by the structural formula 1; may include.

The hybrid epoxy resin composition may further include 20 to 35 parts by weight of a curing agent based on 100 parts by weight of the epoxy resin.

The prepolymer represented by Structural Formula 1 may be blended with the epoxy resin in an interpenetrating polymer network (Interpenetrating 　 Polymer 　 Network) type.

According to another aspect of the present invention,

(a) preparing a mixed solution by dissolving POSS-SH, PEGDMA (Poly(ethylene glycol) dimethacrylate), and a photocatalyst represented by the following Structural Formula 2 in an organic solvent; And

(b) preparing a prepolymer represented by Structural Formula 1 by reacting with thiol-ene by irradiating ultraviolet rays to the mixed solution. A method for preparing a prepolymer for blending an epoxy resin comprising: is provided.

[Structural Formula 2]

In structural formula 2,

이고,R ¹ to R ⁸ are each independently

ego,

l is the number of repetitions, and each independently an integer selected from 0 to 10.

Preferably,

In the above structural formula 2,

l may be 0 to 3.

The mixed solution may contain 4 to 8 mole parts of PEGDMA and 0.05 to 1 mole parts of a photocatalyst, based on 1 mole part of POSS-SH.

The photocatalyst may be any one selected from DMPA (2,2-dimethoxy-2-phenylacetophenone), BP (benzophenone), and TMDPO ((2,4,6-trimethylbenzoyl) diphenylphosphine oxide) 　.

The organic solvent may be any one selected from dichloromethane, tetrahydrofuran (THF), ethanol, methanol, acetone, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and dioxane.

The ultraviolet (UV) irradiation may be performed for 40 to 50 seconds at an intensity of 1 to 20 mW/cm ^2.

The ultraviolet irradiation can be stopped when the viscosity of the prepared prepolymer is at its highest before it becomes a solid.

According to another aspect of the present invention,

(1) mixing an epoxy resin and a curing agent;

(2) preparing an epoxy mixture by adding and stirring the prepolymer for the epoxy resin blend prepared according to the above production method to the result of step (1);

(3) removing air bubbles from the epoxy mixture; And

(4) Curing the epoxy mixture from which air bubbles have been removed; a method for preparing a hybrid epoxy composition comprising: is provided.

In step (1), the mixture of the epoxy resin and the curing agent may be stirred at 60 to 80°C.

In step (1), 20 to 35 parts by weight of a curing agent may be mixed with respect to 100 parts by weight of the epoxy resin.

The curing agent may be any one selected from diphenyldiaminomethane (DDM), metaphenyldiamine (MPDA), and diaminodiphenylsulfone (DDS).

The stirring in step (2) may be performed for 5 to 15 minutes.

In step (2), based on 100 parts by weight of the epoxy resin, 3 to 15 parts by weight of the prepolymer for blending the epoxy resin; may be used.

The curing of step (4) may be performed in two steps of pre-curing at 70 to 90°C and then post-curing at 140 to 160°C.

The pre-curing may be performed for 1.5 to 2.5 hours.

The post-curing may be performed for 3.5 to 4.5 hours.

The prepolymer for epoxy blend of the present invention has good thermal stability and mechanical properties because organic groups and inorganic groups in its own molecule are mixed, and POSS-based, which has the smallest size among silica particles so that the particles can be evenly dispersed in the epoxy matrix. When blended with epoxy, it improves the thermal stability of the epoxy, improves the impact strength that can disperse and absorb strong external impacts, and secures an elastic region by introducing PEGDMA into the organic functional group of POSS. By doing so, it is possible to improve the tensile strength and flexural properties, which are the flexural properties of the epoxy.

