KR101821796B1 - Method of producing alkylated phenol - Google Patents

Abstract

The present invention relates to a method for producing alkylated phenol using certain solid acid catalysts, and the method for producing alkylated phenol of the present invention is a highly efficient method which not only can produce alkylated phenol in high yields with simple processes, high selectivity and conversion rates, but also allow the recovery of solid acid catalysts.

Description

[0001] The present invention relates to a method for producing an alkylated phenol,

The present invention relates to a process for producing alkylated phenols, and more particularly to a process for preparing alkylated phenols by reacting a styrene derivative with a phenol derivative under a specific solid acid catalyst.

Plastics have been applied to virtually every aspect of modern life with the advancement of polymer manufacturing and processing.

However, polymeric compounds are prone to aging due to the effects of oxidizing agents, light and heat, which may result in loss of life, such as loss of strength, stiffness and flexibility of the polymeric compound, discoloration, scratching as well as loss of gloss do.

Various additives are added to the polymer to protect the polymer during processing and to achieve the desired end use properties, as it is known in the art that antioxidants and light stabilizers can prevent or at least reduce such effects.

For example, in Korean Patent No. 10-1558064, polyphosphoric acid is used as a phosphorus-based antioxidant and phenanthritol tetrakis (3-3,5-di -Tetra-butyl-4-hydroxyphenyl) propionate), and Korean Patent Laid-Open Publication No. 2016-0059445 discloses a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur- A resin composition for a hot-melt adhesive is known.

In general, additives are classified into stabilizers and modifiers. Stabilizers such as antioxidants conventionally and recently used can be classified into phenol antioxidants, amine antioxidants, and phosphoric acid antioxidants.

Among the antioxidants, the phenolic antioxidants are produced by the alkylation reaction of phenol, resulting in various byproducts, resulting in low yield and difficulty in refining them.

Korean Patent Laid-Open Publication No. 2002-0065836 discloses a method for producing styrenated phenol using sulfuric acid or the like as a catalyst in order to solve such a problem. However, it is still another object of the present invention to provide a process for producing an alkylated phenol with a high yield and selectivity, Method is required.

Korean Patent No. 10-1558064 Korean Patent Laid-Open Publication No. 2016-0059445 Korean Patent Publication No. 2012-0065836

The present invention provides a process for preparing alkylated phenols which can be used as additives in various fields.

The present invention provides a process for preparing an alkylated phenol which can produce an alkylated phenol with a high yield and selectivity in a simple process, wherein the process for producing the alkylated phenol of the present invention comprises the step of reacting a solid acid catalyst And reacting the styrene derivative with a phenol derivative in the presence of a base to produce an alkylated phenol.

[Chemical Formula 1]

_{(SiO 2) x (AlCl 3} ) y (NiCl 2) z

[In the formula (1), it is a real number satisfying (3 <x <7, 1 <y <5, 0.1 <z <3).

Preferably, the styrene derivative according to one embodiment of the present invention may be represented by the following formula (2).

(2)

[In the formula (2)

R ₁ to R ₅ are independently of each other hydrogen, halogen, (C 1 -C 5) alkyl or (C ₁ -C 5) alkoxy, and R ₁ through R ₅ may be connected to each other to form a (C6-C12) aromatic ring. ]

Preferably, the phenol derivative according to one embodiment of the present invention may be represented by the following formula (3).

(3)

[Formula 3]

R is halogen, (C1-C5) alkyl or (C1-C5) alkoxy;

n is 0 or an integer of 1 to 3, and when n is 2 or more, Rs may be mutually different or the same.]

The solid acid catalyst according to an embodiment of the present invention may be used in an amount of 15 to 30 parts by weight based on 100 parts by weight of the phenol derivative. In the general formula (1), x is 4 to 6, y is 2 to 4, z is 0.5 to 1.5 Can be a real number satisfying the following equation.

The styrene derivative according to an embodiment of the present invention may be used in an amount of 1.5 to 3.5 moles per mole of the phenol derivative, and the reaction may be carried out at 80 to 150 ° C for 4 to 12 hours.

