KR20170062219A

KR20170062219A - Method for manufacturing -methylstyrenated phenol

Info

Publication number: KR20170062219A
Application number: KR1020150167752A
Authority: KR
Inventors: 노기윤; 장정희; 박제영
Original assignee: 금호석유화학 주식회사
Priority date: 2015-11-27
Filing date: 2015-11-27
Publication date: 2017-06-07
Also published as: KR101778778B1

Abstract

One embodiment of the present invention is directed to a process for preparing a first product, comprising: (a) reacting phenol with alpha methylstyrene (AMS) in the presence of a first acid catalyst to produce a first product; And (b) reacting the first product with 1 to 5 equivalents of alpha methyl styrene to 1 equivalent of the phenol in the presence of a second acid catalyst to produce a second product. To provide a process for producing nated phenols.

Description

METHOD FOR MANUFACTURING < RTI ID = 0.0 > α-METHYLSTYRENATED PHENOL &

The present invention relates to a process for preparing alpha methyl styrene-substituted phenols, and more particularly to a process for preparing alpha methyl styrene-substituted phenol as a plasticizer for epoxy paints or as a non-reactive diluent.

A variety of non-reactive diluents have conventionally been used to impart plasticity to compositions of conventional epoxy coatings and for use in diluent applications. Representative non-reactive diluents include alkylphenol compounds such as nonylphenol, dodecylphenol and octylphenol, benzyl alcohol, C ₅ -C ₉ hydrocarbon resins, mixtures of phenol and alpha methylstyrene oligomers, and the like.

Among them, alkylphenol compounds have been widely used as additives for epoxy coatings or surfactants which require plasticity in terms of molecular structure and chemical properties. However, these alkylphenol compounds are known as renal toxins and endocrine disrupters, and they are currently prohibited from being used worldwide or their use is gradually limited.

In addition, since benzyl alcohol has low boiling point, environmental hazard due to volatile organic compounds (VOC) is problematic. In the case of alpha methylstyrene oligomer, a large amount of unreacted petroleum VOC such as benzene, xylene, etc. remains and oligomer structure There is a problem that it is complicated and the composition is not uniform.

In order to solve this problem, an alpha methyl styrene-phenol mixture produced by reacting phenol with alpha methyl styrene in the presence of an acid catalyst has been used as a non-reactive diluent. However, the composition ratio of the resulting mixture can not be controlled to an appropriate range , There are limited acid catalysts that can be used.

In addition, since a high-boiling solvent such as benzene, xylene or xylene is used in the reaction, not only the solvent should be removed in the purification process, but the solvent remains in the final product, which may cause emission of environmentally harmful substances such as VOC.

Therefore, there is a need to develop a process for producing alpha methyl styrene-substituted phenol that can solve the problem of VOC generation due to the use of a solvent and maintain the composition of the product uniformly.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide an epoxy resin composition which does not cause environmental hazard and has excellent economical efficiency and which is excellent in compatibility with a plasticizer for epoxy paints or non- And a method for preparing the same.

According to an aspect of the present invention, there is provided a process for preparing a polyimide precursor, comprising the steps of: (a) reacting phenol with alpha methylstyrene (AMS) in the presence of a first acid catalyst to produce a first product; And (b) reacting the first product with 1 to 5 equivalents of alpha methyl styrene to 1 equivalent of the phenol in the presence of a second acid catalyst to produce a second product. To provide a process for producing nated phenols.

In one embodiment, the first acid catalyst and the second acid catalyst are each selected from the group consisting of sulfuric acid, p -toluenesulfonic acid, methanesulfonic acid, phosphoric acid, boron trifluoride complexes, clays, and ion exchange resins It can be more than one.

In one embodiment, the first and second acid catalysts may be different.

In one embodiment, the equivalent ratio of the phenol and the first acid catalyst may be 1: 0.0001 to 1, respectively.

In one embodiment, the alphamethylstyrene reacting in the steps (a) and (b) with respect to 1 equivalent of the phenol may be 0.1 to 5 equivalents.

