KR20240067719A - Preparation method of isosorbide-based epoxy compounds - Google Patents

Abstract

The present invention provides a method for effectively producing isosorbide-based epoxy compounds with low viscosity and high purity.

Description

Method for producing isosorbide-based epoxy compounds {PREPARATION METHOD OF ISOSORBIDE-BASED EPOXY COMPOUNDS}

The present invention relates to a method for producing isosorbide-based epoxy compounds with low viscosity and high purity.

Generally, polymer compounds are manufactured using raw materials derived from petroleum resources. However, recently, there has been concern about the depletion of petroleum resources, and there is a demand for the provision of polymer resins using raw materials obtained from biomass resources such as plants.

In particular, as environmental problems resulting from the process of using petroleum resources intensify, the sustainability and eco-friendly advantages of biomass resources are becoming more prominent. From this perspective, the development of biomass-based monomer and polymer production technologies is being addressed as an important issue in both academia and industry. In particular, as there are concerns that global warming due to the increase and accumulation of carbon dioxide emissions will cause climate change, there is a demand for the development of polymer resins made from plant-derived monomers that emit extremely low carbon emissions during the manufacturing process.

In addition to the sustainability and environmentally friendly advantages of biomass resources, there is a greater need for the development of polymers with new carbon skeleton structures that can secure mechanical properties equivalent to or superior to those of petroleum polymers and a low glass transition temperature. .

In this respect, isosorbide (1,4:3,6-dianhydrohexitol), unlike existing raw materials based on the petrochemical industry, is used in corn and potatoes. These are raw materials obtained from plant resources, such as: When isosorbide is used as a monomer for engineering plastics such as polycarbonate, it has excellent thermal properties because it is structurally strong.

Methods for producing epoxy by reacting isosorbide with epichlorohydrin are known in various ways and have been described in numerous literature. However, when manufactured using most of the literature methods, it is synthesized in the form of n = 1 or more rather than in the form of isosorbide diglycidyl ether (n = 0), and as a result, it is synthesized with a high viscosity. For example, most of the synthesis methods using commercially applicable caustic soda in the literature were those that showed a viscosity of 10,000 cps or more at room temperature.

However, since most epoxy compounds or compositions containing them are used by mixing with a curing agent at room temperature, if the viscosity is too high, workability is reduced and leveling is poor. In addition, manufacturing with a low content of isosorbide diglycidyl ether (n = 0) means that the content of structures with n = 1 or more is high, which means that the molecular weight between epoxy groups increases, so the curing agent and the three-dimensional polymer network There is a problem in that during formation, the cross-linking points become distant and the cross-linking density decreases.

In particular, the higher the crosslinking density, the better the mechanical properties, the higher the glass transition viscosity (Tg), and the better the chemical resistance.

Therefore, there is a need to develop a new manufacturing method with high isosorbide diglycidyl ether (n=0) content and low viscosity.

Accordingly, the present invention seeks to provide a method for effectively producing an isosorbide-based epoxy compound with low viscosity and high purity, which has the advantages of sustainability of biomass resources and environmental friendliness.

According to one embodiment of the invention,

i) performing a ring-opening reaction by mixing isosorbide and an organic halide in the presence of a phase transfer catalyst; and

ii) after performing the ring-opening reaction, adding a basic compound and performing an epoxy substitution reaction; and

iii) after performing the substitution reaction, performing a ring closure reaction through an azeotropic distillation reaction;

Including,

The phase transfer catalyst is one or more compounds represented by any of the following formulas 1 to 3,

A method for producing an isosorbide-based epoxy compound is provided.

[Formula 1]

Ar _a R ¹ _4-a N ⁺ (X ¹ _b ) ^-

In Formula 1,

Ar are the same or different from each other, and are each independently substituted or unsubstituted C _6-20 aryl, or substituted or unsubstituted C _6-20 aryl substituted C _1-3 alkyl,

R ¹ are the same or different from each other and are each independently C _1-20 alkyl,

X ¹ are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

a is an integer from 1 to 4,

b is an integer from 1 to 3,

[Formula 2]

In Formula 2,

R ² is hydrogen or C _1-20 alkyl,

X ² are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

c is an integer from 1 to 3,

[Formula 3]

In Formula 3 above,

R ³ are the same or different from each other and are each independently hydrogen or C _1-20 alkyl,

X ³ are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

d is an integer from 1 to 3.

According to the present invention, an isosorbide-based epoxy compound with low viscosity and high purity can be effectively produced, which has the advantages of sustainability of biomass resources and environmental friendliness.

Figure 1 shows a gel permeation chromatography (GPC, Gel Permeation Chromatography systems) analysis graph and measurement results for an isosorbide-based epoxy compound synthesized according to Example 1 as an embodiment of the present invention.

In the present invention, terms such as first, second, etc. 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 intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and are intended to indicate the presence of one or more other features or It should be understood that this does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

As used throughout the specification, the terms “about,” “substantially,” and the like are used to mean at or close to a numerical value when manufacturing and material tolerances inherent in the stated meaning are given, and are used to convey the understanding of the present application. Precise or absolute figures are used to assist in preventing unscrupulous infringers from taking unfair advantage of stated disclosures. As used throughout the specification, the terms “step of” or “step of” do not mean “step for.”

In this specification, the term "combination thereof" included in the Markushi format expression means a mixture or combination of one or more components selected from the group consisting of the components described in the Markushi format expression, It means including one or more selected from the group consisting of.

In this specification, and means a bond connected to another substituent.

Since the present invention can make various changes and take various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a 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.

Based on the above definition, implementation examples of the present invention will be described in detail. However, these are presented as examples, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

In one embodiment of the present invention, a novel isosorbide-based epoxy composition is provided, which has the advantages of sustainability of biomass resources and environmental friendliness, and has a high biocarbon content.

Specifically, the method for producing an isosorbide-based epoxy compound according to the present invention is characterized by comprising the following i), ii), and iii):

i) performing a ring-opening reaction by mixing isosorbide and an organic halide in the presence of a phase transfer catalyst; and

ii) after performing the ring-opening reaction, adding a basic compound and performing an epoxy substitution reaction; and

iii) After performing the substitution reaction, performing a ring closure reaction by an azeotropic distillation reaction.

In particular, the method for producing an isosorbide-based epoxy compound according to the present invention is characterized in that the phase transfer catalyst is one or more compounds represented by any of the following formulas 1 to 3.

