KR101094873B1 - Siloxane compound comprising cinnamoyl group and method for preparing the same - Google Patents

Abstract

PURPOSE: A siloxane compound containing cinnamoyl groups and a method for preparing the same are provided to ensure excellent fluent flow, chemical tolerance, and water resistance. CONSTITUTION: A siloxane compound is denoted by one of chemical formulas 2-4. The siloxane compound is prepared by reacting a cinnamoyl-containing compound of chemical formula 5(Ar-CH=CH-CO-R) with a siloxane compound of chemical formula 6 under the presence of a catalyst such an amine or acid compound. A method for preparing crosslinked polymer comprises a step of irradiating light to the siloxaen compound and crosslinking. A protection coating composition contains the crosslinked polymers.

Description

Siloxane compound containing cinnamoyl group and method for preparing the same}

The present invention relates to a siloxane compound containing a cinnamoyl group which can be cured by light as a photocurable curable material applicable to a capsule-type self-healing material, and a manufacturing method thereof.

In the study of conventional polymer materials, the focus has been on giving excellent performance and keeping the performance for a long time. Examples of the performance of such polymers include mechanical properties, rust resistance, heat resistance, and bacteria resistance. That is, the conventional materials do not actively react to external stimuli, and the process of deterioration is continuously performed. For example, if repeated stress is applied to a polymer material, the material is irreversibly damaged by the generation and propagation of cracks. This damage causes a fatal mechanical property deterioration in the structural polymer material and a loss of the protective function in the polymer material for the protective coating. If you give a polymer material a self-healing function to recognize it when a crack has occurred and heal it yourself, or if it can be transferred to a state that can be easily healed by very simple external manipulation, it will be a major breakthrough in the material field. will be. In other words, if the self-healing function is given to the material, the lifespan of the material will be greatly increased, and thus it can be used semi-permanently. In addition, it is possible to heal the damage of the material progressed by crack generation and propagation at the early stage of crack generation, so the development of self-healing material is very important from the viewpoint of safety. Accordingly, interest in self-healing of polymers has recently increased, and various materials have been reported ( Progress in Polymer Science 2008, 33, 479).

One of the typical healing methods for self-healing polymers reported to date is that microencapsulation of the healing material and dispersing it inside the material causes the capsule to break and break the capsule present at the position where the healing material flows. It is a way to heal cracks by penetrating them and causing them to polymerize (Nature 2001, 409, 794).

On the other hand, a method of curing cracks by light irradiation has also been reported ( Chemistry of Materials 2004, 16, 3982; Journal of Nanoscience and Nanotechnology 2010, 10, 1). In this method, an aliphatic compound having a cinnamoyl group was used. Cinnamoyl groups readily undergo a [2 + 2] photoaddition cyclization reaction to form a cyclobutane ring to generate a dimer structure. Therefore, a compound having three or more cinnamoyl groups is cured while forming a crosslinked structure by a [2 + 2] photoaddition cyclization reaction. If such a photocurable healing material is encapsulated and applied as a self-healing material, self-healing by sunlight is considered to be very useful. However, since the cinnamoyl group-containing aliphatic compound reported in the above paper is semisolid or solid at room temperature, there is a problem that it is difficult to apply to a capsule self-healing method. In other words, the capsule in the position where the crack is propagated should be broken and the healing material should flow out. However, since the cinnamoyl group-containing aliphatic compound is semi-solid or solid with no flowability, it is difficult to flow out, and thus it is difficult to apply to the capsule-type self-healing material.