The process for preparing the alkylated phenols of the present invention may further comprise recovering the solid acid catalyst.

Preferably, the alkylated phenol according to one embodiment of the present invention may be represented by the following formula (4).

[Chemical Formula 4]

[Formula 4]

R ₁ to R ₅ independently from each other are hydrogen, halogen, (C 1 -C 5) alkyl or (C 1 -C 5) alkoxy;

R is halogen, (C1-C5) alkyl or (C1-C5) alkoxy;

n is 0 or an integer of 1 to 3, and when n is 2 or more, Rs may be the same or different from each other.

The process for the preparation of the alkylated phenols of the present invention is a simple process which yields products with high selectivity and yield.

The alkylated phenol of the present invention does not require a separate process such as a neutralization process and a salt removal process unlike the conventional process using a liquid acid such as sulfuric acid as a catalyst, It is possible.

The method of producing the alkylated phenol of the present invention does not use toxic acids unlike the conventional liquid acids such as sulfuric acid, so there is no concern about corrosion, and the catalyst can be recovered and reused, thus being environmentally friendly and economical.

1 is a graph showing the results of GC analysis of the alkylated phenol prepared in Example 2 of the present invention.
2 is a graph showing the results of GC analysis of the alkylated phenol prepared in Comparative Example 1 of the present invention.

The present invention provides a process for producing an alkylated phenol wherein the alkylated phenol of the present invention is prepared by reacting a styrene derivative with a phenol derivative in the presence of a solid acid catalyst represented by the following formula 1 to produce an alkylated phenol Step: Include.

[Chemical Formula 1]

_{(SiO 2) x (AlCl 3} ) y (NiCl 2) z

[In the formula (1), it is a real number satisfying (3 <x <7, 1 <y <5, 0.1 <z <3).

The method for producing the alkylated phenol of the present invention is different from the conventional method using a liquid acid such as sulfuric acid, para-toluenesulfonic acid, phosphoric acid and polyphosphoric acid as a catalyst, Sulfuric acid, blue-toluenesulfonic acid, phosphoric acid, and polyphosphoric acid, and is environmentally-friendly because it does not have the danger of handling and corrosion, and the solid acid of the present invention can be recovered after use and reused, which is very economical.

Further, the solid acid represented by the formula (1) of the present invention can be prepared as a main product by controlling the number of alkylated functional groups of phenol formed according to the composition ratio of x, y and z.

,

등), 알킬화된 작용기를 두 개 가지는 페놀(일례로,

,

등) 및 알킬화된 작용기를 세 개가지는 페놀(일례로,

)이 혼합물의 형태로 얻어지는데 상기 화학식 1로 표시되는 고체산은 x, y 및 z의 조성비를 조절함으로써 얻고자하는 생성물이 주생성물이 되도록 조절할 수 있다.That is, the alkylated phenol of the present invention is a product obtained by reacting a styrene derivative with a phenol derivative in the presence of the solid acid catalyst of the present invention represented by the above formula (1), a phenol having one alkylated functional group

,

Etc.), phenols having two alkylated functional groups (e.g.,

,

Etc.) and phenols having three alkylated functional groups (e.g.,

) Can be obtained in the form of a mixture. The solid acid represented by the formula (1) can be controlled so that the product to be obtained is a main product by controlling the composition ratio of x, y and z.

For example, when the composition ratio of x, y, and z of the solid acid catalyst represented by Formula 1 of the present invention is adjusted to 5: 3: 1, phenol (DSP) having two alkylated functional groups can be obtained as a main product.

The solid acid catalyst of the present invention can be produced by sufficiently mixing and stirring the products SiO ₂ , AlCl ₃ and NiCl ₂ in a weight ratio of 3 to 7: 1 to 5: 1 in a solvent such as distilled water, followed by dry calcination.

Mixing stirring can be carried out at room temperature for 1 to 5 hours, and calcining can be carried out at 200 to 400 ° C for 2 to 8 hours.