[Formula 1]

Ar _a R ¹ _4-a N ⁺ (X ¹ _b ) ^-

In Formula 1,

Ar are the same or different from each other, and are each independently substituted or unsubstituted C _6-20 aryl, or substituted or unsubstituted C _6-20 aryl substituted C _1-3 alkyl,

R ¹ are the same or different from each other and are each independently C _1-20 alkyl,

X ¹ are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

a is an integer from 1 to 4,

b is an integer from 1 to 3,

[Formula 2]

In Formula 2,

R ² is hydrogen or C _1-20 alkyl,

X ² are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

c is an integer from 1 to 3,

[Formula 3]

In Formula 3 above,

R ³ are the same or different from each other and are each independently hydrogen or C _1-20 alkyl,

X ³ are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

d is an integer from 1 to 3.

In this specification, unless there is a special limitation, the following terms may be defined as follows.

Halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

The C _1-20 alkyl, that is, the alkyl having 1 to 20 carbon atoms, may be straight-chain, branched-chain, or cyclic alkyl. Specifically, alkyl having 1 to 20 carbon atoms includes straight chain alkyl having 1 to 20 carbon atoms; Straight-chain alkyl having 1 to 15 carbon atoms; Straight-chain alkyl having 1 to 5 carbon atoms; branched or cyclic alkyl having 3 to 20 carbon atoms; Branched chain or cyclic alkyl having 3 to 15 carbon atoms; Alternatively, it may be branched chain or cyclic alkyl having 3 to 10 carbon atoms. For example, the alkyl having 1 to 20 carbon atoms (C _1-20 ) is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl. , cyclohexyl, cycloheptyl, cyclooctyl, etc., but is not limited thereto.

In particular, the C _1-3 alkyl, that is, the alkyl having 1 to 3 carbon atoms, may be straight-chain or branched-chain alkyl. Specifically, alkyl having 1 to 3 carbon atoms includes methyl, ethyl, propyl, isopropyl, etc., but is not limited thereto.

The C _6-20 aryl, that is, an aryl having 6 to 20 carbon atoms, may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. For example, the aryl may include phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, etc., but is not limited thereto.

The above-mentioned substituents are optionally hydroxy groups within the range of having the same or similar effect as the desired effect; halogen; alkyl or alkenyl, aryl, alkoxy; Alkyl or alkenyl, aryl, alkoxy containing one or more heteroatoms from groups 14 to 16; Silyl; Alkylsilyl or alkoxysilyl; Phosphine group; phosphide group; Sulfonate group; and may be substituted with one or more substituents selected from the group consisting of a sulfone group.

Additionally, according to one embodiment of the present invention, there is a method for producing an isosorbide-based epoxy compound represented by the following formula (4).

[Formula 4]

In Formula 4 above,

이고, R ⁴ is H or

ego,

n is an integer from 0 to 100.

For example, R ⁴ may be H.

The isosorbide-based epoxy compound has the advantage that, unlike existing bisphenol-based compounds, it is not an endocrine disruptor and is of biological origin. In addition, the isosorbide-based epoxy compound is characterized by a bicyclic ring structure and can reach a high glass transition temperature.

Specifically, as described above, the isosorbide-based epoxy compound is a bio-derived compound rather than a conventional petroleum-based compound, and is characterized by a biocarbon content of 100% based on 100% of the total carbon number. Here, the biocarbon content can be measured by calculating the ratio of bio-derived carbon to total organic carbon. For example, the biocarbon content of the isosorbide-based epoxy compound can be measured by inferring the radioisotope ( ¹⁴ C) number ratio (%) of the total organic carbon number ratio, and specifically, based on the American Society for Testing and Materials ASTM D 6866. It can be measured. Here, the biocarbon content can be expressed as a number % according to the carbon number ratio.

In addition, the isosorbide-based epoxy compound is understood as a single isosorbide epoxide of Formula 1 or a mixture of isosorbide epoxides with different substituents R ⁴ and/or index n. When multiple types of isosorbide epoxides are present, the substituent R ⁴ can be applied in various ways as specified in Formula 1. Additionally, n is a value satisfying 0 to 100 and can be applied in various ways.

For example, in the isosorbide-based epoxy compound of the present invention, the compound in which n in Formula 1 is 0 may be 40% or more or 40% to 70% of the total weight of the isosorbide-based epoxy compound. Specifically, the compound in Formula 1 where n is 0 accounts for at least 43.5%, or at least 44%, or at least 45% of the total weight of the isosorbide-based epoxy compound in terms of ensuring high processability when applied to a cured product. , or 45.5% or more, or 46% or more, or 47% or more.

According to one embodiment, n is a value satisfying 0 to 100, such as 0 to 80, or 0 to 50, or 0 to 40, or 0 to 30, or 0 to 20, or 0 to 15, or 0 to It may be a value satisfying 12, or 0 to 10, or 0 to 8, or 0 to 6, or 0 to 5. However, this is only an example, and an embodiment of the present invention is not limited to this example.

According to one embodiment, n is a value satisfying 1 to 100, such as 1 to 80, or 1 to 50, or 1 to 40, or 1 to 30, or 1 to 20, or 1 to 15, or 1 to It may be a value satisfying 12, or 1 to 10, or 1 to 8, or 1 to 6, or 1 to 5.

According to one embodiment, n is a value satisfying 2 to 100, such as 2 to 80, or 2 to 50, or 2 to 40, or 2 to 30, or 2 to 20, or 2 to 15, or 2 to 20. It may be a value satisfying 12, or 2 to 10, or 2 to 8, or 2 to 6, or 2 to 5.

According to one embodiment, n is a value satisfying 3 to 100, such as 3 to 80, or 3 to 50, or 3 to 40, or 3 to 30, or 3 to 20, or 3 to 15, or 3 to 30. It may be a value satisfying 12, or 3 to 10, or 3 to 8, or 3 to 6, or 3 to 5.

According to one embodiment, n is a value satisfying 4 to 100, such as 4 to 80, or 4 to 50, or 4 to 40, or 4 to 30, or 4 to 20, or 4 to 15, or 4 to 40. It may be a value satisfying 12, or 4 to 10, or 4 to 8, or 4 to 6, or 4 to 5.

According to one embodiment, n is a value satisfying 5 to 100, such as 5 to 80, or 5 to 50, or 5 to 40, or 5 to 30, or 5 to 20, or 5 to 15, or 5 to 5. It may be a value satisfying 12, or 5 to 10, or 5 to 8, or 5 to 6.