It is an object of the present invention to provide a novel cinnamoyl group-containing siloxane compound which is liquid and photocurable as a photocurable curable material that can be applied to a capsule-type self-healing material, and a manufacturing method thereof.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1):

[Formula 1]

Where

R ₁ represents C _1-4 alkyl, C _6-12 aryl or —R ₉ N (R ₁₀ R ₁₁ ) ₂ ,

Wherein R ₉ and R ₁₀ each independently represent C _1-4 alkylene,

R ₁₁ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar is represented,

R ₂ and R ₃ each independently represent C _1-4 alkyl or —O—SiR ₁₂ R ₁₃ R ₁₄ ,

Wherein R ₁₂ and R ₁₃ each independently represent C _1-4 alkyl,

R ₁₄ represents -R ₁₅ -OR ₁₆ -R ₁₇ ,

Wherein R ₁₅ and R ₁₆ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₁₇ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar,

R ₄ and R ₅ each independently represent C _1-4 alkyl or —R ₁₈ R ₁₉ ,

Wherein R ₁₈ represents C _1-4 alkylene,

R ₁₉ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar is represented,

R ₆ and R ₇ each independently represent C _1-4 alkyl,

R ₈ represents C _1-4 alkyl, —R ₂₀ N (R ₂₁ R ₂₂ ) ₂ , or —R ₂₃ -OR ₂₄ -R ₂₅ ,

Wherein R ₂₀ and R ₂₁ each independently represent C _1-4 alkylene,

R ₂₂ is -OCO-CH = CH-Ar, -NHCO-CH = CH-Ar, -NH (CH ₂ ) _p NHCO-CH = CH-Ar, -O (CH ₂ CH ₂ O) _q CO-CH = CH-Ar is represented,

R ₂₃ and R ₂₄ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₂₅ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar is represented,

Ar is C _1-4 alkyl unsubstituted or substituted with halogen, C _1-4 alkoxy, hydroxy, diC _1-4 alkylamino, halogen, nitro and C _1-4 alkylene unsubstituted or substituted with halogen A phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of dioxy groups,

m represents an integer of 1 to 200, n represents an integer of 0 to 20, p represents an integer of 1 to 4, q represents an integer of 1 to 100,

Have at least one -CH = CH-Ar in the structure.

In one embodiment, the compound of Formula 1 may be a compound represented by Formula 2:

[Formula 2]

Where

R ₁₉ is -OCO-CH = CH-Ar, -NHCO-CH = CH-Ar, -NHCH ₂ CH ₂ NHCO-CH = CH-Ar, -O (CH ₂ CH ₂ O) _q CO-CH = CH- Represents Ar,

Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups Indicates,

m represents an integer of 1 to 200, n represents an integer of 1 to 20, p represents an integer of 1 to 4, q represents an integer of 1 to 100.

In one embodiment, the compound of Formula 1 may be a compound represented by Formula 3:

(3)

Where

R ₁₁ and R ₂₂ represent -OCO-CH = CH-Ar,

Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups Indicates,

m represents the integer of 1-200.

In one embodiment, the compound of Formula 1 may be a compound represented by the following formula (4):

[Formula 4]

Where

R ₁₇ and R ₂₅ are —OCO—CH═CH—Ar,

Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups Indicates.

The present invention also provides a method for preparing a compound of Formula 1, comprising reacting a cinnamoyl group-containing compound represented by Formula 5 with a siloxane compound of Formula 6:

[Chemical Formula 5]

Ar-CH = CH-CO-R

[Formula 6]

In the above formula

R is halogen or hydroxy,

R ₃₁ represents C _1-4 alkyl, C _6-12 aryl or —R ₃₉ N (R ₄₀ R ₄₁ ) ₂ ,

Wherein R ₃₉ and R ₄₀ each independently represent C _1-4 alkylene,

R ₄₁ represents hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , O (CH ₂ CH ₂ O) _p H, or an epoxy group,

R ₃₂ and R ₃₃ each independently represent C _1-4 alkyl or —O—SiR ₄₂ R ₄₃ R ₄₄ ,

Wherein R ₄₂ and R ₄₃ each independently represent C _1-4 alkyl,

R ₄₄ represents -R ₄₅ -OR ₄₆ -R ₄₇ ,

Wherein R ₄₅ and R ₄₆ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₄₇ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,

