KR101696302B1 - Alcohol compound comprising furane, polyurethane compound and thermoreversibly-crosslinked polymer compound - Google Patents

Abstract

Provided are an alcohol compound comprising a furane group, a polyurethane compound, and a thermoreversibly crosslinked polymer compound comprising the same. A self-healing thermoreversible polymer resin is obtained from the alcohol compound. The alcohol compound comprising a furane group is prepared by making a furfuryl amine compound react with at least one alkylene carbonate compound among ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, and glycerin carbonate.

Description

[0001] The present invention relates to an alcohol compound containing a furan group, a polyurethane compound, and a thermo-reversible crosslinked polymer compound,

The present invention relates to an alcohol compound containing a furan group, a polyurethane compound, and a polymer compound including thermoreversible cross-linking thereof, and more particularly to a furan group capable of obtaining a thermally reversible thermosetting resin capable of self-healing A polyurethane compound, and a polymer compound containing thermally reversible crosslinking thereof.

The thermosetting resin forms a three-dimensional network structure by progressing crosslinking when heat is applied, so that even when a large stress is applied, it is not deformed and does not melt in a solvent and is not dissolved even after heating. Depending on the type of heat, some heat can be removed or the strength is lowered, but most of it is decomposed while leaving debris.

Therefore, thermosetting resins generally have good heat resistance, solvent resistance, chemical resistance, mechanical properties, electrical insulation, and can be filled with a filler to form a strong molded article. It is also used to produce fiber-reinforced plastics in combination with high-strength fibers.

The thermosetting resin is used as a protective film or a coating film to prevent external impact or scratch of the product by using excellent mechanical strength. Alternatively, if a thermosetting resin is used for the purpose of enhancing the adhesive performance of the adhesive, the thermosetting is performed by heating for a predetermined time, and the adhesive is completely cured, so that the adhesive object can be completely bonded. In this case, high-temperature stability and high reliability are exhibited by high-density crosslinking, but flexibility is low.

In the case of a thermosetting resin adhesive, since the adhesive is hardened at a high temperature and is adhered, a defect occurs in the process, or when the product fails to use, there is a limit in that the adhesive can not be separated due to high adhesive strength. In addition, in the case of a thermosetting resin protective film or a coating film, it is difficult to remove the surface of the protective film or the coating film due to physical impact exceeding the mechanical limit. However, since the protective film or coating film is hardened, It is impossible to dispose of it.

Thermosetting resins using thermoreversible properties have been proposed to solve these problems. The heat-reversible thermosetting resin can be returned to the original state of the freepolymer or the monomer when heat is applied after curing, so that the damaged part can be formed again, or the adhesive force can be reduced and the object to be bonded can be separated. This is because the thermoreversible polymer has thermoreversible crosslinking in the main chain or side chain, so that the crosslinking is released by heating, and when it is cooled again, crosslinking occurs.

Due to these properties, thermosetting thermosetting resins can decompose the crosslinking easily by applying heat during the manufacture of the product or using the product, and it is possible to re-form or recycle. Therefore, thermo-reversible thermosetting resins are suitable for environmentally friendly products and adhesives with excellent reworkability. In addition, when a thermoreversible polymer is used as a coating material and a film material, it is being spotlighted as a self-healing material through heat treatment.

Therefore, there is a demand for development of a thermally reversible thermosetting resin which is excellent in reworkability and exhibits self-emulsion.

It is an object of the present invention to provide a thermally reversible thermosetting resin capable of self-healing, which comprises a furan group-containing alcohol compound, a polyurethane compound and thermally reversible And to provide a polymer compound containing crosslinking.

In order to accomplish the above object, an alcohol compound containing a furan group according to an embodiment of the present invention includes at least one alkylene carbonate compound of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate and glycerin carbonate, and furfurylamine Is a compound formed by reacting a compound.

According to another aspect of the present invention, there is provided a polyurethane compound formed by polymerizing an alcohol compound, an isocyanate compound and a polyol containing the furan group, wherein the polyol is formed into a main chain, and the alcohol compound containing a furan group includes a furan group formed in a side chain Is provided.