In one embodiment, the first product comprises 30 to 50 wt.% Trimethylphenylindane (TMPI), 1 to 10 wt.% Diphenylmethylpentene (DMP), 5 to 20 wt.% Cumylphenol, alpha methylstyrene trimer 1 To 10% by weight, and balance phenol.

In one embodiment, the equivalent ratio of the phenol and the second acid catalyst may be 1: 0.0001 to 0.1, respectively.

In one embodiment, the second product comprises 5 to 50 wt% of a mixture of trimethylphenylindane (TMPI) and diphenylmethylpentene (DMP), 2 to 20 wt% of cumylphenol, 1 to 10 wt% of dicumene, 20 to 60 wt% of wheat phenol, and 0.1 to 5 wt% of alpha methylstyrene trimer.

In one embodiment, the mixture may be one wherein the trimethylphenylindane (TMPI) and the diphenylmethylpentene (DMP) are mixed at a weight ratio of 1: 1.5 to 8, respectively.

In order to achieve the above object, another aspect of the present invention is to provide a method for producing a thermoplastic resin composition comprising 5 to 50% by weight of a mixture of trimethylphenylindane (TMPI) and diphenylmethylpentene (DMP), 2 to 20% To 10% by weight of dicumylphenol, 20 to 60% by weight of dicumylphenol, and 0.1 to 5% by weight of alpha methylstyrene trimer.

In order to achieve the above object, another aspect of the present invention provides an epoxy coating composition comprising 1 to 50% by weight of the alphamethylstyrene-based phenol, and a residual amount of an epoxy resin.

According to one aspect of the present invention, it is possible to improve the reproducibility and reliability by refining the process steps in the production of alpha methyl styrene-substituted phenol and by controlling the amount of reactants and catalyst used in each step, have.

In addition, when the alpha methyl styrene-naphthol phenol is used as an additive such as an epoxy paint, compatibility and plasticity as a non-reactive diluent can be improved.

In addition, it is possible to diversify the catalyst to be used without using a solvent in the preparation of the alpha methyl styrene-naphthol phenol mixture, so that the environment-friendliness and economical efficiency can be improved as compared with the conventional production method.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

FIG. 1 illustrates a process for preparing alpha methyl styrene-substituted phenol according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly explain the present invention in the drawings, parts not related to the description are omitted.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

FIG. 1 illustrates a process for preparing alpha methyl styrene-substituted phenol according to an embodiment of the present invention. Referring to FIG. 1, a method for producing alpha methyl styrene-substituted phenol according to an aspect of the present invention comprises the steps of (a) reacting phenol with alpha methyl styrene (AMS) in the presence of a first acid catalyst to produce a first product ; And (b) reacting the first product with 1 to 5 equivalents of alphamethylstyrene to 1 equivalent of the phenol in the presence of a second acid catalyst to produce a second product.

[Reaction Scheme 1]

Referring to Reaction Scheme 1, alpha-methyl styrene-substituted phenol can be prepared by reacting phenol with alpha methyl styrene in the presence of an acid catalyst in steps (a) and (b).

The alpha methyl styrene naphthyl phenol, specifically, the alphamethyl styrene naphthol phenol mixture is a mixture of one molecule of phenol and one molecule of alpha methyl styrene combined with one molecule of phenol and two molecules of alpha methyl styrene Dicumylphenol, alpha methyl styrene dimer (AMS dimer) with two molecules of alpha methyl styrene, alpha methyl trimer (AMS trimer) with three alpha methyl styrene bonds, and other unreacted materials .

That is, not only phenol and alpha methyl styrene can react with each other to produce various types of alpha methyl styrene nitrides, but also alpha methyl styrenes may react with each other to produce dimers, trimers, and the like.

At this time, the respective product ratios may vary depending on the equivalence ratio of phenol and alpha methylstyrene as reactants, the kind and content of the catalyst, the reaction temperature, and the reaction time. The term "equivalent " as used herein means a value obtained by dividing the weight of a reactant or catalyst used during the production of the above-mentioned alpha methyl styrene-naphthol phenol, such as phenol, alpha methyl styrene or an acid catalyst, by their molecular weights.

