KR102492005B1 - An additive comprising compound having Si-O bond and a composition for preparing silicon polymer comprising the same - Google Patents

Abstract

The present invention relates to an additive including a compound having a Si-O bond and a composition for synthesizing a silicone polymer including the same.

Description

An additive comprising compound having Si-O bond and a composition for preparing silicon polymer comprising the same}

The present invention relates to an additive including a compound having a Si-O bond and a composition for synthesizing a silicone polymer including the additive.

When a Si-N bond exists in a silicon compound under acid conditions, the stability of the Si-N bond is very low. The reason is that the acid catalyzes breaking the Si-N bond. Naturally, the lower the pH, the lower the stability of Si-N, and the closer the pH is to 0, the closer the stability becomes to 0. Therefore, when synthesizing a silicone polymer or monomer under acidic conditions, the Si-N bond in the silicone compound is too It is easily broken, resulting in a significantly lower yield of the silicon compound, and also a disadvantage in that the purification of the target compound is very difficult due to the generation of side-products.

A structure containing Si-O corresponds to a structure generally included in silicone oil, but conventional silicone oil has been used as an additive for adjusting the formulation of cosmetics, such as Korean Publication No. 10-2014-0062696. , Furthermore, it plays a very important role in various fields such as newborn children and children's products, robot skins that are currently heavily invested, and eco-friendly biodegradable drugs. Despite such an important role, currently there is no active research on the use of silicone polymers or additives for stabilizing specific bonding structures during polymer synthesis and additives for protecting monomers having specific bonding structures, and there is a great need. There are still many research areas to be solved in reality.

Accordingly, the present applicant has devised the present invention to solve the above problems.

Republic of Korea Publication No. 10-2014-0062696

An object of the present invention is to provide an additive for remarkably improving the stability of the nitrogen-silicon bond when synthesizing a silicone polymer having a nitrogen-silicon bond, and a composition for synthesizing a silicone polymer including the same.

The present invention provides an additive containing at least one of the compounds represented by Formulas 1 and 2 below, and a composition for synthesizing a silicone polymer including the same.

[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently an alkyl group; a cycloalkyl group; an alkoxy group; an alkyl ketone group; an alkylamine group; an alkyl hydroxide group; an alkyl ether group; an alkyl sulfate group; an alkyl phosphate group ; An alkylamide group or an alkyl sulfide group,

X ₁ and X ₂ are, each independently, a halogen atom; hydrogen atom; A hydroxyl group; an amine group; or an alkoxy group,

Y ₁ to Y ₄ are each independently a halogen atom; hydrogen atom; hydroxy group; It is an alkoxy group or an amine group.)

[Formula 2]

(In Formula 2 above,

R ₃ and R ₄ are, each independently, an alkylene group,

R ₅ and R ₆ are each independently an alkyl group; cycloalkyl group; alkoxy group; Alkyl carboxy group; Alkyl ketone group; Alkylamine group; Alkyl hydroxide group; Alkyl ether group; Alkyl sulfate group; Alkyl phosphate group; an alkylamide group or an alkyl sulfide;

X ₃ and X ₄ are, each independently, a halogen atom; hydrogen atom; hydroxy group; alkoxy group or amine group

Y ₅ to Y ₈ are each independently a halogen atom; hydrogen atom; hydroxy group; It is an alkoxy group or an amine group.)

In addition, the present invention is the above-mentioned additive; and a monomer having a nitrogen-silicon bond in its molecular structure. A composition for synthesizing a silicone polymer having a nitrogen-silicon bond in its molecular structure.

An object of the present invention is to provide an additive capable of effectively protecting nitrogen-silicon bonds (Si-N), which are difficult to maintain in acid conditions.

In addition, the present invention can effectively protect the monomer having a nitrogen-silicon bond, which is the basis of synthesis, under acid conditions by providing the additive, and can also provide an effect that can protect the polymer and monomer structure synthesized after synthesis. .