Meanwhile, the isosorbide-based epoxy compound has an epoxy group equivalent weight of 120 g/eq to 500 g/eq. For example, the epoxy group equivalent weight of the isosorbide-based epoxy compound is 120 g/eq to 350 g/eq, or 130 g/eq to 300 g/eq, or 135 g/eq to 250 g/eq, or 140 g/eq. eq to 200 g/eq. More specifically, the epoxy group equivalent weight of the isosorbide-based epoxy compound is about 155 g/eq to 173 g/eq. Here, the epoxy group equivalent is the molecular weight divided by the number of reactors, and can be measured by, for example, a neutralization titration method.

Additionally, the isosorbide-based epoxy compound may have a Brookfield viscosity measured at 25°C of 500 mPa·s to 20,000 mPa·s. Specifically, the viscosity of the isosorbide-based epoxy compound is 18000 mPa·s or less, or 15000 mPa·s or less, or 12000 mPa·s or less, or 10000 mPa·s or less, or 9000 mPa·s or less, or 8000 mPa·s or less. mPa·s or less, or 6000 mPa·s or less, or 5000 mPa·s or less, or 4000 mPa·s or less, or 3500 mPa·s or less, or 3000 mPa·s or less, or 2500 mPa·s or less, and 520 mPa ㆍs or more, or 550 mPa·s or more, or 600 mPa·s or more, or 700 mPa·s or more, or 800 mPa·s or more 1000 mPa·s or more, or 1500 mPa·s or more, or 2000 mPa·s or more You can. For example, the Brookfield viscosity of the isosorbide-based epoxy compound is about 500 mPa·s to 2500 mPa·s, or about 2000 mPa·s to 6000 mPa·s, or about 3000 mPa·s to 5000. It may be mPa·s. Here, Brookfield viscosity represents the resistance value of the fluid applied to the spindle using a rotational viscometer, and can be measured using a Brookfield viscometer.

Hereinafter, the method for producing the above-described isosorbide-based epoxy compound will be explained by dividing it into each process step.

Step i) ring-opening reaction in the presence of a phase transfer catalyst;

In one embodiment of the invention, step i) is a step of performing a ring-opening reaction by mixing isosorbide and an organic halide in the presence of a phase transfer catalyst.

In particular, the method for producing an isosorbide-based epoxy compound according to the present invention includes isosorbide and an organic halide in the presence of at least one phase transfer catalyst among the compounds represented by any of the formulas 1 to 3 in step i). It is characterized in that a ring-opening reaction is performed by mixing, and then a three-step process of a substitution reaction and a ring-closing reaction is performed.

Specifically, in step i), the ring-opening reaction may be performed at a temperature of 40°C to 100°C and under pressure conditions of 450 mmHg to 768 mmHg. For example, step i) is performed by mixing isosorbide and an organic halide in the presence of one or more phase transfer catalysts among the compounds represented by any one of Formulas 1 to 3, at a temperature of 40 ℃ to 100 ℃ and 450 mmHg to 768 mmHg. It may be a step of performing a ring-opening reaction under pressure conditions.

For example, the ring-opening reaction pressure in step i) is 450 mmHg or more, 500 mmHg or more, or 550 mmHg or more, or 580 mmHg or more, or 600 mmHg or more, or 650 mmHg or more, or 700 mmHg or more, or 735 mmHg. or more, or more than 750 mmHg, or more than 752 mmHg, or more than 755 mmHg, or more than 758 mmHg, and less than or equal to 768 mmHg, or less than or equal to 765 mmHg, or less than or equal to 763 mmHg, or less than or equal to 762 mmHg, or less than or equal to 760 mmHg. For example, the ring-opening reaction may be performed under pressure conditions of normal pressure or a reduced pressure range close to it, that is, 450 mmHg to 760 mmHg or about 760 mmHg.

In addition, the ring-opening reaction temperature in step i) is 45 ℃ or higher, or 48 ℃ or higher, or 50 ℃ or higher, or 52 ℃ or higher, or 55 ℃ or higher, and 90 ℃ or lower, or 80 ℃ or lower, or 75 ℃ It may be carried out below, or below 73°C, or below 70°C. For example, the ring-opening reaction may be performed under temperature conditions of 58°C to 65°C.

In addition, the ring-opening reaction in step i) can be performed for 0.1 hours to 6 hours, specifically 0.12 hours to 5 hours, or 0.14 hours to 3 hours, or 0.16 hours to 2 hours. there is.

Meanwhile, the phase transfer catalyst in the ring-opening reaction of step i) is one or more compounds represented by any of the following formulas 1 to 3.

[Formula 1]

Ar _a R ¹ _4-a N ⁺ (X ¹ _b ) ^-

In Formula 1,

Ar are the same or different from each other, and are each independently substituted or unsubstituted C _6-20 aryl, or substituted or unsubstituted C _6-20 aryl substituted C _1-3 alkyl,

R ¹ are the same or different from each other and are each independently C _1-20 alkyl,

X ¹ are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

a is an integer from 1 to 4,

b is an integer from 1 to 3,

[Formula 2]

In Formula 2,

R ² is hydrogen or C _1-20 alkyl,

X ² are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

c is an integer from 1 to 3,

[Formula 3]

In Formula 3 above,

R ³ are the same or different from each other and are each independently hydrogen or C _1-20 alkyl,

X ³ are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),

d is an integer from 1 to 3.

Specifically, in step i), the phase transfer catalyst may be an ammonium salt, pyridinium salt, or piperidinium salt represented by any one of Formulas 1 to 3. For example, the phase transfer catalyst is a quaternary ammonium salt containing at least one aryl substituent or an aryl-substituted lower alkyl group, as shown in Formula 1, or as represented in Formula 1 or 2, N It may be a pyridinium salt or a piperidinium salt containing an aromatic or aliphatic ring. Preferably, the phase transfer catalyst may be a quaternary ammonium salt represented by Formula 2, or a pyridinium salt or piperidinium salt represented by Formula 3 or 4. More preferably, the phase transfer catalyst may be a quaternary ammonium salt represented by Formula 2 or a pyridinium salt represented by Formula 3. More preferably, the phase transfer catalyst may be a quaternary ammonium salt represented by Chemical Formula 2.

