KR101646341B1 - Copolymer of Calix[4]arene with tetrahydrazine and Cyclohexane with bisphenylaldehyde, Preparation method thereof and Composition for blocking ultraviolet rays comprising the same - Google Patents

Abstract

The present invention relates to hydrazone copolymers of calix [4] arene, to which tetrahydrazine is introduced, and cyclohexane to which bisphenol aldehyde is introduced, and to a process for producing the same. The present invention also relates to a UV-blocking composition comprising the copolymer.
Hydrazone copolymers of tetrahydrazine-introduced calix [4] arene and bisphenol aldehyde-introduced cyclohexane according to the present invention have excellent physical properties as well as ultraviolet blocking properties.

Description

Technical Field [0001] The present invention relates to a hydrazone copolymer of calix [4] arene and bisphenol aldehyde introduced with tetrahydrazine, a process for producing the same, and a composition for protecting against UV rays containing the same [ with bisphenylaldehyde, Preparation method thereof and Composition for blocking ultraviolet rays comprising the same}

The present invention relates to a hydrazone copolymer of calix [4] arene, to which tetrahydrazine is introduced, and cyclohexane to which bisphenol aldehyde is introduced, a process for producing the same, and a composition for protecting ultraviolet rays comprising the same.

A gel generally refers to a material having a three-dimensional polymer network structure that may contain a large amount of liquid. The gel is capable of absorbing at least 20% of the total weight of the liquid, and absorbing at least 95% of the liquid is called the high absorbency gel. The gel consists of a homopolymer or a copolymer and forms a structurally stable three-dimensional network structure with little fluidity due to external hysteresis. Such a structure may be attributed to various factors such as covalent bonding, hydrogen bonding, van der Waals bonding, . In addition, the gel is thermodynamically stable after swelling in solution and has mechanical and physicochemical properties corresponding to the intermediate form of liquid and solid. In order to form such a gel, crosslinking should be performed between the polymers. Such cross-linking includes physical cross-linking and chemical cross-linking. Physical cross-linking involves the freezing and thawing of the polymer solution, crystallization, irradiation, hydrogen bonding, charge interactions, hydrophobic interactions, And chemical crosslinking is a method in which a polymer chain is covalently bonded and crosslinked using a crosslinking agent.

In addition, since the swelling degree of the gel can be controlled according to the chemical structure, hydrophilicity and cross-linking degree of the polymer chains of the polymer, it is possible to produce gels having various shapes and properties depending on the constitution and manufacturing method.

Since the development of a hydrogel made of poly-2-hydroxyethyl methacrylate (PHEMA) by Wichterle et al. In the 1960s, its hydrophilic nature and biocompatibility have led to steady interest in applications in the field of biomaterials. Since the development of calcium alginate hydrogels around 1980, hydrogels for various biomaterials using natural or synthetic polymers have been developed. As a result of many studies on the physicochemical properties of hydrogels, various kinds of hydrogels have been developed.

In addition, gels show various functions depending on the kinds of functional groups present in the polymer network structure. Many studies have been carried out on the stimulus-sensitive and intelligent polymer gels, which are remarkably distinct and rapidly reacted to external stimuli by introducing these functional groups into the gel come. Various studies have been conducted using sustained-release drug delivery using gels that respond to physical stimuli such as temperature, electricity, solvent, light, pressure, and magnetic force, and chemical stimuli such as ions and specific molecule recognition (Source: Rompp Lexikon Chemie - Version 2.0, Stuttgart / New York: Georg Thieme Verlag 1999).

In the early days, it started to be applied to hygienic products mainly based on superabsorbent properties, and nowadays, by introducing various additional functions, it is possible to provide a drug delivery system, embolization, a support for tissue engineering, a chemical valve, Immunoassays, bioreactors, sensors, chromatography, and cosmetic fillers, which are useful in a wide range of fields from medical applications to industrial applications.

In order to utilize these gels widely in various fields, a gel having excellent physical properties is required, and in order to use these gels industrially, the synthesis must be made simpler and mass-produced. In particular, since hardness as a physical property is an important property that can affect quality in industrial application of gel, production of a gel having excellent hardness is required.

