KR102301335B1 - Diisocyanate compound having anhydrosugar alcohol core and alkylene oxide extension and method for preparing the same - Google Patents

Abstract

The present invention relates to a diisocyanate compound having an anhydrosugar alcohol nucleus and an alkylene oxide extension, and a preparation method thereof, and more particularly, an addition reaction of an alkylene oxide using a renewable plant-based anhydrosugar alcohol as a raw material, Manufactured through reaction with nitrile compound, hydrogenation reaction, and end group substitution reaction, it can be used in various fields such as flexible or rigid polyurethane foam, mold foam, coating, adhesive or adhesive, fiber, and polymer synthesis. , to a diisocyanate compound having an anhydrosugar alcohol nucleus and an alkylene oxide extension, and a method for preparing the same.

Description

DIISOCYANATE COMPOUND HAVING ANHYDROSUGAR ALCOHOL CORE AND ALKYLENE OXIDE EXTENSION AND METHOD FOR PREPARING THE SAME

The present invention relates to a diisocyanate compound having an anhydrosugar alcohol nucleus and an alkylene oxide extension, and a method for producing them, and more particularly, to an addition reaction of an alkylene oxide using an anhydrosugar alcohol, which is a renewable plant-based raw material, as a raw material; Manufactured through reaction with nitrile compound, hydrogenation reaction, and end group substitution reaction, it can be used in various fields such as flexible or rigid polyurethane foam, mold foam, coating, adhesive or adhesive, fiber, and polymer synthesis. , to a diisocyanate compound having an anhydrosugar alcohol nucleus and an alkylene oxide extension, and a method for preparing the same.

Hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5) ), and is classified into tetritol, pentitol, hexitol and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

Anhydrosugar alcohol has the form of a diol having two hydroxyl groups in the molecule, and can be prepared by utilizing hexitol derived from starch (eg, Korean Patent No. 10-1079518, Korean Patent Application Laid-Open No. 10). -2012-0066904). Anhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, and research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these anhydrosugar alcohols, isosorbide prepared from sorbitol has the widest industrial application range at present.

The use of anhydrosugar alcohol is very diverse, such as treatment of heart and vascular diseases, adhesives for patches, pharmaceuticals such as mouthwashes, solvents of compositions in the cosmetic industry, and emulsifiers in the food industry. In addition, it can raise the glass transition temperature of polymer materials such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, and has the effect of improving the strength of these materials. useful. In addition, it is known that it can be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

In the midst of a rapid increase in demand for eco-friendly chemicals due to recent environmental pollution, the anhydrosugar alcohol is a renewable, low-cost raw material derived from plants. or bio-based monomers that can be used in various fields such as adhesives, fibers, and polymer synthesis, and There is a need to develop polymers.

An object of the present invention is to prepare a renewable plant-based anhydrosugar alcohol as a raw material through an addition reaction of an alkylene oxide, a reaction with a nitrile compound, a hydrogenation reaction and a terminal group substitution reaction, and a soft or hard polyurethane To provide a diisocyanate compound having an anhydrosugar alcohol nucleus and an alkylene oxide extension, which can be used in various fields such as foam, mold foam, coating, adhesive or adhesive, fiber, polymer synthesis, and a method for producing the same.

In order to solve the above technical problems, the present invention provides a compound represented by the following formula (A):

[Formula A]

X-Y-O-M-O-Y'-X

In the above formula (A),

X is each independently —CH ₂ NCO,

Y is -[CH ₂ CHR ₁ O] _m -CHR ₂ CHR ₃ -,

Y' is -[CH ₂ CHR ₁ O] _n -CHR ₂ CHR ₃ -,

wherein R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25,

M is a divalent organic group derived from anhydrosugar alcohol.

According to another aspect of the present invention, (1) performing a Michael reaction of anhydrosugar alcohol-alkylene glycol and a nitrile compound; (2) adding hydrogen to the compound obtained from the Michael reaction; and (3) converting a terminal group of the compound obtained from the hydrogenation reaction into an isocyanate, wherein:

[Formula A]

X-Y-O-M-O-Y'-X

In the above formula (A),

X is each independently —CH ₂ NCO,

Y is -[CH ₂ CHR ₁ O] _m -CHR ₂ CHR ₃ -,

Y' is -[CH ₂ CHR ₁ O] _n -CHR ₂ CHR ₃ -,

wherein R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25,

M is a divalent organic group derived from anhydrosugar alcohol.

According to another aspect of the present invention, there is provided a polymer comprising the compound represented by Formula A.

The diisocyanate compound having an anhydrosugar alcohol nucleus and an alkylene oxide extension of the present invention is an addition reaction of an alkylene oxide, a reaction with a nitrile compound, a hydrogenation reaction and a terminal group using a renewable plant-based anhydrosugar alcohol as a raw material. Since it is manufactured through a substitution reaction, it is eco-friendly and can reduce the manufacturing cost. The diisocyanate compound of the present invention can be used alone, used by introducing a trivalent or higher functional group through a cyclization reaction, or used in combination with a petroleum-based isocyanate compound. For example, the diisocyanate compound of the present invention can be used in various fields such as flexible or hard polyurethane foam, mold foam, coating, pressure-sensitive adhesive or adhesive, fiber, polymer synthesis, and the like.

Hereinafter, the present invention will be described in detail.

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

[Formula A]

X-Y-O-M-O-Y'-X

In the above formula (A),

X is each independently —CH ₂ NCO,

Y is -[CH ₂ CHR ₁ O] _m -CHR ₂ CHR ₃ -,

Y' is -[CH ₂ CHR ₁ O] _n -CHR ₂ CHR ₃ -,

wherein R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25,

M is a divalent organic group derived from anhydrosugar alcohol.

The anhydrosugar alcohol is prepared from hydrogenated sugars derived from natural products.

Hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5) ), and is classified into tetritol, pentitol, hexitol and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms.

Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

Anhydrosugar alcohol has the form of a diol having two hydroxyl groups in the molecule, and can be prepared by utilizing hexitol derived from starch (eg, Korean Patent No. 10-1079518, Korean Patent Application Laid-Open No. 10). -2012-0066904). Anhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, and research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these anhydrosugar alcohols, isosorbide prepared from sorbitol has the widest industrial application range at present.

In the compound represented by Formula A of the present invention, M is anhydrosugar alcohol isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1,4-3,6-dianhydromannitol) Or it may be a divalent organic group derived from isoidide (1,4-3,6-dianhydroiditol), and in one embodiment, M may be selected from the following formula.

In the compound represented by Formula A of the present invention, R ₁ is each independently hydrogen, alkyl or aryl, and R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl.

The alkyl is, for example, a substituted or unsubstituted linear alkyl having 1 to 10 carbon atoms (more specifically 1 to 6 carbon atoms); Or it may be a substituted or unsubstituted branched alkyl having 3 to 10 carbon atoms (more specifically 3 to 6), and the aryl is, for example, a substituted or unsubstituted C 6 to 14 carbon atom (more specifically 6 to 12 carbon atoms). ) of monocyclic aryl, polycyclic aryl, or fusedcyclic aryl. In addition, the heteroaryl is, for example, a substituted or unsubstituted 5 to 12 membered (more specifically 5 to 10 membered) monocyclic heteroatom containing one or more hetero atoms selected from N, O, S. It may be aryl, polycyclic heteroaryl, or fused cyclic heteroaryl, and the cycloalkyl may be, for example, a substituted or unsubstituted cycloalkyl having 3 to 8 carbon atoms (more specifically 3 to 6 carbon atoms).

The groups are, for example, with one or more substituents selected from alkyl having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.) or aryl having 6 to 10 carbon atoms (eg, phenyl, benzyl, tolyl, etc.) may be substituted.

In one embodiment, the compound represented by Formula A of the present invention may be a compound represented by Formula 3 below (isosorbide-alkylene glycol-diisocyanate compound):

[Formula 3]

In Formula 3,

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Formula 3 may be compounds of Formulas 3-1 to 3-6, but is not limited thereto.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

In Formulas 3-1 to 3-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, the compound represented by Formula A of the present invention may be a compound represented by Formula 6 below (isomannide-alkylene glycol-diisocyanate compound):

[Formula 6]

In Formula 6,

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Formula 6 may be compounds of Formulas 6-1 to 6-6, but is not limited thereto.

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

[Formula 6-4]

[Formula 6-5]

[Formula 6-6]

In Formulas 6-1 to 6-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, the compound represented by Formula A of the present invention may be a compound represented by the following Formula 9 (isoidide-alkylene glycol-diisocyanate compound):

[Formula 9]

In Formula 9,

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Formula 9 may be compounds of Formulas 9-1 to 9-6, but is not limited thereto.

[Formula 9-1]

[Formula 9-2]

[Formula 9-3]

[Formula 9-4]

[Formula 9-5]

[Formula 9-6]

In Formulas 9-1 to 9-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

According to another aspect of the present invention, (1) performing a Michael reaction of anhydrosugar alcohol-alkylene glycol and a nitrile compound; (2) adding hydrogen to the compound obtained from the Michael reaction; and (3) converting a terminal group of the compound obtained from the hydrogenation reaction to an isocyanate, wherein:

[Formula A]

X-Y-O-M-O-Y'-X

In the above formula (A),

X is each independently —CH ₂ NCO,

Y is -[CH ₂ CHR ₁ O] _m -CHR ₂ CHR ₃ -,

Y' is -[CH ₂ CHR ₁ O] _n -CHR ₂ CHR ₃ -,

wherein R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25,

M is a divalent organic group derived from anhydrosugar alcohol.

In the method for preparing the compound represented by the formula (A) of the present invention, the description of the compound represented by the formula (A) is the same as described above.

In one embodiment, in the method for preparing the compound represented by Formula A, before step (1) of performing the Michael reaction, alkylene oxide is added to both ends of the anhydrosugar alcohol to prepare anhydrosugar alcohol-alkylene glycol It may further include the step of In this case, 1 to 30 molar equivalents of alkylene oxide may be added with respect to 1 molar equivalent of anhydrosugar alcohol. When the molar equivalent of the alkylene oxide is too low, the yield of the anhydrosugar alcohol-alkylene oxide adduct is lowered. Conversely, when the molar equivalent is too high, it is difficult to expect additional effects and the manufacturing cost increases.

In one embodiment, the alkylene oxide may be a linear or branched alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, it may be selected from ethylene oxide, propylene oxide, or a combination thereof. .

In one embodiment, the alkylene oxide addition reaction may be performed at a temperature of 100 to 200 °C, preferably 120 to 160 °C, for 1 to 10 hours, preferably 2 to 4 hours.

In the step (1) of performing the Michael reaction of the anhydrosugar alcohol-alkylene glycol and the nitrile compound, the anhydrosugar alcohol is isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1, 4-3,6-dianhydromannitol), isoidide (1,4-3,6-dianhydroiditol), or a combination thereof.

Examples of the nitrile compound used in step (1) of carrying out the Michael reaction of the method for preparing the compound represented by Formula A of the present invention include acrylonitrile, methacrylonitrile, crotononitrile, cinnamonitrile, 3-(furan). -2-yl) prop-2-ennitrile, cyclohexaneacrylonitrile, or a combination thereof may be used, but is not limited thereto.

In performing the Michael reaction of the anhydrosugar alcohol-alkylene glycol and the nitrile compound in step (1), 1 to 10 molar equivalents of the nitrile compound, preferably 2 to 10 molar equivalents of the anhydrosugar alcohol-alkylene glycol The reaction may be carried out in molar equivalents, more preferably 2 to 5 molar equivalents. When the molar equivalent of the nitrile compound is too low, the yield of the compound represented by Formula A is low. On the contrary, when the molar equivalent of the nitrile compound is too high, it is difficult to expect additional effects, and the manufacturing cost increases.

The Michael reaction in step (1) may be carried out in the presence of a base catalyst, but is not particularly limited, but the Michael reaction may be performed in the presence of 0.005 to 0.05 molar equivalents of a base catalyst with respect to 1 molar equivalent of anhydrosugar alcohol-alkylene glycol. can When the content of the base catalyst is too low, the reaction rate of the Michael reaction is slowed. Conversely, when the content of the base catalyst is too high, it is difficult to expect an additional effect, and the manufacturing cost increases.