In one embodiment, the phase transfer catalyst may be represented by Formula 1 above, and is characterized by including at least one aryl substituent or aryl-substituted lower alkyl group. More specifically, the phase transfer catalyst is tetra(C _6-20 aryl)ammonium chloride, tetra(C _6-20 aryl)ammonium bromide, tetra(C _6-20 aryl)ammonium iodide, and tetra(C _6-20 aryl)ammonium iodide. ) ammonium dichloriodate, and tetra(C _6-20 aryl)ammonium fluoride; Tetra(C _6-20 aryl C _1-3 alkyl)ammonium chloride, tetra(C _6-20 aryl C _1-3 alkyl)ammonium bromide, tetra(C _6-20 aryl C _1-3 alkyl)ammonium iodide, tetra(C _6-20 arylC _1-3 alkyl)ammonium dichloriodate, and tetra(C _6-20 arylC _1-3 alkyl)ammonium fluoride; Tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)ammonium chloride, tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)ammonium bromide, tetra(C _{6 -20} aryl)(C _6-20 arylC _1-3 alkyl)ammonium iodide, tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)ammonium dichloriodate, and tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)ammonium fluoride; Tetra(C _6-20 aryl)(C _1-20 alkyl)ammonium chloride, tetra(C _6-20 aryl)(C _1-20 alkyl)ammonium bromide, tetra(C _6-20 aryl)(C _1-20 alkyl) ) ammonium iodide, tetra(C _6-20 aryl)(C _1-20 alkyl)ammonium dichloriodate, and tetra(C _6-20 aryl)(C _1-20 alkyl)ammonium fluoride; Tetra(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium chloride, tetra(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium bromide, tetra(C _{6 -20} arylC _1-3 alkyl)(C _1-20 alkyl)ammonium iodide, tetra(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium dichloriodate, and tetra(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium fluoride; and tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium chloride, tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl) )(C _1-20 alkyl)ammonium bromide, tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium iodide, tetra(C _6-20 aryl) )(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium dichloriodate, and tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)(C _{1- 20} alkyl) ammonium fluoride; one or two or more selected from the group consisting of may be used.

For example, the phase transfer catalyst represented by Formula 1 includes benzyltrimethyl ammonium chloride (BTMAC), benzyltrimethylammonium bromide, benzyltriethylammonium chloride (BTEAC), benzyltriethylammonium bromide, benzyltributylammonium chloride (BTBAC), and benzyltrimethylammonium chloride (BTMAC). It may be one or more selected from the group consisting of tributylammonium bromide, benzyltrimethylammonium dichloroiodate, benzyltriphenyl ammonium chloride, and methyltriphenyl ammonium chloride. Preferably, the phase transfer catalyst represented by Formula 1 may be one or more of benzyltrimethyl ammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), or benzyltributylammonium chloride (BTBAC).

In another embodiment, the phase transfer catalyst may be represented by Formula 2 or 3, and is characterized by including an aromatic or aliphatic ring containing N. Specifically, the phase transfer catalyst is (C _6-20 alkyl) pyridinium chloride, (C _6-20 alkyl) pyridinium bromide, (C _6-20 alkyl) pyridinium iodide, and (C _6-20 alkyl) pyridinium fluoride; (C _6-20 alkyl)pyridinium chloride, (C _6-20 alkyl)pyridinium bromide, (C _6-20 alkyl)pyridinium iodide, and (C _6-20 alkyl)pyridinium fluoride; and di(C _6-20 alkyl)piperidinium chloride, di(C _6-20 alkyl)piperidinium bromide, di(C _6-20 alkyl)piperidinium iodide, and di(C _6-20 alkyl). ) One or two or more selected from the group consisting of piperidinium fluoride can be used.

For example, the phase transfer catalyst represented by Formula 2 or 3 is hexadecylpyridinium chloride, pyridinium chloride, or pyridinium bromide, pyridinium fluoride, 1-cetylpyridinium chloride monohydrate, and cetylpyridinium bromide. , and N,N-dimethylpiperidinium chloride. One or two or more selected from the group consisting of can be used. Preferably, the phase transfer catalyst represented by Formula 2 may be one or more of hexadecylpyridinium chloride, pyridinium chloride, or pyridinium bromide, or pyridinium fluoride, and the phase transfer catalyst represented by Formula 3 may be N,N-dimethylpiperidinium chloride.

Meanwhile, the phase transfer catalyst may be a derivative of the above-described ammonium salt, pyridinium salt, or piperidinium salt, for example, in an anhydrous form.

Additionally, in step i), the phase transfer catalyst may be added in an amount of 0.1% to 5% by weight based on the weight of the isosorbide. For example, the phase transfer catalyst is present in an amount of 0.2% to 4.5% by weight, or 0.3% to 4% by weight, or 0.4% to 3.5% by weight, or 0.5% to 3% by weight, or 0.6% to 2.5% by weight. %, or 0.7% by weight to 2% by weight, or 0.75% by weight to 1.5% by weight, or 0.8% by weight to 1.2% by weight.

Meanwhile, in step i), the organic halide may be one or more selected from the group consisting of epibromohydrin, epifluorohydrin, epiiodohydrin, and epichlorohydrin.

Additionally, in step i), the organic halide may be added in an amount of 1.0 to 20.0 mol relative to the isosorbide hydroxyl group. For example, the organic halide is 1.5 mole to 18.0 mole, or 2.0 mole to 15.0 mole, or 2.5 mole to 10.0 mole, or 3.0 mole to 8.0 mole, or 3.2 mole to 5.0 mole, or It can be added in an amount of 3.5 moles to 4.8 moles, or 3.7 moles to 4.5 moles, or 3.8 moles to 4.2 moles.

Step ii) adding a basic compound and performing an epoxy substitution reaction;

In one embodiment of the invention, step ii) is a step of performing the ring-opening reaction of step i), then adding a basic compound and performing an epoxy substitution reaction.

Specifically, in step ii), the ring-opening reaction of step i) is performed in the presence of at least one phase transfer catalyst among the compounds represented by any one of Formulas 1 to 3, and then a basic compound is added and the temperature is 40°C to 100°C. The epoxy substitution reaction can be performed under pressure conditions of 450 mmHg to 768 mmHg.

For example, the substitution reaction pressure in step ii) is 450 mmHg or higher, 500 mmHg or higher, or 550 mmHg or higher, or 580 mmHg or higher, or 600 mmHg or higher, or 650 mmHg or higher, or 700 mmHg or higher, or 735 mmHg. or more, or more than 750 mmHg, or more than 752 mmHg, or more than 755 mmHg, or more than 758 mmHg, and less than or equal to 768 mmHg, or less than or equal to 765 mmHg, or less than or equal to 763 mmHg, or less than or equal to 762 mmHg, or less than or equal to 760 mmHg. For example, the substitution reaction may be performed under pressure conditions of normal pressure or a reduced pressure range close to it, that is, 450 mmHg to 760 mmHg or about 760 mmHg.

In addition, the substitution reaction temperature in step ii) is 45 ℃ or higher, or 48 ℃ or higher, or 50 ℃ or higher, or 52 ℃ or higher, or 55 ℃ or higher, and 90 ℃ or lower, or 80 ℃ or lower, or 75 ℃ It may be carried out below, or below 73°C, or below 70°C. For example, the substitution reaction may be performed under temperature conditions of 58°C to 65°C.