At this time, the isocyanate compound may be 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 2,6- But are not limited to, 2,6-toluene diisocyanate (TDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1,4-cyclohexane diisocyanate (1,4- Dimethyldiisocyanate (CHDI), isophorone diisocyanate (IPDI), tetramethyl-1,3-xylene diisocyanate (TMXDI), dimeryl diisocyanate (DDI) , Hexamethylene diisocyanate (HDI), 1,1,6,6-tetrahydroperfluoro-hexamethylene diisocyanate (THFDI), and diisocyanate Trimer chain HDI-trimer (HDI-trimer) and IPDI-trimer It may be at least one of (IPDI-trimer).

According to another aspect of the present invention, there is provided a polyurethane compound comprising a furan group formed by reacting a urethane prepolymer and a furfurylamine compound formed by reacting glycerin carbonate and a diisocyanate trimer.

According to another aspect of the present invention, there is provided a thermoreversible crosslinking reaction comprising a polyurethane compound containing a furan group, wherein the polyurethane compound containing a furan group is thermally reversibly crosslinked by a Diels-Alder reaction Bond is provided. The polymer compound containing a thermoreversible crosslinking may further comprise a polyfunctional maleimide compound, wherein the polyfunctional maleimide compound is 1,1- (methylenedi-4,1-phenylene) bismaleimide (1,1 - (Methylenedi-4,1-phenylene) bismaleimide, BMI), 1,4-Di (maleimido) butane, N, N- (1,3-phenylene) dimaleimide, N, N- (1,4-phenylene) dimaleimide, and N, N - (o-phenylene) dimaleimide (N, N- (o-Phenylene) dimaleimide).

According to another aspect of the present invention there is provided a thermally reversible film comprising a polymeric compound comprising a thermoreversible crosslinking.

As described above, according to the embodiments of the present invention, thermally reversible polymers that can be reversibly crosslinked and used in various fields, particularly removable adhesives or self-healing polymeric films or coatings, There is an effect that it can be manufactured by using.

Hereinafter, embodiments of the present invention will be described.

According to an aspect of the present invention, there is provided an alcohol compound comprising a furan group, which is a compound formed by reacting an alkylene carbonate compound and a furfurylamine compound of at least any one of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate and glycerin carbonate / RTI >

In the present invention, an alcohol compound containing a furan group is synthesized, and a polyurethane compound containing a furan group is synthesized using the alcohol compound. Polyurethanes containing furan groups are used in polymeric compounds containing thermo-reversible cross-linking because the furan group allows a Diels-Alder reaction. In the present invention, the term " thermoreversible crosslinking "means that crosslinking is formed by heating, and heating at a higher temperature means reversible crosslinking due to heat breakage.

This reaction takes place at a relatively low temperature to form a crosslinked bond, and upon heating, the crosslinked bond is broken. Generally, crosslinking is formed at 50 ° C to 70 ° C, and crosslinking at 100 ° C to 120 ° C may be broken. The binding and decomposition of the thermoreversible crosslinking is possible by the furan group of the alcohol compound containing the furan group synthesized in the present invention.

The alcohol compound containing a furan group according to the present invention can be obtained by reacting an alkylene carbonate compound represented by the following formula (1) with a furfurylamine compound represented by the following formula (2).

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, methyl or methanol.

Where R ₁ and R ₂ are both hydrogen, and R ₁ and R ₂ Is hydrogen and the remainder is methyl, propylene carbonate, and when R ₁ and R ₂ are both methyl, it is 1,2-butylene carbonate. R ₁ and R ₂ Is hydrogen and the remainder is methanol is glycerin carbonate.

(2)

The furfurylamine compound represented by the general formula (2) is a compound containing both a furfuryl group and an amine group.

The alcohol compound containing a furan group according to the present invention is synthesized by reacting an alkylene carbonate with a furfurylamine compound to cause an amine group of a furfurylamine compound to react with a C = O bond of an alkylene carbonate to cause a ring-opening reaction of an alkylene carbonate .

The alcohol compound containing the furan group according to the present invention can be synthesized with a monol compound having one hydroxyl group, a diol compound having two hydroxy groups, and a furane trimer compound having three hydroxy groups.