R ₃₄ and R ₃₅ each independently represent C _1-4 alkyl or —R ₄₈ R ₄₉ ,

Wherein R ₄₈ represents C _1-4 alkylene,

R ₄₉ represents hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,

R ₃₆ and R ₃₇ each independently represent C _1-4 alkyl,

R ₃₈ represents C _1-4 alkyl, -R ₅₀ N (R ₅₁ R ₅₂ ) ₂ , or -R ₅₃ -OR ₅₄ -R ₅₅ ,

Wherein R ₅₀ and R ₅₁ each independently represent C _1-4 alkylene,

R ₅₂ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,

R ₅₃ and R ₅₄ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₅₅ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,

m represents an integer of 1 to 200, n represents an integer of 0 to 20, p represents an integer of 1 to 4, q represents an integer of 1 to 100.

The present invention also provides a polymer in which the compound of Formula 1 is crosslinked.

The present invention also provides a method for producing a crosslinked polymer comprising the step of crosslinking by irradiating light to the compound of formula (1).

The present invention also provides a protective coating composition comprising the polymer.

The invention also

Board; And

It provides a composite comprising the polymer coating layer formed on the substrate.

The invention also

Coating the compound of Formula 1 on a substrate; And

It provides a method for healing cracks comprising the step of crosslinking by irradiating the compound with light.

Since the cinnamoyl group-containing siloxane compound of the present invention is in a liquid state, it is excellent in flowability, can be encapsulated and used as a self-healing material, and has excellent chemical resistance, weather resistance, and water resistance, and thus can exhibit excellent properties after a curing reaction. . In addition, when the cinnamoyl group-containing siloxane compound is used as the photocurable protective coating itself, it can exhibit the above excellent properties.

EMBODIMENT OF THE INVENTION Hereinafter, the structure of this invention is demonstrated concretely.

The present invention relates to a compound represented by the following general formula (1):

[Formula 1]

Where

R ₁ represents C _1-4 alkyl, C _6-12 aryl or —R ₉ N (R ₁₀ R ₁₁ ) ₂ ,

Wherein R ₉ and R ₁₀ each independently represent C _1-4 alkylene,

R ₁₁ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar is represented,

R ₂ and R ₃ each independently represent C _1-4 alkyl or —O—SiR ₁₂ R ₁₃ R ₁₄ ,

Wherein R ₁₂ and R ₁₃ each independently represent C _1-4 alkyl,

R ₁₄ represents -R ₁₅ -OR ₁₆ -R ₁₇ ,

Wherein R ₁₅ and R ₁₆ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₁₇ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar,

R ₄ and R ₅ each independently represent C _1-4 alkyl or —R ₁₈ R ₁₉ ,

Wherein R ₁₈ represents C _1-4 alkylene,

R ₁₉ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar is represented,

R ₆ and R ₇ each independently represent C _1-4 alkyl,

R ₈ represents C _1-4 alkyl, —R ₂₀ N (R ₂₁ R ₂₂ ) ₂ , or —R ₂₃ -OR ₂₄ -R ₂₅ ,

Wherein R ₂₀ and R ₂₁ each independently represent C _1-4 alkylene,

R ₂₂ is -OCO-CH = CH-Ar, -NHCO-CH = CH-Ar, -NH (CH ₂ ) _p NHCO-CH = CH-Ar, -O (CH ₂ CH ₂ O) _q CO-CH = CH-Ar is represented,

R ₂₃ and R ₂₄ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₂₅ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar is represented,

Ar is C _1-4 alkyl unsubstituted or substituted with halogen, C _1-4 alkoxy, hydroxy, diC _1-4 alkylamino, halogen, nitro and C _1-4 alkylene unsubstituted or substituted with halogen A phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of dioxy groups,

m represents an integer of 1 to 200, n represents an integer of 0 to 20, p represents an integer of 1 to 4, q represents an integer of 1 to 100,

Have at least one -CH = CH-Ar in the structure.

