KR101836967B1 - Self-healing polyethers and process for the preparation thereof - Google Patents

Abstract

The present invention relates to a polyether compound having a self-healing function and having a weight average molecular weight of 5,000 to 5,000,000, preferably 5,000 to 500,000, a process for producing the same, and a polymer thin film composed of the same.
[Chemical Formula 1]

The polyether compound having self-healing function used in the present invention is an economical material that is easy to process and easily coated on various substrates, and is easy to produce a polymer thin film using a polyether compound having a self-healing function.
In addition, the polymer thin film can recover the micro-damage of the surface due to the self-healing property of polyether, and it is possible to maximize the recovery ability by using the self-healing functional molecule and to recover effectively repeatedly.

Description

[0001] SELF-HEALING POLYETHER COMPOUND AND PROCESS FOR PREPARING THE SAME [0002]

The present invention relates to a novel polyether compound which self-heals scratches and the like of a polymer coating film, a method for producing the same, and a polymer coating film prepared therefrom.

Conventionally known methods for self-healing such as scratching of a polymer coating can be classified into two methods.

One method is to introduce healing agents into capsular system or vascular system and to recover by microinflammation when the healing agent leaks and fills the damaged area. And the other is the elasticity of the material itself, the polymer chain mobility (not shown) without the aid of the external healing agent Chain Mobility), a photoreactive functional group, a thermoreactive functional group, and a noncovalent functional functional group (Japanese Patent Laid-Open Nos. 10-2012-0076149, 10-2015-0097902, 10-2016-0028556 ).

The recovery methods using the healing agents introduced in the first mentioned capsules and vents can restore a wide range of damage, but have limited repetitive recovery and the integrity of the healing agent.

In order to overcome these disadvantages, it is necessary to introduce elasticity, chain mobility, light / heat-reactive functional groups, and supramolecules possessed by the material itself in order to impart the repetitive recovery ability of the self- Researches have been carried out to improve the recovery ability of the patients.

In particular, in order to be applied as a surface protecting material for electronic devices and display devices, which are indispensable elements in modern society, it is necessary to have a repetitive recovery ability and it is necessary to restore the inherent physical properties of the material after recovery .

Accordingly, the self-healing brush polymer using the brush polymer is a potent substance that can meet the aforementioned requirements.

KR 102004005997 A KR 1020150049852 A KR 101168038 B1 KR 101498361 B1 KR 1020120076149 A KR 1020150097902 A KR 1020160028556 A

It is an object of the present invention to provide a polyether compound that maximizes self-healing ability by introducing various functional molecules into a brush of a polyether resin, a process for producing the same, and a polymer coating film prepared therefrom.

In order to solve the above problems, the present invention provides a polyether compound having a self-healing functional molecule at the brush end, a process for producing the same, and a thin film using the same.

[Chemical Formula 1]

Brush polymer materials can exhibit various chemical and physical properties depending on the chemical structure of the polymer main chain and the introduced brush, and particularly affect the elasticity, entanglement, and chain mobility of the polymer.

This property can be applied to the self-healing application of polymers, and it is possible to maximize the self-healing ability by introducing various functional molecules into the brush.

The self-healing brush polymer material used in the present invention not only has inherent physical properties such as elastic properties and chain flexibility possessed by the material itself, but also imparts repetitive recovery ability by using the self-healing functional molecules introduced into the brush, And non-covalent bonding, it is expected that it will be possible to apply it as a surface protecting material by utilizing this effective self-healing ability.

The thin film of the polymer formed by the polyether compound of the present invention can be applied as a self-healing functional material by a self-healing functional molecule, which is introduced side chain into the polymer main chain.

The polyether compound of the present invention has an effect of maximizing the self-healing ability by introducing various functional molecules into the brush introduced into the polymer main chain.