The type of the base catalyst is not particularly limited, but for example, alkali metal hydroxides (specifically, hydroxides of Li, Na, K, Rb or Cs, etc.), alkaline earth metal hydroxides (specifically, Mg, Ca, Sr) or hydroxides of Ba, etc.), carbonates of alkali metals (specifically, carbonates of Li, Na, K, Rb or Cs, etc.), alcoholates of alkali metals or alkaline earth metals (specifically, sodium methylate, sodium ethylate or potassium) t-butylate, etc.), or a basic organic catalyst (specifically, 1,8-diazabicyclo[5.4.0]undec-7-ene (1,8-Diazabicyclo[5.4.0]undec-7-ene) ) or 4-(dimethylamino)pyridine (4-(dimethylamino)pyridine, etc.), preferably a basic organic catalyst.

When a basic organic catalyst is used as a basic catalyst, compared to a basic inorganic catalyst, the Michael reaction (nitrile addition reaction) rate is accelerated, thereby solving a serious exothermic problem due to accumulation of unreacted raw materials upon addition of a nitrile compound.

In step (1) of performing the Michael reaction of the anhydrosugar alcohol-alkylene glycol and the nitrile compound, the step of stirring the product of the Michael reaction for 1 to 10 hours may be further included. If the stirring time is too short, the yield of the compound represented by Formula A may be low, and conversely, if the stirring time is too long, it is difficult to expect an additional effect.

The product of the Michael reaction may be cooled to room temperature after the stirring step, and the cooled product of the Michael reaction is treated with an organic solvent (eg, ethyl acetate, dichloromethane, 2-methyltetrahydrofuran, diethyl ether, etc.) After dilution, it may be sequentially washed with an aqueous hydrochloric acid solution, an aqueous sodium hydroxide solution and distilled water. Thereafter, the step of concentration under reduced pressure may be further performed.

In the method for preparing the compound represented by Formula A of the present invention, the compound obtained from the Michael reaction in step (1) may be a compound represented by the following Formula A':

[Formula A']

X'-Y-O-M-O-Y'-X'

In the formula A',

X' is -CN,

Y is -[CH ₂ CHR ₁ O] _m -CHR ₂ CHR ₃ -,

Y' is -[CH ₂ CHR ₁ O] _n -CHR ₂ CHR ₃ -,

wherein R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25,

M is a divalent organic group derived from anhydrosugar alcohol.

In Formula A', alkyl is, for example, a substituted or unsubstituted linear alkyl having 1 to 10 carbon atoms (more specifically 1 to 6 carbon atoms); Or it may be a substituted or unsubstituted branched alkyl having 3 to 10 carbon atoms (more specifically 3 to 6), and the aryl is, for example, a substituted or unsubstituted C 6 to 14 carbon atom (more specifically 6 to 12 carbon atoms). ) of monocyclic aryl, polycyclic aryl, or fusedcyclic aryl. In addition, the heteroaryl is, for example, a substituted or unsubstituted 5 to 12 membered (more specifically 5 to 10 membered) monocyclic heteroatom containing one or more hetero atoms selected from N, O, S. It may be aryl, polycyclic heteroaryl, or fused cyclic heteroaryl, and the cycloalkyl may be, for example, a substituted or unsubstituted cycloalkyl having 3 to 8 carbon atoms (more specifically 3 to 6 carbon atoms).

The groups are, for example, with one or more substituents selected from alkyl having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.) or aryl having 6 to 10 carbon atoms (eg, phenyl, benzyl, tolyl, etc.) may be substituted.

In one embodiment, the compound represented by Formula A' may be a compound represented by Formula 1 below (isosorbide-alkylene glycol-dinitrile compound):

[Formula 1]

In Formula 1,

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Formula 1 may be compounds of Formulas 1-1 to 1-6, but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, the compound represented by Formula A' may be a compound represented by Formula 4 below (isomannide-alkylene glycol-dinitrile compound):

[Formula 4]

In Formula 4,

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Formula 4 may be compounds of Formulas 4-1 to 4-6, but is not limited thereto.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

In Formulas 4-1 to 4-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, the compound represented by Formula A' may be a compound represented by Formula 7 below (isoidide-alkylene glycol-dinitrile compound):

[Formula 7]

In Formula 7,

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Chemical Formula 7 may be compounds of the following Chemical Formulas 7-1 to 7-6, but are not limited thereto.

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

[Formula 7-4]

[Formula 7-5]

[Formula 7-6]

In Formulas 7-1 to 7-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In the method for producing the compound represented by the formula (A) of the present invention, the step (2) of adding hydrogen to the compound obtained from the Michael reaction may be advantageously carried out in the presence of ammonia, and may be carried out under the following conditions .

The step (2) is 40 ℃ to 180 ℃, preferably 50 ℃ to 130 ℃ temperature conditions, hydrogen pressure conditions of 5 to 30 bar, and based on 100 parts by weight of the compound represented by the formula A', 0.1 to It may be carried out in the presence of 20 parts by weight, preferably 0.5 to 10 parts by weight of the hydrogenation catalyst.

If the hydrogen pressure is too low, hydrogen may not be sufficiently added and the yield of the hydrogenation product may be lowered. Conversely, if the hydrogen pressure is too high, it is difficult to expect an additional effect.

Step (2) may be performed without using a solvent or may be performed in a solvent. When step (2) is performed in a solvent, the solvent may be selected from water or a linear or branched C1-C5 alcohol.

In the method for preparing the compound represented by the formula (A) of the present invention, the compound obtained from the hydrogenation reaction in step (2) may be a compound represented by the following formula (A″):

[Formula A″]

X″-Y-O-M-O-Y’-X″

In the above formula A″,

X″ is —CH ₂ NH ₂ ,

Y is -[CH ₂ CHR ₁ O] _m -CHR ₂ CHR ₃ -,

Y' is -[CH ₂ CHR ₁ O] _n -CHR ₂ CHR ₃ -,

wherein R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25,

M is a divalent organic group derived from anhydrosugar alcohol.

In the formula A″, alkyl is, for example, substituted or unsubstituted linear alkyl having 1 to 10 carbon atoms (more specifically 1 to 6 carbon atoms); Or it may be a substituted or unsubstituted branched alkyl having 3 to 10 carbon atoms (more specifically 3 to 6), and the aryl is, for example, a substituted or unsubstituted C 6 to 14 carbon atom (more specifically 6 to 12 carbon atoms). ) of monocyclic aryl, polycyclic aryl, or fusedcyclic aryl. In addition, the heteroaryl is, for example, a substituted or unsubstituted 5 to 12 membered (more specifically 5 to 10 membered) monocyclic heteroatom containing one or more hetero atoms selected from N, O, S. It may be aryl, polycyclic heteroaryl, or fused cyclic heteroaryl, and the cycloalkyl may be, for example, a substituted or unsubstituted cycloalkyl having 3 to 8 carbon atoms (more specifically 3 to 6 carbon atoms).

The groups are, for example, with one or more substituents selected from alkyl having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.) or aryl having 6 to 10 carbon atoms (eg, phenyl, benzyl, tolyl, etc.) may be substituted.

In one embodiment, the compound represented by Formula A″ may be a compound represented by Formula 2 below (isosorbide-alkylene glycol-diamine compound):

[Formula 2]

In Formula 2,

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Chemical Formula 2 may be compounds of the following Chemical Formulas 2-1 to 2-6, but is not limited thereto.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, the compound represented by Formula A″ may be a compound represented by Formula 5 below (isomannide-alkylene glycol-diamine compound):

[Formula 5]

In Formula 5,

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Formula 5 may be compounds of Formulas 5-1 to 5-6, but is not limited thereto.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

In Formulas 5-1 to 5-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, the compound represented by Formula A″ may be a compound represented by Formula 8 below (isoidide-alkylene glycol-diamine compound):

[Formula 8]

In the formula (8),

R ₁ is each independently hydrogen, alkyl or aryl,

R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In one embodiment, examples of the compound represented by Formula 8 may be compounds of Formulas 8-1 to 8-6 below, but is not limited thereto.

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

[Formula 8-4]

[Formula 8-5]

[Formula 8-6]

In Formulas 8-1 to 8-6,

R ₁ is each independently hydrogen, alkyl or aryl,

m and n are each independently an integer from 0 to 15,

m+n is an integer from 1 to 25;

In the method for producing the compound represented by the formula (A) of the present invention, the step (3) of converting the terminal group of the compound obtained from the hydrogenation reaction to an isocyanate is a diamine compound obtained from the hydrogenation reaction into a carbonate-based compound; phosgene-based compounds; carbon monoxide and oxygen; or by reacting with carbon dioxide.

The carbonate-based compound that can be used in step (3) is di-tert-butyl dicarbonate, di-methyl dicarbonate, diethyl dicarbonate, dibenzyl dicarbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylmethyl It may be a carbonate or a combination thereof, but is not limited thereto.

In the step (3), when the compound obtained from the hydrogenation reaction is reacted with a carbonate-based compound, the reaction may be carried out at a temperature condition of -20°C to 100°C, preferably 10°C to 80°C, and the carbonate The content of the system compound may be 2 to 10 molar equivalents, preferably 2 to 5 molar equivalents, based on 1 molar equivalent of the compound obtained from the hydrogenation reaction.

As the phosgene-based compound that can be used in step (3), a compound selected from phosgene, diphosgene, triphosgene, or a combination thereof may be used, but is not limited thereto.

In the step (3), when the compound obtained from the hydrogenation reaction is reacted with a phosgene-based compound, the reaction may be performed at a temperature condition of -60°C to 200°C, preferably 0°C to 150°C, and the phosgene The content of the system compound may be 2 to 10 molar equivalents, preferably 2 to 5 molar equivalents, based on 1 molar equivalent of the compound obtained from the hydrogenation reaction.

The reaction of step (3) may be carried out in the presence of a catalyst, and the catalyst includes 4-dimethylaminopyridine, zinc acetate, sodium methoxide, trialkylamine (eg, triethylamine, etc.), Group III A metal halide (eg, AlCl _{3 ,} etc.) or a combination thereof may be used, but is not limited thereto.

When a catalyst is used in step (3), the content of the catalyst may be 0.01 to 3 molar equivalents, preferably 0.03 to 1 molar equivalent, based on 1 molar equivalent of the compound obtained from the hydrogenation reaction.

The compound represented by the formula (A) according to the present invention can be used for various uses requiring isocyanate, and the compound represented by the formula (A) may be used alone, or mixed with a polyisocyanate having a divalent or higher value other than the compound represented by the formula (A) can also be used.

The compound represented by Formula A according to the present invention is a thermoplastic polyurethane (TPU); flexible or rigid polyurethane foam; flexible or rigid polyurethane molded foam; coatings; adhesive; glue; fiber; It can be used in various fields such as polymer synthesis.

Accordingly, according to another aspect of the present invention, there is provided a polymer comprising the compound represented by the formula (A) according to the present invention.

Since the compound represented by Formula A according to the present invention has a high bio content, it is possible to significantly improve the eco-friendliness of the polymer prepared using the compound.

The polymer according to the invention may be, for example, a thermoplastic polyurethane (TPU), a flexible or rigid polyurethane foam, a polyurea, a polyamide, a polyimide, a binder resin, a thermoplastic polyester elastomer, a synthetic leather polyurethane or an emulsion polymer. can, but is not limited thereto.

In addition, the compound represented by Formula A according to the present invention may be used in a powder coating composition, an adhesive composition, or an adhesive composition.

Although not particularly limited, the lower limit of the content of the compound represented by Formula A included in the polymer according to the present invention is 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, based on 100 parts by weight of the polyol. , 40 parts by weight or more, 45 parts by weight or more, 50 parts by weight or more, 55 parts by weight or more, or 60 parts by weight or more, and the upper limit is 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less, for example, 20 to 80 parts by weight based on 100 parts by weight of polyol parts, 20 to 70 parts by weight, 25 to 60 parts by weight, 30 to 60 parts by weight, 34 to 55 parts by weight, or 34 to 53 parts by weight. If the content of the compound represented by the formula (A) is too small, tensile strength and elongation may be poor, and conversely, if the content is too high, it is difficult to expect additional effects.