The terms used in the substituent definitions of the compounds of the present invention are as follows.

"Halogen" is -F, -Cl, -Br or -I.

"Alkyl" refers to a straight or branched chain or cyclic saturated hydrocarbon having 1 to 4 carbon atoms unless otherwise stated. Examples of C _1-4 alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl and tert-butyl.

"Alkylene" is a divalent organic derived from said alkyl, with the preferred range of carbon atoms being the same as said alkyl.

"Aryl" refers to a 6 to 12-reduced aromatic cyclic compound unless otherwise stated. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl and anthracenyl.

Specifically, the compound of Formula 1,

R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent C _1-4 alkyl,

R ₄ represents -R ₁₈ R ₁₉ , wherein R ₁₈ represents C _1-4 alkylene,

R ₁₉ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar can be represented.

Compound of Formula 1 of the present invention may be a compound represented by the formula (2) more specifically:

[Formula 2]

Where

R ₁₉ is -OCO-CH = CH-Ar, -NHCO-CH = CH-Ar, -NHCH ₂ CH ₂ NHCO-CH = CH-Ar, -O (CH ₂ CH ₂ O) _q CO-CH = CH- Represents Ar,

Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups Indicates,

m represents an integer of 1 to 200, n represents an integer of 1 to 20, p represents an integer of 1 to 4, q represents an integer of 1 to 100.

The compound of Formula 2 may be more specifically a compound represented by Formula 2a:

(2a)

Where

m is an integer from 1 to 120,

n represents the integer of 1-15.

In addition, the compound of Formula 1 of the present invention is more specifically

R ₁ represents —R ₉ N (R ₁₀ R ₁₁ ) ₂ ,

Wherein R ₉ and R ₁₀ each independently represent C _1-4 alkylene,

R ₁₁ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar is represented,

R ₂ , R ₃ , R ₆ and R ₇ each independently represent C _1-4 alkyl,

R ₈ represents —R ₂₀ N (R ₂₁ R ₂₂ ) ₂ ,

Wherein R ₂₀ and R ₂₁ each independently represent C _1-4 alkylene,

R ₂₂ is -OCO-CH = CH-Ar, -NHCO-CH = CH-Ar, -NH (CH ₂ ) _p NHCO-CH = CH-Ar, -O (CH ₂ CH ₂ O) _q CO-CH = CH-Ar is represented,

n may be zero.

The compound of Formula 1 may be a compound represented by Formula 3 more specifically:

(3)

Where

R ₁₁ and R ₂₂ represent -OCO-CH = CH-Ar,

Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups Indicates,

m represents the integer of 1-200.

More specifically, the compound of Formula 3 may be a compound represented by the following Formula 3a:

[Chemical Formula 3]

Where

n represents the integer of 1-100.

In addition, the compound of Formula 1 of the present invention is more specifically

R ₁ represents C _6-12 aryl,

R ₂ and R ₃ each independently represent —O—SiR ₁₂ R ₁₃ R ₁₄ ,

Wherein R ₁₂ and R ₁₃ each independently represent C _1-4 alkyl,

R ₁₄ represents -R ₁₅ -OR ₁₆ -R ₁₇ ,

Wherein R ₁₅ and R ₁₆ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₁₇ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar,

R ₆ and R ₇ each independently represent C _1-4 alkyl,

R ₈ represents -R ₂₃ -OR ₂₄ -R ₂₅ ,

Wherein R ₂₃ and R ₂₄ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₂₅ is —OCO—CH═CH—Ar, —NHCO—CH═CH—Ar, —NH (CH ₂ ) _p NHCO—CH═CH—Ar, —O (CH ₂ CH ₂ O) _q CO—CH = CH-Ar,

n may be zero.