Under these circumstances, the inventors of the present invention have been studying a new gel having excellent physical properties, while the tetrahydrazine-introduced calix [4] arene and the hydrazone copolymer of bis-aldehyde-introduced hydrazone have excellent physical properties , And exhibited an ultraviolet blocking effect, and completed the present invention.

An object of the present invention is to provide a novel hydrazone copolymer having excellent physical properties and having an ultraviolet blocking effect.

It is another object of the present invention to provide a method for producing the copolymer.

It is still another object of the present invention to provide a UV-blocking composition comprising the copolymer.

In order to achieve the above object, the present invention provides a copolymer having a number average molecular weight of 4000 to 5000, which has at least one repeating unit selected from the group consisting of repeating units represented by the following formulas (1), (2) to provide.

[Chemical Formula 1]

(2)

(3)

The "calixarene" of the present invention is a cyclic macromolecule or cyclic oligomer based on the hydroxyalkylation of phenols and aldehydes. Calixarene has a hydrophobic space to hold smaller molecules or ions and belongs to the class of cavitand known in Host-Guest chemistry. Calix [4] Allen refers to Calix Areen, which has four units in a ring.

The term "hydrazone" of the present invention means an organic compound having the structure of R ₁ R ₂ C = NNH ₂ , in which the oxygen atom of ketone or aldehyde is substituted with a functional group of NNH ₂ . These are usually formed by the reaction of hydrazine with a ketone or aldehyde. In the present invention, a hydrazone bond is formed by the reaction of hydrazine substituted with calix [4] arene and phenylaldehyde substituted with cyclohexane, thereby forming a copolymer.

The term "gel" of the present invention means a material having a three-dimensional polymer network structure capable of containing a large amount of liquid.

Hydrazone, a structure similar to amide, is an essential component for self-assembly due to non-covalent intermolecular bonding because it is capable of hydrogen bonding and is capable of providing electrons. The hydrazine-containing compound represented by the following formula (4), which is one component of the copolymer of the present invention, is a 1,3-alternate type calix [4] arene having a hydrazine capable of hydrogen bonding and a phenyl group having a hydrophobic bond have.

[Chemical Formula 4]

The compound represented by the following general formula (5) having bis-phenylaldehyde, which is another component of the copolymer of the present invention, acts as a crosslinking agent so as to have a three-dimensional network structure and simultaneously undergoes a polymerization reaction, .

[Chemical Formula 5]

The hydrazone copolymer of the present invention produced by the reaction of the compounds of the formulas (4) and (5) is prepared by reacting one molecule of calixarene having four hydrazines in a solution and one molecule of cyclohexane Two molecules are formed in the form of a gel by forming a network structure.

In addition, the physical properties of the gel can be changed by controlling the rate of progress of the reaction with an acid catalyst and a proton magnetic base catalyst, and dynamic covalent chemistry can be applied thereto.

Specifically, the transparency of the gel and the hardness of the gel can be controlled by changing the pH in the production of the gel. In the manufacturing process, the gel becomes opaque and the production time decreases as the pH is changed from neutral to acidic. The reason why the gel becomes opaque as it goes from neutral to acid is because the hydrazone reaction is fast in acidic conditions and randomly arranged.

According to one embodiment of the present invention, in order to investigate the rheological properties of the gel prepared according to the change of the pH, gels were prepared at pH 5, pH 6 or pH 7, and the rheological properties thereof were measured with a rheometer Lt; / RTI > As a result, it was found that the hardness increases with increasing pH, but the time required for gel formation increases. When the pH is high, it is possible to produce a hard and transparent gel if the gel formation takes time but if it is left for a certain period of time.

In addition, the copolymer of the present invention can be applied as an ultraviolet (UV) blocking film by absorbing light in the ultraviolet region and transmitting the light in the visible region, thereby producing the film.

In another aspect, the present invention provides a process for preparing a compound represented by the following general formula (1), (2) and (3), which comprises a step of reacting a compound represented by the following general formula There is provided a process for producing a copolymer having a number average molecular weight of 4000 to 5000, which has a repeating unit.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

The mixing ratio of the compound of Formula 4 and the compound of Formula 5 in Step 1 is preferably 1: 1 to 1: 5, more preferably 1: 1 to 1: 1.1, based on the weight.