In one embodiment, the content of the compound represented by Formula A included in the polymer according to the present invention is preferably an amount of 70 to 130 in terms of an isocyanate index, particularly preferably an amount of 80 to 120, An amount of 100 to 120 is even more preferable. The isocyanate index is the ratio of the number of hydroxyl group equivalents present in the polyol in the urethane reactant to the number of equivalents of isocyanate, and means the amount of isocyanate used relative to the theoretical equivalent. An isocyanate index of less than 100 means that an excess of polyol is present, and an isocyanate index of greater than 100 means that an excess of isocyanate is present. If the isocyanate index is less than 70, there is a problem in that the gelling reaction is delayed due to poor reactivity and curing is not performed.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto. In the following, the deionhydrohexitol-alkylene glycol, the deionhydrohexitol-alkylene glycol dinitrile compound and the deionhydrohexitol-alkylene glycol diamine compound are the deionhydrohexitol-alkylene glycol diisocyanate compounds. It was used as an intermediate compound for the preparation.

[Example]

<Preparation of dianhydrohexitol-alkylene glycol>

manufacturing example 1-1 to 1-4: isosorbide- of ethylene glycol Preparation (in formulas 1 and 2, m+n=3, 5, 10 or 25)

1 mole of isosorbide (146 g); 3 moles, 5 moles, 10 moles or 25 moles of ethylene oxide (132 g, 220 g, 441 g or 1,101 g); And sodium hydroxide (0.4 g) as a catalyst was put into a pressurizable reaction device equipped with a column equipped with a nitrogen gas pipe and a cooling device, a stirrer, a thermometer and a heater, and the temperature was gradually increased. Isosorbide is a form in which the hydrogen of the hydroxyl groups at both ends of the isosorbide is substituted with 3 moles, 5 moles, 10 moles or 25 moles of ethylene oxide groups by reacting at a temperature of 120 ° C. to 160 ° C. for 2 hours to 4 hours. Ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct), isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide 5 mole adduct), isosorbide-ethylene glycol (Preparation Example 1-3) : Ethylene oxide 10 mol adduct) and isosorbide-ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mol adduct) were prepared, respectively.

manufacturing example 2-1 to 2-4: isosorbide-preparation of propylene glycol (in formulas 1 and 2, m+n=3, 5, 10 or 25)

1 mole of isosorbide (146 g); 3 moles, 5 moles, 10 moles or 25 moles of propylene oxide (174 g, 290 g, 581 g or 1,452 g); And sodium hydroxide (0.4 g) as a catalyst was put into a pressurizable reaction device equipped with a column equipped with a nitrogen gas pipe and a cooling device, a stirrer, a thermometer and a heater, and the temperature was gradually increased. Isosorbide is a form in which the hydrogen of the hydroxyl groups at both ends of the isosorbide is substituted with 3 moles, 5 moles, 10 moles or 25 moles of propylene oxide groups by reacting at a temperature of 120 ° C. to 160 ° C. for 2 hours to 4 hours. -Propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct), isosorbide-propylene glycol (Preparation Example 2-2: propylene oxide 5 mole adduct), isosorbide-propylene glycol (Preparation Example 2- 3: Propylene oxide 10 mole adduct) and isosorbide-propylene glycol (Preparation Example 2-4: Propylene oxide 25 mole adduct) were prepared, respectively.

< dianhydrohexitol -Alkylene glycol- dinitrile Preparation of compound (compound of formula A')>

Example A1-1 to A1-4: isosorbide- of ethylene glycol of diacrylonitrile Produce

1 mol of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mol adduct) prepared in Preparation Examples 1-1 to 1-4, isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide) 5 mol adduct) 1 mol, isosorbide-ethylene glycol (Preparation Example 1-3: ethylene oxide 10 mol adduct) 1 mol and isosorbide-ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mol adduct) Put each 1 mol in a glass reactor together with 1.5 g (0.01 mol) of 1,8-Diazabicyclo[5.4.0]undec-7-ene, and after raising the internal temperature to 70~75℃, 159g of acrylonitrile (3 mol) ) was slowly added dropwise over about 4 hours so that the internal temperature did not exceed 80°C. After completion of the dropwise addition, the internal temperature was adjusted to 70-75°C, stirred for 3 hours, and then cooled to room temperature. After diluting the reaction mixture with 500 g of ethyl acetate, it was sequentially washed with 250 g of 1-N aqueous hydrochloric acid solution, 250 g of 1-N aqueous sodium hydroxide solution and 250 g of distilled water, and then concentrated under reduced pressure with isosorbide ethylene glycol (Preparation Example 1-1: Ethylene oxide 3) molar adduct) of diacrylonitrile (Example A1-1, in Formula 1, when m+n=3 and R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-ethylene glycol ( Preparation Example 1-2: When diacrylonitrile (Example A1-2, Formula 1, m+n=5, and R ₁ , R ₂ and R ₃ are all hydrogen atoms) of ethylene oxide 5 molar adduct) ), isosorbide-diacrylonitrile of ethylene glycol (Preparation Example 1-3: 10 mol adduct of ethylene oxide) (Example A1-3, in Formula 1, m+n=10, R ₁ , R ₂ And when R ₃ are all hydrogen atoms) and isosorbide-diacrylonitrile of ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mole adduct) (Example A1-4, in Formula 1, m+n =25, and when R ₁ , R ₂ and R ₃ are all hydrogen atoms), each was obtained in a yield of 85% to 95%.

Example A2-1 to A2-4: isosorbide-propylene glycol of diacrylonitrile Produce

1 mol of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mol adduct) prepared in Preparation Examples 2-1 to 2-4, isosorbide-propylene glycol (Preparation Example 2-2: propylene Oxide 5 mole adduct) 1 mol, isosorbide-propylene glycol (Preparation Example 2-3: propylene oxide 10 mole adduct) 1 mol and isosorbide-propylene glycol (Preparation Example 2-4: propylene oxide 25 mole addition) water) 1 mol each with 1.5 g (0.01 mol) of 1,8-Diazabicyclo[5.4.0]undec-7-ene, put into a glass reactor, and after raising the internal temperature to 70~75℃, 159g of acrylonitrile (3 mol) was slowly added dropwise over about 4 hours so that the internal temperature did not exceed 80°C. After completion of the dropwise addition, the internal temperature was adjusted to 70-75°C, stirred for 3 hours, and then cooled to room temperature. After diluting the reaction mixture with 500 g of ethyl acetate, it was sequentially washed with 1 n aqueous hydrochloric acid solution 250 g, 1 n aqueous sodium hydroxide solution 250 g and distilled water 250 g, and then concentrated under reduced pressure to isosorbide-propylene glycol (Preparation Example 2-1: propylene diacrylonitrile (Example A2-1, in formula 1, when m+n=3, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms) of oxide 3 molar adduct), isosorbent Diacrylonitrile (Example A2-2, in Formula 1, m+n=5, R ₁ is methyl, R ₂ and When R ₃ is all hydrogen atoms), isosorbide-diacrylonitrile of propylene glycol (Preparation Example 2-3: 10 mol adduct of propylene oxide) (Example A2-3, in Formula 1, m+n= 10, R ₁ is methyl, R ₂ and R ₃ are both hydrogen atoms) and diacrylonitrile of isosorbide-propylene glycol (Preparation Example 2-4: propylene oxide 25 mole adduct) (Example) A2-4, in Formula 1, when m+n=25, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms), each was obtained in 85% to 95% yield.

Example A3-1 to A3-4: isosorbide- of ethylene glycol of dicrotononitrile Produce

1 mol of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mol adduct) prepared in Preparation Examples 1-1 to 1-4, isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide) 5 mol adduct) 1 mol, isosorbide-ethylene glycol (Preparation Example 1-3: ethylene oxide 10 mol adduct) 1 mol and isosorbide-ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mol adduct) Put each 1 mol in a glass reactor together with 1.5 g (0.01 mol) of 1,8-Diazabicyclo[5.4.0]undec-7-ene, raise the internal temperature to 70-75 ℃, and then 201 g (3 mol) of crotononitrile was slowly added dropwise over about 4 hours so that the internal temperature did not exceed 80 °C. After completion of the dropwise addition, the internal temperature was adjusted to 70-75°C, stirred for 3 hours, and then cooled to room temperature. The reaction mixture was diluted with 500 g of ethyl acetate, and then washed with 1 normal aqueous hydrochloric acid solution (250 g), 1 normal sodium hydroxide aqueous solution (250 g) and distilled water (250 g), and then concentrated under reduced pressure with isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide) 3 molar adduct) of dicrotononitrile (Example A3-1, in formula 1, when m+n=3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), isosorbide -Dicrotononitrile of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) (Example A3-2, in Formula 1, m+n=5, R ₁ and R ₃ are both hydrogen atoms , when R ₂ is methyl), isosorbide-dicrotononitrile of ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) (Example A3-3, in Formula 1, m+n=10 and R ₁ and R ₃ are both hydrogen atoms and R ₂ is methyl -4, in Formula 1, when m+n=25, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), each of which was obtained in 85% to 95% yield.

Example A4-1 to A4-4: isosorbide- of ethylene glycol of dimethacrylonitrile Produce

1 mol of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mol adduct) prepared in Preparation Examples 1-1 to 1-4, isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide) 5 mol adduct) 1 mol, isosorbide-ethylene glycol (Preparation Example 1-3: ethylene oxide 10 mol adduct) 1 mol and isosorbide-ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mol adduct) Put each 1 mol in a glass reactor together with 1.5 g (0.01 mol) of 1,8-Diazabicyclo[5.4.0]undec-7-ene, and raise the internal temperature to 70-75 ° C. Then, 201 g (3 mol) of methacrylonitrile ) was slowly added dropwise over about 4 hours so that the internal temperature did not exceed 80°C. After completion of the dropwise addition, the internal temperature was adjusted to 70-75°C, stirred for 3 hours, and then cooled to room temperature. After diluting the reaction mixture with 500 g of ethyl acetate, it was sequentially washed with 1 n aqueous hydrochloric acid solution (250 g), 1 n aqueous sodium hydroxide solution (250 g) and distilled water (250 g), and then concentrated under reduced pressure with isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide) 3 molar adduct) of dimethacrylonitrile (Example A4-1, in formula 1, when m+n=3, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbent Bead-dimethacrylonitrile (Example A4-2, in Formula 1, m+n=5, R ₁ and R ₂ are both hydrogen atom and R ₃ is methyl), isosorbide-dimethacrylonitrile of ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) (Example A4-3, in Formula 1, m+ When n=10, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl) and isosorbide-dimethacrylonitrile of ethylene glycol (Preparation Example 1-4: ethylene oxide 25 molar adduct) (Example A4-4, in Formula 1, when m+n=25, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl) Each was obtained in 85% to 95% yield.

