KR20240047725A - Novel compound, method for preparing thereof, and composition comprising the same - Google Patents

Abstract

The present invention relates to novel compounds, methods for their preparation and compositions containing them.

Description

Novel compound, method for preparing same, and composition comprising the same}

The present invention relates to a novel compound, a method for producing the same, and a composition containing the same, and more specifically, to a novel isosorbide epoxy acrylate-based compound, a method for producing the same, and a composition containing the same.

Currently used bisphenol-based epoxy resins are widely used in various industrial fields such as coatings, adhesives, electrical and electronics, and civil engineering due to their excellent adhesion, mechanical properties, and chemical resistance, and low shrinkage deformation when cured. These chemicals based on bisphenol-based epoxy resin are derived from petroleum and generate chemicals harmful to the human body, such as environmental hormones, during manufacturing and use.

The chemicals that we currently use based on bisphenol-based epoxy are chemical products derived from petroleum resources, and the use of these irreversible fossil resources is expected to result in enormous environmental costs. Therefore, research is being conducted to obtain bisphenol-based epoxies derived from existing petroleum resources from renewable resources, the most representative being isosorbide (1,4:3,6), which uses carbohydrate-based natural raw materials as a source. -dianhydrosorbitol), isoidide (1,4:3,6-dianhydroiditol), and isomannide (1,4:3,6-dianhydromannitol). Related research has already been conducted to produce epoxy by applying isosorbide instead of bisphenol A. (East A, Jaffe M, Zhang Y, Catalani LH. US patent 20080021209, 2008)

Isosorbide-based epoxy, especially isosorbide epoxy acrylate, manufactured by reacting isosorbide epoxy with acrylic acid, has non-yellowing properties and has the advantage of excellent physical properties such as mechanical strength and thermal properties upon polymerization. . However, isosorbide epoxy acrylate has a problem that it is difficult to use alone due to its high viscosity. Accordingly, the use of a diluent is essential to lower the viscosity, but due to poor compatibility with general diluents, there are restrictions on the type and amount of appropriate diluent used.

Accordingly, research is needed to improve compatibility with diluents while maintaining the physical properties of isosorbide-based epoxy acrylate.

The present invention is intended to provide a compound with excellent mechanical properties and improved compatibility with a diluent, a method for producing the same, and a composition containing the same.

The present invention provides a compound represented by the following formula (1):

[Formula 1]

In Formula 1, i) at least one of R ₁ and R ₂ , and ii) at least one of R ₃ and R ₄ is a linking group represented by the following Formula 1-1,

When R ₁ to R ₄ are not a linking group represented by the following formula 1-1, they are each independently hydrogen or straight or branched alkyl having 1 to 10 carbon atoms;

[Formula 1-1]

In Formula 1-1,

(*) is the part connected to Formula 1 above,

R ₅ is a single bond or straight or branched alkyl having 1 to 5 carbon atoms,

R ₆ to R ₈ are each independently linear or branched alkylene having 1 to 5 carbon atoms,

R ₉ is hydrogen or methyl.

In addition, the present invention includes the steps of reacting an acid anhydride and a hydroxyalkyl acrylate in the presence of a catalyst and a polymerization inhibitor to prepare a carboxyl-ester acrylate represented by the following formula 2-1 (step 1); and reacting the carboxyl-ester acrylate with the isosorbide epoxy represented by the following formula 2-2 in the presence of a catalyst and a polymerization inhibitor to prepare an oligomer (step 2). :

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,

R ₁ , and R ₄ to R ₉ are as previously defined.

The present invention also provides a composition comprising a compound according to the invention, a reactive diluent and a photoinitiator.

Furthermore, the present invention provides a polymer comprising repeating units derived from the compound according to the present invention.

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another component.

Additionally, the terminology used herein is only used to describe exemplary embodiments and is not intended to limit the invention.

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

In this specification, terms such as “comprise,” “comprise,” or “have” are used to describe implemented features, numbers, steps, components, or combinations thereof, and include one or more other features, numbers, or steps. , does not exclude the possibility of components, combinations or additions thereof.

Since the present invention can be subject to various changes and can take various forms, specific embodiments will be illustrated and described in detail below. However, this does not limit the present invention to the specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Hereinafter, the present invention will be described in detail.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n. -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited to these.