1 is a flow chart showing a method of manufacturing the prepolymer for an epoxy blend of the present invention.
FIG. 2 is a schematic diagram of a thiol-ene reaction for preparing a hybrid prepolymer of Preparation Example 1. FIG.
3 schematically shows the preparation of a hybrid IPN epoxy according to Example 1.
4 is a result of confirming the synthesis of POSS-SH according to Experimental Example 1.
5 is an FT-IR analysis result of Experimental Example 2.
6 shows the conversion rate to the prepolymer according to the UV irradiation time of Experimental Example 2.
7 is a result of confirming the curing of the hybrid epoxy composition of Experimental Example 3.
8 is a thermal characteristic analysis result of Experimental Example 4.
9 is a result of analyzing tensile properties of Experimental Example 5.
10 is a result of analyzing the bending characteristics of Experimental Example 5.
11 is an analysis result of the impact strength of Experimental Example 5.
12 to 14 are SEM images according to Experimental Example 6.
15 is an optical photograph according to Experimental Example 6.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present invention.

However, the following description is not intended to limit the present invention to a specific embodiment, and in describing the present invention, when it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted. .

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the existence of features, numbers, steps, actions, elements, or combinations thereof described in the specification, but one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, actions, elements, or combinations thereof is not preliminarily excluded.

Hereinafter, the prepolymer for blending the epoxy resin of the present invention will be described.

The prepolymer for blending an epoxy resin of the present invention is characterized in that it is represented by the following Structural Formula 1.

[Structural Formula 1]

In structural formula 1,

또는

이거나, 또는 R¹ 내지 R⁸ 중 선택된 어느 둘은

의 양단 각각에 결합되어 융합고리를 형성하고, R¹ 내지 R⁸은 동시에 모두

는 아니고,R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,

l, m and p are the number of repetitions, and each independently an integer selected from 0 to 10,

n and q are the number of repetitions, and each independently an integer selected from 5 to 50.

Preferably, in the structural formula 1,

또는

이거나, 또는 R¹ 내지 R⁸ 중 선택된 어느 둘은

의 양단 각각에 결합되어 융합고리를 형성하고, R¹ 내지 R⁸은 동시에 모두

는 아니고,R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,

l, m and p are repeating numbers, and each independently an integer selected from 0 to 3,

n and q are the number of repetitions, and each may be an integer independently selected from 10 to 15.

More preferably, in the structural formula 1,

또는

로 치환될 수 있다.4 or more of R ¹ to R ^{8 are}

or

Can be substituted with

The prepolymer for blending the epoxy resin may be in a semi-cured state, and when the curing rate exceeds 40%, it may be solidified and it may be difficult to blend with the epoxy resin.

Hereinafter, the hybrid epoxy resin composition of the present invention will be described.

The hybrid epoxy resin composition of the present invention is an epoxy resin; And a prepolymer for blending an epoxy resin represented by Structural Formula 1 above.

The hybrid epoxy resin composition,

With respect to 100 parts by weight of the epoxy resin, 3 to 15 parts by weight of the prepolymer for the epoxy resin blend represented by Structural Formula 1; It is preferable to include, and more preferably 5 to 10 parts by weight.

Preferably, the hybrid epoxy resin composition may further include 20 to 35 parts by weight of a curing agent, more preferably 25 to 30 parts by weight, based on 100 parts by weight of the epoxy resin.

The prepolymer represented by Structural Formula 1 may be blended with the epoxy resin in an interpenetrating polymer network type.

Hereinafter, a method of preparing the prepolymer for an epoxy blend of the present invention will be described.

First, represented by the following structural formula 2 POSS - SH , PEGDMA( Poly ( ethylene glycol ) dimethacrylate), and Photocatalyst Dissolve in an organic solvent to prepare a mixed solution (step a).

[Structural Formula 2]

In structural formula 2,

이고,R ¹ to R ⁸ are each independently

ego,

l is the number of repetitions, and each independently an integer selected from 0 to 10.

Preferably, in Structural Formula 2, l may be 0 to 3.

The mixed solution preferably contains 4 to 8 mole parts of PEGDMA and 0.05 to 1 mole parts of a photocatalyst, based on 1 mole part of POSS-SH.