In addition, the polyether compound used in the present invention not only has inherent physical properties such as elastic properties and chain flexibility possessed by the material itself, but also imparts repetitive recovery ability by using self-healing functional molecules introduced into the brush, It is possible to maximize the recovery ability through the complementary combination of non-covalent bonding. It is expected that various applications as surface protecting materials are expected to be possible by utilizing such effective self-healing ability.

1 is a schematic view for explaining self-healing characteristics of a polymer thin film according to an embodiment of the present invention.
FIG. 2 is an image showing an optical microscope camera image of the self-healing polymer thin film of the present invention before and after self-healing.
FIG. 3 is a graph showing a change in thickness of a surface of a polymer thin film obtained through a surface step difference meter of the self-healing polymer thin film of the present invention.

In the present invention, a self-healing functional polyether compound represented by the following formula (1) is provided.

[Chemical Formula 1]

Wherein L is an aliphatic or aromatic derivative having from 1 to 20 carbon atoms;

R ₁ and R ₂ are each independently hydrogen or an aliphatic derivative having 1 to 20 carbon atoms, and p is a repeating unit of 0 to 20 integers;

m and n represent the content (mol%) of the polyether unit, 0 <m = 100 and 0 = n <100, and m + n = 100;

Y is _{H, -CH 2 X (X =} F, Cl, Br or I), a ring carbon and an aliphatic derivative comprising a U in 1 to 20 aliphatic derivatives or -Z-terminal;

Z is -CH ₂ SRO-, -CH ₂ SROCO-, -CH ₂ SRCO-, -CH ₂ SRO-, -CH ₂ SRNHCO-, -CH ₂ SROCO (CH ₂ ) ₂ OCO-, -CH ₂ SRCO-, -CH ₂ SO ₂ RO-, -CH ₂ SO ₂ ROCO-, -CH ₂ SO ₂ RCOO-, -CH ₂ SO ₂ RNHCO-, -CH ₂ SO ₂ ROCO (CH ₂ ) ₂ OCO-, -CH ₂ SO _{2 RCO-, -OCORO-, -OCOROCO-, -OCORCOO-} , -OCORNHCO-, -OCOROCO (CH 2) 2 OCO-, -OCORCO-, -COORO-, -COOROCO-, -COORCOO-, -COORNHCO-, -COOROCO (CH ₂ ) ₂ OCO-, -COORCO-, -ORO-, -OROCO-, -ORCOO-, -ORNHCO-, -OROCO (CH ₂ ) ₂ OCO-, -ORCO-, -NHRO-, -NHROCO -, -NHRCOO-, -NHRNHCO-, -NHCO (CH ₂ ) ₂ OCO-, -NHRCO-, -CH ₂ RO-, -CH ₂ ROCO-, -CH ₂ RCOO-, -CH ₂ RNHCO-, -CH ₂ ROCO (CH ₂ ) ₂ OCO-, -OC ₆ H ₄ RO-, -OC ₆ H ₄ ROCO-, -OC ₆ H ₄ RCOO-, -OC ₆ H ₄ RNHCO-, -OC ₆ H ₄ ROCO _{2) 2 OCO-, -OC 6 H} 4 RCO-, -OC 6 H 4 COOROCO-, -OC 6 H 4 COORCOO-, -OC 6 H 4 COORO-, -OC 6 H 4 COORNHCO-, -OC 6 H ₄ COOROCO (CH ₂ ) ₂ OCO-, -OC ₆ H ₄ COORCO- or -OC ₆ H ₄ CONHROCO-, -OC ₆ H ₄ CONHRCOO-, -OC ₆ H ₄ CONHRO-, -OC ₆ H ₄ CONHRNHCO-, -OC ₆ H ₄ CONHROCO (CH ₂ ) ₂ OCO-, -OC ₆ H ₄ CONHRCO- Lt; / RTI &gt; is an aliphatic or aromatic derivative selected from the group consisting of:

U is selected from 2 to 10 chemical derivatives, preferably 2 to 5 chemical derivatives, in the group consisting of hydroxyl groups or chemical derivatives indicated below. Wherein R is hydrogen, an aliphatic or aromatic derivative of 1 to 20 carbon atoms.