In addition, the substitution reaction in step ii) may be performed for 0.1 to 6 hours, specifically for 0.5 to 5 hours, or 1.0 to 4 hours, or 1.5 to 3 hours. there is.

Meanwhile, in the substitution reaction in step ii), the basic compound may be one or more alkali metal hydroxides.

More specifically, the basic compound in step ii) may be one or more selected from the group consisting of lithium hydroxide, potassium hydroxide, calcium hydroxide, and sodium hydroxide.

Additionally, in step ii), the basic compound may be added in an amount of 0.05 to 2.5 moles relative to the isosorbide hydroxyl group. For example, the basic compound is 0.05 mole to 2.0 mole, or 0.06 mole to 1.5 mole, or 0.06 mole to 1.0 mole, or 0.06 mole to 0.8 mole, or 0.07 mole to 0.5 mole, or 0.08 mole, relative to the isosorbide hydroxyl group. It can be added in the amount of mole to 0.3 mole, or 0.08 mole to 0.2 mole.

Meanwhile, the pressure difference (ΔmmHg) between the ring-opening reaction in step i) and the substitution reaction in step ii) is close to 0, and can be performed under substantially the same pressure conditions.

Step iii) azeotropic distillation reaction under reduced pressure;

In one embodiment of the invention, step iii) is a step of performing a ring closure reaction by azeotropic distillation reaction after performing the substitution reaction of step ii).

Specifically, step iii) is performed by performing the ring-opening reaction of step i) in the presence of one or more phase transfer catalysts among the compounds represented by any one of Formulas 1 to 3, then adding a basic compound and performing epoxy substitution of step ii). After performing the reaction, a ring closure reaction may be performed by azeotropic distillation under reduced pressure conditions of 70 mmHg to 500 mmHg at a temperature of 40°C to 100°C.

For example, the azeotropic distillation reaction pressure in step iii) is 75 mmHg or more, or 80 mmHg or more, or 85 mmHg or more, 90 mmHg or more, or 95 mmHg or more, or 100 mmHg or more, or 110 mmHg or more, or 120 mmHg or higher, or 130 mmHg or higher, or 140 mmHg or higher, or 150 mmHg or higher, or 160 mmHg or higher, but 480 mmHg or lower, or 450 mmHg or lower, or 420 mmHg or lower, or 400 mmHg or lower, or 380 mmHg or lower, or 350 mmHg or less, or 320 mmHg or less, or 300 mmHg or less, or 280 mmHg or less, or 250 mmHg or less, or 220 mmHg or less, or 200 mmHg or less. For example, the azeotropic distillation reaction may be performed under pressure conditions of 175 to 185 mmHg.

Additionally, the azeotropic distillation reaction temperature in step iii) may be 40°C to 100°C. Specifically, the azeotropic distillation reaction temperature is 45 ℃ or higher, or 48 ℃ or higher, or 50 ℃ or higher, or 52 ℃ or higher, or 55 ℃ or higher, or 58 ℃ or higher, or 60 ℃ or higher, or 62 ℃ or higher, or It may be carried out at 65°C or higher and at 90°C or lower, or 85°C or lower, or 80°C or lower, or 78°C or lower, or 75°C or lower, or 72°C or lower. For example, the azeotropic distillation reaction may be performed under temperature conditions of 68°C to 72°C.

Meanwhile, in step iii), a basic compound may be additionally added to perform the azeotropic distillation reaction, and the basic compound may be one or more alkali metal hydroxides.

More specifically, the basic compound in step iii) may be one or more selected from the group consisting of lithium hydroxide, potassium hydroxide, calcium hydroxide, and sodium hydroxide.

Additionally, in step iii), the basic compound may be added in an amount of 0.05 to 2.5 moles relative to the isosorbide hydroxyl group. For example, the basic compound is 0.08 mol to 2.0 mol, or 0.1 mol to 1.8 mol, or 0.2 mol to 1.6 mol, or 0.3 mol to 1.5 mol, or 0.4 mol to 1.35 mol, or 0.5 mol, relative to the isosorbide hydroxyl group. It can be added in the amount of mole to 1.2 mole, or 0.7 mole to 1 mole.

For example, the amount of the basic compound added in the ring-closure reaction of step iii) is the amount of the basic compound added in the ring-closure reaction of step iii) while the basic compound is previously added in a molar ratio in the substitution reaction of step ii). In the substitution reaction of step ii), the basic compound may be added in an amount of about 2 times to about 15 times, or about 3.5 times to about 12.5 times, or about 4 times to about 9 times, based on weight.

In addition, the azeotropic distillation reaction of step iii) may be performed for 0.5 hours to 10 hours, specifically for 1 hour to 9 hours, or 2 hours to 8 hours, or 3 hours to 7 hours. You can.

Meanwhile, the pressure difference (△mmHg) between the ring-opening reaction in step i) and the azeotropic distillation reaction in step iii) may be 200 mmHg or more or 200 mmHg to 698 mmHg, and specifically, 250 mmHg or more or 250 mmHg. It may be between mmHg and 630 mmHg, or above 270 mmHg, or between 270 mmHg and 580 mmHg. In particular, in the present invention, the ring-opening reaction in step i) is performed under pressure conditions close to normal pressure, while the azeotropic distillation reaction in step iii) is performed under conditions of a relatively large degree of reduced pressure.

In addition, the pressure difference (△mmHg) between the substitution reaction in step ii) and the azeotropic distillation reaction in step iii) may be 200 mmHg or more or 200 mmHg to 698 mmHg, and specifically, 250 mmHg or more or 250 mmHg to 698 mmHg. It may be 630 mmHg, greater than 270 mmHg, or between 270 mmHg and 580 mmHg. In particular, in the present invention, the substitution reaction in step ii) is performed under pressure conditions close to normal pressure, while the azeotropic distillation reaction in step iii) is performed under conditions of a relatively large degree of reduced pressure.