The phenol may be used alone or in admixture with derivatives thereof to obtain a greater variety of alphamethylstyrene nitrile phenols. That the phenol derivatives o - cresol, m - cresol, p - cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol, o - Ethylphenol, m -ethylphenol, p -ethylphenol, p - tert -butylphenol, p -octylphenol, m -methoxyphenol, p -methoxyphenol, 3,4-dimethoxyphenol, 4-methyl phenol, m - ethoxy phenol, p - ethoxy phenol, m - propoxy phenol, p - propoxy phenol, m - butoxy phenol, p - butoxy phenol, 2-methyl-4-isopropyl And may be at least one selected from the group consisting of phenol, o -chlorophenol, m -chlorophenol, p -chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol no.

On the other hand, the first acid catalyst and the second acid catalyst may be at least one member selected from the group consisting of sulfuric acid, p -toluenesulfonic acid, methanesulfonic acid, phosphoric acid, boron trifluoride complex, clay, Preferably, the first acid catalyst may be clay or phosphoric acid, and the second acid catalyst may be sulfuric acid, but is not limited thereto.

The step (a) may be performed at a reaction temperature of 50 ° C to 200 ° C, preferably 70 ° C to 150 ° C, since the temperature increases during the reaction corresponding to the exothermic reaction. If the reaction temperature is lower than 50 캜, the catalytic activity may be lowered and the reaction rate may be lowered. If the reaction temperature is higher than 200 캜, the product may be discolored during the reaction.

In the step (a), the equivalence ratios of the phenol and the first acid catalyst may be 1: 0.0001 to 1, preferably 0.001 to 1, respectively. If the amount of the first acid catalyst is less than 0.0001 equivalents based on 1 equivalent of the phenol, the reaction rate may decrease. If the amount of the first acid catalyst exceeds 1 equivalent, the composition of the first product may be difficult to control due to excessive reactivity.

In the step (a), cumylphenol is reacted by reaction between one molecule of phenol and one molecule of alpha methylstyrene, and alpha methyl dimethysiloxane (AMS dimer) is reacted with two molecules of alphamethylstyrene, The AMS trimer may be produced by the liver reaction, and the first product may be present in the form of a mixture.

The cumylphenol is present as a mixture of o -cumylphenol, m -cumylphenol, and p -cumylphenol combined with the alpha methylstyrene at the ortho, meta, and para positions of the phenol However, p - cumylphenol can predominantly be generated by a steric factor of alpha methyl styrene and phenol due to the hydroxyl group of the phenol as the electron donor (EDG).

Further, the reaction between the two molecules of alphamethylstyrene progresses and an alpha methyl styrene dimer (AMS dimer) including trimethylphenyl indene (TMPI) and diphenyl methyl pentene (DMP) can be produced depending on the bonding position, 3-phenyl, the diphenylmethylpentene is 4-methyl-2,4-diphenyl-1-pentene and 4-methyl- 4-diphenyl-2-pentene.

Specifically, the first product comprises 30 to 50 wt% of the trimethylphenyl indene, 1 to 10 wt% of the diphenylmethylpentene, 5 to 20 wt% of cumylphenol, 1 to 10 wt% of the alpha methylstyrene trimer, Of phenol.

In the step (b), the first product may be further reacted with 1 to 5 equivalents of alpha methylstyrene to 1 equivalent of the phenol in the presence of a second acid catalyst to produce a second product.

Wherein the second product is further reacted with an unreacted residual phenol and the first product to form a mixture of cumylphenol, dicumylphenol, dicumene, AMS dimer, and alpha methylstyrene trimer (AMS trimer). &Lt; / RTI >

The step (b) may also be carried out at a reaction temperature of 70 ° C to 150 ° C, preferably 80 ° C, since the temperature increases during the reaction corresponding to the exothermic reaction.