The photocatalyst may be DMPA (2,2-dimethoxy-2-phenylacetophenone), BP (benzophenone), TMDPO ((2,4,6-trimethylbenzoyl) diphenylphosphine oxide) 　, etc., but the scope of the present invention is not limited thereto.

The organic solvent may be dichloromethane, tetrahydrofuran (THF), ethanol, methanol, acetone, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), dioxane, and the like, but the scope of the present invention is not limited thereto. .

Next, by irradiating the mixed solution with ultraviolet rays Thiolen ( Thiol - ene ) Reacted and represented by the above structural formula 1 Prepolymer To prepare (step b).

The ultraviolet (UV) irradiation is preferably performed for 40 to 50 seconds at an intensity of 1 to 20 mW/cm ^2.

The ultraviolet irradiation is preferably stopped when the viscosity of the prepared prepolymer is at its highest before becoming a solid, and when ultraviolet irradiation for 50 seconds or more is solidified, blending with the epoxy resin may become difficult afterwards.

1 is a flowchart sequentially showing a method of manufacturing a hybrid epoxy resin composition of the present invention. Hereinafter, a method of manufacturing the hybrid epoxy resin composition of the present invention will be described with reference to FIG. 1.

First, the epoxy resin and the curing agent are mixed (step 1).

At this time, the mixing of the epoxy resin and the curing agent is preferably stirred at 60 to 80 °C, and when it exceeds 80 °C, the curing reaction starts, and blending with the prepolymer may become difficult.

With respect to 100 parts by weight of the epoxy resin, it is preferable to mix 20 to 35 parts by weight of a curing agent, and more preferably 25 to 30 parts by weight may be mixed.

The curing agent may be diphenyldiaminomethane (DDM), metaphenyldiamine (MPDA), diaminodiphenylsulfone (DDS), and the like, but the scope of the present invention is not limited thereto.

Thereafter, the epoxy resin prepared as described above in the result of step (1) For blending Put the prepolymer By stirring Prepare an epoxy mixture (step 2).

The stirring may be performed for 5 to 15 minutes.

With respect to 100 parts by weight of the epoxy resin, 3 to 15 parts by weight of the prepolymer for the epoxy resin blend is preferably used, and more preferably 5 to 10 parts by weight may be used.

Next, air bubbles are removed from the epoxy mixture (step 3).

If the air bubbles are not completely removed, the physical properties of the final epoxy composition may be greatly deteriorated. Therefore, it is preferable to completely remove the air bubbles through a high vacuum treatment.

Finally, cure the blistered epoxy mixture hybrid To prepare an epoxy resin composition (step 4).

The curing is preferably carried out in two steps of pre-curing at 70 to 90°C and then post-curing at 140 to 160°C.

The pre-curing is preferably performed for 1.5 to 2.5 hours, and the post-curing is preferably performed for 3.5 to 4.5 hours.

Hereinafter, an embodiment according to the present invention will be described in detail.

[ Example ]

Manufacturing example One: hybrid Prepolymer Produce

(One) POSS - SH Synthesis of

POSS-SH was synthesized according to the following reaction formula, and MPTS (15 ml) was added to MeOH (360 ml) with concentrated HCl (37%, 30 ml) and stirred at 90° C. for 24 hours to obtain a precipitated POSS-SH. I did. The product was washed 3 times with cold MeOH to remove unreacted MPTS.

The viscous solution was dissolved in dichloromethane and washed 3 times with distilled water. The dichloromethane solution was dried over anhydrous MgSO ₄ and filtered. Finally, it was concentrated using an evaporator and POSS-SH was obtained in 87% yield.

¹ H-NMR (400 MHz, CDCl ₃ , δ): 0.78 (double, Si-CH ₂ -), 1.4 (br, -SH), 1.72 (s, -CH ₂ -), 2.58 (s, -CH ₂ -S).