Example A5-1 to A5-4: isosorbide-propylene glycol of dicinamonitrile Produce

1 mol of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mol adduct) prepared in Preparation Examples 2-1 to 2-4, isosorbide-propylene glycol (Preparation Example 2-2: propylene Oxide 5 mole adduct) 1 mol, isosorbide-propylene glycol (Preparation Example 2-3: propylene oxide 10 mole adduct) 1 mol and isosorbide-propylene glycol (Preparation Example 2-4: propylene oxide 25 mole addition) water) 1 mol each with 1.5 g (0.01 mol) of 1,8-Diazabicyclo[5.4.0]undec-7-ene, put in a glass reactor, and after raising the internal temperature to 70~75℃, 387 g of cinnamonitrile (3 mol) was slowly added dropwise over about 4 hours so that the internal temperature did not exceed 80°C. After completion of the dropwise addition, the internal temperature was adjusted to 70-75°C, stirred for 5 hours, and then cooled to room temperature. After diluting the reaction mixture with 500 g of ethyl acetate, it was sequentially washed with 1 n aqueous hydrochloric acid solution 250 g, 1 n aqueous sodium hydroxide solution 250 g and distilled water 250 g, and then concentrated under reduced pressure to isosorbide-propylene glycol (Preparation Example 2-1: propylene dicinamonitrile (Example A5-1, in formula 1, when m+n=3, R ₁ is methyl, R ₂ is phenyl, R ₃ is a hydrogen atom) of dicinamonitrile of an oxide 3 molar adduct), iso sorbide-propylene glycol (Preparation Example 2-2: propylene oxide 5 molar adduct) disinamo nitrile (Example A5-2, in Formula 1, m+n=5, R ₁ is methyl, R ₂ is When phenyl and R ₃ is a hydrogen atom), isosorbide-disinanitrile of propylene glycol (Preparation Example 2-3: propylene oxide 10-molar adduct) (Example A5-3, in Formula 1, m+n =10, when R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom) and dicinamonitrile of isosorbide-propylene glycol (Preparation Example 2-4: propylene oxide 25 molar adduct) ( Example A5-4, in Formula 1, when m+n=25, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), each was obtained in 80% to 90% yield.

Example A6-1 to A6-4: isosorbide- of ethylene glycol of di(3-furyl)acrylonitrile Produce

1 mol of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mol adduct) prepared in Preparation Examples 1-1 to 1-4, isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide) 5 mol adduct) 1 mol, isosorbide-ethylene glycol (Preparation Example 1-3: ethylene oxide 10 mol adduct) 1 mol and isosorbide-ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mol adduct) Put each 1 mol in a glass reactor together with 1.5 g (0.01 mol) of 1,8-Diazabicyclo[5.4.0]undec-7-ene, and after raising the internal temperature to 70~75℃, 3-(furan-2-yl) ) Prop-2-ennitrile (3- (Furan-2-yl) prop-2-enenitrile) 357 g (3 mol) was slowly added dropwise over about 4 hours so that the internal temperature did not exceed 80 ℃. After completion of the dropwise addition, the internal temperature was adjusted to 70-75° C., stirred for 12 hours, and then cooled to room temperature. After diluting the reaction mixture with 500 g of ethyl acetate, it was sequentially washed with 1 n aqueous hydrochloric acid solution (250 g), 1 n aqueous sodium hydroxide solution (250 g) and distilled water (250 g), and then concentrated under reduced pressure with isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide) 3 molar adduct) of di(3-furyl)acrylonitrile (Example A6-1, in Formula 1, when m+n=3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl ), isosorbide-di (3-furyl) acrylonitrile of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) (Example A6-2, in Formula 1, m + n = 5, When R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl), isosorbide-di (3-furyl) acrylonitrile of ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) ( Example A6-3, in Formula 1, when m+n=10, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl) and isosorbide-ethylene glycol (Preparation Example 1-4: Ethylene di(3-furyl)acrylonitrile (Example A6-4, in formula 1, m+n=25, R ₁ and R ₃ are both hydrogen atoms, R ₂ is furyl) of 25 molar oxide adduct) case) each was obtained in 80% to 90% yield

Example A7-1 to A7-4: isosorbide-propylene glycol of di(3-cyclohexyl)acrylonitrile Produce

1 mol of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mol adduct) prepared in Preparation Examples 2-1 to 2-4, isosorbide-propylene glycol (Preparation Example 2-2: propylene Oxide 5 mole adduct) 1 mol, isosorbide-propylene glycol (Preparation Example 2-3: propylene oxide 10 mole adduct) 1 mol and isosorbide-propylene glycol (Preparation Example 2-4: propylene oxide 25 mole addition) water) 1 mol each with 1.5 g (0.01 mol) of 1,8-Diazabicyclo[5.4.0]undec-7-ene, put in a glass reactor, and after raising the internal temperature to 70~75℃, 405 g of cyclohexaneacrylonitrile (3 mol) was slowly added dropwise over about 4 hours so that the internal temperature did not exceed 80°C. After completion of the dropwise addition, the internal temperature was adjusted to 70-75° C., stirred for 6 hours, and then cooled to room temperature. After diluting the reaction mixture with 500 g of ethyl acetate, it was sequentially washed with 1 n aqueous hydrochloric acid solution 250 g, 1 n aqueous sodium hydroxide solution 250 g and distilled water 250 g, and then concentrated under reduced pressure to isosorbide-propylene glycol (Preparation Example 2-1: propylene di(3-cyclohexyl)acrylonitrile (Example A7-1, formula 1, wherein m+n=3, R ₁ is methyl, R ₂ is cyclohexyl, R _{3 of an oxide 3 molar adduct)} is a hydrogen atom), isosorbide-di(3-cyclohexyl)acrylonitrile of propylene glycol (Preparation Example 2-2: propylene oxide 5 mol adduct) (Example A7-2, in Formula 1, m When +n=5, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom), isosorbide-di of propylene glycol (Preparation Example 2-3: 10 molar adduct of propylene oxide) (3-cyclohexyl)acrylonitrile (Example A7-3, in formula 1, when m+n=10, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom) and iso sorbide-di(3-cyclohexyl)acrylonitrile of propylene glycol (Preparation Example 2-4: 25 mol adduct of propylene oxide) (Example A7-4, in Formula 1, m+n=25, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom), each of which was obtained in 80% to 90% yield.

< dianhydrohexitol -Alkylene glycol- diamine Preparation of compound (compound of formula A″)>

Example B1-1 to B1-4: isosorbide- of ethylene glycol of diacryloamine Produce

Diacrylonitrile of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3-molar adduct) prepared in Examples A1-1 to A1-4 (Example A1-1, in Formula 1, m+ When n=3 and R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-diacrylonitrile of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) (Example A1) -2, in Formula 1, m+n=5, R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) of diacrylonitrile (Example A1-3, in Formula 1, when m+n=10 and R ₁ , R ₂ and R ₃ are all hydrogen atoms) and isosorbide-ethylene glycol (Preparation Example 1- 4: 1,000 g each of diacrylonitrile (Example A1-4, in Formula 1, when m+n=25 and R ₁ , R ₂ and R _{3 are all hydrogen atoms) of ethylene oxide 25 molar adduct)} was put into a high-pressure reactor together with 2,000 g of purified water, 50 g of Raney nickel and 300 g of aqueous ammonia, and sealed, and then hydrogen was added at 10 bar. While maintaining the hydrogen pressure, the internal temperature was heated to 130° C. and stirred for 4 hours. After completion of the reaction, the catalyst was recovered through filtration, and the filtrate was concentrated to diacryloamine (Example B1-1, in Formula 2) of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) , m+n=3, and when R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-diacryloamine of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) ( Example B1-2, in Formula 2, when m+n=5, R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-ethylene glycol (Preparation Example 1-3: 10 moles of ethylene oxide adduct) of diacryloamine (Example B1-3, in Formula 2, when m+n=10 and R ₁ , R ₂ and R ₃ are all hydrogen atoms) and isosorbide-ethylene glycol (preparation Example 1-4: Diacryloamine of ethylene oxide 25 mole adduct) (Example B1-4, in Formula 2, when m+n=25 and R ₁ , R ₂ and R ₃ are all hydrogen atoms) Each was obtained in 75%-85% yield.

Example B2-1 to B2-4: isosorbide-propylene glycol of diacryloamine Produce

Diacrylonitrile (Example A2-1, in Formula 1, m +n=3, R ₁ is methyl, R ₂ and R ₃ are both hydrogen atoms), diacrylonitrile of isosorbide-propylene glycol (Preparation Example 2-2: propylene oxide 5 molar adduct) (Example A2-2, in Formula 1, when m+n=5, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms), isosorbide-propylene glycol (Preparation Example 2-3: diacrylonitrile (Example A2-3, in formula 1, when m+n=10, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms) of propylene oxide 10 molar adduct) and iso sorbide-diacrylonitrile of propylene glycol (Preparation Example 2-4: 25 mol adduct of propylene oxide) (Example A2-4, in Formula 1, m+n=25, R ₁ is methyl, R ₂ and R ₃ are all hydrogen atoms) 1,000 g of each was put into a high-pressure reactor together with 2,000 g of purified water, 50 g of Raney nickel, and 300 g of ammonia water, and sealed, and then hydrogen was added at 10 bar. While maintaining the hydrogen pressure, the internal temperature was heated to 130° C. and stirred for 4 hours. After completion of the reaction, the catalyst was recovered through filtration, and the filtrate was concentrated to diacryloamine (Example B2-1, Formula 2) of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct) In, when m+n=3, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms), isosorbide-di of propylene glycol (Preparation Example 2-2: 5 molar adduct of propylene oxide) Acryloamine (Example B2-2, in Formula 2, when m+n=5, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms), isosorbide-propylene glycol (Preparation Example 2) -3: when propylene oxide 10 mole adduct) of diacryloamine (Example B2-3, in Formula 2, m+n=10, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms) ) and diacryloamine of isosorbide-propylene glycol (Preparation Example 2-4: 25 mol adduct of propylene oxide) (Example B2-4, in Formula 2, m+n=25, R ₁ is methyl , R ₂ and R ₃ are all hydrogen atoms) each was obtained in a yield of 75% to 85%.

Example B3-1 to B3-4: isosorbide- of ethylene glycol of dicrotonoamine Produce

Dicrotononitrile of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3-molar adduct) prepared in Examples A3-1 to A3-4 (Example A3-1, in Formula 1, m+ When n = 3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), isosorbide-dicrotononitrile of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) ( Example A3-2, in Formula 1, when m+n=5, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), isosorbide-ethylene glycol (Preparation Example 1-3: Ethylene dicrotononitrile (Example A3-3, in formula 1, where m+n=10, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl) of an oxide 10 molar adduct) and isosorbate Bead-Dicrotononitrile of ethylene glycol (Preparation Example 1-4: 25 mole adduct of ethylene oxide) (Example A3-4, in Formula 1, m+n=25, R ₁ and R ₃ are both hydrogen atoms and R ₂ is methyl) each 1,000 g of purified water, 2,000 g of purified water, 50 g of Raney nickel, and 300 g of aqueous ammonia were put into a high-pressure reactor, sealed, and then hydrogen was added at 10 bar. While maintaining the hydrogen pressure, the internal temperature was heated to 130° C. and stirred for 4 hours. After completion of the reaction, the catalyst was recovered through filtration, and the filtrate was concentrated to dicrotonoamine (Example B3-1, in Formula 2) of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) , m+n=3, when R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), isosorbide-Dicro of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) Tonoamine (Example B3-2, in Formula 2, when m+n=5, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), isosorbide-ethylene glycol (Preparation Example 1- 3: Dicrotonoamine of ethylene oxide 10 molar adduct) (Example B3-3, in Formula 2, when m+n=10, _{both R 1} and R ₃ are hydrogen atoms, and R ₂ is methyl) and isosorbide-dicrotonoamine of ethylene glycol (Preparation Example 1-4: 25 mol adduct of ethylene oxide) (Example B3-4, in Formula 2, m+n=25, and both _{R 1} and R _{3 )} is a hydrogen atom and R ₂ is methyl), each obtained in a yield of 75% to 85%.

Example B4-1 to B4-4: isosorbide- of ethylene glycol of dimethacryloamine Produce

Dimethacrylonitrile of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3-molar adduct) prepared in Examples A4-1 to A4-4 (Example A4-1, in Formula 1, m +n=3, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbide-dimethacryloyl of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) Nitrile (Example A4-2, in Formula 1, when m+n=5, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbide-ethylene glycol (Preparation Example 1-3) : Dimethacrylonitrile of ethylene oxide 10 molar adduct (Example A4-3, in Formula 1, when m+n=10, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl) and isosorbide-dimethacrylonitrile of ethylene glycol (Preparation Example 1-4: 25 mole adduct of ethylene oxide) (Example A4-4, in Formula 1, m+n=25, R ₁ and R ₂ are all hydrogen atoms, and R ₃ is methyl) 1,000 g of each was put into a high-pressure reactor together with 2,000 g of purified water, 50 g of Raney nickel, and 300 g of aqueous ammonia, sealed, and then hydrogen was added at 10 bar. While maintaining the hydrogen pressure, the internal temperature was heated to 130° C. and stirred for 4 hours. After completion of the reaction, the catalyst was recovered through filtration, and the filtrate was concentrated to dimethacryloamine (Example B4-1, Formula 2) of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) In, when m+n=3, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbide-di of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) Methacryloamine (Example B4-2, in Formula 2, when m+n=5, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbide-ethylene glycol (Preparation Example) 1-3: dimethacryloamine of ethylene oxide 10 molar adduct) (Example B4-3, in formula 2, m+n=10, R ₁ and R ₂ are both hydrogen atoms, R ₃ is methyl ) and isosorbide-dimethacryloamine of ethylene glycol (Preparation Example 1-4: 25 mol adduct of ethylene oxide) (Example B4-4, in Formula 2, m+n=25, R ₁ and R ₂ is both a hydrogen atom and R ₃ is methyl), each of which was obtained in a yield of 75-85%.