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>

Example 1

100 g of isosorbide (ISB) and 510 g of epichlorohydrin were added to a 1000 mL round bottom flask equipped with a decanter, a stirrer, and a nitrogen inlet, and were dissolved while raising the temperature to 60°C. Here, epichlorohydrin (ECH) was added in an amount of 4 moles compared to isosorbide hydroxyl group (OH). When the solution in the system was completely dissolved, 9 g of benzyltriethylammonium bromide (BTEAC) was added and the ring-opening reaction was performed for 10 minutes under conditions of 60°C and normal pressure (760 mmHg). Here, benzyltriethylammonium bromide (BTEAC), a phase transfer catalyst, was added at 2% by weight based on 100% by weight of isosorbide. After the ring-opening reaction, 22 g of a 50% aqueous solution of caustic soda (NaOH) was added in two portions every hour, and the epoxy substitution reaction was performed for 2 hours at 60°C and normal pressure (760 mmHg). Here, the molar ratio of caustic soda was added to be 0.2 mole compared to isosorbide hydroxyl group (OH). Afterwards, the temperature was raised to 70°C, and 88 g of a 50% caustic soda (NaOH) aqueous solution was metered in for 4 hours under a pressure of 180 mmHg, while the reaction water was continuously removed through a reflux reaction and an epoxy ring closure reaction was performed through a reduced pressure azeotropic distillation reaction. proceeded. Here, the caustic soda molar ratio was added to be 0.8 mole compared to isosorbide hydroxyl group (OH). The total amount of caustic soda added in the substitution reaction and ring closure reaction was added to be 1 mole compared to isosorbide hydroxyl group (OH).

After completing the above-described ring closure reaction, the reactant was filtered, and the filtered reactant was gradually heated and reduced to 160°C and 30 mmHg to recover unreacted epichlorohydrin and produce an isosorbide-based epoxy compound of the following formula 1-1. got it

[Formula 1-1]

이다.In Formula 1-1, n1 is 0 to 5 and R ¹ is H or

am.

At this time, the epoxy equivalent of the produced isosorbide-based epoxy compound is 159.3 g/eq, Brookfiled viscosity is 1070 mPa·s at 25 ℃, and the content of mononuclear difunctional epoxy (n=0) is determined through GPC molecular weight distribution analysis. n=0, confirmed to be 58.8%.

Examples 2 and 3

In Example 1, the same amount as Example 1 was used, except that the amount of benzyltriethylammonium bromide (BTEAC) used as a phase transfer catalyst for the ring-opening reaction was varied at 1% by weight and 3% by weight relative to the weight of isosorbide, respectively. The isosorbide-based epoxy compounds of Examples 2 and 3 were prepared by performing a ring-opening reaction, a substitution reaction, and a ring-closing reaction.

Examples 4 and 5

In Example 2, the ring-opening reaction, substitution reaction, and ring-closure reaction were performed in the same manner as Example 2, except that the reaction pressure among the ring-opening reaction conditions was used differently at 600 mmHg and 450 mmHg, respectively, and Example 4 and The isosorbide-based epoxy compound of 5 was prepared.

Example 6

In Example 2, the ring opening reaction and substitution reaction were carried out in the same manner as in Example 1, except that the phase transfer catalyst for the ring opening reaction was used instead of benzyltriethylammonium bromide (BTEAC) as benzyltrimethylammonium chloride (BTMAC). And ring-closure reaction was performed to prepare the isosorbide-based epoxy compound of Example 6.

Comparative Example 1

100 g of isosorbide and 510 g of epichlorohydrin were added to a 1000 mL round bottom flask equipped with a decanter, a stirrer, and a nitrogen inlet, and were dissolved while raising the temperature to 60°C. When the solution in the system was completely dissolved, 22 g of 50% caustic soda aqueous solution was added in two portions every hour to proceed with the epoxy substitution reaction without ring-opening reaction. Thereafter, the temperature was raised to 70°C, and 88 g of 50% caustic soda aqueous solution was metered injected under reduced pressure of 180 mmHg for 4 hours, and the epoxy ring closure reaction was performed while continuously removing reaction water through reflux reaction.

The main reaction conditions and reaction yields in the manufacturing process of the isosorbide-based epoxy compound according to Examples 1 to 6 and Comparative Example 1 are shown in Table 1 below.

Example 1 Example
2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 ECH/OH 4 4 4 4 4 4 4 step
i)
opening
reaction catalyst BTEAC BTEAC BTEAC BTEAC BTEAC BTMAC doesn't exist Catalyst input amount
(wt%) 2 One 3 One One One doesn't exist Reaction temperature (℃) 60 60 60 60 60 60 doesn't exist Response pressure (mmHg) 760 760 760 600 450 760 doesn't exist step
ii)
substitution
reaction basic compound NaOH NaOH NaOH NaOH NaOH NaOH NaOH basic compound
input
(mole/OH) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Reaction temperature (℃) 60 60 60 60 60 60 75 Response pressure (mmHg) 760 760 760 600 450 760 760 step
iii)
closure
reaction basic compound NaOH NaOH NaOH NaOH NaOH NaOH NaOH basic compound
input
(mole/OH) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Reaction temperature (℃) 70 70 70 70 70 70 75 Response pressure (mmHg) 180 180 180 180 180 180 180 Pressure difference between steps i) and ii) (△mmHg, mmHg) 0 0 0 0 0 0 0 Pressure difference between steps i) and iii) (△mmHg, mmHg) 580 580 580 420 270 580 560 transference number (%) 94.4 92.7 95.4 98.2 94.6 93.4 86.7

In Table 1, the pressure difference between steps i) and ii) and the pressure difference between steps i) and iii) are the pressure of i) the substitution reaction process compared to the pressure of the ii) substitution reaction process or iii) the ring closure reaction process. The difference value is expressed as an absolute value (△mmHg, mmHg), and the reaction yield is calculated by i) the total weight of isosorbide introduced in the substitution reaction process and iii) the total weight of the isosorbide-based epoxy compound produced after the ring closure reaction process. It is a value expressed as a percentage (%).

<Test Example 1>

The physical properties of the isosorbide-based epoxy compounds obtained according to Examples 1 to 6 and Comparative Example 1 were evaluated as follows, and the measured values are shown in Table 2 below.

a) Content of n=0 compound in isosorbide epoxy resin

The isosorbide epoxy resin synthesized according to Examples 1 to 6 and Comparative Example 1 was dissolved in THF at a concentration of 2.5 wt% and subjected to gel permeation chromatography (GPC, Gel Permeation Chromatography systems; Shimazu, Shodex, KF-801, Columns 802, 803, and 805) analysis was performed. At this time, the analysis temperature was 40°C, and Tetrahydrofuran (HPLC grade) was flowed at 1 mL/min as the mobile phase. Through the GPC data measured in this way, the content (GPC, %) of the isosorbide diglycidyl ether (n=0) compound was confirmed.