First, the monol compound is synthesized as shown in the following reaction formula (1).

[Reaction Scheme 1]

Wherein R ₁ and R ₂ are each independently hydrogen or methyl.

That is, the monool compound is cut off from the C═O bond of the alkylene carbonate and reacted with the NH ₂ group of the furfuryl amine compound to obtain the following monool compound.

(3)

Wherein R ₁ and R ₂ are each independently hydrogen or methyl.

That is, the monool compound is a compound containing both a hydroxyl group, a furan group and a urethane group, and the furan group exists for later thermoreversible crosslinking.

The diol compound of the alcohol compound containing the furan group according to the present invention is synthesized as shown in the following reaction formula 2 by the reaction of glycerin carbonate and furfurylamine compound.

[Reaction Scheme 2]

That is, in the diol compound, the C═O bond of the glycerin carbonate is broken and reacts with the NH ₂ group of the furfuryl amine compound to obtain two types of diol compounds represented by the following formulas (4) and (5).

[Chemical Formula 4]

[Chemical Formula 5]

The diol compound may exist in either of the formulas (4) and (5) depending on the position of the C═O bond to be cut off.

[Chemical Formula 6]

Finally, the furan trimer compound having three hydroxy groups can be synthesized by reacting trimers such as Hexamethylene diisocyanate-trimer and IPDI-trimer, such as triisocyanate, first with glycerin carbonate (1) And then reacted again with the furfurylamine compound (2) to synthesize it as shown in the following reaction formula (3).

[Reaction Scheme 3]

In the formula, x is a structure represented by the following formula (7) or (8).

(7)

[Chemical Formula 8]

That is, the furan trimer compound may be a compound represented by the following formula (9).

[Chemical Formula 9]

In the formula, x is a structure represented by the formula (7) or (8).

According to another aspect of the present invention, there is provided a polyurethane compound formed by polymerizing an alcohol compound, an isocyanate compound and a polyol containing a furan group, wherein the polyol is formed into a main chain, and the alcohol compound containing a furan group includes a furan group formed in a side chain A polyurethane compound is provided.

Alcohol compounds containing a furan group are not directly used for compounds containing thermo-reversible crosslinking, but are used as polymer compounds containing thermo-reversible crosslinking by synthesizing polyurethane.

Therefore, the polyurethane is synthesized by polymerizing an isocyanate compound and a polyol on an alcohol compound containing a furan group, wherein the polyol is a main chain of the polyurethane, and the alcohol compound containing a furan group is formed into a side chain to include a furan group upon thermoreversible cross- To be used.

At this time, the isocyanate compound which can be used for preparing the polyurethane compound of the present invention is 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (2,4 Toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1, 1,4-cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), tetramethyl-1,3-xylene diisocyanate (TMXDI) , Dimeryl diisocyanate (DDI), hexamethylene diisocyanate (HDI), 1,1,6,6-tetrahydroperfluoro-hexamethylene diisocyanate (1,1,6,6, -Tetrahydroperfluoro-hexamethylene diisocyanate, THFDI) and diisocyanate But is not limited to, at least one of a cyanate trimer chain HDI-trimer and an IPDI-trimer.

Even in the case of a polyol, any polymer having a hydroxy group capable of forming the main chain of the polyurethane compound can be used without limitation.

Hereinafter, examples of preparing a polyurethane compound with a monoor compound, a diol compound and a furan trimer compound will be described.

First, a polyurethane compound using a monoor compound including a furan group can be prepared by reacting a monool compound with a prepolymer or a diisocyanate derivative capped at the NCO end, and synthesized as shown in the following reaction formula (4).

[Reaction Scheme 4]

Wherein R ₁ and R ₂ are each independently hydrogen or methyl, and P indicates that the polyurethane chain is connected to the main chain.

As a result, the polymer chain of the polyol becomes the main chain and the monool compound of the general formula (3) including the furan group is bonded to the side chain.

Or a furan group, can be obtained by reacting a monoor compound with an HDI trimer or an IPDI trimer, and can be synthesized as shown in the following reaction formula (5).