Example B5-1 to B5-4: isosorbide-propylene glycol of dicinamoamine Produce

Disinanitrile (Example A5-1, in Formula 1, m+ of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct) prepared in Examples A5-1 to A5-4 When n=3, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), dicinamonitrile of isosorbide-propylene glycol (Preparation Example 2-2: propylene oxide 5 molar adduct) ( Example A5-2, in Formula 1, when m+n=5, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), isosorbide-propylene glycol (Preparation Example 2-3 : Disinamonitrile of propylene oxide 10 molar adduct) (Example A5-3, in Formula 1, when m+n=10, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom) And isosorbide- propylene glycol (Preparation Example 2-4: propylene oxide 25 mole adduct) of dicinamonitrile (Example A5-4, in Formula 1, m+n=25, R ₁ is methyl, R _{If divalent} phenyl and R ₃ is a hydrogen atom) 1,000 g each was put into a high-pressure reactor together with 2,000 g of purified water, 50 g of Raney nickel, and 300 g of aqueous ammonia, sealed, and then hydrogen was added at 10 bar. While maintaining the hydrogen pressure, the internal temperature was heated to 130° C. and stirred for 4 hours. After completion of the reaction, the catalyst was recovered through filtration, and the filtrate was concentrated to dicinamoamine (Example B5-1, in Formula 2) of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mol adduct) , m+n=3, R ₁ is methyl, R ₂ is phenyl, R ₃ is a hydrogen atom), isosorbide-propylene glycol (Preparation Example 2-2: propylene oxide 5 molar adduct) Disinamoamine (Example B5-2, in Formula 2, when m+n=5, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), isosorbide-propylene glycol (prepared Example 2-3: Disinamoamine (Example B5-3, formula 2, m+n=10, R ₁ is methyl, R ₂ is phenyl, R ₃ is hydrogen of propylene oxide 10-molar adduct) when the phosphorus atom) and isosorbide-propylene glycol (Preparation example 2-4: in a dish cinnamoyl-amine (example 25 mol propylene oxide adduct) B5-4, formula 2, m + n = 25, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), each obtained in 70% to 80% yield.

Example B6-1 to B6-4: isosorbide- of ethylene glycol of di(3-furyl)acryloamine Produce

Di (3-furyl) acrylonitrile of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3-molar adduct) prepared in Examples A6-1 to A6-4 (Example A6-1, Chemical formula In 1, m+n=3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl), isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide 5 mole adduct) Di(3-furyl)acrylonitrile (Example A6-2, in Formula 1, when m+n=5, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl), isosorbide- Di(3-furyl)acrylonitrile of ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) (Example A6-3, in Formula 1, m+n=10, R ₁ and R ₃ are All are hydrogen atoms and R ₂ is furyl) and isosorbide-di(3-furyl)acrylonitrile of ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mole adduct) (Example A6-4, In Formula 1, when m+n=25, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl) 1,000 g each, purified water 2,000 g, Raney nickel 50 g, and ammonia water 300 g together with 1,000 g each and sealed in a high-pressure reactor After that, hydrogen was added to 10 bar. While maintaining the hydrogen pressure, the internal temperature was heated to 130° C. and stirred for 4 hours. After completion of the reaction, the catalyst was recovered through filtration, and the filtrate was concentrated to di(3-furyl)acryloamine (Example B6- 1, in Formula 2, m+n=3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl), isosorbide-ethylene glycol (Preparation Example 1-2: addition of 5 moles of ethylene oxide di(3-furyl)acryloamine of water) (Example B6-2, in Formula 2, when m+n=5, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl), iso sorbide-di(3-furyl)acryloamine of ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) (Example B6-3, in Formula 2, m+n=10, R ₁ and When R ₃ is all hydrogen atoms and R ₂ is furyl) and isosorbide-di(3-furyl)acryloamine of ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mole adduct) (Example B6) -4, in Formula 2, when m+n=25, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl), each of which was obtained in 70% to 80% yield.

Example B7-1 to B7-4: isosorbide-propylene glycol of di(3-cyclohexyl)acryloamine Produce

Di (3-cyclohexyl) acrylonitrile (Example A7-1) of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3-molar adduct) prepared in Examples A7-1 to A7-4 , in Formula 1, when m+n=3, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom), isosorbide-propylene glycol (Preparation Example 2-2: Propylene oxide 5 molar adduct) of di(3-cyclohexyl)acrylonitrile (Example A7-2, in formula 1, m+n=5, R ₁ is methyl, R ₂ is cyclohexyl, R ₃ is hydrogen in the case of an atom), isosorbide-di(3-cyclohexyl)acrylonitrile of propylene glycol (Preparation Example 2-3: 10 mol adduct of propylene oxide) (Example A7-3, in Formula 1, m+n =10, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom) and di(3 of isosorbide-propylene glycol (Preparation Example 2-4: Propylene oxide 25 molar adduct) -Cyclohexyl) acrylonitrile (Example A7-4, in Formula 1, when m+n=25, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom) 1,000 g each 2,000 g of purified water, 50 g of Raney nickel, and 300 g of aqueous ammonia were put into a high-pressure reactor and sealed, and then hydrogen was added at 10 bar. While maintaining the hydrogen pressure, the internal temperature was heated to 130° C. and stirred for 4 hours. After completion of the reaction, the catalyst was recovered through filtration, and the filtrate was concentrated to di(3-cyclohexyl)acryloamine of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct) (Example) B7-1, in Formula 2, when m+n=3, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom), isosorbide-propylene glycol (Preparation Example 2-2: di(3-cyclohexyl)acryloamine (Example B7-2, in formula 2, m+n=5, R ₁ is methyl, R ₂ is cyclohexyl, R _trivalent hydrogen atom), isosorbide-di (3-cyclohexyl) acryloamine of propylene glycol (Preparation Example 2-3: 10 mol adduct of propylene oxide) (Example B7-3, in Formula 2, m+n=10, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom) and isosorbide-propylene glycol (Preparation Example 2-4: propylene oxide 25 molar adduct) di(3-cyclohexyl)acryloamine (Example B7-4, in Formula 2, when m+n=25, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom) each was obtained in a yield of 75% to 85%.

<Isosorbide-alkylene glycol- diisocyanate Preparation of compound (compound of formula A)>

Example C1-1 to C1-4: isosorbide- of ethylene glycol of dipropyl isocyanate Manufacturing (using carbonate)

After 300 ml of methylene chloride was put into a four-neck reactor equipped with a condenser, an internal thermometer and a nitrogen injection line, 0.05 molar equivalents of 4-dimethylaminopyridine (DMAP) and 3.0 molar equivalents of di-tert-butyldicarbonate (DBDC) were added and dissolved in methylene chloride. Then, the temperature inside the reactor was maintained at 0-5° C. using an ice bath under a nitrogen atmosphere. Diacryloamine (Example B1-) of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) prepared in Examples B1-1 to B1-4 above in 200 ml of methylene chloride 1, in Formula 2, m+n=3, R ₁ , R ₂ and R _{3 When} all are hydrogen atoms), isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) Diacryloamine (Example B1-2, in Formula 2, when m+n=5 and R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-ethylene glycol (Preparation Example 1-3 : Diacryloamine (Example B1-3, in Formula 2, m+n=10, and R ₁ , R ₂ and R ₃ are all hydrogen atoms) of ethylene oxide 10 molar adduct) and isosorbide -Diacryloamine of ethylene glycol (Preparation Example 1-4: 25 mol adduct of ethylene oxide) (Example B1-4, in Formula 2, m+n=25, and R ₁ , R ₂ and R ₃ are all A solution prepared by dissolving 1.0 molar equivalent of each hydrogen atom) was added dropwise to the reactor, at which time the internal temperature of the reactor was maintained at 0-5°C. After completion of the dropwise addition, the temperature inside the reactor was raised to 25° C., and the reaction was carried out for 3 hours.

Methylene chloride was removed from the obtained reaction product using a concentrator, and the reaction products were extracted using hexane and third distilled water. After removing moisture using magnesium sulfate, hexane is removed from the extract using a concentrator, and dipropyl isocyanate of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) (Example C1- 1, in Formula 3, m+n=3, and R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) Dipropyl isocyanate (Example C1-2, in Formula 3, when m+n=5 and R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-ethylene glycol (Preparation Example 1-3: Dipropylisocyanate (Example C1-3, in formula 3, when m+n=10 and R ₁ , R ₂ and R ₃ are all hydrogen atoms) of ethylene oxide 10 molar adduct) and isosorbide-ethylene Dipropyl isocyanate of glycol (Preparation Example 1-4: 25 mol adduct of ethylene oxide) (Example C1-4, in Formula 3, m+n=25, and R ₁ , R ₂ and R ₃ are all hydrogen atoms case) were obtained in 80-90% yield, respectively.

As a result of confirming the isocyanate content in the dipropyl isocyanate of the isosorbide-ethylene glycol of Examples C1-1 to C1-4 obtained above through the potentiometric method of ISO 14896, Example C1-1 is 19.1 ± 0.2 mass% _NCO level (theoretical value = 18.9 mass % _NCO ), Examples C1-2 have 16.0 ± 0.2 mass % _NCO level (theoretical = 15.8 mass % _NCO ), Examples C1-3 have 11.0 ± 0.2 mass % _NCO level (theoretical value = 11.1 mass% _NCO ), Examples C1-4 were identified with a _{level of 6.1 ± 0.2 mass% NCO} (theoretical = 5.9 mass% _NCO ). _{The mass % NCO, which} is a unit of the isocyanate content, means the mass % of NCO groups present in the dipropyl isocyanate of isosorbide-ethylene glycol as a sample.

Example C2-1 to C2-4: isosorbide-propylene glycol of dipropyl isocyanate Produce

After 300 ml of methylene chloride was put into a four-neck reactor equipped with a condenser, an internal thermometer and a nitrogen injection line, 0.05 molar equivalents of 4-dimethylaminopyridine (DMAP) and 3.0 equivalents of di-tert-butyldicarbonate (DBDC) were added. It was dissolved in methylene chloride. Then, the temperature inside the reactor was maintained at 0-5° C. using an ice bath under a nitrogen atmosphere. Diacryloamine (Example B2) of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct) prepared in Examples B2-1 to B2-4 above in 200 ml of methylene chloride -1, in Formula 2, m+n=3, R ₁ is methyl, R ₂ and R ₃ are both hydrogen atoms), isosorbide-propylene glycol (Preparation Example 2-2: propylene oxide 5 moles) adduct) of diacryloamine (Example B2-2, in formula 2, when m+n=5, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms), isosorbide-propylene Diacryloamine of glycol (Preparation Example 2-3: 10 mol adduct of propylene oxide) (Example B2-3, in Formula 2, m+n=10, R ₁ is methyl, R ₂ and R ₃ are When both are hydrogen atoms) and diacryloamine (Example B2-4, Formula 2, m+n=25, When R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms), a solution prepared by dissolving 1.0 molar equivalents of each was added dropwise to the reactor, in which case the internal temperature of the reactor was maintained at 0-5°C. After completion of the dropwise addition, the temperature inside the reactor was raised to 25° C., and the reaction was carried out for 3 hours.