In addition, the composition for synthesizing silicone polymers containing the additives of the present invention protects the nitrogen-silicon bonds in the monomers to be synthesized under acidic conditions, thereby providing an effect capable of synthesizing the target polymer to be synthesized with significantly improved yield. .

In describing the embodiments disclosed in this specification, if it is determined that detailed descriptions of related known technologies may obscure the gist of the embodiments disclosed in this specification, the detailed descriptions thereof will be omitted. In addition, the accompanying drawings are only for easy understanding of the embodiments disclosed in this specification, the technical idea disclosed in this specification is not limited by the accompanying drawings, and all changes included in the spirit and technical scope of the present invention , it should be understood to include equivalents or substitutes.

Singular expressions include plural expressions unless the context clearly dictates otherwise.

In the present invention, the term "comprises" or "has" is intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

The present invention provides an additive containing at least one of the compounds represented by Formula 1 and Formula 2 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an alkyl group; cycloalkyl group; alkoxy group; Alkyl carboxy group; Alkyl ketone group; Alkylamine group; Alkyl hydroxide group; Alkyl ether group; Alkyl sulfate group; Alkyl phosphate group; An alkylamide group or an alkyl sulfide group,

X ₁ and X ₂ are, each independently, a halogen atom; hydrogen atom; hydroxy group; an alkoxy group or an amine group,

Y ₁ to Y ₄ are each independently a halogen atom; hydrogen atom; hydroxy group; It is an alkoxy group or an amine group.

More specifically, R ₁ and R ₂ in Formula 1 are each independently a C ₁ to C ₂₀ alkyl group; a C ₃ to C ₂₀ cycloalkyl group; A C ₁ to C ₂₀ alkoxy group; C ₁ to C ₂₀ Alkyl carboxy group; A C ₁ to C ₂₀ alkyl ketone group; A C ₁ to C ₂₀ alkylamine group; C ₁ to C ₂₀ Alkyl hydroxide group; C ₁ to C ₂₀ Alkyl sulfate group; A C ₁ to C ₂₀ alkyl phosphate group; a C ₁ to C ₂₀ alkylamide group; Or a C ₁ to C ₂₀ alkyl sulfide group, and

X ₁ and X ₂ are each independently fluorine; Goat; bromine; iodine; hydrogen atom; a hydroxy group or a C ₁ to C ₂₀ alkoxy group or an amine group;

Y ₁ to Y ₄ are each independently fluorine; Goat; bromine; iodine; hydrogen atom; hydroxy group; It may be a C ₁ to C ₂₀ alkoxy group or an amine group,

The amine group is -NH ₂ -; -NHR ₇ or -NR ₈ R ₉ It may be one selected from the formula shown _.

In -NHR ₇ in the formula representing the amine group, R ₇ is a C ₁ to C ₂₀ alkyl group; a C ₃ to C ₂₀ cycloalkyl group; A C ₁ to C ₂₀ alkoxy group; C ₁ to C ₂₀ carboxy group; A C ₁ to C ₂₀ alkyl ketone group; A C ₁ to C ₂₀ alkylamine group; C ₁ To C ₂₀ Alkyl hydroxide group; C ₁ To C ₂₀ Alkyl ether group; C ₁ to C ₂₀ Alkyl sulfate group; A C ₁ to C ₂₀ alkyl phosphate group; A C ₁ to C ₂₀ alkylamide group; A C ₁ to C ₂₀ alkylamide group or a C ₁ to C ₂₀ alkyl sulfide group;

In the formula representing the amine group _- NR ₈ R ₉ , R ₈ or R ₉ are each independently a C ₁ to C ₂₀ alkyl group; a C ₃ to C ₂₀ cycloalkyl group; A C ₁ to C ₂₀ alkoxy group; C ₁ to C ₂₀ carboxy group; A C ₁ to C ₂₀ alkyl ketone group; A C ₁ to C ₂₀ alkylamine group; C ₁ To C ₂₀ Alkyl hydroxide group; C ₁ To C ₂₀ Alkyl ether group; C ₁ to C ₂₀ Alkyl sulfate group; A C ₁ to C ₂₀ alkyl phosphate group; A C ₁ to C ₂₀ alkylamide group; A C ₁ to C ₂₀ alkylamide group or a C ₁ to C ₂₀ alkyl sulfide group.