Conventionally, isosorbide epoxy acrylate is formed by reacting isosorbide epoxy and acrylic acid. Isosorbide epoxy acrylate has a high viscosity, making it difficult to use alone, so the use of a diluent (acrylate monomer or solvent) to lower the viscosity is essential. Most of the diluents are hydrophobic substances, but isosorbide epoxy acrylate has hydrophilic properties due to the cyclic ether structure derived from isosorbide in the molecular structure. Therefore, isosorbide epoxy acrylate has very poor compatibility with diluents, so there were restrictions on the amount and type of diluent used.

Accordingly, the researchers of the present invention completed the present invention by confirming that compatibility with a diluent was improved by introducing a carboxyl-ester acrylate capable of expressing hydrophobicity into the molecular main chain of the isosorbide epoxy acrylate.

Specifically, the compound of the present invention is a compound in which each ring in the isosorbide-based compound represented by the following formula (1) is substituted with at least one linking group represented by the following formula (1-1):

[Formula 1]

In Formula 1, i) at least one of R ₁ and R ₂ , and ii) at least one of R ₃ and R ₄ is a linking group represented by the following Formula 1-1,

When R ₁ to R ₄ are not a linking group represented by the following formula 1-1, they are each independently hydrogen or straight or branched alkyl having 1 to 10 carbon atoms;

[Formula 1-1]

In Formula 1-1,

(*) is the part connected to Formula 1 above,

R ₅ is a single bond or straight or branched alkyl having 1 to 5 carbon atoms,

R ₆ to R ₈ are each independently linear or branched alkylene having 1 to 5 carbon atoms,

R ₉ is hydrogen or methyl.

The compound represented by Formula 1-1 has a hydrophobic carboxyl-ester acrylate structure, and the carboxyl terminal reacts with epoxy to form a linking group.

Preferably, R ₁ and R ₄ are a linking group represented by Formula 1-1, and R ₂ and R ₃ are hydrogen.

Preferably, R ₅ is a single bond.

Preferably, R ₆ to R ₈ are each independently methylene, ethylene, or n-propylene. More preferably, R ₆ is methylene, R ₇ is ethylene, and R ₈ is ethylene or n-propylene.

Preferably, the linking group represented by Formula 1-1 is represented by the following Formula 1-2:

[Formula 1-2]

Meanwhile, the present invention involves reacting an acid anhydride and a hydroxyalkyl acrylate in the presence of a catalyst and a polymerization inhibitor to prepare a carboxyl-ester acrylate represented by the following formula 2-1 (step 1); and reacting the carboxyl-ester acrylate with the isosorbide epoxy represented by the following formula 2-2 in the presence of a catalyst and a polymerization inhibitor to prepare an oligomer (step 2). :

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,

R ₁ , and R ₄ to R ₉ are as previously defined.

The compound represented by Formula 2-1 is the above-mentioned carboxyl-ester acrylate, and is a compound that has a carboxylic acid group at one end and an acrylate group at the other end, and an ester group in the molecular structure. The terminal carboxylic acid group and acrylate group react with the epoxy group of the isosorbide epoxy represented by Formula 2-2 to form the compound represented by Formula 1.

The compound of the present invention has a structure derived from the compound represented by Formula 2-1 introduced into the main chain of the molecule, making it more hydrophobic compared to the structure forming only the existing isosorbide epoxy, and thus compatibility with hydrophobic diluents can be improved.

Step 1 of the epoxy resin production method of the present invention is to prepare the above-described carboxyl-ester acrylate, and step 2 is to prepare an oligomer by reacting the carboxyl-ester acrylate prepared in step 1 with isosorbide epoxy. This is the step.

Preferably, step 1 is carried out at 50 to 120 °C. If the reaction temperature is less than 50 ℃, the reaction may not proceed, and if it is higher than 120 ℃, the raw material acid anhydride or hydroxy alkyl achylate may evaporate, resulting in loss of raw materials, and unwanted side reactions may proceed. , there may be a risk of gel generation due to radical generation. More preferably, step 1 may be carried out at 55 ℃ or higher, 60 ℃ or higher, 65 ℃ or higher, or 70 ℃ or lower and 115 ℃ or lower, 110 ℃ or lower, 105 ℃ or lower, 100 ℃ or lower, or 90 ℃ or lower. .

Catalysts used in step 1 include ammonium salt catalysts such as triphenylphosphine, benzyl triethyl ammonium chloride, and tetramethyl ammonium chloride, which can be used alone or in a mixture of two or more types.