On the other hand, the equivalence ratios of the phenol and the second acid catalyst may be 1: 0.0001 to 0.1, respectively. If the amount of the second acid catalyst is less than 0.0001 equivalents based on 1 equivalent of the phenol, the yield of the final product, alpha methyl styrene-nitrile phenol, may be lowered. If the amount is more than 0.1 equivalents, the composition of the second product is difficult to control due to excessive reactivity .

The total amount of the alphamethylstyrene to be reacted in the steps (a) and (b) with respect to 1 equivalent of the phenol may be 0.1 to 5 equivalents. Among them, the alpha methylstyrene to be added in the step (b) may be 1 to 5 equivalents based on 1 equivalent of the phenol.

If the amount of the alpha methylstyrene further added in step (b) is less than 1 equivalent, the unreacted residual phenol may be present in an excess amount to reduce the economical efficiency. If the amount exceeds 5 equivalents, the reaction with cumylphenol predominates, As the content increases, the viscosity of the final product may increase and the compatibility and plasticity of the paint may be lowered when mixed with the epoxy paint.

The alpha methyl styrene reacts with cumyl phenol in the first product to form dicumyl phenol. Specifically, the alphamethylstyrene may react with p -cumylphenol to produce 2,4-dicumylphenol and react with o -cumylphenol to produce 2,6-dicumylphenol.

Also, the alpha methylstyrene may react with diphenylmethylpentene (DMP) in the first product to produce an alpha methylstyrene trimer. Specifically, the alpha methylstyrene may react with 4-methyl-2,4-diphenyl-1-pentene to produce 2,4,6-triphenyl-4,6-dimethylhept- 4-methyl-2,4-diphenyl-2-pentene to give 2,4,6-triphenyl-4,6-dimethylhept-2-ene.

Specifically, the second product may contain 5 to 50 wt% of a mixture of trimethylphenylindane (TMPI) and diphenylmethylpentene (DMP) in a weight ratio of 1: 1.5 to 8, 2 to 20 wt% of cumylphenol, From 1 to 10% by weight of man, from 20 to 60% by weight of dicumylphenol, and from 0.1 to 5% by weight of alpha methylstyrene trimer.

Preferably, the content of the mixture of trimethylphenylindane (TMPI) and diphenylmethylpentene (DMP) is 20 wt% to 50 wt%, more preferably 25 wt% to 40 wt%, 30 wt% to 37 wt% %. &Lt; / RTI >

The trimethylphenyl indene and the diphenylmethylpentene are compounds which give plasticity and control viscosity when mixed with an epoxy paint. When the total content thereof exceeds 50% by weight, the viscosity of the final product increases, and when mixed with the epoxy paint The compatibility of the coating material may be deteriorated.

When the content of the cumylphenol and the dicumylphenol is within the above range, the hydroxyl value (OH Value) can be maintained at 60 to 100, which can improve the adhesion of the epoxy paint upon curing. The above-mentioned dicumene is used as a flame retardant when mixed with an epoxy paint to impart fire resistance.

After completion of the reaction of step (b), a basic aqueous solution is added to the second product to perform a neutralization reaction. The resulting solution is concentrated under reduced pressure to remove moisture and residual compounds, &Lt; / RTI > to obtain purified alpha methyl styrene-substituted phenol.

The basic aqueous solution may be at least one selected from the group consisting of an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of sodium hydroxide, and an aqueous solution of potassium hydroxide. However, the basic aqueous solution is not limited thereto. May be used.

As described above, the alpha methyl styrene-substituted phenol can be used in place of the existing compounds by being mixed with the epoxy paint, and the use range can also be used for both the main part and the hardener part of the epoxy paint. In particular, The compatibility can be improved. The mixing ratio can be used within a range of 1 to 50% by weight, taking into account the physical properties of the product.

Hereinafter, embodiments of the present invention will be described in detail.