The compound of Formula 1 may be a compound represented by Formula 4 more specifically:

[Formula 4]

Where

R ₁₇ and R ₂₅ are —OCO—CH═CH—Ar,

Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups Indicates.

The compound of Formula 4 may be more specifically a compound represented by Formula 4a:

[Chemical Formula 4a]

The present invention also relates to a method for preparing a compound of Formula 1, comprising reacting a cinnamoyl group-containing compound represented by Formula 5 with a siloxane compound of Formula 6:

[Chemical Formula 5]

Ar-CH = CH-CO-R

[Formula 6]

Where

R is halogen or hydroxy,

R ₃₁ represents C _1-4 alkyl, C _6-12 aryl or —R ₃₉ N (R ₄₀ R ₄₁ ) ₂ ,

Wherein R ₃₉ and R ₄₀ each independently represent C _1-4 alkylene,

R ₄₁ represents hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , O (CH ₂ CH ₂ O) _p H, or an epoxy group,

R ₃₂ and R ₃₃ each independently represent C _1-4 alkyl or —O—SiR ₄₂ R ₄₃ R ₄₄ ,

Wherein R ₄₂ and R ₄₃ each independently represent C _1-4 alkyl,

R ₄₄ represents -R ₄₅ -OR ₄₆ -R ₄₇ ,

Wherein R ₄₅ and R ₄₆ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₄₇ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,

R ₃₄ and R ₃₅ each independently represent C _1-4 alkyl or —R ₄₈ R ₄₉ ,

Wherein R ₄₈ represents C _1-4 alkylene,

R ₄₉ represents hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,

R ₃₆ and R ₃₇ each independently represent C _1-4 alkyl,

R ₃₈ represents C _1-4 alkyl, -R ₅₀ N (R ₅₁ R ₅₂ ) ₂ , or -R ₅₃ -OR ₅₄ -R ₅₅ ,

Wherein R ₅₀ and R ₅₁ each independently represent C _1-4 alkylene,

R ₅₂ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,

R ₅₃ and R ₅₄ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,

R ₅₅ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,

m represents an integer of 1 to 200, n represents an integer of 0 to 20, p represents an integer of 1 to 4, q represents an integer of 1 to 100.

The compound of formula 1 of the present invention may be prepared by reacting a siloxane compound having a hydroxy, amino, epoxy group and the like with a cinnamoyl group-containing compound.

The siloxane compound of Formula 6 may preferably be any one of compounds represented by the following Formulas 7 to 9:

[Formula 7]

[Formula 8]

[Formula 9]

Where

R ₄₉ is —OH, —NH ₂ , —NHCH ₂ CH ₂ NH ₂ , or —O (CH ₂ CH ₂ O) _q H, wherein q represents an integer from 1 to 100,

m represents an integer of 1 to 200 and n represents an integer of 1 to 20.

The reaction between the siloxane compound and the cinnamoyl group containing compound may occur under a catalyst.

The catalyst may be an amine compound such as dimethylaminopyridine, pyridine, triethylamine or an acid compound such as sulfuric acid or para-toluenesulfonic acid.

In one embodiment, in the reaction of a cinnamoyl group-containing compound of Formula 5 with a compound of Formula 7 or 8, when R of Formula 5 is halogen, an amine compound may be used as a catalyst, and R is hydroxy. Acid compounds can be used as catalysts. Through the reaction, a compound of Chemical Formula 2 or 3 may be prepared.

In one embodiment, the reaction of the cinnamoyl group-containing compound of Formula 5 with the epoxy compound of Formula 9 may use an amine compound as a catalyst. Through the reaction, a compound of Chemical Formula 4 may be prepared.

In one embodiment, the compound of formula (2) or (3) can be prepared through the reaction can be obtained as a liquid having a low flow rate and excellent flow. In this case, the compound of Formula 2 or 3 can be used as a self-healing material by encapsulating itself.

In one embodiment, the compound of formula 4 is obtained in a gum state, so that it may be dissolved in an appropriate solvent and encapsulated.