[Reaction Scheme 5]

Wherein R ₁ and R ₂ are each independently hydrogen or methyl, and x is a structure represented by formula (7) or (8).

The polyurethane compound using a diol compound containing a furan group can be obtained by reacting a diol compound with a diisocyanate and a polyol or by reacting a diol compound with a prepolymer capped with NCO.

[Reaction Scheme 6]

In the formulas, P represents that the polyurethane chain is connected to the main chain, and n is an integer of 1 to 1000.

Polyurethanes having furan groups prepared as described above can be used as thermally reversible films with thermoreversible cross-linking.

The polymer compound containing a thermoreversible cross-linkage forms a thermoreversible cross-linkage by using a polyurethane having a furan group. For example, a polymer compound containing a thermoreversible cross-link is a polyurethane compound containing a furan group, Thermally reversible cross-linking can be formed by the Diels-Alder reaction. The Diels-Alder reaction is a reaction in which a conjugated diene and a dienophile are thermally converted by 1,4-addition to form a cyclohexammonoene derivative, and a dienophyl group of a conjugate diene and a maleimide compound of the furan group And then crosslinking can be formed.

Therefore, the polymer compound containing thermo-reversible crosslinking may further contain a compound capable of reacting with a furan group to a Diels-Alder reaction, which is a polyfunctional maleimide compound. The cross-linking of the polyfunctional maleimide compound and the furan group in accordance with the Diels-Alder reaction is carried out at a low temperature as described above, so that the polymer compound containing thermo-reversible cross-linking is cured and the bond is broken at a temperature of about 100 ° C, Fluidity may appear in polymeric compounds including reversible crosslinking. Therefore, it is a polymer compound including a thermoreversible crosslinking which is excellent in reworkability because the adhesive force is lowered at a relatively low temperature instead of a high temperature like a hot melt adhesive.

The multifunctional maleimide compounds that can be used in the present invention include 1,1- (Methylenedi-4,1-phenylene) bismaleimide (BMI), 1 , 4-Di (maleimido) butane, N, N- (1,3-phenylene) dimaleimide, , N, N- (1,4-phenylene) dimaleimide, and N, N- (o-phenylene) dimaleimide o-Phenylene) dimaleimide), but the present invention is not limited thereto.

Polymeric compounds containing such thermoreversible crosslinks can be usefully employed as thermally reversible films, such as coatings, protective films or adhesives, which are reworkable due to their thermoreversible function. A coating film and a protective film comprising a polymer compound including thermoreversible crosslinking can be reused by heating again after breakage such as scratches after thermosetting. In addition, when used as an adhesive film, it is possible to reuse the components by adhering them as thermosetting and then heating them again as necessary to separate the objects to be bonded.

Hereinafter, the present invention will be described in more detail with reference to Examples.

<Examples>

[Synthesis of monol compound: Synthesis Example 1]

Alkylenecarbonate (15 mmol) and furfurylamine (15 mmol) were added to the flask, followed by addition of dibutyltin dilaurate (0,01 g) and reaction at 60 ° C for 2 hours.

[Synthesis of diol compound: Synthesis Example 2]

Glycerol-1,2-carbonate (61 mmol), furfurylamine (61 mmol) and dibutyltin dilaurate (0,01 g) were added to the flask and reacted at 60 ° C for 3 hours.

[Synthesis of triol compound: Synthesis Example 3]

To the flask, triisocyanate (3.9 mmol) was dissolved in DMF (5 g), glycerol carbonate (11.8 mmol) and dibutyltin dilaurate (0,01 g) were added and reacted at 60 ° C. for 2 hours. Then, furfurylamine (11.8 mmol) was added, and the mixture was further reacted at 60 ° C. for 2 hours.

[Synthesis of polyurethane using diol compound: Synthesis Example 4]

The diol (5.1 mmol) synthesized in Synthesis Example 2, IPDI (10.2 mmol), polyol (5.1 mmol) and dibutyltin dilaurate (0.01 g) were dissolved in MEK (9 g) and reacted at 60 ° C for 2 hours .