The weight-average molecular weight of the self-healing functional polyether compound is 5,000 to 5,000,000, preferably 5,000 to 500,000.

The self-healing polyether compound used in the present invention is an economical material that is easy to process and easily coated on various substrates, and is easy to produce a polymer thin film using self-healing polyether.

In addition, the polymer thin film can recover the micro-damage on the surface due to the self-healing property of the polymer, and it is possible to maximize the recovery ability by using the self-healing functional molecule, and to recover effectively repeatedly.

Representative examples of the polymer of Formula 1 according to the present invention include poly [oxy ((N-acetylglycinyloxy) hexylthiomethyl) ethylene-l-oxy ((cinnamoyloxy) hexylthiomethyl) ((6- (3,5-dimethyl-1H-pyrazole-1-carboxyimidohexylcarbamate (ethyl) )) Hexylthiomethyl) ethylene-l-oxy (6-hydroxyhexylthiomethyl) ethylene-l-oxy (chloromethyl) ethylene].

In the following compound 2, four self-healing functional molecules selected from the group consisting of the chemical derivatives of U shown in the above formula (1) are represented as representative examples. The self-healing functional polyether compounds shown in the present invention are represented by the following formula It is not limited to a single polymer compound but can be easily substituted with the above-described derivative compounds.

(2)

P, q, r, and n representing the content (mol%) of the polyether unit in the polyether compound having the self-healing functional molecule of Formula 2 as a brush terminal satisfy 0 < 100, 0 <p? 100, 0? Q? 100, 0? R <100, 0? N <100, l + o + p + q + r + n = 100; Preferably, 0 <l? 50, 0 <o? 50, 0 <p = 50, 0 <q? 50, 0? R <50, 0? N <50.

The polyether compound of formula (1) according to the present invention first synthesizes a polyether compound represented by the following formula (4) by using the cationic ring-opening polymerization of the monomer of formula (3).

(3)

[Chemical Formula 4]

Wherein L is an aliphatic or aromatic derivative having from 1 to 20 carbon atoms;

R ₁ and R ₂ are each independently hydrogen or an aliphatic derivative having 1 to 20 carbon atoms, ρ is a repeating unit of 0 to 20 integers, X is F, Cl, Br And I, and m representing the content (mol%) of the polyether unit is m = 100, and A is hydrogen, an aliphatic derivative or CH ₂ X.

The polyether compound represented by the following formula (5) can be prepared by subjecting a polyether compound represented by the above-mentioned compound (4) in an organic solvent to a halogen substitution reaction.

In an embodiment of the present invention, the halogen substitution reaction can be introduced by reacting a CH ₂ X group with a mixture of NaSROH and NaSR, wherein R and ROH are alkyl and alkoxy having 1 to 20 carbon atoms.

Examples of the solvent include dimethylacetamide, dimethylformamide, diethyl ether, dichloromethane, tetrahydrofuran or a mixed solution thereof.

The reaction at this stage is preferably carried out at a temperature of -100 to 100 DEG C and a pressure of 1 to 5 atm.

[Chemical Formula 5]

Wherein L is an aliphatic derivative or an aromatic derivative having 1 to 20 carbon atoms, R ₁ and R ₂ are each independently a hydrogen, an aliphatic derivative having 1 to 20 carbon atoms, and p is a repeating unit of 0 to 20 integers Y is H, -CH ₂ X (X═F, Cl, Br or I), an aliphatic derivative having 1 to 20 carbon atoms, or a ring and aliphatic derivative containing at the -Z end.

In the above formula, substantially W is a hydroxyl group (-OH) and Z is a linker.

In the present invention, the polyether compound of formula (1) is prepared through condensation reaction between the hydroxyl group of formula (5) and the chemical derivative represented by U in formula (1).