Tetrahydrofuran, 1,4-dioxane, phenylacetate, chloroform, acetone, acetonitrile, dimethyl sulfoxide, N , N -dimethylformamide, methylene chloride, etc. may be used as the solvent. It is not limiting.

The present invention also relates to a polymer in which the compound of formula 1 is crosslinked.

The compound of Formula 1 may be cured by light to form a crosslinked polymer by [2 + 2] photodimerization of cinnamoyl group.

The present invention also relates to a method for producing a crosslinked polymer comprising the step of crosslinking by irradiating the compound of formula (1) with light.

When irradiated with a light irradiator equipped with a xenon lamp to the compound of Formula 1 and analyzed by infrared spectroscopy, cross-linking polymerization by the [2 + 2] photodimerization reaction of cinnamoyl group may proceed.

In one embodiment, the conversion rate of the photodimerization reaction was analyzed by infrared spectroscopy, resulting in about 70% conversion by 8 hours of light irradiation.

The present invention also relates to a protective coating composition comprising the polymer.

Since the compound containing the cinnamoyl group of the present invention is liquid at room temperature, it has excellent flowability, can be encapsulated and used as a self-healing material, and exhibits excellent properties such as chemical resistance, weather resistance, and water resistance, and thus a photocurable protective coating agent. Can be used as

In one embodiment, the compound of Formula 2 or 3 is low in viscosity can be obtained as a liquid having excellent flowability. In this case, the compound of Formula 2 or 3 can be used as a self-healing material by encapsulating itself.

In one embodiment, the compound of formula 4 is obtained in a gum state, so that it may be dissolved in an appropriate solvent and encapsulated.

The invention also

Board; And

It relates to a composite comprising the polymer coating layer formed on the substrate.

The composite of the present invention can be produced by forming a coating layer of a crosslinked polymer by applying a cinnamoyl group-containing compound of the present invention onto a substrate and irradiating with light.

The coating layer is capable of self-healing by sunlight or the like against irreversible damage caused by cracking and propagation when repeated stress is applied.

The invention also

Coating the compound of Formula 1 on a substrate; And

It relates to a method of healing cracks comprising the step of crosslinking by irradiating the compound with light.

Since the cinnamoyl group-containing compound of the present invention exists as a liquid at room temperature, it has excellent flowability and is coated on a substrate in the form of a capsule to break the capsule at a position where cracks propagate, and a healing substance flows out to heal the crack.

Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention, but the scope of the present invention is not limited by the following Examples.

Example 1 Preparation of a Compound of Formula 2a

Cinnamoyl chloride (0.250 g, 1.5 mmol), triethylamine (0.152 g, 1.5 mmol), a compound of formula 7 (R ₄₉ = -NH ₂ , 4.50 g), tetrahydrofuran (60 mL) in a two-necked round bottom flask After dissolving, the mixture was stirred for 24 hours. Tetrahydrofuran was removed under reduced pressure, then the residue was dissolved in methylene chloride and the solution was washed with 0.5M aqueous NaOH solution and saturated brine. Magnesium sulfate was added to remove water, and methylene chloride was removed under reduced pressure to obtain a compound of formula 2a in a liquid state.

¹ H NMR (CDCl ₃ , 400 MHz): δ (ppm) 0.03 (s), 0.05 (s), 0.54 (t), 1.64 (quintet), 3.35 (q), 5.65 (s), 6.35 (d), 7.33 -7.35 (m), 7.47-7.50 (m), 7.60 (d).

Example 2 Preparation of a Compound of Formula 3a

Cinnamoyl chloride (0.584 g, 3.4 mmol), compound of formula 8 (2.550 g), 4-dimethylaminopyridine (0.421 g, 3.4 mmol), and tetrahydrofuran (60 mL) were dissolved in a two-neck round bottom flask. It was then refluxed for 20 hours. Tetrahydrofuran was removed under reduced pressure, then the residue was dissolved in methylene chloride and the solution was washed with 0.5M aqueous NaOH solution and saturated brine. Magnesium sulfate was added to remove water, and then methylene chloride was removed under reduced pressure to obtain 2.628 g of a compound of Chemical Formula 3a in a liquid state.