The reaction of step 1 may be carried out at a pH of 3 to 7. Preferably at a pH of 5 to 7.

The hydrazone copolymer of the present invention may have one or more repeating units selected from the group consisting of the repeating units represented by the formulas (1), (2) and (3) according to the pH condition to be prepared. The type and ratio of units and sub-repeating units may vary.

Specifically, when the copolymer is produced under neutral conditions (pH = 7), the copolymer may be substantially composed of the repeating unit of formula (1).

When prepared at acidic conditions (pH < 7), the copolymer may have a repeating unit of formula (2) and a repeating unit of formula (3), wherein the repeating unit of formula (2) Is a by-product (minor). That is, the main repeating unit in the copolymer may be a repeating unit of the formula (2) and the repeating unit of the formula (3) may be present as a smaller number of the repeating units.

Roughly, the ratio of the main product and the by-product can be 1: 0.001 to 0.5.

In step 1, an acid may be further added to adjust the pH. The acid may be at least one member selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid. In one embodiment of the present invention, hydrochloric acid was used.

According to one embodiment of the present invention, the copolymer in the neutral condition can be prepared by dissolving the compound of formula (IV) and the compound of formula (5) prepared above in a solvent to complete the polymerization reaction and cooling at room temperature.

According to another embodiment of the present invention, in the production of the copolymer in an acidic condition, the compound of the formula (4) and the compound of the formula (5) prepared as described above are dissolved in a solvent, the acid is added to complete the polymerization reaction, &Lt; / RTI &gt; and stirred until clear.

The solvent in step 1 may be dimethyl sulfoxide (DMSO).

In one embodiment of the present invention, the copolymer is prepared by reacting a compound represented by the following formula (6) with hydrazinyl hydrate to prepare a calix [4] areene having tetrahydrazine introduced thereinto, Reacted with cyclohexane-dicarboxylic acid and thionyl chloride (SOCl ₂ ), and then reacted with 4-hydroxybenzaldehyde under the base condition to prepare cyclohexane having bisphenol aldehyde of formula (5) And a compound represented by the general formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In another embodiment, the present invention provides a UV-blocking composition comprising the copolymer.

The composition may be in the form of a UV-blocking film or membrane.

According to an embodiment of the present invention, water is added to the gel prepared above, and the dimethylsulfoxide (DMSO) solution is solvent-exchanged with water (H ₂ O) and dried to form an ultraviolet screening composition Can be prepared.

The hydrazone copolymer of tetrahydrazine-introduced calix [4] arene and bisphenol aldehyde-introduced cyclohexane according to the present invention has a network structure of one molecule of calixarene derivative and two molecules of cyclohexane derivative Is formed in the form of a gel in one solution.

The hydrazone copolymer has an ultraviolet shielding property for absorbing light in the ultraviolet region and transmitting light in the visible region, thus being useful for ultraviolet ray blocking.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a predictive schematic diagram of the structure of the hydrazone copolymer of the present invention. The hydrazone copolymer of calix [4] arene and bisphenol aldehyde-introduced cyclohexane having tetrahydrazine of the present invention can be obtained by a method in which a molecule of a calixarene derivative and a molecule of a cyclohexane derivative form a network structure .
FIG. 2 is a graph showing the permeability of the gel formed by the hydrazone copolymer of the present invention with respect to pH. FIG.
3 is a graph of rheometer measurement by pH of the gel formed by the hydrazone copolymer of the present invention.
FIG. 4 is a graph showing a stress-strain curve obtained by preparing a gel formed by the hydrazone copolymer of the present invention in the form of a film, a kinetic analysis by pH, and a DMA of a gel prepared by pH ((A) pH 5, (B) pH 6, (C) pH 7).
5 is an NMR spectrum of the hydrazone copolymer in gel form at pH 7 according to the present invention. (a) after 5 minutes, (b) after 12 hours, (c) after 18 hours, (d) after 36 hours, (e) after 42 hours, (f) (h) After 84 hours)
6 shows the NMR spectra of the hydrazone copolymer in gel form at pH 6 of the present invention after the addition of HCl. ((A) Before the addition of HCl, after the addition of HCl (b) After (d) 20 minutes, (e) 30 minutes, (f) 60 minutes, (g) 90 minutes, (h) 120 minutes,
FIG. 7 is an NMR spectrum of the hydrazone copolymer in gel form at pH 5 according to the present invention after the addition of HCl. FIG. (d) after 20 minutes, (e) after 30 minutes, (f) after 60 minutes, (g) after 90 minutes, (g) after 90 minutes, Min, (h) after 120 min)