In the present invention, it may be more preferable that Formula 1 has a structure of Formula 3 and/or Formula 4 below.

[Formula 3]

[Formula 4]

[Formula 2]

In Formula 2, R ₃ and R ₄ are each independently an alkylene group,

R ₅ and R ₆ are each independently an alkyl group; cycloalkyl group; alkoxy group; Alkyl carboxy group; Alkyl ketone group; Alkylamine group; Alkyl hydroxide group; Alkyl ether group; Alkyl sulfate group; Alkyl phosphate group; an alkylamide group or an alkyl sulfide;

X ₃ and X ₄ are each independently a halogen atom; hydrogen atom; hydroxy group; an alkoxy group or an amine group;

Y ₅ to Y ₈ are each independently a halogen atom; hydrogen atom; hydroxy group; It is an alkoxy group or an amine group.

More specifically, R ₃ and R ₄ in Formula 2 are each independently a C ₁ to C ₂₀ alkylene group, and R ₅ and R ₆ are each independently a C ₁ to C ₂₀ alkyl group; A C ₃ to C ₂₀ cycloalkyl group; A C ₁ to C ₂₀ alkoxy group; C ₁ to C ₂₀ Alkyl carboxyl group; A C ₁ to C ₂₀ alkyl ketone group; A C ₁ to C ₂₀ alkylamine group; C ₁ to C ₂₀ Alkyl sulfate group; A C ₁ to C ₂₀ alkyl phosphate group; A C ₁ to C ₂₀ alkylamide group or a C ₁ to C ₂₀ alkyl sulfide group, and X ₃ and X ₄ are, each independently, Fluorine; Chlorine; Bromine; Iodine; Hydrogen atom; A hydroxy group or a C ₁ to C ₂₀ alkoxy group, Y ₅ to Y ₈ are, each independently, Fluorine; Chlorine; Bromine; Iodine; Hydrogen atom; It may be a hydroxy group or a C ₁ to C ₂₀ alkoxy group.

In the present invention, Formula 2 may more preferably include one or more of the compounds having structures represented by Formulas 5 to 7 below.

[Formula 5]

[Formula 6]

[Formula 7]

The additives of the present invention are characterized in that they are for increasing the stability of nitrogen-silicon bonds in molecules of silicone compounds and/or polymers or monomers under acidic conditions.

Specifically, when an additive having the chemical structure of the present invention is added under acid conditions, the additive wraps the Si-N bond by dipole-dipole and van der Waals forces. When the additive covers the Si-N structure, the acid attack is reduced and it is induced to be stably in the acid.

In the present invention, the acid condition may mean less than pH 7. The acid condition may be included without limitation as long as the acid forms a pH of less than 7, but more specifically, acetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, nitric acid, nitrous acid, formic acid, hydrochloric acid, boric acid, acid having a carboxyl group, and It may be desirable to include one or more acids selected from hydrofluoric acid.

In the present invention, the acid having the carboxyl group is acetic acid (carboxylic acid); It may be at least one selected from oxalic acid and benzoic acid.

The additive of the present invention is characterized by maintaining 63% or more of the silicon-nitrogen bond in the molecule of the silicon compound under acid conditions.

In the present invention, the additive may be included from 50 ppm to 500000 ppm. When included below the above range, the efficacy is insignificant and there is no effect, and when it is included above the above range, it is not economical in terms of efficiency as it is included beyond the range that can produce the effect to be achieved.

In addition, the present invention is one or more additives selected from the compounds represented by the above formula (1) and formula (2); and a monomer having a nitrogen-silicon bond in its molecular structure.

In the present invention, the monomer having a nitrogen-silicon bond in the molecular structure may be one or more monomers selected from compounds represented by Chemical Formulas 8 to 11.