Preferably, the solid acid catalyst is used in a weight ratio of SiO ₂ : AlCl ₃ : NiCl ₂ of 4.5 to 5.5: 2.5 to 3.5: 1 in view of obtaining the main products of phenol (DSP) having two alkylated functional groups of the present invention .

In Formula 1 according to an embodiment of the present invention, x is 4 to 6, y is 2 to 4, z may be a real number satisfying 0.5 to 1.5, preferably x is 4.5 to 5.5, and y is 2.5 to 3.5, and z may be a real number satisfying 0.5 to 1.5.

Preferably, the styrene derivative according to one embodiment of the present invention may be represented by the following formula (2).

(2)

[In the formula (2)

R ₁ to R ₅ are independently of each other hydrogen, halogen, (C 1 -C 5) alkyl or (C ₁ -C 5) alkoxy, and R ₁ through R ₅ may be connected to each other to form a (C6-C12) aromatic ring. ]

In the formula (2), R ₁ to R ₅ may be 1-vinylnaphthalene, for example, when they are connected to each other to form a (C6-C12) aromatic ring.

Preferably, R ₁ to R ₅ in the formula (2) according to an embodiment of the present invention may independently be hydrogen, halogen or (C 1 -C 5) alkyl, more preferably hydrogen or (C 1 -C 5) .

Preferably, the phenol derivative according to one embodiment of the present invention may be represented by the following formula (3).

(3)

[Formula 3]

R is halogen, (C1-C5) alkyl or (C1-C5) alkoxy;

n is 0 or an integer of 1 to 3, and when n is 2 or more, Rs may be mutually different or the same.]

Preferably, R in the formula (3) of the present invention may be halogen or (C1-C5) alkyl, more preferably phenol in which n is 0.

The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both linear and branched forms and are those having 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms, Has from 1 to 3 carbon atoms.

The solid acid catalyst according to an embodiment of the present invention may be used in an amount of 15 to 30 parts by weight based on 100 parts by weight of the phenol derivative, and the styrene derivative may be used in an amount of 1.5 to 3.5 parts by mol based on 1 mol of the phenol derivative.

The reaction according to one embodiment of the present invention may be carried out in an alkylation reaction at 80 to 150 캜 for 4 to 12 hours, preferably at 100 to 130 캜 for 4 to 8 hours.

The process for preparing the alkylated phenols of the present invention may further comprise recovering the solid acid catalyst.

The solid acid catalyst of the present invention can be recovered by filtration after completion of the reaction, and can be reused after washing and drying, which is very economical.

Preferably, the alkylated phenol according to one embodiment of the present invention may be represented by the following formula (4).

[Chemical Formula 4]

[Formula 4]

R ₁ to R ₅ independently from each other are hydrogen, halogen, (C 1 -C 5) alkyl or (C 1 -C 5) alkoxy;

R is halogen, (C1-C5) alkyl or (C1-C5) alkoxy;

n is 0 or an integer of 1 to 3, and when n is 2 or more, Rs may be the same or different from each other.

According to one embodiment of the present invention, R ₁ to R ₅ and R in Formula 4 may be independently selected from halogen, (C 1 -C 3) alkyl or (C 1 -C 3) alkoxy, Lt; RTI ID = 0.0 &gt; 0 &lt; / RTI &gt;

Hereinafter, specific examples and comparative examples of the present invention will be described, but the scope of the present invention is not limited to the specific examples and comparative examples of the present invention.

[Example 1] Synthesis of catalyst

Add AlCl ₃ (3.0 g) to a 200 cc flask, add distilled water, and stir for 10 minutes to make the solution transparent. Then, NiCl ₂ (1.0 g) was added thereto, and the mixture was stirred for 10 minutes. SiO ₂ (5.0 g) was added thereto and stirred at room temperature for 3 hours. The reaction mixture was dried at 200 ° C. for 12 hours, and then calcined at 300 ° C. for 6 hours to obtain a catalyst having a catalytic activity.