[Reaction Scheme]

(2) hybrid Prepolymer ( POSS - SH : PEGDMA ) synthesis

A schematic diagram of a thiol-ene reaction for preparing the hybrid prepolymer of Preparation Example 1 is shown in FIG. 2. According to this, a hybrid prepolymer is prepared according to a thiol-ene reaction through UV irradiation between the functional group of POSS-SH (-SH) and the functional group (double bond ene) of PEGDMA by DMPA (photocatalyst).

Specifically, 1 mmol of POSS-SH, 4 mmol of PEGDMA, and 0.05 mmol of a thiol-ene reaction photocatalyst (DMPA) were dissolved in a 50 mL flask using 1 mL of the minimum solvent THF. After completely dissolving, UV irradiation was performed at a wavelength of 365 nm and an ^{intensity of 10 mW/cm 2} to stop UV irradiation after about 50 seconds when the viscosity was the highest before being completely cured. When it is completely cured, it is not possible to blend with the epoxy, so be careful.

Manufacturing example 2: hybrid Prepolymer Produce

A hybrid prepolymer was prepared in the same manner as in Preparation Example 1, except that 8 mmol of PEGDMA and 0.09 mmol of DMPA were used instead of 4 mmol of PEGDMA and 0.05 mmol of DMPA.

Manufacturing example 3: hybrid Prepolymer Produce

POSS-SH 1 mmol, PEGDMA 4 mmol, DMPA 0.05 mmol, THF 1 mL instead of POSS-SH 2 mmol, PEGDMA 8 mmol, DMPA 0.1 mmol, THF 2 mL, except that the hybrid in the same manner as in Preparation Example 1 A prepolymer was prepared.

Manufacturing example 4: hybrid Prepolymer Produce

POSS-SH 1 mmol, PEGDMA 4 mmol, DMPA 0.05 mmol, THF 1 mL instead of POSS-SH 2 mmol, PEGDMA 16 mmol, DMPA 0.18 mmol, THF 2 mL, except that the hybrid in the same manner as in Preparation Example 1 A prepolymer was prepared.

Comparative Production Example One: Prepolymer Produce

A prepolymer was prepared in the same manner as in Preparation Example 1, except that POSS-SH was not used and 0.04 mmol of DMPA was used.

Table 1 below summarizes the prepolymer preparation conditions of Preparation Examples 1 to 4 and Comparative Preparation Example 1.

division POSS-SH PEGDMA DMPA Solvent(THF) Comparative Production Example (5g) - 4mmol 0.04mmol 1ml Preparation Example 1 (5g) 1mmol 4mmol 0.05mmol 1ml Preparation Example 2 (5g) 1mmol 8mmol 0.09mmol 1ml Preparation Example 3 (10g) 2mmol 8mmol 0.1mmol 2ml Preparation Example 4 (10g) 2mmol 16mmol 0.18mmol 2ml

Example One: hybrid Epoxy manufacturing

3 schematically shows the preparation of a hybrid IPN epoxy according to Example 1. With reference to this, the first embodiment will be described.

After putting DGEBA (100g, 0.28 mol) and DDM (27g, 0.14 mol) in a 150 ml beaker, the DDM was completely dissolved at 70° C. using a mechanical stirrer. At high temperature, DGEBA can lower the viscosity and help dissolve DDM, but when it is dissolved above 80°C, the curing reaction starts and blending with the prepolymer is impossible.

Next, when the DDM is completely dissolved, the prepolymer prepared in advance according to Preparation Example 1 was added, and then vigorously stirred using a mechanical stirrer for about 10 minutes. When the stirring was over, air bubbles formed in the epoxy mixture were completely removed by using a high vacuum in a vacuum oven for about 15 minutes. If there are even a few air bubbles, the properties may deteriorate. Then, it was put into a mold conforming to ASTM standards (D256, D790, D638), pre-cured at about 80° C. for 2 hours, and then post cured at 150° C. for 4 hours.