[Synthesis of polyurethane using monol compound: Synthesis Example 5]

Triisocyanate (4 mmol) was dissolved in DMF (4.3 g) and the monool (12 mmol) synthesized in Synthesis Example 1 was added to the flask. The reaction is then allowed to proceed at a temperature of 60 DEG C for 2 hours.

[Synthesis of polymer compound having thermoreversible crosslinking: Synthesis Example 6]

BMI (2.5 mmol) was added to the polyurethane obtained in Synthesis Example 4 and the mixture was reacted for 6 hours to obtain a polymer compound. The polymer was coated on a glass plate and heated in an oven at 50 ° C for 12 hours to obtain a thermoreversible film.

[Synthesis of polymer compound having thermoreversible crosslinking: Synthesis Example 7]

BMI (6 mmol) was added to the polyurethane obtained in Synthesis Example 5 and reacted for 20 minutes to obtain a polymer compound. The polymer was coated on a glass plate and heated in an oven at 50 ° C for 12 hours to obtain a thermoreversible film.

[Synthesis of polymer compound having thermoreversible crosslinking: Synthesis Example 8]

BMI (5.9 mmol) was added to the polyurethane obtained in Synthesis Example 3 and the reaction was carried out for 20 minutes to obtain a polymer compound. The polymer was coated on a glass plate and heated in an oven at 50 ° C for 12 hours to obtain a thermoreversible film.

The thermo-reversible films were obtained by heating the polymer compounds containing the thermoreversible crosslinking obtained in Synthesis Examples 6 to 8 at a low temperature of about 50 ° C by thermosetting. Each of the thermoreversible films was heated to 120 ° C, To remove it easily from the glass. In the case of the thermosetting film, the solvent resistance is generally high after the curing and is generally insoluble in the solvent. However, since the thermoreversible film obtained in the above Synthesis Example contains thermally reversible crosslinking, crosslinking is broken at 120 캜, .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the invention as defined by the appended claims. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.

Claims (8)

An alcohol compound comprising a furan group formed by reacting an alkylene carbonate compound of at least one of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate and glycerin carbonate with a furfurylamine compound.
A polyurethane compound formed by polymerizing an alcohol compound, an isocyanate compound and a polyol containing a furan group of claim 1,
A polyurethane compound comprising a furan group in which the polyol is formed into a main chain, and the alcohol compound containing a furan group is formed in a side chain.
The method of claim 2,
The isocyanate compound,
4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (2, 6-Toluene diisocyanate (TDI), 4,4'-Dicyclohexylmethane diisocyanate (HMDI), 1,4-cyclohexane diisocyanate (CHDI) But are not limited to, isophorone diisocyanate (IPDI), tetramethyl-1,3-xylene diisocyanate (TMXDI), dimeryl diisocyanate (DDI), hexamethylene diisocyanate Hexamethylene diisocyanate (HDI), 1,1,6,6-tetrahydroperfluoro-hexamethylene diisocyanate (THFDI) and diisocyanate trimer HDI-trimer (HDI-trimer) and an IPDI-trimer Lt; RTI ID = 0.0 &gt; furan &lt; / RTI &gt; group.
A urethane prepolymer formed by reacting glycerin carbonate and a diisocyanate trimer; And a furfuryl amine compound; and a furan group formed by reacting the furfuryl amine compound and the furfuryl amine compound.
A polyurethane compound comprising a furan group according to any one of claims 2 and 4, wherein the polyurethane compound containing the furan group is thermally reversible crosslinked by a Diels-alder reaction A polymer compound comprising a thermoreversible crosslinking.
The method of claim 5,
A polymer compound comprising thermo-reversible crosslinking, which further comprises a polyfunctional maleimide compound.
The method of claim 6,
The polyfunctional maleimide compound
1,1- (Methylenedi-4,1-phenylene) bismaleimide (BMI), 1,4-di (maleimido) butane (1, 4-Di (maleimido) butane, N, N- (1,3-phenylene) dimaleimide, N, N- ) Of at least one of N, N- (1,4-phenylene) dimaleimide and N, N- (o-Phenylene) dimaleimide Polymeric compound comprising a thermally reversible crosslinking.
A thermally reversible film comprising a polymeric compound comprising thermo-reversible crosslinking according to claim 5.