[Example 2] Synthesis of Styrenated Phenol

 After replacing the 100cc flask with argon, phenol (2.35g, 0.025mol) and catalyst (0.524g, 6wt%) were added thereto and stirred at 80 ° C until the phenol was completely dissolved. When phenol was dissolved, styrene (7.15 ml, 0.0625 mol) was added dropwise and the mixture was stirred at 120 ° C for 6 hours. After the reaction was completed, the catalyst was filtered off and the styrenated phenol mixture was analyzed by GC. The conversion of phenol was 99.9% and the conversion of styrene was 94.9%. Table 1 shows GC analysis conditions, and FIG. 1 and Table 2 show the results of the analysis.

GC M600D Sampling 5 μL (30 wt% toluene solution) Carrier gas He, 1 mL min-1 Column Capillary column HP-5 Oven tem. 100 ° C → 10 ° C / min ↑ → 130 ° C →
18 占 폚 / min? 300 占 폚 (15 min Hold) Injection tem. 300 ° C Detector tem. 300 ° C (FID) Split ratio 1/50

Furtherance(%) MSP DSP TSP Example 2 9.6 66.1 24.3 Comparative Example 1 26.2 50.9 22.9

[Comparative Example 1] Synthesis of Styrenated Phenol

The procedure of Example 2 was repeated except that concentrated sulfuric acid (0.289 mL) was used instead of the solid acid of the present invention and the reaction mixture was neutralized with sodium carbonate after completion of the reaction. Respectively. The main product was distyrylated phenol. The conversion of phenol was 99.9% and the conversion of styrene was 92.4%.

Compared with Comparative Example 1, the process for preparing an alkylated phenol according to an embodiment of the present invention does not require a step of removing salts generated in a neutralization process and a neutralization process, and a conversion ratio of a starting material is also high.

Further, in addition to being used as an antioxidant, the alkylated phenol of the present invention can selectively obtain distyrylated phenol (DSP) which is easily usable as a surfactant by introducing an epoxy group into an alkylated phenol, The selectivity is very low and the conversion rate is low.

Claims (9)

Reacting a styrene derivative represented by the following formula (2) with a phenol derivative represented by the following formula (3) in the presence of a solid acid catalyst to produce an alkylated phenol represented by the following formula (4)
The solid acid catalyst is SiO _2: AlCl _3: the weight ratio of NiCl ₂ 4.5 to 5.5: 2.5 to 3.5: 1 is used as a method of manufacturing an alkylated phenol is prepared.
(2)

[In the formula (2)
Wherein R ₁ to R ₅ are independently of each other hydrogen, halogen, (C 1 -C 5) alkyl or (C ₁ -C 5) alkoxy and R ₁ to R ₅ may be connected to each other to form a (C6-C12)
(3)

[Formula 3]
R is halogen, (C1-C5) alkyl or (C1-C5) alkoxy;
n is 0 or an integer of 1 to 3, and when n is 2 or more, Rs may be the same or different from each other]
[Chemical Formula 4]

[Formula 4]
R ₁ to R ₅ independently from each other are hydrogen, halogen, (C 1 -C 5) alkyl or (C 1 -C 5) alkoxy;
R is halogen, (C1-C5) alkyl or (C1-C5) alkoxy;
n is O or an integer of 1 to 3, and when n is 2 or more, Rs may be the same or different from each other] delete delete delete The method according to claim 1,
Wherein the solid acid catalyst is used in an amount of 15 to 30 parts by weight based on 100 parts by weight of the phenol derivative. The method according to claim 1,
Wherein the styrene derivative is used in an amount of 1.5 to 3.5 mol per 1 mol of the phenol derivative. The method according to claim 1,
Wherein the reaction is carried out at 80 to &lt; RTI ID = 0.0 &gt; 150 C &lt; / RTI &gt; for 4 to 12 hours. The method according to claim 1,
And recovering the solid acid catalyst. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; delete

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