¹ H NMR (CDCl ₃ , 400 MHz): δ (ppm) 0.03 (s) 0.05 (s), 0.49 (t), 1.48 (m), 2.58 (t), 2.88 (t), 4.28 (t), 6.42 ( d), 7.24-7.36 (m), 7.46-7.50 (m), 7.65 (d).

Example 3 Preparation of a Compound of Formula 4a

Cinnamic acid (1.856g, 12mmol), 4-dimethylaminopyridine (1.148g, 12mmol), compound of formula 9 (1.913g, 27mmol) and tetrahydrofuran (60mL) were dissolved in a two-neck round bottom flask. It was refluxed for 6 hours. Tetrahydrofuran was removed under reduced pressure, then the residue was dissolved in methylene chloride and the solution was washed with 0.5M NaOH aqueous solution and 0.5M HCl aqueous solution. Magnesium sulfate was added to remove water, and then methylene chloride was removed under reduced pressure to obtain 2.413 g of a compound of formula 4a in a gum state.

¹ H NMR (CDCl ₃ , 400 MHz): δ (ppm) 0.02-0.09 (m), 0.46-0.51 (m), 1.57 (quintet), 3.10-3.14 (m), 3.39-3.45 (m), 3.46-3.57 (m), 4.05-4.10 (m), 4.20-4.33 (m), 6.56 (d), 7.25-7.36 (m), 7.45-7.49 (m), 7.68 (d).

Example 4 Photocrosslinking Polymerization of Compounds of Formulas 2a to 4a

The compound of formula 2a, 3a, or 4a was applied onto the KBr substrate, and cross-polymerized using a light irradiator equipped with a xenon lamp. As a result, a transparent film showing rubber elasticity and adhesiveness was obtained.

Polymerization conversion was measured by transmission using an infrared absorption spectrometer, and the area reduction of the absorption band (1637 cm ^-1 ) of the carbon-carbon double bond was measured based on the area of the absorption band (1734 cm ^-1 ) due to carbonyl. Calculated by The equation used for this calculation is:

% Conversion = (1- (C = C absorption band area / C = O absorption band area) _{after exposure} / (C = C absorption band area / C = O absorption band area) _{before exposure} } × 100

As a result of the measurement, the compounds of Formulas 2a, 3a and 4a showed 71%, 68% and 70% conversion, respectively, by 8 hours of light irradiation.

Claims (20)

The siloxane compound represented by any one of the following Chemical Formulas 2 to 4:
(2)

(3)

[Chemical Formula 4]

Where
R ₁₁ , R ₁₇ , R ₁₉ , R ₂₂ and R ₂₅ are each independently -OCO-CH = CH-Ar, -NHCO-CH = CH-Ar, -NH (CH ₂ ) _p NHCO-CH = CH-Ar Or -O (CH ₂ CH ₂ O) _q CO-CH = CH-Ar,
Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups Indicates,
m represents an integer of 1 to 200, n represents an integer of 1 to 20, p represents an integer of 1 to 4, q represents an integer of 1 to 100.
delete delete The method of claim 1
Compound of Formula 2 is a compound represented by Formula 2a:
(2a)

Where
m is an integer from 1 to 120,
n represents the integer of 1-15.
delete The method of claim 1,
Compound of Formula 3 is a compound wherein R ₁₁ and R ₂₂ represent -OCO-CH = CH-Ar,
Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups Indicates,
m is a compound which shows the integer of 1-200.
The method of claim 6,
A compound of formula 3 is a compound represented by formula 3a:
[Chemical Formula 3]