Example 2: hybrid Epoxy manufacturing

A hybrid epoxy was prepared in the same manner as in Example 1, except that the prepolymer prepared according to Preparation Example 2 was used instead of Preparation Example 1.

Example 3: hybrid Epoxy manufacturing

A hybrid epoxy was prepared in the same manner as in Example 1, except that the prepolymer prepared according to Preparation Example 3 was used instead of Preparation Example 1.

Example 4: hybrid Epoxy manufacturing

A hybrid epoxy was prepared in the same manner as in Example 1, except that the prepolymer prepared according to Preparation Example 4 was used instead of Preparation Example 1.

Comparative example One: hybrid Epoxy manufacturing

A hybrid epoxy was prepared in the same manner as in Example 1, except that the prepolymer prepared according to Comparative Preparation Example 1 was used instead of Preparation Example 1.

In Table 2 below, the conditions for preparing the hybrid epoxy of Examples 1 to 4 and Comparative Example 1 are summarized.

division DGEBA(g) DDM(g) Prepolymer (g) Pure epoxy (EP) 100 27 - Comparative Example 1 Comparative Production Example 1 (5) Example 1 Manufacturing Example 1 (5) Example 2 Production Example 2 (5) Example 3 Manufacturing Example 3 (10) Example 4 Production Example 4 (10)

[ Experimental example ]

Experimental example One: POSS - SH Synthesis confirmation

Before preparing POSS-SH and PEGDMA as a prepolymer, the results of analyzing whether POSS-SH was accurately synthesized through H-NMR are shown in FIG. 4.

According to this, (a) of FIG. 4 is an NMR spectrum of (3-Mercaptopropyl)trimethoxysilane, and this material is synthesized as POSS-SH through a hydrolysis and condensation reaction of 3.5 ppm of a methoxy group through a sol-gel reaction. In FIG. 4 (b), the areas a, b, c, and d of POSS-SH are widened, and it can be seen that POSS-SH is completely synthesized through the disappearance of the methoxy group of e.

Experimental example 2: Prepolymer Synthesis confirmation

FT-IR analysis was performed to see if the prepolymer was introduced through the Thiol-ene reaction through UV irradiation with the functional group -SH group of POSS-SH and the functional group (double bond ene) of PEGDMA as DMPA (photocatalyst). It is shown in 5. In (a) of FIG. 5, the ratio of POSS-SH/PEGDMA is 1:4 (Preparation Examples 1 and 3), and in (b), the ratio of POSS-SH/PEGDMA is 1:8 (Preparation Examples 2 and 4). The reason for this synthesis is to find an optimized ratio when applied to epoxy, and to the degree of reaction (conversion rate) according to UV irradiation.

According to this, first, there are two peaks that can be seen in POSS-SH, the -SH group peak seen at ^{2557 cm- 1} and the Si-O-Si peak seen at ^{1107 cm- 1, and PEGDMA is 1635 cm. It} can be seen in both the graphs (a) and (b) that there is a double bond peak that can be seen at -1.

In addition, the conversion rate to the prepolymer according to the UV irradiation time is shown in FIG. 6. According to this, it was confirmed that as the UV irradiation time elapsed, the -SH and double bond peaks decreased, and the thiol-ene reaction proceeded with time to the UV irradiation, thereby changing into a semi-cured prepolymer. In other words, depending on the UV irradiation time, the liquid state -> viscosity occurs -> does not flow -> completely hardens. When the semi-curing conversion rate according to the UV irradiation time is calculated through FT-IR data, irradiation for 60 seconds is approx. If it has a conversion rate of 40% or more, the prepolymer changes from liquid to solid, making it difficult to blend with the epoxy. Therefore, it is preferable to blend with the epoxy in a state where the reaction is stopped after about 50 seconds, just before hardening. Therefore, it could be confirmed that the UV irradiation time is about 50 seconds and is most suitable for blending with epoxy when the prepolymer conversion rate is less than 40%.