Preferably, step 2 is performed at 50 to 120 °C. If the reaction temperature is less than 50°C, the reaction may not proceed, and if it is higher than 120°C, side reactions or excessive polymerization may proceed. More preferably, step 2 may be carried out at 55 ℃ or higher, 60 ℃ or higher, 65 ℃ or higher, or 70 ℃ or higher and 115 ℃ or lower, 110 ℃ or lower, 105 ℃ or lower, or 100 ℃ or lower.

Catalysts used in step 2 include benzyl triethyl ammonium chloride, tetramethyl ammonium chloride, chromium compounds, and tertiary amine compounds such as triethyl amine, which can be used alone or in a mixture of two or more types.

The polymerization inhibitors used in Step 1 and Step 2 may be the same or different. Available polymerization inhibitors are mono methyl ether hydroquinone, hydroquinone, tert-butylhydroquinone, butylated hydroxytoluene, toluhydroquinone, 4-tert-butylcatechol, butylated hydroxyanisole, propyl gallate, mono t-butyl hydroquinone, p-methoxyphenol, p-tert-butylcatechol, N A group consisting of N-diethylhydroxylamine, N-nitrosoethylisopropylamine, p-benzoquinone, 2,6-Di-t-butyl-4-methylphenol, phenothiazine, and (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl It may contain one or more types selected from, and in addition, amine-based compounds, sulfone-based compounds, and metal compounds can be used.

Meanwhile, the present invention can provide an epoxy resin composition containing the above-described compound of the present invention, a reactive diluent, and a photoinitiator.

The reactive diluents include Tripropylene glycol diacrylate, Dipropylene glycol diacrylate, Ethoxylated trimethylolpropane triacrylate, Trimethylolpropane triacrylate, Hexanediol diacrylate, Isobornyl acrylate, Cyclic trimethylolpropane formal acrylate, 3 3,5-trimethylcyclohexyl acrylate, Tetrahydrofurfuryl acrylate, Triethylene glycol diacrylate. late, Polyethylene glycol diacrylate, Polypropylene glycol diacrylate, Trimethylolpropane propoxylate triacrylate, Tris(2-Hydroxy Ethyl) isocyanurate triacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, Ditrimethylolpropane tetraacrylate, Pentaerythritol tetraacrylate, Benzyl methacrylate, Lauryl methacrylate, Isodecyl methaacrylate, Phen oxyethyl methacrylate, 1,6-hexanediol dimethacrylate, Neopentyl glycol dimethacrylate, Ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, Bisphenol A ethoxylate dimethacrylate, Polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, Ethoxylated polypropylene dimethacrylate, Caprolactone acrylate, Phenoxy benzyl acrylate, Benzyl Acrylate late, Biphenylmethyl Acrylate, Lauryl Acrylate, Poly(ethylene glycol) phenyl ether acrylate, Isodecyl acrylate, 4-tert-butylcyclohexyl acrylate, Pentaerythritol triacrylate, Glyceryl propoxy triacrylate, Polypropylene glycol dimethacrylate, Trimethylolpropane trimethacrylate, Glycerol trimethacrylate, and Trimethylolpropane ethoxylate trimethacrylate and E as a representative solvent. thyl acetate, methyl Examples include ethyl ketone, propylene glycol monomethyl ether acetate, and toluene, which can be used alone or in combination of two or more.

In addition, the photoinitiator includes Benzil dimethyl ketal, Hydroxy cyclohexyl phenyl ketone, Hydroxy dimethyl acetophenone, Methyl-(4 methylthiophenyl)-2-morpholine propanone, 2,4-Diethylthioxanthone, Ethyl-4-dimethylaminobenzoate, Benzophenone, 4-Phenylbenzophenone, 2, Examples include 4,6-Trimethylbenzoyldiphenyl phosphine oxide, 2-Hydroxy-2-methyl-1-phenyl-1-propanone, and Methyl benzoylformate, which can be used alone or in combination of two or more.

Additionally, the present invention provides a polymer comprising repeating units derived from the compounds of the present invention described above.

The polyester resin according to the present invention described above has excellent mechanical properties and excellent compatibility with diluents, so it can be applied to various products.

Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited thereto.