In the practice of the present invention, the polyether compound of the above formula (4) can be prepared by a known method, and the cyclic ether compound can be prepared by reacting the cyclic ether compound with triphenylphosphine in a solvent such as dichloromethane, chloroform, A cationic ring-opening polymerization in the presence of a cationic initiator such as carbonylium hexafluorophosphate or triphenylcarbenium hexachloroantimonate, alkyl aluminum, and the like.

The condensation reaction is a condensation reaction of a hydroxyl group (-OH) at the end of the brush with a chemical derivative represented by U in Chemical Formula 1, and examples of the solvent include dimethylacetamide, dimethylformamide, diethyl ether, dichloromethane, tetrahydrofuran, Mixed solution, and the like.

Hereinafter, the method for producing the polyether compound of the present invention will be described by way of examples.

However, the present invention is not limited only to the following examples. Any person skilled in the art can apply various binders or substituents included in the present invention to obtain polyether compounds having various substituents belonging to the scope of the present invention It is quite possible to manufacture.

<Synthesis 1>

40 ml of epichlorohydrin was placed in a 100 ml round bottom flask and cooled to 5 캜 under a nitrogen atmosphere. A solution of 0.10 g of triphenylcarbenium hexafluorophosphate in dichloromethane was added thereto, followed by stirring at room temperature for 4 days.

The reaction product was dissolved in a small amount of dichloromethane and then purified by reprecipitation in methanol. The reaction product was dried at 40 ° C under vacuum for 8 hours to prepare polyepichlorohydrin.

Yield: 65%. ¹ H-NMR (300 MHz, CDCl ₃ ):? (Ppm) = 3.89-3.49 (br, 5H, -OCH-, -OCH ₂ -, -CH ₂ Cl); ¹³ C-NMR (75 MHz, CDCl ₃ ):? (Ppm) = 79.70, 70.32, 44.31; FTIR (in film):? (Cm ^-1 ) = 2960, 2915, 2873, 1427, 1348, 1299, 1263, 1132, 750, 707.

<Synthesis 2>

To a solution of 558 mg of the polyepichlorohydrin compound obtained in Synthesis 1 in 5 ml of dimethylacetamide was added a solution of 942 mg of sodium 6-hydroxyhexylthiolate in 10 ml of dimethylacetamide.

The mixture was stirred at 50 ° C for 2 hours, extracted with chloroform, washed with water to remove the solvent, and then precipitated in hexane.

The precipitate was dried under vacuum at 40 캜 for 8 hours to obtain the target compound.

^{1 H-NMR (300 MHz,} CDCl 3): δ (ppm) = 3.70-3.49 (br, -OCH-, -OCH 2 -, HOCH 2 -, -CH 2 Cl), 2.75-2.52 (m, -CH ₂ SCH ₂ -), 1.57-1.13 (m, - (CH ₂ ) ₄ -);

<Synthesis 3>

A 100 ml round bottom flask was charged with 1.20 g of 4-sulfobenzoic acid potassium salt and 10 ml of thionyl chloride and refluxed under nitrogen atmosphere for 4 hours with a drop of dimethylformamide.

When the reaction is completed, the solvent is cooled to remove the precipitate through the filter, and the remaining solvent is removed by decompression and heating to obtain colorless crystals.

Yield: 90%. ^{1 H-NMR (300 MHz,} CDCl 3): δ (ppm) = 8.35 (d, 2H), 8.18 (d, 2H).

To the obtained colorless crystals, 4.01 g of 4- (chlorosulfonyl) benzyl chloride and 10 ml of triethylamine were dissolved in 5 ml of dichloromethane, and the mixture was cooled to 0 캜. Then, 3 ml of 2,2-dimethyl- Dimethylamino) pyridine (0.10 g), and the mixture was stirred at room temperature for 4 hours.

At the end of the reaction, the solvent is removed by reduced pressure heating and purified by silica gel chromatography (1: 6 ethyl acetate and petroleum ether).