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

The composition for synthesizing a silicone polymer having a nitrogen-silicon bond in the molecular structure of the present invention may further contain an acid.

The composition for synthesizing a silicone polymer having a nitrogen-silicon bond in the molecular structure of the present invention is characterized by maintaining 63% or more of the silicon-nitrogen bond in the molecule of the silicone compound.

Preparation of Examples and Comparative Examples

Preparation of Comparative Example 1 : 10 g of a compound having the following structure of Formula 8 was added to a 10% nitric acid solution (Nitric acid 10% by volume) without an additive providing stability to nitrogen-silicon under acid conditions, and mixed at room temperature ( Room temp.) and left for 12 hours to check the decomposition of nitrogen-silicon bonds in the compound by time. The results are shown in Table 2.

Preparation of Examples 1 to 5 : The experiment was conducted in the same manner as in Comparative Example 1, except that the conditions and compounds in Table 1 were used, and it was confirmed whether nitrogen-silicon bonds were decomposed in the compound over time. The results are listed in Table 2.

mountain conditions silicone compound additive Example 1 Trifluoroacetic acid 10% by volume 100000 ppm of the compound of [Formula 9] 150000 ppm of the compound of [Formula 3] Example 2 Nitric Acid 10% by volume 100000 ppm of the compound of [Formula 8] 50000 ppm of the compound of [Formula 3] Example 3 Sulfuric Acid 5% by volume 100000 ppm of the compound of [Formula 10]
30000 ppm of the compound of [Formula 5] Example 4 Acetic acid 20% by volume 200000 ppm of the compound of [Formula 11] 100000 ppm of the compound of [Formula 6] Example 5 Formic Acid 30% by volume 100000 ppm of the compound of [Formula 8] 50000 ppm of the compound of [Formula 7] Example 6 Phosphoric Acid 85% by volume 200000 ppm of the compound of [Formula 11] 50000 ppm of the compound of [Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

Experimental Example 1: Determining the possibility of maintaining the stability of nitrogen-silicon bonds in molecules of silicon compounds under acidic conditions (pH < 7)

Using gas chromatography, the decomposition of Si—N bonds per hour in the compounds of Examples 1 to 6 and Comparative Example 1 was measured, and the results are shown in Table 2.

0h 1h 4h 8h 12h Comparative Example 1 100% 30% 10% 3% < 1% Example 1 100% 99% 97% 95% 94% Example 2 100% 98% 90% 85% 81% Example 3 100% 95% 85% 76% 68% Example 4 100% 99% 98% 96% 94% Example 5 100% 97% 85% 81% 75% Example 6 100% 98% 95% 93% 91%

As a result of the experiment, in the case of Comparative Example 1, which does not contain the additive having the structure of the present invention, the Si-N bond in the silicon compound having a Si-N bond is decomposed by more than 70% after 1 hour, and only 30% of the included compounds The Si-N bond was maintained, and it was confirmed that the Si-N bond in the compound was almost decomposed after 12 hours. On the other hand, in the case of Examples 1 to 6 including the additive of the present invention, it was confirmed that the Si-N bond in the silicon compound was hardly decomposed within 1 hour, and even after 12 hours, 63% of the included compound It was confirmed that the abnormality existed without disassembly of the Si-N bond. In particular, it was confirmed that the cases of Examples 1, 4 and 6 had remarkably excellent effects even after 12 hours or more.

Claims (9)

Including one or more of the compounds represented by the following formula (1) and formula (2),
Chemical Formula 2 includes at least one compound having a structure represented by Chemical Formulas 5 to 7 below.
[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently an alkyl group; a cycloalkyl group; an alkoxy group; an alkyl carboxy group; an alkyl ketone group; an alkyl amine group; an alkyl hydroxide group; an alkyl ether group; an alkyl sulfate group An alkyl phosphate group; An alkyl amide group or an alkyl sulfide group;
X ₁ and X ₂ are, each independently, a halogen atom; hydrogen atom; hydroxy group; an alkoxy group or an amine group,
Y ₁ to Y ₄ are each independently a halogen atom; hydrogen atom; hydroxy group; It is an alkoxy group or an amine group.)
[Formula 2]