Example One

An acid clay catalyst (0.04 g) was added to phenol (60 g, 1 eq) and the dropwise addition of alpha methyl styrene (52.7 g, 0.7 eq) was continued for 30 minutes until the temperature increased from 70 ° C to 80 ° C. After the addition of the alpha methylstyrene was completed, the reaction was further allowed to proceed at the same temperature for 1 hour.

Then sulfuric acid catalyst (0.0625 g, 0.001 eq) was added at the same temperature and alpha methylstyrene (211 g, 2.8 eq) was added dropwise for another 180 min. After the dropping of the alpha methyl styrene was completed, the reaction was further carried out at the same temperature for 1 hour to obtain a solution containing alpha methyl styrene.

Sodium carbonate (0.0676 g, 0.001 eq) was dissolved in distilled water and neutralized for 60 minutes while adding at 100 캜. The resulting solution was concentrated under reduced pressure to remove water and residual compounds, and then the neutralized salt was removed using a filtration filter to obtain a purified alpha methyl styrene-phenol mixture.

Comparative Example One

Xylene (450 ml) and BF ₃ OEt ₂ catalyst (1.49 g, 0.0045 eq) were added to phenol (220 g, 1 eq) and alpha methylstyrene (911.7 g, 3.3 eq) was added dropwise at 90 ° C for 200 minutes. The reaction temperature rises from 90 占 폚 to 100 占 폚. After the addition of the alpha methylstyrene was completed, the reaction was further carried out at the same temperature for 1 hour to obtain a solution containing the alpha methyl styrene-phenol mixture.

Comparative Example 2

Xylene (35 ml) and BF ₃ MeOH catalyst (0.46 g, 0.003 eq) were added to phenol (20 g, 1 eq) and alpha methyl styrene (113 g, 3 eq) was added dropwise at 60 ° C for 70 minutes. The reaction temperature rises from 60 占 폚 to 80 占 폚. After the addition of the alpha methylstyrene was completed, the reaction was further carried out at the same temperature for 1 hour to obtain a solution containing the alpha methyl styrene-phenol mixture.

Comparative Example 3

Sulfuric acid catalyst (0.11 g, 0.0036 eq) was added to phenol (30 g, 1 eq), and alpha methylstyrene (131.9 g, 3.5 eq) was added dropwise at 90 캜 for 90 minutes. The reaction temperature rises from 90 占 폚 to 100 占 폚. After the addition of the alpha methylstyrene was completed, the reaction was further carried out at the same temperature for 1 hour to obtain a solution containing the alpha methyl styrene-phenol mixture.

Experimental Example 1: Analysis of the composition of the final product according to the type of catalyst and the production method

Gas chromatography (GC) analysis was performed to analyze the composition of the alpha methyl styrene-naphthol phenol mixture prepared according to Example 1 and Comparative Examples 1 to 3, and the results are shown in Table 1 below. At this time, in analyzing the above Examples 1 and 2, the compositions of the intermediate product (first product) and the final product (second product) were respectively analyzed.

division Analysis target GC analysis (peak area%) phenol AMS TMPI DMP Cumulus
phenol Dickey Mill
phenol Decumen AMS
trimer Example 1 The first product 42.19 0 35.46 2.59 10.01 0 0 8.07 The second product 0 0 15.61 18.64 11.15 40.52 5.19 3.9 Comparative Example 1 product 0 0.55 16.15 18.93 16.03 40.74 2.34 0.66 Comparative Example 2 product 1.39 0.70 5.16 44.05 36.37 5.83 1.24 0 Comparative Example 3 product 0 0.62 1.14 29.10 9.42 43.22 7.36 2.71

Referring to Table 1, the alpha methyl styrene-phenol mixture prepared in Step 2 according to Example 1 was prepared by using an acid clay, phosphoric acid, or sulfuric acid catalyst, Residual phenol and the first product to obtain a second product having a total content of TMPI and DMP of 40% by weight or less based on the total weight of the second product, 2 to 20% by weight of cumylphenol, 20 to 60% by weight of dicumylphenol, To 10% by weight, and AMS trimer in the range of 0.1 to 5% by weight.

