KR101397655B1 - Styrenated phenol useful curing agent or plasticizer for epoxy resin - Google Patents

Abstract

The present invention relates to a styrene-substituted phenol useful as a curing agent or plasticizer of an epoxy resin, and more particularly to a styrene-substituted phenol having viscosity and curing properties similar to those of nonylphenol, To styrene-butadiene phenol as a curing agent or plasticizer for epoxy curing paints.

Description

Styrenated phenol useful curing agents or plasticizers for epoxy resins useful as hardeners or plasticizers for epoxy resins,

The present invention relates to styrenated phenols useful as hardeners or plasticizers for epoxy resins.

Epoxy resins are used in a wide range of applications such as paints, electrical and electronic insulating materials, and adhesives because the cured products have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance and adhesiveness.

The epoxy resin is excellent in physical properties such as hardness, hardness, resistance to light and workability, and does not cause volatilization during shrinking or shrinkage of the volume. Therefore, the epoxy resin is mixed with a hardener suitable for epoxy resin, It is also used as a paint. Compared to other types of paints used for concrete protection, epoxy curing paints are suitable for high performance paints because of their low shrinkage and high mechanical and chemical resistance.

Nonylphenol, on the other hand, has been applied to a wide variety of applications in various industrial fields, including its use as a hardener or plasticizer in the field of epoxy curing paints due to its inherent physico-chemical properties. However, since nonylphenol is known to be a renal toxic and endocrine hormone disruptant, its use in the industry has been banned or its use has been limited. In Europe in particular, in 2003, some sectors have already prohibited the use of nonylphenol in a total amount or more than 0.1% in products. [EU Directive 2003/53 / EC] is also regulated and managed in the EU Reach. [Restricted Substances of REACH Regulation Annex 17] In Korea, the report on nonylphenol has been strengthened and the use of nonylphenol has been strengthened.

However, the substitution of nonylphenol has not been developed and there are many difficulties in the industry. For use as a substitute for nonylphenol, it should first have the same or similar physicochemical properties as nonylphenol.

Accordingly, the inventors of the present invention focused on the fact that the viscosity property and the curing property of the styrene-nylated phenol are similar to that of nonylphenol, and applied styrene-nylated phenol as a substitute for nonylphenol which is used as a curing agent or plasticizer of an epoxy resin .

Styrenated phenol is prepared by alkylation of phenol with phenol and styrene. The styrene-substituted phenol may be a phenol (MSP) having one styrene group bonded to a benzene ring of phenol, a phenol (DSP) having two styrene groups bonded together, and a phenol (TSP) compound having three styrene groups bonded thereto have. Such styrene-based phenol is mainly used as an antioxidant for synthetic rubbers or resins, and there has been no report to date that styrene-based phenols are used as curing agents or plasticizers for epoxy resins.

An object of the present invention is to provide a use of styrene-based phenol as a curing agent for an epoxy resin.

It is another object of the present invention to provide a use of styrene-based phenol as a plasticizer of an epoxy resin.

It is also an object of the present invention to provide an epoxy paint containing styrene-butadiene phenol as a hardener or plasticizer.

In order to solve the above-mentioned problems, the present invention is characterized by a curing agent or a plasticizer of an epoxy resin containing styrene-naphthyl phenol represented by the following formula (1).

[Chemical Formula 1]

(In the above formula (1), n is 1, 2, or 3)

Further, the present invention is characterized by an epoxy paint comprising a main portion comprising an epoxy resin and a curing agent portion containing styrene-nidated phenol represented by Formula 1 above.

Styrene-based phenols have physicochemical properties similar to those of nonylphenol, but have inherent applicability of nonylphenol, and possess viscosity improving and curing promoting properties at the same time, and thus are useful as substitutes for nonylphenol. That is, styrene-based phenol is useful as a curing agent or plasticizer for an epoxy resin.

Further, when applied to an epoxy paint comprising a main portion comprising an epoxy resin and a curing agent portion containing styrene-nidated phenol represented by Formula 1, it is excellent in adhesion to concrete, less shrinkage of the coating film during curing , And excellent in mechanical and chemical resistance of the cured coating film, so that it is useful as a thick film type coating material.

The present invention relates to the use of styrene-based phenol as a curing agent or plasticizer in the preparation of epoxy curing type coatings, confirming that the viscosity characteristics and curing properties of styrene-based phenols are similar to nonylphenol.

The styrene-substituted phenol in the present invention can be represented by the following formula (1).

[Chemical Formula 1]

(In the above formula (1), n is 1, 2, or 3)

In the present invention, the compound having n = 1 is abbreviated as 'MSP', the compound having n = 2 is abbreviated as 'DSP', and the compound having n = 3 Is abbreviated as 'TSP'.
The styrene-substituted phenol represented by the formula (1) is prepared by alkylating phenol and styrene under an acid catalyst at a temperature of 100 to 150 ° C. More specifically, when 1 to 1.5 moles of styrene is reacted with 1 mole of phenol, the compounds of MSP, DSP and TSP are contained in a ratio of MSP: DSP: TSP = 50 to 75: 15 to 35: 1 to 8% A compound is produced.