Where
n represents the integer of 1-100.
delete The method of claim 1,
Compound ₁₇ is R ₁₇ and R ₂₅ is -OCO-CH = CH-Ar,
Wherein Ar is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of methoxy, methyl, hydroxy, dimethylamino, trifluoromethyl, fluoro, chloro, bromo, nitro and methylenedioxy groups The compound which is a compound which shows.
10. The method of claim 9,
A compound of formula 4 is a compound represented by formula 4a:
[Formula 4a]

A method for preparing the siloxane compound of claim 1 comprising reacting a cinnamoyl group-containing compound represented by Formula 5 with a siloxane compound of Formula 6:
[Chemical Formula 5]
Ar-CH = CH-CO-R

[Formula 6]

Where
R is halogen or hydroxy,
R ₃₁ represents C _1-4 alkyl, C _6-12 aryl or —R ₃₉ N (R ₄₀ R ₄₁ ) ₂ ,
Wherein R ₃₉ and R ₄₀ each independently represent C _1-4 alkylene,
R ₄₁ represents hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , O (CH ₂ CH ₂ O) _p H, or an epoxy group,
R ₃₂ and R ₃₃ each independently represent C _1-4 alkyl or —O—SiR ₄₂ R ₄₃ R ₄₄ ,
Wherein R ₄₂ and R ₄₃ each independently represent C _1-4 alkyl,
R ₄₄ represents -R ₄₅ -OR ₄₆ -R ₄₇ ,
Wherein R ₄₅ and R ₄₆ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,
R ₄₇ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,
R ₃₄ and R ₃₅ each independently represent C _1-4 alkyl or —R ₄₈ R ₄₉ ,
Wherein R ₄₈ represents C _1-4 alkylene,
R ₄₉ represents hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,
R ₃₆ and R ₃₇ each independently represent C _1-4 alkyl,
R ₃₈ represents C _1-4 alkyl, -R ₅₀ N (R ₅₁ R ₅₂ ) ₂ , or -R ₅₃ -OR ₅₄ -R ₅₅ ,
Wherein R ₅₀ and R ₅₁ each independently represent C _1-4 alkylene,
R ₅₂ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,
R ₅₃ and R ₅₄ each independently represent C _1-4 alkylene unsubstituted or substituted with hydroxy,
R ₅₅ represents a hydroxy, amino, —NH (CH ₂ ) _p NH ₂ , —O (CH ₂ CH ₂ O) _q H, or an epoxy group,
m represents an integer of 1 to 200, n represents an integer of 0 to 20, p represents an integer of 1 to 4, q represents an integer of 1 to 100.
The method of claim 11,
A method for preparing a siloxane compound, wherein the siloxane compound of Formula 6 is any one of the compounds represented by Formulas 7 to 9 below:
[Formula 7]

[Chemical Formula 8]

[Formula 9]

Where
R ₄₉ is —OH, —NH ₂ , —NHCH ₂ CH ₂ NH ₂ , or —O (CH ₂ CH ₂ O) _q H, wherein q represents an integer from 1 to 100,
m represents an integer of 1 to 200 and n represents an integer of 1 to 20.
The method of claim 11,
The reaction is carried out under a catalyst.
The method of claim 13,
The catalyst is a method for producing a siloxane compound is an amine compound or an acid compound.
The method of claim 14,
The catalyst is a method for producing a siloxane compound, which is any one of dimethylaminopyridine, pyridine, triethylamine, sulfuric acid, or para-toluenesulfonic acid.
A polymer wherein the compound of claim 1 is crosslinked.
A method for producing a crosslinked polymer, comprising the step of crosslinking by irradiating the compound of claim 1 with light.
A protective coating composition comprising the polymer of claim 16.
Board; And
A composite comprising the polymer coating layer of claim 16 formed on said substrate.
Coating the compound of claim 1 on a substrate; And
Irradiating the compound with light to crosslink it.