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples

Preparation Example 1: Preparation of calix [4] arene with tetrahydrazine introduced

To 80 mL of ethanol was added 3.5 g of the compound of formula (VI) and dissolved by heating at 80 占 폚. To the solution was added 5 mL of hydrazine hydrate and allowed to react for 12 hours. The solvent was removed from the solution and the resulting reaction was washed with 100 mL (1: 1 v / v) of a mixed solution of methanol / ethyl ether. The resulting gelator was dried to yield 2.91 g of the compound of formula 4 in 89.5% yield.

mp 285; FT-IR (KBr): v = 3414, 3397, 3373, 3255, 3019, 2916, 1685, 1617, 1570, 1528, 1459, 1445, 1353, 1323, 1249, 1209, 1191, 1161, 1096, 1060, , 976, 922, 856, 772, 691, 629, 570, 555, 513, 435; ^{1 H NMR (300 MHz, DMSO} -d δ) δ ppm 7.29 (s, 4H), 7.04 (d, J = 7.55 Hz, 4H), 6.81 (t, J = 7.46 Hz, 4H), 4.14 (d, J = 3.81 Hz, 8H), 4.03 (s, 8H), 3.89 (s, 8H); &Lt; ¹³ &gt; C NMR (75 MHz, DMSO- _delta ) 167.04, 155.27, 133.85, 129.25, 123.44, 69.15, 36.61; _{ESI-MS: Calculated for C 36} H 40 N 8 O 8 [M + H] + 713.30 [M + Na] + 735.29, Found 713.25, 735,33; Anal. _{Calcd for C 36 H 40 N 8} O 8: C, 60.66; H, 5.66; N, 15.72; Found: C, 60.72; H, 5.64; N, 16.17.

Production Example 2: Preparation of cyclohexane into which biphenylaldehyde was introduced

3 g of trans-1,4-cyclohexane-dicarboxylic acid was added to 30 mL of toluene, and the mixture was heated to 80 DEG C to dissolve it. To the solution was added a drop of thionyl chloride (SOCl ₂ ) (12.8 mL) and dimethylformamide (DMF) and refluxed for 3 hours. After cooling the solution to ambient temperature, the solvent was removed and 20 mL of dichloromethane (DCM) was added. A solution of 4-hydroxybenzaldehyde and 4 mL of triethylamine (TEA) in 20 mL of dichloromethane in an ice bath was slowly added dropwise to the reaction mixture. After the dropwise addition, the reaction mixture was stirred at room temperature for 3 hours. After removal of the solvent, the product was recrystallized from dichloromethane and methanol and dried to give 5.21 g of a white solid compound of the formula (5) in 78.6% yield.

mp 168; FT-IR (KBr): v = 2962,2949 2936,2864,1758,1681,1596,1585,1500,1455,1424,1391,1320,1305,1247,1122,1007,970,921,904,848, 776, 664, 616, 515; ^{1 H NMR (300 MHz, DMSO} -d δ) δ ppm 10.01 (s, 2H) 7.99 (d, J = 8.58 Hz, 4H), 7.39 (d, J = 8.50 Hz, 4H), 2.71 (m, 2H) , 2.20 (d, J = 7.08 Hz, 4H), 1.62 (m, 4H); ¹³ C NMR (75 MHz, DMSO- _delta ) 192.49, 173.53, 155.58, 134.36, 131.57, 123.16, 41.90, 27.68; _{ESI-MS: Calculated for C 22} H 20 O 6 [M + Na] + 403.12, Found 403.12; Anal. _{Calcd for C 22 H 20 O 6} : C, 69.46; H, 5.30. Found: C, 69.44; H, 5.24.

Example 1: Preparation of a gel-like copolymer at pH 7

120 mg of the compound of Formula 4 and 128 mg of the compound of Formula 5 prepared above were added to 2 mL of dimethylsulfoxide (DMSO) and completely dissolved by heating. It was then cooled at room temperature for 24 hours.