b) Epoxy group equivalent

The epoxy group equivalent weight of the isosorbide epoxy resin synthesized according to Examples 1 to 6 and Comparative Example 1 was measured by neutralization titration method. Specifically, the epoxy resin was dissolved in 1,4-Dioxane, reacted by adding 0.2N-HCl solution, and then titrated with 0.1N-NaOH Methanol solution to measure the epoxy group equivalent weight (EEW, g/eq). Here, the epoxy group equivalent (EEW, g/eq) represents the molecular weight divided by the number of reactors, and can be measured by, for example, a neutralization titration method.

c) viscosity

For the isosorbide epoxy resins synthesized according to Examples 1 to 6 and Comparative Example 1, the viscosity (mPa·s) was measured using a rotational viscometer and a Brookfield viscometer at 25°C. At this time, Brookfield viscosity represents the resistance value of the fluid applied to the spindle using a rotational viscometer.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 n=0 content
(GPC, %) 58.8 47.3 62.1 58 49 57.6 39.6 EEW (g/eq) 159.3 167.2 155.7 159.6 166.6 160.1 174.6 25℃ viscosity
(mPaㆍs) 1070 1760 700 1093 2300 1120 4856 transference number (%) 94.4 92.7 95.4 98.2 94.6 93.4 86.7

As shown in Table 2, Examples 1 to 6, in which the three-stage process of ring-opening reaction, substitution reaction, and ring-closure reaction were performed under optimized conditions according to the present invention, carried out the substitution reaction directly without ring-opening reaction in the conventional method. Compared to Comparative Example 1, the content of the n=0 compound in the isosorbide epoxy increased significantly, and as a result, it was confirmed that an epoxy with a significantly low viscosity of 700 mPa·s to 2300 mPa·s could be produced. In addition, the production yield of the isosorbide-based epoxy compounds according to Examples 1 to 6 was 92.7% to 98.2%, which was significantly higher than 86.7% in Comparative Example 1.

In addition, the gel permeation chromatography (GPC, Gel Permeation Chromatography systems) analysis graph and measurement results for the isosorbide-based epoxy compound synthesized according to Example 1 according to the present invention are shown in Figure 1. With reference to Figure 1, the n=0 content of the isosorbide-based epoxy compound can be confirmed.

<Test Example 2>

Using the isosorbide-based epoxy compound obtained according to Example 2 and Comparative Example 1, isophorone diamine (IPDA, manufacturer: Evonik, viscosity 5-10 mPa·s) as a curing agent and the molar number of epoxy functional groups were used. After mixing at an equivalence ratio of 1:1 and preparing a cured specimen by curing at 25°C for 14 hours and then at 80°C for 2 hours, the physical properties were evaluated in the following manner, and the measurement results are shown in Table 3 below. .

a) Gelation time

The gel time of 100 g of the mixture of the isosorbide-based epoxy compound obtained according to Example 2 and Comparative Example 1 and the curing agent was measured. Specifically, gelation time (Gel Time) was measured by stirring at the same speed using a gel timer at room temperature (25°C).

b) Drying time

Mix the hardener and isosorbide epoxy compound at an equivalent ratio of 1:1 and apply it to the glass specimen. Then, using a BK recorder, drying time is measured at 25°C according to ASTM D5 895 while the needle moves the coating film at one end of the glass specimen. Measured.

Specifically, T2 and T3 are values representing the drying time for each step, T2 is a measurement of the adhesion drying time, and T3 is a measurement of the adhesion drying time.

c) Glass transition temperature

The glass transition temperature was measured by increasing the temperature at a rate of 10 °C/min using differential scanning calorimetry (DSC) to obtain a DSC curve, and then measuring the glass transition temperature (Tg, °C).

d) Shore D hardness

The curing agent and the isosorbide-based epoxy compound were mixed at an equivalence ratio of 1:1 and cured for a week at room temperature, and then the surface of the cured sample was flattened using a metal file. Afterwards, Shore D hardness was measured 10 times using a digitest Ⅱ Gelomat hardness tester and the average value was recorded.

e) Moisture absorption rate

The moisture absorption rate is determined by mixing the curing agent and the isosorbide-based epoxy compound at an equivalent ratio of 1:1 to prepare a cured specimen, then immersing the cured specimen in water at 25°C for a certain period of time, that is, 1 day. After leaving for 4 days and 7 days, the difference between the initial weight of the specimen and the weight after water absorption was measured, and the water uptake rate (water uptake) was expressed as a percentage based on the weight of the initial specimen. %) was measured.

Example 2 Comparative Example 1 hardener IPDA IPDA curing conditions After curing at 25℃ for 14 hours
Curing at 80℃ for 2 hours After curing at 25℃ for 14 hours
Curing at 80℃ for 2 hours Gel Time 45h 1h 5m drying time T2 6h 55m 6h T3 9h 25m 9h 30m Tg (℃, DSC) 62.4 51.1 Shore D hardness 93.4 93.5 Water uptake (%) 1 day 3.6 6.8 4 days 6.93 12.5 7 days 8.3 16.2

In Table 3, the measured values of gel time and drying time are expressed as h in time units and m as minutes. For example, when the drying time was measured as “6 hours 55 minutes,” it was displayed as “6h 55m.”

As shown in Table 3, Example 2, in which a ring-opening reaction was performed in the presence of a specific phase transfer catalyst according to the present invention, and then a three-step process of substitution reaction and ring-closure reaction was performed, was carried out in the conventional manner without ring-opening reaction. Compared to Comparative Example 1, in which the substitution reaction was performed immediately, it was confirmed that the epoxy equivalent of the isosorbide-based epoxy compound decreased, and as a result, the cured density increased during curing, resulting in a decrease in gel time, an increase in Tg, and a significant decrease in water absorption.

Claims (23)

i) performing a ring-opening reaction by mixing isosorbide and an organic halide in the presence of a phase transfer catalyst; and
ii) after performing the ring-opening reaction, adding a basic compound and performing an epoxy substitution reaction; and
iii) after performing the substitution reaction, performing a ring closure reaction through an azeotropic distillation reaction;
Including,
The phase transfer catalyst is one or more compounds represented by any of the following formulas 1 to 3,
Method for producing isosorbide-based epoxy compounds:
[Formula 1]
Ar _a R ¹ _4-a N ⁺ (X ¹ _b ) ^-
In Formula 1,
Ar are the same or different from each other, and each independently represents substituted or unsubstituted C _6-20 aryl, or substituted or unsubstituted C _6-20 aryl substituted C _1-3 alkyl,
R ¹ are the same or different from each other and are each independently C _1-20 alkyl,
X ¹ are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),
a is an integer from 1 to 4,
b is an integer from 1 to 3,
[Formula 2]

In Formula 2,
R ² is hydrogen or C _1-20 alkyl,
X ² are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),
c is an integer from 1 to 3,
[Formula 3]

In Formula 3 above,
R ³ are the same or different from each other and are each independently hydrogen or C _1-20 alkyl,
X ³ are the same or different from each other and are each independently chloro (Cl), bromo (Br), iodine (I), or fluorine (F),
d is an integer from 1 to 3.