Methylene chloride was removed from the obtained reaction product using a concentrator, and the reaction products were extracted using hexane and third distilled water. After removing moisture using magnesium sulfate, hexane is removed from the extract using a concentrator, and dipropyl isocyanate of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct) (Example C2) -1, in Formula 3, m+n=3, R ₁ is methyl, R ₂ and R ₃ are both hydrogen atoms), isosorbide-propylene glycol (Preparation Example 2-2: 5 moles of propylene oxide) adduct) of dipropylisocyanate (Example C2-2, in formula 3, when m+n=5, R ₁ is methyl, and R ₂ and R ₃ are both hydrogen atoms), isosorbide-propylene glycol (Preparation Example 2-3: 10 mol adduct of propylene oxide) of dipropyl isocyanate (Example C2-3, in Formula 3, m+n=10, R ₁ is methyl, R ₂ and R ₃ are both hydrogen isosorbide-dipropylisocyanate (in Example C2-4, Formula 3, m+n=25, and R ₁ is methyl, and when R ₂ and R ₃ are both hydrogen atoms), each was obtained in 70-80% yield.

As a result of confirming the isocyanate content in the dipropyl isocyanate of the isosorbide-propylene glycol of Examples C2-1 to C2-4 obtained through the potentiometric method of ISO 14896, Example C2-1 is 17.1 ± 0.3 mass% _NCO Level (theoretical = 17.3 mass% _NCO ), Example C2-2 is 13.9 ± 0.1 mass% _NCO level (theoretical = 13.9 mass% _NCO ), Example C2-3 is 9.6 ± 0.2 mass% _NCO Level (theoretical = 9.4 mass % _NCO ), Example C2-4 was identified as 4.8 ± 0.1 mass % _NCO level (theoretical = 4.8 mass % _NCO ). _{The mass % NCO, which} is a unit of the isocyanate content, means the mass % of NCO groups present in the dipropyl isocyanate of isosorbide-propylene glycol as a sample.

Example C3-1 to C3-4: isosorbide- of ethylene glycol of dicrotonoisocyanate. Produce

After 300 ml of methylene chloride was put into a four-neck reactor equipped with a condenser, an internal thermometer and a nitrogen injection line, 0.05 molar equivalents of 4-dimethylaminopyridine (DMAP) and 3.0 molar equivalents of di-tert-butyldicarbonate (DBDC) were added and dissolved in methylene chloride. Then, the temperature inside the reactor was maintained at 0-5° C. using an ice bath under a nitrogen atmosphere. Dicrotonoamine (Example B3-) of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) prepared in Examples B3-1 to B3-4 above in 200 ml of methylene chloride 1, in Formula 2, when m+n=3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), isosorbide-ethylene glycol (Preparation Example 1-2: Addition of 5 moles of ethylene oxide dicrotonoamine of water) (Example B3-2, in Formula 2, when m+n=5, _{both R 1} and R ₃ are hydrogen atoms, and R ₂ is methyl), isosorbide-ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) of dicrotonoamine (Example B3-3, in Formula 2, m+n=10, R ₁ and R ₃ are both hydrogen atoms, R ₂ is methyl) and isosorbide-dicrotonoamine of ethylene glycol (Preparation Example 1-4: 25 mol adduct of ethylene oxide) (in Example B3-4, Formula 2, m+n=25, R _When both 1 and R ₃ are hydrogen atoms and R ₂ is methyl), a solution prepared by dissolving 1.0 molar equivalents of each was added dropwise to the reactor, at which time the internal temperature of the reactor was maintained at 0-5°C. After completion of the dropwise addition, the temperature inside the reactor was raised to 25° C., and the reaction was carried out for 3 hours.

Methylene chloride was removed from the obtained reaction product using a concentrator, and the reaction products were extracted using hexane and third distilled water. After removing moisture using magnesium sulfate, hexane is removed from the extract using a concentrator, and dicrotonoisocyanate of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) (Example C3) -1, in Formula 3, when m+n=3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide 5 moles) adduct) of dicrotonoisocyanate (Example C3-2, in formula 3, when m+n=5, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is methyl), isosorbide-ethylene Dicrotonoisocyanate (Example C3-3, in Formula 3, m+n=10, R ₁ and R ₃ are both hydrogen atoms, R _{When divalent} methyl) and isosorbide-dicrotonoisocyanate of ethylene glycol (Preparation Example 1-4: 25 mole adduct of ethylene oxide) (Example C3-4, in Formula 3, m+n=25, When both R ₁ and R ₃ are hydrogen atoms and R ₂ is methyl), each was obtained in 80-90% yield.

As a result of confirming the isocyanate content in the dicrotonoisocyanate of Examples C3-1 to C3-4 isosorbide-ethylene glycol obtained through the potentiometric method of ISO 14896, Example C3-1 is 17.8 ± 0.1 mass% _NCO level (theoretical value = 17.8 mass% _NCO ), Example C3-2 has a 14.9 ± 0.1 mass% _NCO level (theoretical value = 15.0 mass% _NCO ), Example C3-3 has a 10.5 ± 0.3 mass% _NCO level (theoretical value = 10.8 mass % _NCO ), Example C3-4 was identified with a _{level of 5.7 ± 0.1 mass % NCO} (theoretical = 5.8 mass % _NCO ). _{The mass% NCO, which} is a unit of the isocyanate content, means the mass% of NCO groups present in the dicrotonoisocyanate of isosorbide-ethylene glycol as a sample.

Example C4-1 to C4-4: isosorbide- of ethylene glycol of dimethacryloisocyanate Produce

After 300 ml of methylene chloride was put into a four-neck reactor equipped with a condenser, an internal thermometer and a nitrogen injection line, 0.05 molar equivalents of 4-dimethylaminopyridine (DMAP) and 3.0 molar equivalents of di-tert-butyldicarbonate (DBDC) were added and dissolved in methylene chloride. Then, the temperature inside the reactor was maintained at 0-5° C. using an ice bath under a nitrogen atmosphere. Dimethacryloamine (Example B4) of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) prepared in Examples B4-1 to B4-4 above in 200 ml of methylene chloride -1, in Formula 2, when m+n=3, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide 5 moles) adduct) of dimethacryloamine (Example B4-2, in Formula 2, when m+n=5, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbide- Dimethacryloamine of ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) (Example B4-3, in Formula 2, m+n=10, R ₁ and R ₂ are both hydrogen atoms , when R ₃ is methyl) and isosorbide-dimethacryloamine of ethylene glycol (Preparation Example 1-4: 25 mole adduct of ethylene oxide) (Example B4-4, in Formula 2, m+n= 25, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl) by dissolving 1.0 molar equivalent of each) was added dropwise to the reactor, and the reactor internal temperature was maintained at 0-5 ° C. made to be After completion of the dropwise addition, the temperature inside the reactor was raised to 25° C., and the reaction was carried out for 3 hours.

Methylene chloride was removed from the obtained reaction product using a concentrator, and the reaction products were extracted using hexane and third distilled water. After removing moisture using magnesium sulfate, hexane is removed from the extract using a concentrator, and dimethacryloisocyanate of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) (Example) C4-1, in Formula 3, m+n=3, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbide-ethylene glycol (Preparation Example 1-2: Ethylene oxide 5 molar adduct) of dimethacryloisocyanate (Example C4-2, in formula 3, when m+n=5, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl), isosorbide -Dimethacryloisocyanate of ethylene glycol (Preparation Example 1-3: 10 mol adduct of ethylene oxide) (Example C4-3, in Formula 3, m+n=10, and R ₁ and R ₂ are both hydrogen atoms and R ₃ is methyl) and isosorbide-dimethacryloisocyanate of ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mole adduct) (Example C4-4, in Formula 3, m+n =25, R ₁ and R ₂ are both hydrogen atoms, and R ₃ is methyl) each was obtained in a yield of 75-85%.

As a result of confirming the isocyanate content in the dimethacryloisocyanate of the isosorbide-ethylene glycol of Examples C4-1 to C4-4 obtained through the potentiometric measurement method of ISO 14896, Example C4-1 is 17.5 ± 0.3 mass% _NCO level (theoretical = 17.8 mass% _NCO ), Example C4-2 has 15.0 ± 0.2 mass% _NCO level (theoretical = 15.0 mass% _NCO ), Example C4-3 has 10.9 ± 0.3 mass% _NCO level (theoretical) Value = 10.8 mass % _NCO ), Example C4-4 was identified with a _{level of 5.9 ± 0.2 mass % NCO} (theoretical value = 5.8 mass % _NCO ). _{The mass % NCO, which} is a unit of the isocyanate content, means the mass % of NCO groups present in the dimethacryloisocyanate of isosorbide-ethylene glycol as a sample.

Example C5-1 to C5-4: isosorbide-propylene glycol of dicinamoisocyanate Produce

After 300 ml of methylene chloride was put into a four-neck reactor equipped with a condenser, an internal thermometer and a nitrogen injection line, 0.05 molar equivalents of 4-dimethylaminopyridine (DMAP) and 3.0 molar equivalents of di-tert-butyldicarbonate (DBDC) were added and dissolved in methylene chloride. Then, the temperature inside the reactor was maintained at 0-5° C. using an ice bath under a nitrogen atmosphere. Dicinamoamine (Example B5- 1, in the formula, when m+n=3, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), isosorbide-propylene glycol (Preparation Example 2-2: 5 moles of propylene oxide) adduct) of disinamoamine (Example B5-2, in formula 2, when m+n=5, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), isosorbide-propylene Disinamoamine of glycol (Preparation Example 2-3: propylene oxide 10 molar adduct) (Example B5-3, in Formula 2, m+n=10, R ₁ is methyl, R ₂ is phenyl, R _trivalent hydrogen atom) and isosorbide-disinamoamine of propylene glycol (Preparation Example 2-4: 25 mol adduct of propylene oxide) (Example B5-4, in Formula 2, m+n=25, When R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), a solution prepared by dissolving 1.0 molar equivalent of each was added dropwise to the reactor, in which case the internal temperature of the reactor was maintained at 0-5° C. did. After completion of the dropwise addition, the temperature inside the reactor was raised to 25° C., and the reaction was carried out for 4 hours.

Methylene chloride was removed from the obtained reaction product using a concentrator, and the reaction products were extracted using hexane and third distilled water. After removing moisture using magnesium sulfate, hexane is removed from the extract using a concentrator, and dicinamoisocyanate (Example C5) of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct) -1, in Formula 3, when m+n=3, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), isosorbide-propylene glycol (Preparation Example 2-2: Propylene oxide 5 molar adduct) of dicinamoisocyanate (Example C5-2, in formula 3, when m+n=5, R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), isosorbide -Disinamoisocyanate of propylene glycol (Preparation Example 2-3: 10 mol adduct of propylene oxide) (Example C5-3, in Formula 3, m+n=10, R ₁ is methyl, R ₂ is phenyl , when R ₃ is a hydrogen atom) and isosorbide-disinamoisocyanate (Example C5-4, in Formula 3, m+n=25 , R ₁ is methyl, R ₂ is phenyl, and R ₃ is a hydrogen atom), respectively, in 75-80% yield.

As a result of confirming the isocyanate content in the isosorbide-propylene glycol of the isosorbide-propylene glycol of Examples C5-1 to C5-4 obtained through the potentiometric method of ISO 14896, Example C5-1 is 13.5 ± 0.3 mass% _NCO level (theoretical = 13.2 mass% _NCO ), Example C5-2 at 11.3 ± 0.2 mass% _NCO level (theoretical = 11.1 mass% _NCO ), Example C5-3 at 8.0 ± 0.3 mass% _NCO level (theoretical value) = 8.0 mass % _NCO ), Example C5-4 was identified with a _{level of 4.2 ± 0.2 mass % NCO} (theoretical value = 4.4 mass % _NCO ). _{The mass % NCO, which} is a unit of the isocyanate content, refers to the mass % of NCO groups present in the disinamoisocyanate of isosorbide-propylene glycol as a sample.