Experimental example 3: hybrid Epoxy composition curing confirmation

Whether the epoxy composition was properly cured or not was analyzed through FT-IR, and the results are shown in FIG. 7. Here, (a) DGEBA, (b) Pure epoxy, (c) Comparative Example 1, (d) Example 1, (e) Example 2, (f) Example 3, (g) prepared according to Example 4 It is an epoxy composition.

According to this, the peak of the hybrid prepolymer was less than that of DGEBA and was not seen because it was overlapped by the peak of DGEBA, but the most important (a) the hardening reaction was successfully carried out by confirming that the COC epoxide peak from ^{914cm -1 of DGEBA disappeared.} I could see that it was.

Experimental example 4: Thermal characterization

8 is a TGA (Thermogravimetric Analyzer) analysis result (a), DTG for the epoxy composition prepared according to Comparative Example 1 and Examples 1 to 4 (Derivative TG) The analysis result (b) is shown.

Basically, when an elastic region is given to an epoxy, thermal stability is poor. This is because the material providing the elastic region has low thermal stability, and it cannot withstand heat well due to plasticization. However, it can be seen that the epoxy containing only PEGDMA of Comparative Example 1 has higher thermal stability than pure epoxy, because the acrylic group at the end of the PEGDMA during the curing process was thermally polymerized to form an IPN structure. In addition, it was found through TGA analysis that the hybrid IPN-type epoxy of Examples 1 to 4 has increased thermal stability than that of pure epoxy, and it was confirmed that the decomposition rate was decreased through DTG. The reason is that because POSS was added, the thermal stability of the epoxy was improved, and it acted as a crosslinking point of PEGDMA to react well with PEGDMA. In fact, it is judged that the structure became resistant to heat through two matrices, namely, IPN structure, on the POSS limit.

Experimental example 5: physical property test

Fig. 9 shows the results of analyzing tensile properties obtained by repeating at least five times or more by making a specimen according to ASTM-638 standard through UTM. According to this, pure epoxy is strong and hard with properties similar to glass, so its modulus is high and its bendability, that is, its flexibility or tensile strength is inferior. From the epoxy of Comparative Example 1, PEGDMA imparts elasticity, thereby increasing tensile strength and increasing modulus. However, the strong properties of the epoxy and the softness of PEGDMA coexist to have strong and tough properties. Tensile strength increased as the amount of PEGDMA increased, and the modulus was optimized in terms of tensile strength + modulus of 1:8 ratio (Examples 2 and 4) than POSS-SH/PEGDMA-1:4 ratio (Examples 1 and 3). It confirmed that it was a ratio.

In addition, the results of analyzing the flexural characteristics obtained by repeating at least five times or more by making a specimen according to ASTM-790 standard through UTM are shown in FIG. 10. The results for the flexural properties showed a similar tendency to the tensile properties described above.

On the other hand, the impact strength analysis results obtained by repeating at least five times or more by making an Izod specimen according to ASTM-256 standard through an impact strength test system are shown in FIG. 11. According to this, since pure epoxy is hard but not soft, it has brittleness and is weak against impact. However, PEGDMA can increase the impact strength while imparting elasticity to the epoxy, and the POSS-SH/PEGDMA hybrid of Examples 1 to 4 of the present invention than the epoxy composition of Comparative Example 1 using PEGDMA alone, and a hybrid used as a prepolymer It was confirmed that the impact strength of the epoxy composition was further increased. In addition, the hybrid prepolymer of POSS-SH/PEGDMA was found to have higher impact strength of the hybrid IPN epoxy prepared in the 1:8 ratio (Examples 2 and 4) than the 1:4 ratio (Examples 1 and 3), As for the amount of prepolymer, it was found that the impact strength of the epoxy blended with 10 g was higher than that of 5 g. Therefore, in terms of impact strength, the POSS-SH:PEGDMA ratio of 1:8 was the most excellent, and in terms of both prepolymers, it was confirmed that the epoxy composition blended with 10g was more excellent.