Yield: 80%. ^{1 H-NMR (300 MHz,} CDCl 3): δ (ppm) = 8.24 (d, 2H), 8.00 (d, 2H), 4.1 (s, 2H), 3.79 (s, 2H), 1.15 (s, 9H ), 0.90 (s, 9H).

3.4 g of the obtained neopentyl 4 - ((neopentyloxy) sulfonyl) benzoate was dissolved in 15 ml of THF, and 0.52 g of lithium hydroxide monohydrate was added to dissolve in 15 ml of distilled water, followed by stirring for 4 hours do.

At the end of the reaction, add 5% hydrochloric acid solution to make acidic solution of pH 2.

THF is removed by reduced pressure and heating, 100 ml of dichloromethane is added, and the mixture is washed with distilled water.

The extracted organic solvent is removed by using magnesium sulfite, and the solvent is removed by heating under reduced pressure and then dried to obtain 4 - ((neopentyloxy) sulfonyl) benzoic acid.

Yield: 80%. ^{1 H-NMR (300 MHz,} CDCl 3): δ (ppm) = 8.24 (d, 2H), 8.00 (d, 2H), 3.79 (s, 2H), 0.90 (s, 9H).

<Synthesis 4>

5.77 g of 3,5-dimethylpyrazole and 0.02 g of dibutyltin laurate were dissolved in 120 mL of toluene, and 9.64 mL of hexamethylene diisocyanate dissolved in 25 mL of toluene was slowly added to a 10 mL round bottom flask give.

After reflux for 3 hours, cool the solution and store at 0 ° C for 12 hours.

When a white precipitate is formed in the solution, it is collected through a decompression filter and dissolved again in chloroform solution. The remaining precipitate is again removed through a filter, and the remaining organic solvent is removed by reduced pressure heating and vacuum drying is performed.

Yield: 50%. ^{1 H-NMR (300 MHz,} CDCl 3): δ (ppm) = 7.24 (s, 1H), 5.89 (s, 1H), 3.34 (m, 2H), 3.19 (m, 2H), 2.54 (s, 3H ), 2.19 (s, 3H), 1.8-1.25 (m, 8H).

<Synthesis 5>

27 mg of the compound obtained in Synthesis 3, 172 mg of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride, 30 mg of N- (Dimethylamino) pyridine were dissolved in 10 ml of dimethylformamide, and the mixture was stirred while heating at 50 占 폚 for 24 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature and then precipitated in 200 ml of methanol / distilled water (methanol = 20 vol%: distilled water = 80 vol%). The precipitating solvent was removed, and the remaining solid matter was dissolved in dichloromethane to remove moisture with magnesium sulfite .

The solvent from which the moisture has been removed is removed through reduced pressure and heating, and vacuum drying is performed.

^{1 H-NMR (300 MHz,} CDCl 3) 8.20 (d, Ar-H), 8.01 (d, Ar-H), 7.65 (d, -CH =), 7.51 (m, Ar-H), 7.40 (m , 4.40 (t, -CH ₂ OCO-), 4.20 (m, -CH ₂ OCO-), 4.08 (m, -CH ₂ OCO-), 3.90 _{3.40 (br, -OCH-, -OCH 2} -, HOCH 2 -, -CH 2 Cl-, -NHCH 2 COO-), 2.81-2.54 (m, -CH 2 SCH 2 -), 2.10 (s, -NHCOCH ₃ ), 1.90-1.2 (m, - (CH ₂ ) ₄ -), 0.90 (s, -CH ₃ );

<Synthesis 6>

363 mg of the polymer compound obtained in Synthesis 5, 52 mg of 3,5-dimethylpyrazole block isocyanate and 1 ml of triethylamine were dissolved in 10 ml of dimethylformamide, followed by stirring at room temperature for 24 hours.