(In Formula 2,
R ₃ and R ₄ are, each independently, an alkylene group,
R ₅ and R ₆ are, each independently, an alkyl group; a cycloalkyl group; alkoxy group; An alkyl ketone group; an alkyl amine group; an alkyl hydroxide group; an alkyl ether group; an alkyl sulfate group; an alkyl phosphate group; an alkyl amide group or an alkyl sulfide group;
X ₃ and X ₄ are, each independently, a halogen atom; hydrogen atom; hydroxy group; alkoxy group or amine group
Y ₅ to Y ₈ are each independently a halogen atom; hydrogen atom; hydroxy group; It is an alkoxy group or an amine group.)
[Formula 5]

[Formula 6]

[Formula 7]

The method of claim 1,
Nitrogen-silicon is present in the structures of Formulas 1 and 2 themselves,
The additive is for increasing the stability of the nitrogen-silicon bond in the molecule of the silicon compound under acid conditions, Additives. The method of claim 1,
R ₁ and R ₂ in Formula 1 are each independently a C ₁ to C ₂₀ alkyl group; a C ₃ to C ₂₀ cycloalkyl group; A C ₁ to C ₂₀ alkoxy group; C ₁ to C ₂₀ Alkyl carboxy group; A C ₁ to C ₂₀ alkyl ketone group; A C ₁ to C ₂₀ alkylamine group; C ₁ To C ₂₀ Alkyl hydroxide group; C ₁ To C ₂₀ Alkyl ether group; C ₁ to C ₂₀ Alkyl sulfate group; A C ₁ to C ₂₀ alkyl phosphate group; A C ₁ to C ₂₀ alkylamide group or a C ₁ to C ₂₀ alkyl sulfide group,
X ₁ and X ₂ are each independently a fluorine; chlorine; bromine; iodine; hydrogen atom; hydroxy group; A C ₁ to C ₂₀ alkoxy group or an amine group;
Y ₁ to Y ₄ are each independently a fluorine; chlorine; bromine; iodine; hydrogen atom; hydroxy group; It is a C ₁ to C ₂₀ alkoxy group or an amine group. The method of claim 1,
R ₃ and R ₄ in Formula 2 are each independently a C ₁ to C ₂₀ alkylene group,
R ₅ and R ₆ are each independently a C ₁ to C ₂₀ alkyl group; a C ₃ to C ₂₀ cycloalkyl group; A C ₁ to C ₂₀ alkoxy group; C ₁ to C ₂₀ Alkyl carboxy group; A C ₁ to C ₂₀ alkyl ketone group; A C ₁ to C ₂₀ alkylamine group; C ₁ to C ₂₀ Alkyl hydroxide group; C ₁ to C ₂₀ Alkyl sulfate group; A C ₁ to C ₂₀ alkyl phosphate group; A C ₁ to C ₂₀ alkylamide group or a C ₁ to C ₂₀ alkyl sulfide group,
X ₃ and X ₄ are, each independently, Fluorine; Chlorine; Bromine; Iodine; Hydrogen atom; hydroxy group; A C ₁ to C ₂₀ alkoxy group or an amine group;
Y ₅ to Y ₈ are each independently fluorine; Chlorine; Bromine; Iodine; Hydrogen atom; hydroxy group; It is a C ₁ to C ₂₀ alkoxy group or an amine group. The method of claim 1,
Formula 1 is to include one or more of the compounds having the structure of Formula 3 and Formula 4, Additives.
[Formula 3]

[Formula 4]

delete The method of claim 2,
The acid condition is that the pH is less than 7, additives. The method of claim 2,
The acid conditions include acetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, nitric acid, nitrous acid, formic acid, hydrochloric acid, boric acid, one or more acids selected from acids having a carboxyl group and hydrofluoric acid, additives. The method of claim 1,
The additive is characterized in that it retains 63% or more of the silicon-nitrogen bond in the molecule of the silicone compound under acid conditions.