Example C6-1 to C6-4: isosorbide- of ethylene glycol of di(3-furyl)acryloisocyanate Produce

After 300 ml of methylene chloride was put into a four-neck reactor equipped with a condenser, an internal thermometer and a nitrogen injection line, 0.05 molar equivalents of 4-dimethylaminopyridine (DMAP) and 3.0 molar equivalents of di-tert-butyldicarbonate (DBDC) were added and dissolved in methylene chloride. Then, the temperature inside the reactor was maintained at 0-5° C. using an ice bath under a nitrogen atmosphere. Di (3-furyl) acryloamine of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) prepared in Examples B6-1 to B6-4 above in 200 ml of methylene chloride (Example B6-1, in Formula 2, when m+n=3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl), isosorbide-ethylene glycol (Preparation Example 1-2: di(3-furyl)acryloamine of ethylene oxide 5 molar adduct) (Example B6-2, in formula 2, m+n=5, R ₁ and R ₃ are both hydrogen atoms, R ₂ is furyl isosorbide-di(3-furyl)acryloamine of ethylene glycol (Preparation Example 1-3: 10 molar adduct of ethylene oxide) (Example B6-3, in Formula 2, m+n=10 and R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl) and isosorbide-di (3-furyl) acrylo of ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mole adduct) A solution prepared by dissolving 1.0 molar equivalent of an amine (Example B6-4, in Formula 2, when m+n=25, R ₁ and R ₃ are both hydrogen atoms, and R _{2 is furyl)} It was added dropwise to the reactor, and at this time, the temperature inside the reactor was maintained at 0-5°C. After completion of the dropwise addition, the temperature inside the reactor was raised to 25° C., and the reaction was carried out for 3 hours.

Methylene chloride was removed from the obtained reaction product using a concentrator, and the reaction products were extracted using hexane and third distilled water. After removing moisture using magnesium sulfate, hexane is removed from the extract using a concentrator to di (3-furyl) acrylo of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) Isocyanate (Example C6-1, in Formula 3, when m+n=3, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl), isosorbide-ethylene glycol (Preparation Example 1-2 : di(3-furyl)acryloisocyanate of ethylene oxide 5 molar adduct (Example C6-2, in Formula 3, m+n=5, R ₁ and R ₃ are both hydrogen atoms, R ₂ is in case of furyl), isosorbide-di(3-furyl)acryloisocyanate of ethylene glycol (Preparation Example 1-3: ethylene oxide 10-molar adduct) (Example C6-3, in Formula 3, m+n= 10, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl) and isosorbide-di(3-furyl)acryl of ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mole adduct) Rhoisocyanate (Example C6-4, in Formula 3, when m+n=25, R ₁ and R ₃ are both hydrogen atoms, and R ₂ is furyl) Each was obtained in 70-80% yield.

As a result of confirming the isocyanate content in di (3-furyl) acryloisocyanate of C6-1 to C6-4 isosorbide-ethylene glycol obtained through the potentiometric method of ISO 14896, Example C6-1 is 14.8 ± 0.3 Mass % _NCO level (theoretical = 14.6 mass % _NCO ), Example C6-2 at 12.7 ± 0.2 mass % _NCO level (theoretical = 12.6 mass % _NCO ), Example C6-3 at 9.5 ± 0.1 mass % _NCO level (theoretical value = 9.5 mass % _NCO ), Example C6-4 was identified with a _{level of 5.2 ± 0.3 mass % NCO} (theoretical value = 5.4 mass % _NCO ). _{The mass% NCO, which} is a unit of the isocyanate content, refers to the mass% of NCO groups present in di(3-furyl)acryloisocyanate of isosorbide-ethylene glycol as a sample.

Example C7-1 to C7-4: isosorbide - Preparation of di (3-cyclohexyl) acryloisocyanate of propylene glycol

After 300 ml of methylene chloride was put into a four-neck reactor equipped with a condenser, an internal thermometer and a nitrogen injection line, 0.05 molar equivalents of 4-dimethylaminopyridine (DMAP) and 3.0 molar equivalents of di-tert-butyldicarbonate (DBDC) were added and dissolved in methylene chloride. Then, the temperature inside the reactor was maintained at 0-5° C. using an ice bath under a nitrogen atmosphere. Di (3-cyclohexyl) acryl of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct) prepared in Examples B7-1 to B7-4 above in 200 ml of methylene chloride Roamine (Example B7-1, in Formula 2, when m+n=3, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom), isosorbide-propylene glycol (prepared Example 2-2: Di(3-cyclohexyl)acryloamine (Example B7-2, in Formula 2, m+n=5, R ₁ is methyl, R ₂ is di(3-cyclohexyl)acryloamine of propylene oxide 5 molar adduct) When cyclohexyl and R ₃ is a hydrogen atom), isosorbide-di (3-cyclohexyl) acryloamine of propylene glycol (Preparation Example 2-3: 10 mol adduct of propylene oxide) (Example B7-3 , in Formula 2, when m+n=10, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom) and isosorbide-propylene glycol (Preparation Example 2-4: Propylene oxide 25 molar adduct) of di(3-cyclohexyl)acryloamine (Example B7-4, in formula 2, m+n=25, R ₁ is methyl, R ₂ is cyclohexyl, R ₃ is hydrogen In the case of atoms), a solution prepared by dissolving 1.0 molar equivalent of each was added dropwise to the reactor, at which time the temperature inside the reactor was maintained at 0-5°C. After completion of the dropwise addition, the temperature inside the reactor was raised to 25° C., and the reaction was carried out for 4 hours.

Methylene chloride was removed from the obtained reaction product using a concentrator, and the reaction products were extracted using hexane and third distilled water. After removing moisture using magnesium sulfate, hexane is removed from the extract using a concentrator, and di(3-cyclohexyl) of isosorbide-propylene glycol (Preparation Example 2-1: propylene oxide 3 mole adduct) Acryloisocyanate (Example C7-1, in Formula 3, when m+n=3, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom), isosorbide-propylene glycol ( Preparation 2-2: Di (3-cyclohexyl) acryloisocyanate (Example C7-2, in Formula 3, m+n=5, R ₁ is methyl, R _{2 of propylene oxide 5 mol adduct)} is cyclohexyl and R ₃ is a hydrogen atom), isosorbide-di(3-cyclohexyl)acryloisocyanate (Example C7-) of propylene glycol (Preparation Example 2-3: 10 mol adduct of propylene oxide) 3, in Formula 3, when m+n=10, R ₁ is methyl, R ₂ is cyclohexyl, and R ₃ is a hydrogen atom) and isosorbide-propylene glycol (Preparation Example 2-4: Propylene oxide) 25 molar adduct) of di(3-cyclohexyl)acryloisocyanate (Example C7-4, in formula 3, m+n=25, R ₁ is methyl, R ₂ is cyclohexyl, R ₃ is in the case of hydrogen atoms) were obtained in 80-90% yield.

As a result of confirming the isocyanate content in the di(3-cyclohexyl)acryloisocyanate of the C7-1 to C7-4 isosorbide-propylene glycol obtained through the potentiometric method of ISO 14896, Example C7-1 is 12.9 ± 0.1 mass % _NCO level (theoretical = 12.9 mass % _NCO ), Example C7-2 is 11.2 ± 0.3 mass % _NCO level (theoretical = 11.2 mass % _NCO ), Example C7-3 is 7.9 ± 0.1 mass % _NCO level (theoretical = 7.9 mass % _NCO ), Example C7-4 was identified as 4.3 ± 0.2 mass % _NCO level (theoretical = 4.4 mass % _NCO ). _{The mass% NCO, which} is a unit of the isocyanate content, refers to the mass% of NCO groups present in di(3-cyclohexyl)acryloisocyanate of isosorbide-propylene glycol as a sample.

Example D1-1 to D1-4: isosorbide- of ethylene glycol of dipropyl isocyanate Manufactured (using triphosgene)

Put 30 ml of methylene chloride in a reactor equipped with a phosgene gas inlet, internal thermometer, dropping funnel, dry ice cooling condenser, and a gas discharge line connected to the hood line, and use dry ice to cool and maintain the internal temperature of the reactor to -50°C. did. After connecting the phosgene generator and the reactor having 1 molar equivalent of triphosgene with a hose, the phosgene generator was heated to 100° C. using an oil bath, and prepared in Examples B1-1 to B1-4 diacryloamine (Example B1-1, in Formula 2, m+n=3, R ₁ , R ₂ and R _When all 3 are hydrogen atoms), diacryloamine of isosorbide-ethylene glycol (Preparation Example 1-2: ethylene oxide 5-molar adduct) (Example B1-2, in Formula 2, m+n=5 and R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-diacryloamine (Example B1-3, In Formula 2, when m+n=10, R ₁ , R ₂ and R ₃ are all hydrogen atoms) and diacryl of isosorbide-ethylene glycol (Preparation Example 1-4: ethylene oxide 25 mole adduct) 1 molar equivalent of each loamine (in Example B1-4, in Formula 2, when m+n=25 and R ₁ , R ₂ and R ₃ are all hydrogen atoms) was slowly added dropwise and vigorously stirred, at this time the reactor The internal temperature was maintained at -30°C. Thereafter, a mixture solution obtained by dissolving 3 molar equivalents of triethylamine in 200 ml of methylene chloride was slowly added dropwise so that the temperature inside the reactor was maintained at -25°C to -30°C. After completion of the dropwise addition, the temperature inside the reactor was raised and reacted at 0° C. for 30 minutes.

Methylene chloride was removed from the obtained reaction product using a concentrator, dissolved in hexane, washed three times with 1N HCl solution, once with 1N NaOH solution, and 3 times with tertiary distilled water, then using magnesium sulfate Moisture in the organic layer was removed, and hexane was removed from the extract using a concentrator, and dipropyl isocyanate (Example D1-1, Formula 3) of isosorbide ethylene glycol (Preparation Example 1-1: ethylene oxide 3 mole adduct) In, when m+n=3, and R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-dipropyl isocyanate of ethylene glycol (Preparation Example 1-2: ethylene oxide 5 molar adduct) ( Example D1-2, in Formula 3, when m+n=5, R ₁ , R ₂ and R ₃ are all hydrogen atoms), isosorbide-ethylene glycol (Preparation Example 1-3: 10 moles of ethylene oxide adduct) of dipropyl isocyanate (Example D1-3, in Formula 3, when m+n=10 and R ₁ , R ₂ and R ₃ are all hydrogen atoms) and isosorbide-ethylene glycol (Preparation Example) 1-4: 25 molar adduct of ethylene oxide) of dipropylisocyanate (Example D1-4, in Formula 3, when m+n=25 and R ₁ , R ₂ and R ₃ are all hydrogen atoms) each It was obtained in 85-95% yield.

As a result of confirming the isocyanate content in the dipropyl isocyanate of isosorbide-ethylene glycol of D1-1 to D1-4 obtained through the potentiometric method of ISO 14896, Example D1-1 is 19.0 ± 0.1 mass% _NCO level (theoretical value) = 18.9 mass % _NCO ), Example D1-2 has a 15.7 ± 0.2 mass % _NCO level (theoretical value = 15.8 mass % _NCO ), Examples D1-3 have a 11.1 ± 0.2 mass % _NCO level (theoretical value = 11.1 mass %) _NCO ), Examples D1-4 were identified with a _{level of 5.8 ± 0.2 mass% NCO} (theoretical value = 5.9 mass% _NCO ). _{The mass % NCO, which} is a unit of the isocyanate content, means the mass % of NCO groups present in the dipropyl isocyanate of isosorbide-ethylene glycol as a sample.

< dianhydrohexitol and alkylene oxide extension having diisocyanate Preparation of Polymer Comprising Compound (Compound of Formula A)>

Example E1 to E8: Example Preparation of polyurethane foam using the compounds of C1-1 to C7-1 and D1-1

A polyol premix composition (first component) was prepared by mixing a polyol, a foam stabilizer, a catalyst and a foaming agent according to the components and content ratios shown in Table 1 below, and sufficiently stirring for 1 to 3 minutes at a stirring speed of 3,000 rpm.