The formation of the copolymer at pH 7 was confirmed by NMR, and the NMR spectrum thereof was shown in FIG.

Example 2: Preparation of a gel-like copolymer at pH 6

120 mg of the compound of Formula 4 and 128 mg of the compound of Formula 5 prepared above were added to 2 mL of dimethylsulfoxide (DMSO) and completely dissolved by heating. After cooling at room temperature, 10 L of concentrated hydrochloric acid (HCl) was added, stirred until clear, and then allowed to stand for 30 minutes.

The formation of the copolymer at pH 6 was confirmed by NMR, and the NMR spectrum thereof was shown in FIG.

Example 3: Preparation of a gel-like copolymer at pH 5

120 mg of the compound of Formula 4 and 128 mg of the compound of Formula 5 prepared above were added to 2 mL of dimethylsulfoxide (DMSO) and completely dissolved by heating. After cooling at room temperature, 40 L of concentrated hydrochloric acid (HCl) was added, stirred until clear, and then left for 10 minutes.

The formation of the copolymer at the prepared pH 5 was confirmed by NMR, and the NMR spectrum thereof was shown in FIG.

Example 4 - 6: Preparation of ultraviolet screening film

30 mL of water (H ₂ O) was added to the gels of Examples 1 to 3 prepared at the respective pHs, and dimethylsulfoxide (DMSO) was subjected to solvent exchange with water (H ₂ O). Then, the solvent-exchanged gel was dried to obtain respective films.

Experimental Example 1: Measurement of gel permeability according to pH

The ultraviolet blocking effect of the gel prepared in Examples 1 to 3 was measured using a spectrophotometer (UV / VIS Spectrophotometer). The gel prepared at each pH was measured for light transmittance at a wavelength of 200 to 800 nm.

As a result, as shown in FIG. 2, the transmittance in an ultraviolet region having a wavelength of about 330 nm or less was close to 0% at all pH conditions, indicating that the prepared gel had an ultraviolet blocking effect.

Thus, it was found that the gel could be used in the form of a film and used as an ultraviolet shielding film.

Experimental Example 2: Rheometer measurement of gel according to pH

To determine the rheological properties of the gels prepared in Examples 1 to 3, the rheometer of the gel at pH 5, 6 or 7 was measured.

As a result, as shown in FIG. 3, it was observed that the hardness increases with increasing pH.

Thus, it was confirmed that the film had a high hardness at high pH, that is, excellent physical properties and thus could be used as a film.

Experimental Example 3: Kinetic Analysis of Gel According to pH

The gel prepared in the above Examples 1 to 3 was dried, and the solvent was replaced with water (H ₂ O), and the film was formed into a film and subjected to dynamic mechanical analysis.

As a result, as shown in FIG. 4, the stress-strain curve graph shows that as the pH value increases, the value of the strain and tensile force of the gel increases. When the pH was 5, the strain was 40% at 1 MPa, while the strain was 60% at 8 MPa when the pH was 7.

Therefore, it can be seen that the film using the gel prepared above has high tensile strength and can be used as various types of ultraviolet shielding composition.

Claims (9)

Which has at least one repeating unit selected from the group consisting of repeating units represented by the following formulas (1), (2) and (3) and has a number average molecular weight of 4,000 to 5,000 and which forms a gel by self- .
[Chemical Formula 1]

(2)

(3)

The copolymer according to claim 1, wherein the copolymer has a property of blocking ultraviolet rays.
A process for producing a copolymer according to claim 1, comprising the step of reacting a compound of the following formula (4) with a compound of the following formula (5) (step 1).
[Chemical Formula 4]

[Chemical Formula 5]

4. The method according to claim 3, wherein the mixing ratio of the compound of Formula 4 and Formula 5 is 1: 1 to 1: 5 by weight.
4. The process according to claim 3, wherein the reaction of step 1 is carried out at a pH of from 3 to 7.
4. The method according to claim 3, wherein an acid is further added in the step (1).
7. The method according to claim 6, wherein the acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid.
A composition for blocking ultraviolet rays comprising the copolymer of claim 1.
The composition according to claim 8, wherein the composition is in the form of a film or a membrane.

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