Also, it was confirmed that the alpha-methyl styrene-naphthoene phenol mixture prepared through one step according to Comparative Example 1 was also produced in a composition ratio similar to that of the alpha methyl styrene-naphthol phenol mixture prepared according to Example 1 above. However, in the case of the alpha methyl styrene nitrile phenol mixture prepared according to Example 1, the acid catalyst used can be neutralized with a base such as sodium carbonate and can be easily removed. On the other hand, the alpha methyl In the case of the styrene-substituted phenol mixture, the acid catalyst used can not be easily removed as in Example 1, and the use of the xylene solvent causes a problem that an organic solvent, which is a VOC inducing factor, remains in the final compound.

On the other hand, in the case of the alpha-methyl styrene-based phenol mixture prepared according to Comparative Examples 2 to 3, it was confirmed that the contents of the alpha-methyl styrene-butadiene phenol mixture prepared in Example 1 were different from each other .

As described above, the production method of alpha methyl styrene-naphthol phenol according to Example 1 is environmentally friendly because it does not use a solvent as compared with Comparative Examples 1 to 3 or conventional production methods, And the viscosity of the final product is decreased, so that compatibility and plasticity can be improved when used in combination with an epoxy paint.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims

(a) reacting phenol with alpha methyl styrene (AMS) in the presence of a first acid catalyst to produce a first product; And
(b) further reacting the first product with 1 to 5 equivalents of alpha methylstyrene to 1 equivalent of the phenol in the presence of a second acid catalyst to produce a second product, Lt; / RTI >

The method according to claim 1,
Wherein the first acid catalyst and the second acid catalyst are at least one selected from the group consisting of sulfuric acid, p -toluenesulfonic acid, methanesulfonic acid, phosphoric acid, boron trifluoride complex, clay, , And a method for producing alpha methyl styrene-substituted phenol.

3. The method of claim 2,
Wherein the first and second acid catalysts are different. &Lt; RTI ID = 0.0 > 18. < / RTI >

The method according to claim 1,
Wherein the equivalence ratios of the phenol and the first acid catalyst are 1: 0.0001 to 1, respectively.

The method according to claim 1,
Wherein the alpha methylstyrene reacted in the step (a) and the step (b) is 0.1 to 5 equivalents based on 1 equivalent of the phenol.

The method according to claim 1,
Wherein the first product comprises 30 to 50 wt% trimethylphenyl indene (TMPI), 1 to 10 wt% diphenylmethylpentene (DMP), 5 to 20 wt% cumyl phenol, 1 to 10 wt% alpha methylstyrene trimer, and Lt; RTI ID = 0.0 > phenol. &Lt; / RTI >

The method according to claim 1,
Wherein the equivalence ratios of the phenol and the second acid catalyst are 1: 0.0001 to 0.1, respectively.

The method according to claim 1,
Wherein the second product comprises 5 to 50% by weight of a mixture of trimethylphenylindane (TMPI) and diphenylmethylpentene (DMP), 2 to 20% by weight cumylphenol, 1 to 10% by weight of dicumene, 20 to 60% by weight of dicumylphenol By weight, and 0.1 to 5% by weight of alpha methylstyrene trimer.

9. The method of claim 8,
Wherein the mixture is prepared by mixing the trimethylphenylindane (TMPI) and the diphenylmethylpentene (DMP) in a weight ratio of 1: 1.5 to 8, respectively.

5 to 50% by weight of a mixture of trimethylphenylindane (TMPI) and diphenylmethylpentene (DMP), 2 to 20% by weight of cumylphenol, 1 to 10% by weight of dicumene, 20 to 60% by weight of dicumylphenol, And 0.1 to 5% by weight of styrene trimer.

11. The method of claim 10,
Wherein the mixture comprises trimethylphenylindane (TMPI) and diphenylmethylpentene (DMP) in a weight ratio of 1: 1.5 to 8, respectively.

1 to 50% by weight of alpha methyl styrene naphthophenol according to claim 10, and
Lt; / RTI > epoxy resin.