Example 1

Succinic anhydride (200 g), 2-hydroxyl propyl acrylate (2-HPA, 300 g), and monomethyl ether hydroquinone (MEHQ, 0.4 g) were added, the temperature was raised to 70°C, and the catalyst triphenylphosphine (TPP, 5 g) was added. was invested. After adding the catalyst, the temperature is raised to 90°C to continue the reaction. The end point of the reaction was considered the point at which the acid anhydride peak (1790 cm ^-1 ) of IR disappeared. When the reaction was completed, it was cooled to 70°C and ISB epoxy (KDBM-1040, Kukdo Chemical, 356 g) was added. In addition, the antioxidant Sodium monohydrogen phosphate (0.9 g) was added to minimize discoloration of the resin color.

At 70°C, the catalyst Benzyl triethyl ammonium chloride (BTEAC, Daejeong Chemical, 4.3 g) was added, and 0.4 g of MEHQ was additionally added. Afterwards, the temperature was raised to 100°C, the reaction was continued, and the reaction was terminated at an acid value of 5 or less and an EEW of 10,000 or more, thereby obtaining an epoxy acrylate-based compound. The viscosity (60°C) of the produced epoxy resin was 2,500 cps.

Comparative Example 1

ISB epoxy (KDBM-1040, Kukdo Chemical, 500 g), acrylic acid (204.5 g), sodium monohydrogen phosphate (0.7 g), and MEHQ (0.7 g) were added, and after raising the temperature to 70°C, BTEAC was added. The reaction was continued at a reaction temperature of 100°C, and the reaction was terminated at an acid value of 5 or less and an EEW of 10,000 or more, to obtain an epoxy acrylate-based compound represented by the following formula (A). The viscosity (60°C) of the produced epoxy resin was 5,500 cps.

[Formula A]

The epoxy acrylate-based compounds of the above Examples and Comparative Examples were evaluated for compatibility with the following reactive diluents. Specifically, in the compatibility evaluation, the diluent ratio was mixed uniformly by increasing the diluent ratio in 5% increments, and the occurrence of phase separation or cloudiness (content appearing cloudy due to incompatibility) was observed at room temperature (25°C).

For example, in the comparative example, the meaning of TPGDA 35 is that up to 35% by weight of TPGDA has good compatibility and is uniformly mixed without clouding, but at 40% by weight, a cloudy phenomenon occurs. In addition, Example DPGDA >80 means that it has good compatibility at 80% by weight and is mixed uniformly and transparently.

The reactive diluents used for compatibility evaluation are as follows.

TPGDA: Tripropylene glycol diacrylate

DPGDA: Dipropylene glycol diacrylate

TMP(EO) ₃ TA: Ethoxylated trimethylolpropane triacrylate

TMPTA: Trimethylolpropane triacrylate

HDDA: Hexanediol diacrylate

EA: Ethyl acetate

MEK: Methyl ethyl ketone

PGMEA (PMA): Propylene glycol monomethyl ether acetate

Comparative Example 1 Example 1 TPGDA <35 <60 DPGDA <55 >80 TMP(EO) ₃ TA <50 >80 TMPTA <50 >80 HDDA <50 >80 EA <40 >80 MEK <40 >80 PGMEA(PMA) <40 >80

As can be seen in Table 1, the epoxy acrylate-based compound of the present invention was confirmed to have excellent compatibility with the reactive diluent compared to Comparative Example 1.

Example 2

The epoxy acrylate compound prepared in Example 1 (75 g) and the reactive diluent dipropylene glycol diacrylate (DPGDA, 25 g) were mixed to adjust the viscosity to 15,000 cps. Afterwards, a photoinitiator (a mixture of Irgacure TPO (Diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide) and Omnirad 1173 (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 3 g) was mixed. After coating the glass with 100 μm, UV curing was performed (1000 mJ). After curing, specimens were prepared in film form to evaluate the physical properties of the prepared resin composition.

Comparative Example 2

A resin composition was prepared in the same manner as in Example 2, except that the epoxy acrylate compound of Comparative Example 1 was used instead of the epoxy acrylate compound prepared in Example 1.

Comparative Example 3

A resin composition was prepared in the same manner as in Example 2, except that a commercial epoxy resin (KDU-1100, Kukdo Chemical, general purpose Bisphenol A type epoxy acrylate) was used instead of the epoxy acrylate compound prepared in Example 1. .

The physical properties of the resin compositions of the above examples and comparative examples were evaluated as follows, and the results are shown in Table 2 below.