According to paragraph 1,
The isosorbide-based epoxy compound is represented by the following formula (4),
Method for producing isosorbide-based epoxy compounds:
[Formula 4]

In Formula 4 above,
R ⁴ is H or

ego,
n is an integer from 0 to 100.
According to paragraph 1,
The isosorbide-based epoxy compound has an epoxy group equivalent weight of 120 g/eq to 500 g/eq,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
The isosorbide-based epoxy compound has a Brookfield viscosity measured at 25°C of 500 mPa·s to 20,000 mPa·s,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the ring-opening reaction is performed under pressure conditions of 450 mmHg to 768 mmHg at a temperature of 40 ℃ to 100 ℃,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the ring-opening reaction is performed for 0.1 to 6 hours,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the phase transfer catalyst is,
Tetra(C _6-20 aryl)ammonium chloride, tetra(C _6-20 aryl)ammonium bromide, tetra(C _6-20 aryl)ammonium iodide, tetra(C 6-20 aryl)ammonium dichloriodate, and tetra(C _6-20 aryl)ammonium dichloriodate. (C _6-20 aryl)ammonium fluoride;
Tetra(C _6-20 aryl C _1-3 alkyl)ammonium chloride, tetra(C _6-20 aryl C _1-3 alkyl)ammonium bromide, tetra(C _6-20 aryl C _1-3 alkyl)ammonium iodide, tetra(C _6-20 arylC _1-3 alkyl)ammonium dichloriodate, and tetra(C _6-20 arylC _1-3 alkyl)ammonium fluoride;
Tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)ammonium chloride, tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)ammonium bromide, tetra(C _{6 -20} aryl)(C _6-20 arylC _1-3 alkyl)ammonium iodide, tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)ammonium dichloriodate, and tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)ammonium fluoride;
Tetra(C _6-20 aryl)(C _1-20 alkyl)ammonium chloride, tetra(C _6-20 aryl)(C _1-20 alkyl)ammonium bromide, tetra(C _6-20 aryl)(C _1-20 alkyl) ) ammonium iodide, tetra(C _6-20 aryl)(C _1-20 alkyl)ammonium dichloriodate, and tetra(C _6-20 aryl)(C _1-20 alkyl)ammonium fluoride;
Tetra(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium chloride, tetra(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium bromide, tetra(C _{6 -20} arylC _1-3 alkyl)(C _1-20 alkyl)ammonium iodide, tetra(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium dichloriodate, and tetra(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium fluoride; and
Tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium chloride, tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl) (C _1-20 alkyl)ammonium bromide, tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium iodide, tetra(C _6-20 aryl) (C _6-20 arylC _1-3 alkyl)(C _1-20 alkyl)ammonium dichloriodate, and tetra(C _6-20 aryl)(C _6-20 arylC _1-3 alkyl)(C _1-20 Alkyl) ammonium fluoride; at least one selected from the group consisting of,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the phase transfer catalyst includes benzyltrimethyl ammonium chloride (BTMAC), benzyltrimethylammonium bromide, benzyltriethylammonium chloride (BTEAC), benzyltriethylammonium bromide, benzyltributylammonium chloride, benzyltributylammonium bromide, and benzyltrimethylammonium chloride. At least one member selected from the group consisting of benzyltrimethylammonium dichloroiodate, benzyltriphenyl ammonium chloride, and methyltriphenyl ammonium chloride,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the phase transfer catalyst is,
(C _6-20 alkyl)pyridinium chloride, (C _6-20 alkyl)pyridinium bromide, (C _6-20 alkyl)pyridinium iodide, and (C _6-20 alkyl)pyridinium fluoride;
(C _6-20 alkyl)pyridinium chloride, (C _6-20 alkyl)pyridinium bromide, (C _6-20 alkyl)pyridinium iodide, and (C _6-20 alkyl)pyridinium fluoride; and
Di(C _6-20 alkyl)piperidinium chloride, di(C _6-20 alkyl)piperidinium bromide, di(C _6-20 alkyl)piperidinium iodide, and di(C _6-20 alkyl) At least one member selected from the group consisting of piperidinium fluoride,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the phase transfer catalyst is hexadecylpyridinium chloride, pyridinium chloride, or pyridinium bromide, pyridinium fluoride, 1-cetylpyridinium chloride monohydrate, cetylpyridinium bromide, and N,N -at least one member selected from the group consisting of dimethylpiperidinium chloride,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the phase transfer catalyst is added in an amount of 0.1% to 5% by weight based on the weight of the isosorbide.
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the organic halide is at least one selected from the group consisting of epibromohydrin, epifluorohydrin, epiiodohydrin, and epichlorohydrin,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step i), the organic halide is added in an amount of 1.0 mol to 20.0 mol relative to the isosorbide hydroxyl group,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step ii), the substitution reaction is performed under pressure conditions of 450 mmHg to 768 mmHg at a temperature of 40 ℃ to 100 ℃,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step ii), the ring-opening reaction is performed for 0.1 to 6 hours,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step ii), the basic compound is one or more alkali metal hydroxides.
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step ii), the basic compound is at least one selected from the group consisting of lithium hydroxide, potassium hydroxide, calcium hydroxide, and sodium hydroxide,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step ii), the basic compound is added in an amount of 0.05 mole to 2.5 mole relative to the isosorbide hydroxyl group.
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step iii), a basic compound is additionally added and the azeotropic distillation reaction is performed,
Method for producing isosorbide-based epoxy compounds.
According to clause 19,
In step iii), the basic compound is at least one selected from the group consisting of lithium hydroxide, potassium hydroxide, calcium hydroxide, and sodium hydroxide,
Method for producing isosorbide-based epoxy compounds.
According to clause 19,
In step iii), the basic compound is added in an amount of 0.05 mole to 2.5 mole relative to the isosorbide hydroxyl group.
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
In step iii), the azeotropic distillation reaction is a ring closure reaction performed for 0.5 to 10 hours,
Method for producing isosorbide-based epoxy compounds.
According to paragraph 1,
The pressure difference (ΔmmHg) between the ring-opening reaction in step i) and the ring-closure reaction of azeotropic distillation in step iii) is 200 mmHg or more,
Method for producing isosorbide-based epoxy compounds.