After the reaction is completed, precipitate in methanol / distilled water (methanol = 20 vol%: distilled water = 80 vol%), remove the precipitating solvent, dissolve the remaining solid matter in dichloromethane, and remove moisture with magnesium sulfite.

The solvent from which moisture has been removed is removed through reduced pressure and heating, and vacuum dried.

^{1 H-NMR (300 MHz,} CDCl 3) 8.20 (d, Ar-H), 8.01 (d, Ar-H), 7.65 (d, -CH =), 7.51 (m, Ar-H), 7.40 (m , Ar-H), 6.41 ( d, -CH =), 5.90 (s, -CH = C (CH 3) -), 4.40 (t, -CH 2 OCO-), 4.20 (m, -CH 2 OCO- ), 4.08 (m, -CH ₂ OCO-), 3.90-3.40 (br, -OCH-, -OCH ₂ -, HOCH ₂ -, -CH ₂ Cl-, -NHCH ₂ COO-), 3.40 _{CH 2 NHCO-), 3.20 (m} , -CH 2 NHCO-), 2.81-2.45 (m, -CH 2 SCH 2 -), 2.54 (s, -CH 3), 2.20 (s, -CH 3), 2.10 _{(s, -NHCOCH 3), 1.90-1.2} (m, - (CH 2) 4 -), 0.90 (s, -CH 3);

&Lt; Formation and Evaluation of Polymer Thin Films >

The final polyether compound (l = 10, o = 10, p = 10, q = 10, r = 10, n = 50) prepared above was dissolved in chloroform solvent (1-7 wt% , 0.2 micro filter was coated with a resin solution filtered with a syringe filter by a method such as spin coating, spray coating, electrostatic coating, dip coating, blit coating, ink jet coating and roll coating on a glass slide, Treated for 12 hours to form a polymer thin film having a thickness of 30 탆 on a glass slide.

The self-healing properties of the polymer thin films prepared above were evaluated as follows.

First, to evaluate the self-healing properties, two conditions were given: heat treatment and UV irradiation.

In order to measure the degree of recovery of micro-damage on the surface of the polymer polymer thin film, micro-damage was applied to the surface using a razor, and the heat treatment was performed by controlling the time at 100 ° C. for 1-3 hours in the nitrogen atmosphere In the UV irradiation process, the UV irradiation time was adjusted to a range of 5 minutes to 1 hour using a UV exposure apparatus, and UV irradiation was performed (see FIG. 1).

Then, the thickness variation of the surface of the polymer thin film was measured using a surface step measuring instrument (see FIG. 3), images were obtained using an optical microscope camera, and self-healing characteristics were evaluated by comparing the difference between before and after the heat treatment and UV irradiation Reference).

As shown in the above results, it was confirmed that the polyether compound of the present invention has an excellent self-healing function against the coating film.

The drawings and the detailed description of the invention are merely illustrative of the invention and are used merely for the purpose of describing the invention and not for limiting the scope of the invention as set forth in the claims or the claims.

Therefore, those skilled in the art will appreciate that various modifications and equivalent embodiments are possible without departing from the scope of the present invention.

Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (5)

(Self-healing functional polyether compound), poly [oxy ((N-acetylglycinyloxy) hexylthiomethyl) ethylene-ranoxy (cinnamoyloxy) hexylthiomethyl) ethylene-ranoxy ((6- (3,5-dimethyl-1H-pyrazole-1-carboximidohexylcarbamate)) hexylthiomethyl) ethylene- (6-hydroxyhexylthiomethyl) ethylene-l-oxy (chloromethyl) ethylene] ethylene-co-healing function polyether compound.
(2)

100, 0 < p < 100, 0 < p < = 100, 0 < q < = 100, 100, 0? R <100, 0? N <100 and l + o + p + q + r + n = 100) delete The method according to claim 1,
Wherein the self-healing function polyether compound has a weight average molecular weight of 5,000 to 5,000,000. delete A self-healing functional polymer thin film comprising the self-healing polyether compound according to claim 1.

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