The weight ratio of MSP, DSP and TSP is determined by the reaction molar ratio of phenol and styrene used as reactants. The styrene-butadiene phenol suitable for the present invention is preferably adjusted so that the content of MSP is 50% by weight or more, preferably 50 to 75% by weight. As described above, in the present invention, styrene-substituted phenol having a relatively high content of MSP is used because the viscosity of the MSP is higher as the content of MSP is higher, so that plasticity is imparted when mixed with an epoxy resin, The OH value is kept the same as that of the existing nonylphenol (240 ~ 250), thereby accelerating the curing reaction.

Table 1 below shows the physical properties of styrene-butadiene-phenol, which is commercially available as Kumanox-3110, and nonylphenol, which is classified as a regulated substance.

division Nonylphenol Kumanox-3110 CAS number 84852-15-3 61788-44-1 constitutional formula C ₁₅ H ₂₄ O Styrene-nitrated phenol
(MSP content 50-70%) Weight average molecular weight (Mw) 220.3 220 OH value 240-250 240-250 Viscosity (25 캜 cps) 1,000 to 1,200 400 Color value (G) 0.3 (Max 1.5) 0.5 (Max 1.5) Water content% 0.1 (Max 0.2%) 0.1 (Max 0.2%) Remarks Toxic Non-toxic

As shown in Table 1 above, styrene-nylated phenol is a non-toxic substance and has an advantage of being excellent in environmental compatibility, and has a weight average molecular weight, a hydroxy value (OH value), a viscosity, a color value, Similarity can be seen. Particularly, since the viscosity of styrene-butadiene-phenol is kept lower than that of nonylphenol, it has a special advantage that the plasticity is improved when mixed with an epoxy resin, and the workability is excellent.

Therefore, the styrene-substituted phenol represented by the above formula (1) is useful as a substitute for nonylphenol, and is a non-toxic substance and is excellent in environmental compatibility.

In the meantime, the present invention is characterized in that the styrene-naphthyl phenol represented by the formula (1) is used as a curing agent for an epoxy paint containing an epoxy resin as a subject.

The epoxy paint may be specifically divided into an epoxy main portion and a hardener portion. The main part constituting the epoxy paint comprises an epoxy resin, a non-reactive diluent, a plasticizer and the like, and the curing agent part includes a curing accelerator, a plasticizer and the like. Various compositions and composition ratios of epoxy paints have been studied up to the present time. In the present invention, there are no particular restrictions on these composition ratios and composition ratios. The present invention is characterized in that styrene-naphthyl phenol represented by the above-mentioned formula (1) is applied as a curing agent constituting a curing agent part in an epoxy paint or as a plasticizer. The curing agent portion containing the styrene-substituted phenol may specifically include 1 to 40% by weight of styrene-naphthol phenol as a curing agent or plasticizer and 60 to 99% by weight of a conventional epoxy curing agent. Examples of the present invention specifically exemplify the use of a polyether diamine curing agent as an ordinary epoxy curing agent, but the present invention does not place any particular limitation on the selection of the usual epoxy curing agent component.

When the curing agent part containing the styrene-substituted phenol is used as a two-part type epoxy paint, workability is improved because the viscosity of the paint is low, the workability is improved by shortening the curing time, the hardness of the paint surface is increased, .

The curing agent part is usually compounded in an amount of 1 to 40 parts by weight based on 100 parts by weight of the epoxy main part to form a curing film.

The present invention will now be described in more detail with reference to the following examples, but the present invention is not limited thereto.

In addition, the physical properties measured in the following examples were measured by the following methods.

[Measurement of physical properties]

1) Viscosity

Viscosities were measured at 25 ° C using a rotational viscometer (Brookfield HAT Viscometer or rookfield LV DVE 230 Viscometer).

2) Color

The color was measured using a color measuring instrument (NIPPON DENSHOKU OME 2000).

3) Amine

Amine was determined by 0.1N-HCl titration.

4) Curing time

The curing time was measured at room temperature at 25 ° C (50 ° C (0.1) mercury thermometer) at a scale of 100 g.

5) Shore hardness

Hardness was measured using a hardness measuring device (e-Asker Durometer Super EX Type-D). The final hardness means the hardness of the sample cured by heating at 80 ° C for 2 hours, and the change in hardness of the sample cured at room temperature at room temperature was measured.

[Example]

Example 1 Preparation of Styrene Nitride Phenol

Phenol (300 g), phosphoric acid (H ₃ PO ₄ ) catalyst (1.876 g, 0.006 eq) was added and heated to 140 ° C. Styrene (381.6 g, 1.15 eq) was slowly added dropwise over 120 minutes. The reaction temperature was increased from 140 ° C to 170 ° C depending on the dropping amount of styrene. When the dropwise addition of styrene was completed, an additional 1 hour was further added at the same reaction temperature. In order to remove unreacted materials, the reaction temperature was lowered to 110 ° C, sulfuric acid (H ₂ SO ₄ ) catalyst (0.02 g, 1-3 wt% based on phosphoric acid catalyst) was added to the reaction, And reacted for 30 minutes in that state. The temperature of the reaction product was adjusted to 80 캜, and an aqueous solution of sodium carbonate was added thereto in the same ratio as the sulfuric acid used above and neutralized for 30 minutes. The resulting neutralized salt was removed by filtration after removing water through concentration under reduced pressure to obtain styrene-nidated phenol (reaction conversion 97%, purity 97% or more).