Experimental example 6: surface analysis

12 to 14 are SEM surface images of pure epoxy, Comparative Example 1, and epoxy compositions prepared according to Examples 1 to 4, which are images of the fractured surfaces after impact testing of the epoxy composition. According to this, in the order of epoxy, Comparative Example 1, and Examples 1 to 4, that is, as the impact strength increases, the roughness of the fractured surface increases, which increases surface energy at the fracture surface when the epoxy is fractured. Therefore, it can be seen that as the impact energy is absorbed, dispersed, and canceled, the impact test value and the SEM image of the fracture surface and the results appear in the same trend.

15 is an optical photograph of an epoxy composition prepared according to pure epoxy, Comparative Example 1, and Examples 1 to 4. FIG. According to this, it was confirmed that the hybrid prepolymer was blended with the epoxy and uniformly dispersed.

Table 3 below summarizes the results of pure epoxy, Comparative Example 1, and EDX (Energy Dispersive X-ray Spectroscopy) analysis according to Examples 1 to 4.

division Elemental analysis (%) C O S Si Pure epoxy 84.03 15.97 - - Comparative Example 1 80.68 19.31 - - Example 1 82.43 16.9 0.38 0.29 Example 2 84.19 15.61 0.1 0.1 Example 3 78.12 20.9 0.46 0.52 Example 4 82.12 17 0.46 0.42

According to this, it was confirmed that the ratio of each element of the epoxy compositions analyzed through EDX showed a tendency of the Si content of POSS as in the design of the Example.

In the above, embodiments of the present invention have been described, but those of ordinary skill in the relevant technical field add, change, delete or add components within the scope not departing from the spirit of the present invention described in the claims. It will be possible to variously modify and change the present invention by means of the like, and it will be said that this is also included within the scope of the present invention.

Claims (21)

It is represented by the following structural formula 1,
In the following structural formula 1

And

The organic functional group containing is a prepolymer forming an elastic region,
The prepolymer is a prepolymer for blending an epoxy resin, characterized in that it includes the purpose of improving the warpability;
[Structural Formula 1]

In structural formula 1,
R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,
l, m and p are the number of repetitions, and each independently an integer selected from 0 to 10,
n and q are the number of repetitions, and each independently an integer selected from 5 to 50. The method of claim 1,
In the above structural formula 1,
R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,
l, m and p are repeating numbers, and each independently an integer selected from 0 to 3,
n and q are repeating numbers, and each independently an integer selected from 10 to 15. Prepolymer for epoxy resin blends. delete The method of claim 1,
The prepolymer for the epoxy resin blend is a prepolymer for an epoxy resin blend, characterized in that in a semi-cured state. Epoxy resin; And a prepolymer for blending an epoxy resin represented by the following Structural Formula 1;
In the following structural formula 1

And

The organic functional group comprising a form an elastic region,
The prepolymer is a hybrid epoxy resin composition, characterized in that it includes the purpose of improving the warpability;
[Structural Formula 1]

In structural formula 1,
R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,
l, m and p are the number of repetitions, and each independently an integer selected from 0 to 10,
n and q are the number of repetitions, and each independently an integer selected from 5 to 50. The method of claim 5,
The hybrid epoxy resin composition,
A hybrid epoxy resin composition comprising: 3 to 15 parts by weight of a prepolymer for blending an epoxy resin represented by Structural Formula 1, based on 100 parts by weight of the epoxy resin. The method of claim 5,
The hybrid epoxy resin composition,
Hybrid epoxy resin composition, characterized in that it further comprises 20 to 35 parts by weight of a curing agent based on 100 parts by weight of the epoxy resin. The method of claim 5,
The prepolymer represented by the structural formula 1 is a hybrid epoxy resin composition, characterized in that blended with the epoxy resin in an interpenetrating polymer network (Interpenetrating Polymer Network) type. (a) preparing a mixed solution by dissolving POSS-SH, PEGDMA (Poly(ethylene glycol) dimethacrylate), and a photocatalyst represented by the following Structural Formula 2 in an organic solvent; And
(b) reacting thiol-ene by irradiating ultraviolet rays to the mixed solution to prepare a prepolymer represented by the following structural formula 1; including,
The PEGDMA (poly(ethylene glycol) dimethacrylate) forms an elastic region,
The prepolymer is a method of producing a prepolymer for blending an epoxy resin, characterized in that it includes the purpose of improving the warpability;
[Structural Formula 1]