(1) Tensile strength and tensile elongation

Specimens were prepared according to the specifications of ASTM D882. The specimen was left in a constant temperature and humidity room adjusted to a temperature of 23°C and a relative humidity of 50% for 24 hours and then subjected to a tensile test.

The tensile strength (MPa) and elongation of the specimen were measured according to the standard test method of ASTM D882 using a universal testing machine (UTM) from LLOYD Instruments. According to the standard test method of ASTM D882, the gap between the grips holding the specimen at both ends was set to 100 mm, and the test was performed under a constant tensile speed of 50 mm/min crosshead speed.

(2) Pendulum hardness

It was evaluated according to the ASTM D4355 standard using modle BGD 509 from the manufacturer Biuged. The unit was recorded as the time for the pendulum angle to reach 3°. The evaluation was conducted three times, and the average value is shown.

(3) Pencil hardness

Pencil hardness was measured according to ASTM D 3363. Specifically, after fixing the angle of the pencil at 45°, the surface of the specimen was scratched about 6.5 mm to evaluate whether scratches were observed with the naked eye, and the test was repeated by changing the strength of the pencil.

(4) Chemical resistance

Changes in the coating surface were observed by applying toluene, IPA, Acetone, or Water to cotton and moving it back and forth 100 times with constant force. If there was no change before or after evaluation, it was marked as pass.

Example 2 Comparative Example 2 Comparative Example 3 Tensile Strength (psi) 470 10500 8500 Tensile elongation (%) 15 <3 <3 Pendulum hardness (sec) 73 150 150 pencil hardness HB F HB chemical resistance pass Pass pass

As can be seen in Table 2, the resin composition containing the epoxy acrylate-based compound according to the present invention was confirmed to have physical properties equivalent to or superior to existing epoxy acrylate resins.

Claims (12)

Compound represented by Formula 1:
[Formula 1]

In Formula 1, i) at least one of R ₁ and R ₂ , and ii) at least one of R ₃ and R ₄ is a linking group represented by the following Formula 1-1,
When R ₁ to R ₄ are not a linking group represented by the following formula 1-1, they are each independently hydrogen or straight or branched alkyl having 1 to 10 carbon atoms;
[Formula 1-1]

In Formula 1-1,
(*) is the part connected to Formula 1 above,
R ₅ is a single bond or straight or branched alkyl having 1 to 5 carbon atoms,
R ₆ to R ₈ are each independently linear or branched alkylene having 1 to 5 carbon atoms,
R ₉ is hydrogen or methyl.
According to paragraph 1,
R ₁ and R ₄ are linking groups represented by Formula 1-1, and R ₂ and R ₃ are hydrogen,
compound.
According to paragraph 1,
R ₅ is a single bond,
compound.
According to paragraph 1,
R ₆ to R ₈ are each independently methylene, ethylene, or n-propylene,
compound.
According to paragraph 1,
The linking group represented by Formula 1-1 is represented by Formula 1-2 below,
compound:
[Formula 1-2]

Preparing a carboxyl-ester acrylate represented by the following formula 2-1 by reacting an acid anhydride and a hydroxyalkyl acrylate in the presence of a catalyst and a polymerization inhibitor (step 1); and
Comprising: preparing an oligomer by reacting the carboxyl-ester acrylate with the isosorbide epoxy represented by the following formula 2-2 in the presence of a catalyst and a polymerization inhibitor (step 2);
Compound Preparation Method:
[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,
R ₁ , and R ₄ to R ₉ are as defined in clause 1.
According to clause 6,
Step 1 is carried out at 50 to 120 ° C.
Method of preparing the compound.
According to clause 6,
Step 2 is carried out at 50 to 120 ° C.
Method of preparing the compound.
Comprising a compound according to claims 1 to 5, a reactive diluent and a photoinitiator,
Composition.
According to clause 9,
The reactive diluent includes one or more selected from the group consisting of Tripropylene glycol diacrylate, Dipropylene glycol diacrylate, Ethoxylated trimethylolpropane triacrylate, Trimethylolpropane triacrylate, Hexanediol diacrylate, Ethyl acetate, Methyl ethyl ketone, and Propylene glycol monomethyl ether acetate.
Composition.
According to clause 9,
The reactive diluent is included in an amount of 5 to 40 parts by weight based on 100 parts by weight of the composition.
Composition.
A polymer comprising repeating units derived from the compound according to claim 1.