GC analysis of the obtained styrene-butadiene phenol showed that the ratio of MSP 67 wt%, DSP 27 wt%, TSP 6 wt% was achieved.

Example 2. Preparation of curing agent part for epoxy paint

2-1) Curing agent part (A) containing styrene-

198 g of D-230 (Jeffamine, manufactured by National Tofu Chemical Co., Ltd., polyether diamines) and 102 g of styrene-naphthyl phenol prepared in Example 1 were fed into a 500-mL volume container made of polyether and stirred using a magnetic stirrer Respectively. When the exothermic phenomenon was over, the temperature was raised to 70 DEG C, and the mixture was further stirred for 30 minutes. Then, the mixture was filtered through 100 mesh molecular sieves to obtain 300 g of the curing agent part (A).

2-2) Curing agent part containing nonylphenol (B)

198 g of D-230 (Jeffamine, a product of National Kyodo Chemical Co., Ltd., polyether diamines) and 102 g of nonylphenol were charged into a 500-mL volume container made of polyether, and the mixture was stirred using a magnetic stirrer. When the exothermic phenomenon was terminated, the temperature was raised to 70 ° C., and the mixture was further stirred for 30 minutes. Then, the mixture was filtered through 100 mesh molecular sieves to obtain 300 g of a curing agent part (B).

The viscosity and amine value of each of the curing agent parts (A) and (B) prepared in Example 2 were measured and shown in Table 2 below.

division Viscosity (cps) Amine judgment The curing agent part (A) 55 305.9 Similar properties The curing agent part (B) 48 309.5

Experimental example. Comparison of physical properties of epoxy paints

100 parts by weight of an epoxy main part containing 90% by weight of KER-828 (Kumho P & B Chemicals, epoxy resin) and 10% by weight of benzyl alcohol was added to each of the curing agent parts 40 Were mixed and cured.

division Hardener part judgment Curing agent part A Hardener part B Curing time 3 hours 10 minutes 3 hours 25 minutes Curing time of hardener part A is shorter
Shore hardness 2 days 51 45 The curing hardness of the curing agent portion A is greater 5 days 79 76 7 days 85 84

As described above, the styrene-based phenol has physicochemical properties similar to or similar to nonylphenol in physical properties such as viscosity and amine value, and styrene-butadiene-styrene The curing agent portion containing nated phenol has an improved effect of improving workability and durability because of short curing time, high hardness of cured coating film and excellent physical properties.

Therefore, the styrene-substituted phenol is useful as a curing agent or plasticizer of an epoxy resin.

Claims (9)

1. A curing agent for an epoxy resin containing styrene-naphthyl phenol represented by the following formula (1).
[Chemical Formula 1]

(In the above formula (1), n is 1, 2, or 3)
The method according to claim 1,
Wherein the styrene-based phenol has a content of styrene-butadiene phenol of n = 1 in an amount of 50 wt% or more.
The method according to claim 1,
The styrene-based phenol comprises 50 to 75% by weight of styrene-naphthyl phenol (MSP) with n = 1, 15 to 35% by weight of styrene-nitrated phenol (DSP) with n = 2 and styrene- ) Of 1 to 8% by weight based on the total weight of the curing agent.
A plasticizer of an epoxy resin containing styrene-naphthyl phenol represented by the following formula (1).
[Chemical Formula 1]

(In the above formula (1), n is 1, 2, or 3)
5. The method of claim 4,
Wherein the styrene-based phenol has a content of styrene-butadiene phenol (MSP) of n = 1 in an amount of 50 wt% or more.
5. The method of claim 4,
The styrene-based phenol comprises 50 to 75% by weight of styrene-naphthyl phenol (MSP) with n = 1, 15 to 35% by weight of styrene-nitrated phenol (DSP) with n = 2 and styrene- ) Of 1 to 8% by weight based on the total weight of the plasticizer.
A main portion including an epoxy resin;
A curing agent part comprising styrene-naphthyl phenol represented by the following formula (1);
Lt; / RTI >
[Chemical Formula 1]

(In the above formula (1), n is 1, 2, or 3)
8. The method of claim 7,
Wherein the styrene-based phenol has a content of styrene-butadiene phenol (MSP) with n = 1 of 50 wt% or more.
8. The method of claim 7,
The styrene-based phenol comprises 50 to 75% by weight of styrene-naphthyl phenol (MSP) with n = 1, 15 to 35% by weight of styrene-nitrated phenol (DSP) with n = 2 and styrene- ) Of 1 to 8% by weight based on the total weight of the epoxy resin composition.