As a polyisocyanate component (second component) in the prepared polyol premix composition (first component), C1-1 to C7-1 and D1-1 prepared in Examples C1-1 to C7-1 and D1-1, respectively The compound of was added and stirred for 7 to 10 seconds at a stirring speed of 3,000 rpm, to prepare a composition for forming a two-component polyurethane foam.

Then, a polyethylene film was coated in a square shape in a box mold having a square shape of 250mm×250mm, and the composition for forming a polyurethane foam prepared above was poured thereon. At this time, the reaction initiation time (cream time), the maximum volume reaching time (rise time) and the gel time were measured and recorded using a second watch, and it was observed whether health bubbles were generated. As a result of checking the curing reaction heat of the polyurethane foam with a bar thermometer, it was confirmed that it was 120 ~ 130 ℃. Thereafter, physical properties were measured by the following evaluation method for the prepared polyurethane foam specimen, and the results are shown in Table 1 below.

comparative example E1: Toluene diisocyanate (TDI) Manufacture of polyurethane foam using

A polyurethane foam specimen was prepared in the same manner as in Examples E1 to E8, except that toluene diisocyanate (TDI) was used as the polyisocyanate component (two components), and the polyurethane foam specimen by the following evaluation method was measured, and the results are shown in Table 1 below.

comparative example E2: 4,4- methylenediphenyl diisocyanate Preparation of polyurethane foam using (MDI)

Polyurethane foam specimens were prepared in the same manner as in Examples E1 to E8, except that 4,4'-methylenediphenyl diisocyanate (MDI) was used as the polyisocyanate component (two components), and the following evaluation The physical properties of the polyurethane foam specimen were measured by the method, and the results are shown in Table 1 below.

<Ingredients used>

1) polyols

PPG-3022: A trifunctional polyether polyol having an active hydrogen equivalent of 3,000 and a hydroxyl value of 54 to mgKOH/g (PPG-3022 from Kumho Petrochemical)

2) Silicone foam stabilizer

L-580K: polyalkylene oxide methylsiloxane copolymer (Niax L-580K from Momentive)

3) Amine-based catalyst

- L-33: triethylenediamine/dipropylene glycol solution with a concentration of 67% by weight (TEDA L-33 manufactured by Toso Corporation)

- A-1: bis-(20 dimethylaminoethyl) ether/propylene glycol solution at a concentration of 70 wt% (Niax Catalyst A-1 from Momentive)

4) organometallic catalyst

DBTDL: Organometallic Catalyst (DBTDL by Sigma Aldrich)

5) blowing agent

water

6) polyisocyanate component

① T-80: toluene diisocyanate (TDI) (2,4-/2,6-isomer ratio = 80:20) (Lupranate T-80 from BASF Korea)

② ME: 4,4-methylenediphenyl diisocyanate (MDI) (Lupranate ME product of BASF Korea)

③ SYC-ISO1.1: diisocyanate compound of Example C1-1

④ SYC-ISO2.1: diisocyanate compound of Example C2-1

⑤ SYC-ISO3.1: diisocyanate compound of Example C3-1

⑥ SYC-ISO4.1: diisocyanate compound of Example C4-1

⑦ SYC-ISO5.1: diisocyanate compound of Example C5-1

⑧ SYC-ISO6.1: diisocyanate compound of Example C6-1

⑨ SYC-ISO7.1: diisocyanate compound of Example C7-1

⑩ SYC-ISO8.1: diisocyanate compound of Example D1-1

<Method of measuring physical properties>

Descriptions of the physical properties listed in Table 1 are as follows.

1) Cream time (seconds): The time taken from the time the polyurethane foam undiluted solution is mixed to when the undiluted solution starts to swell, that is, the reaction initiation time. It doesn't matter how fast or slow the cream is, but if I have to divide it, a shorter cream time is preferable because the foam formation (or cell formation) may become irregular as the cream time becomes longer, but if it is too short, it may not be properly mixed. (eg, 7 seconds to 14 seconds) is required.

2) Rise time (sec): The time taken from the time the polyurethane foam undiluted solution is mixed to the time the foam is swelled to the maximum, that is, the time to reach the maximum volume. Because the part is important, it is difficult to say good/bad based only on fast and slow rise time. If the rise time is too fast, the foam will collapse (the phenomenon that the foam collapses before it hardens, mainly due to the wrong undiluted solution or insufficient mixing of raw materials), and if the rise time is too slow, the foam will gel while foaming (foam foaming stops). ), a suitable rise time (eg, 108 seconds to 124 seconds) is required because foaming may not be possible. “Unmeasurable” in rise time means that the composition does not swell and form no foam.

3) Gel time: It refers to the time taken from the time the polyurethane stock solution is mixed to the point when the stock solution has gel strength that can withstand light impact and takes on a stable spatial shape. Specifically, the foam reacting with wooden chopsticks, etc. It means the point at which at least 3 to 4 urethane fibers come out when stabbed.

4) Health Foam: Shows small bubbles that burst out to the surface of the upper part of the foam immediately after inflating to the maximum.

○: Health bubble is present

×: Health cannon does not exist

5) Form status:

- Good: The state in which the foam has been blown (swelled), and appears to be curled, cracked (a phenomenon in which the inside of the foam is cracked due to the process of forming the foam or external conditions after it is formed) or shrinkage (the inside of the foam) due to gelling It refers to a state in which the gas trapped in the foam is cooled, which reduces the original size of the foam) does not occur.

- Sink: It means the state in which the foam is not formed due to the cell bursting while the foam is being blown and it is sitting down.

6) Molding density: Measured according to ASTM D 1621.

7) Hardness: It was measured according to KS M 6672.

8) Tensile strength: measured according to KS M 6518.

9) Elongation: Measured according to KS M 6518.

As shown in Table 1, in the case of the polyurethane foams of Examples E1 to E8 prepared by using the diisocyanate compound represented by Formula A according to the present invention as a polyisocyanate component, the molding density is about 35 kg/m ³ level, tensile strength of 1.2 kg/cm ³ or more, and elongation of 190% or more, indicating excellent foam properties.

On the other hand, in the case of polyurethane foams of E1 and E2 in comparison prepared using TDI and MDI, which are diisocyanate compounds commonly used as polyisocyanate components in the production of polyurethane foam, respectively, the molding density is about 35 kg/m ³ , and the tensile strength was 1.2 kg/cm ³ or more, but the elongation was at a level of 130% to 140%, which was inferior to that of the polyurethane foams of Examples E1 to E8.

In particular, 1.6 kg/cm ³ to 1.7 kg/cm ^{3 When} comparing Examples E5 to E7 and Comparative Example E1 having a similar tensile strength of the level, the elongation of the polyurethane foams of Examples E5 to E7 was 190% to 200%, 130 of Comparative Example E1 %, and from this, it can be seen that the polyurethane foam of the example exhibits higher toughness than the polyurethane foam of the comparative example also in terms of toughness that is proportional to tensile strength and elongation.

Also 1.2 kg/cm ³ Even when comparing Examples E1 to E4 and E8 and Comparative Example E2 having a similar tensile strength of to 1.3 kg/cm ³ , the elongation of the polyurethane foams of Examples E1 to E4 and E8 was 210% to 220%. It exhibited a significantly higher elongation than 140% of Comparative Example E2, from which it can also be seen that the polyurethane foam of the example exhibits higher toughness than the polyurethane foam of the comparative example.

Claims (19)

A compound represented by the following formula (A):
[Formula A]
XYOMO-Y'-X
In the above formula (A),
X is each independently —CH ₂ NCO,
Y is -[CH ₂ CHR ₁ O] _m -CHR ₂ CHR ₃ -,
Y' is -[CH ₂ CHR ₁ O] _n -CHR ₂ CHR ₃ -,
wherein R ₁ is each independently hydrogen, alkyl or aryl,
R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
m and n are each independently an integer from 0 to 15, provided that m+n is an integer from 1 to 25,
M is a divalent organic group derived from anhydrosugar alcohol. The compound according to claim 1, wherein M is a divalent organic group derived from isosorbide, isomannide or isoidide. The compound of claim 1 , wherein M is selected from the formula:

According to claim 1, wherein the compound represented by the formula (3):
[Formula 3]

In Formula 3,
R ₁ is each independently hydrogen, alkyl or aryl,
R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
m and n are each independently an integer from 0 to 15, provided that m+n is an integer from 1 to 25. According to claim 1, wherein the compound represented by the formula (6):
[Formula 6]

In Formula 6,
R ₁ is each independently hydrogen, alkyl or aryl,
R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
m and n are each independently an integer from 0 to 15, provided that m+n is an integer from 1 to 25. According to claim 1, wherein the compound represented by the formula (9):
[Formula 9]

In Formula 9,
R ₁ is each independently hydrogen, alkyl or aryl,
R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
m and n are each independently an integer from 0 to 15, provided that m+n is an integer from 1 to 25. (1) performing a Michael reaction of anhydrosugar alcohol-alkylene glycol with a nitrile compound;
(2) adding hydrogen to the compound obtained from the Michael reaction; and
(3) converting the terminal group of the compound obtained from the hydrogenation reaction to an isocyanate;
A method for preparing a compound represented by the formula (A):
[Formula A]
XYOMO-Y'-X
In the above formula (A),
X is each independently —CH ₂ NCO,
Y is -[CH ₂ CHR ₁ O] _m -CHR ₂ CHR ₃ -,
Y' is -[CH ₂ CHR ₁ O] _n -CHR ₂ CHR ₃ -,
wherein R ₁ is each independently hydrogen, alkyl or aryl,
R ₂ and R ₃ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
m and n are each independently an integer from 0 to 15,
m+n is an integer from 1 to 25,
M is a divalent organic group derived from anhydrosugar alcohol. The method according to claim 7, wherein M is a divalent organic group derived from isosorbide, isomannide or isoidide. The method of claim 7, wherein M is selected from the formula:

The method according to claim 7, wherein the nitrile compound in step (1) is acrylonitrile, crotononitrile, methacrylonitrile, cinnamonitrile, 3-(furan-2yl)prop-2-ennitrile, cyclohexaneacryl A method for preparing a compound represented by Formula A, which is selected from the group consisting of ronitrile or a combination thereof. The method for producing a compound represented by the formula (A) according to claim 7, wherein in step (1), 1 to 10 molar equivalents of the nitrile compound are reacted with respect to 1 molar equivalent of anhydrosugar alcohol-alkylene glycol. The method for preparing a compound represented by the formula (A) according to claim 7, wherein in step (1), the Michael reaction is performed in the presence of 0.005 to 0.05 molar equivalents of a base catalyst based on 1 molar equivalent of anhydrosugar alcohol-alkylene glycol. [Claim 8] The method of claim 7, further comprising, after step (1), stirring the product of the Michael reaction for 1 to 10 hours. The method of claim 7, wherein in step (2), hydrogenation is performed under a hydrogen pressure of 5 to 30 bar. The method according to claim 7, wherein in step (3), the compound obtained from the hydrogenation reaction is reacted with a carbonate-based compound; phosgene-based compounds; carbon monoxide and oxygen; Or a method for producing a compound represented by the formula (A), which is carried out by reacting with carbon dioxide. The method of claim 15, wherein the carbonate-based compound is di-tert-butyldicarbonate, dimethyl dicarbonate, diethyl dicarbonate, dibenzyl dicarbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylmethyl carbonate, or a combination thereof. is selected from the group consisting of
The phosgene-based compound is selected from the group consisting of phosgene, diphosgene, triphosgene, or a combination thereof, a method for producing a compound represented by Formula A. 8. The method of claim 7, wherein step (3) is carried out in the presence of a catalyst selected from the group consisting of 4-dimethylaminopyridine, zinc acetate, sodium methoxide, trialkylamine, a Group III metal halide, or a combination thereof. A method for producing a compound represented by the formula (A). A polymer comprising a compound represented by Formula A according to any one of claims 1 to 6. The polymer of claim 18 , which is a thermoplastic polyurethane (TPU), a flexible or rigid polyurethane foam, a polyurea, a polyamide, a polyimide, a binder resin, a thermoplastic polyester elastomer, a faux leather polyurethane or an emulsion polymer.