In structural formula 1,
R ¹ to R ⁸ are the same as or different from each other, and each independently

or

Or, or any two selected from ^{R 1} to R ^{8 are}

Is bonded to each of both ends of to form a fused ring, and R ¹ to R ⁸ are all at the same time

Not,
l, m and p are the number of repetitions, and each independently an integer selected from 0 to 10,
n and q are the number of repetitions, and each independently an integer selected from 5 to 50.
[Structural Formula 2]

In structural formula 2,
R ¹ to R ⁸ are each independently

ego,
l is the number of repetitions, and each independently an integer selected from 0 to 10. The method of claim 9,
In the above structural formula 2,
l is a method for producing a prepolymer for blending an epoxy resin, characterized in that 0 to 3. The method of claim 9,
The mixed solution comprises 4 to 8 mole parts of PEGDMA and 0.05 to 1 mole part of a photocatalyst, based on 1 mole part of POSS-SH. The method of claim 9,
The photocatalyst is any one selected from DMPA (2,2-dimethoxy-2-phenylacetophenone), BP (benzophenone), and TMDPO ((2,4,6-trimethylbenzoyl) diphenylphosphine oxide). Method of manufacturing. The method of claim 9,
The organic solvent is any one selected from dichloromethane, tetrahydrofuran (THF), ethanol, methanol, acetone, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and dioxane. Method for producing a prepolymer for use. The method of claim 9,
The ultraviolet (UV) irradiation is a method for producing a prepolymer for an epoxy resin blend, characterized in that performed for 40 to 50 seconds at an intensity ^{of 1 to 20 mW / cm 2.} The method of claim 9,
The ultraviolet irradiation is a method of producing a prepolymer for an epoxy resin blend, characterized in that the prepolymer to be produced is stopped when the viscosity is the highest before becoming a solid. (1) mixing an epoxy resin and a curing agent;
(2) preparing an epoxy mixture by adding and stirring the prepolymer for an epoxy resin blend prepared according to any one of items 9 to 15 in the resultant of step (1);
(3) removing air bubbles from the epoxy mixture; And
(4) Curing the epoxy mixture from which air bubbles have been removed; a method for producing a hybrid epoxy composition comprising. The method of claim 16,
In step (1), the mixing of the epoxy resin and the curing agent is a method for producing a hybrid epoxy composition, characterized in that stirring at 60 to 80 ℃. The method of claim 16,
In step (1), with respect to 100 parts by weight of the epoxy resin, a method for producing a hybrid epoxy composition, characterized in that mixing 20 to 35 parts by weight of a curing agent. The method of claim 16,
The method of manufacturing a hybrid epoxy composition, wherein the curing agent is any one selected from diphenyldiaminomethane (DDM), metaphenyldiamine (MPDA), and diaminodiphenylsulfone (DDS). The method of claim 16,
In step (2), based on 100 parts by weight of the epoxy resin, 3 to 15 parts by weight of the prepolymer for blending the epoxy resin; a method for producing a hybrid epoxy composition, characterized in that using. The method of claim 16,
The method of producing a hybrid epoxy composition, characterized in that the curing of step (4) is carried out in two steps of precuring at 70 to 90°C and then post-curing at 140 to 160°C.

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