KR102115976B1 - Self-healing polysilsesquioxanes and hybrid film using the same - Google Patents

Abstract

The present invention relates to a self-healing polysilsesquioxane and a hybrid film using the same.
The polysilsesquioxane copolymer according to various embodiments of the present invention is capable of self-healing within a few minutes at a temperature of 100 to 120 ° C. after a crosslinking reaction is performed.
In addition, a polysilsesquioxane copolymer having the self-healing function may be used to prepare a film that is a hybrid material, and the produced hybrid film exhibits self-healing properties, so it has excellent restoration ability due to external damage. Therefore, it can be applied without limitation to various fields such as a gas separation membrane.

Description

Self-healing polysilsesquioxanes and hybrid film using the same}

The present invention relates to a self-healing polysilsesquioxane and a hybrid film using the same.

Crosslinked polymer materials have excellent mechanical properties, thermal stability, and solvent resistance, and have been studied and used in various fields. However, the crosslinked polymer material is sensitive to unexpected mechanical damage due to continuous force and external action, and thus has a limitation in that its lifetime is limited in reuse.

The development of self-healing polymer materials as a material for overcoming these problems has attracted attention as a new technology. Self-healing polymers can be largely divided into 1) Extrinsic self-healing polymers and 2) Intrinsic self-healing polymers. The external self-healing polymer is self-healing by direct injection of a healing additive, and the internal self-healing polymer can self-heal using a chemical bond of a substance.

In particular, in the production of internal self-healing polymers, the dies-elder reaction in which crosslinking is formed and uncoiled using temperature is most studied. Self-healing polymer materials have been proposed through many papers and patents, and self-healing polymers using polysilsesquioxane, an organic-inorganic hybrid material, have also been studied.

However, the existing self-healing polymer materials are a compound of diene and dienophile, respectively, in the dies-elder reaction, and require a blending process. Therefore, there are limitations in miscibility and uniformity in nanoscale. It has a problem that it does not have, and also has a problem of non-uniformity of the film surface, low transparency, incomplete crosslinking, and reusability.

Korean Registered Patent No. 10-0932765

Accordingly, an object of the present invention for solving the conventional problems is to prepare a polysilsesquioxane copolymer capable of self-healing and can be used in various fields such as a gas separation membrane using the copolymer. It is intended to provide a hybrid film.

According to an exemplary aspect of the present invention, the present invention relates to a polysilsesquioxane copolymer having a self-healing function represented by Chemical Formula 1 below.

[Formula 1]

(However, in Formula 1, R ₁ to R ₆ are different from each other, and each independently hydrogen or -R ₇ R ₈ ,

R ₇ is hydrogen or an alkyl group having 1 to 6 carbon atoms,

R ₈ is selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms, -OR ₉ , an organic functional group containing diene, and an organic functional group containing dienophyl,

R ₉ is selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an acrylic group, an epoxy group, and an epoxycyclohexyl,

X = 1-10,000, y = 1-10,000, and z = 1-10,000.)

According to another representative aspect of the present invention, it relates to a hybrid film comprising the polysilsesquioxane copolymer.

According to another exemplary aspect of the present invention, the present invention relates to a gas separation membrane comprising the polysilsesquioxane copolymer.

According to various embodiments of the present invention, a polysilsesquioxane copolymer capable of self-healing within a few minutes at a temperature of 100 to 120 ° C. after a crosslinking reaction at a temperature of 80 to 100 ° C. In the polysilsesquioxane copolymer, diene and dienophil are introduced together in the copolymer, and thus, application to a single material is possible.

In addition, when the polysilsesquioxane copolymer having a self-healing function is applied to a hybrid material such as a film, the physical properties of heat resistance, mechanical strength, light transmittance, solubility and processability are significantly improved, and thus display or It can be widely applied as a coating material for automobiles.

1 is a graph showing the results of analyzing the polysilsesquioxane copolymers of Examples 1 to 7 by ¹ H NMR (Nuclear Magnetic Resonance).
2 is a graph showing the results of analyzing the polysilsesquioxane copolymer of Example 1 by ²⁹ Si NMR (Nuclear Magnetic Resonance).
3 is a graph showing the results of analyzing the polysilsesquioxane copolymers of Examples 1 to 7 with a Fourier-transform infrared spectrometer (FT-IR).
4 is a graph showing the results of analyzing the hybrid films of Examples 8 to 11 with a Thermogravimetry Analyzer (TGA).
5 is a graph showing the results of analyzing the hybrid films of Examples 8 to 11 by DSC (Differential Scanning Calorimetry).
6 is a graph showing the results of analyzing the transparency of the hybrid films of Examples 8 to 11 by UV-vis (Ultraviolet-visible spectroscopy).
7 is a graph showing the results of analyzing the films after curing by applying heat to the hybrid films of Examples 8 to 11 by FT-IR.
8 is a graph showing the results of XRD analysis of the polysilsesquioxane copolymer of Example 1.
9 is an image showing the results of the scratch test (scratch test) before and after thermal reversible self-healing (self-healing) for the hybrid film of Examples 8 to 11.
10 is a graph showing the results of the nanoindentation analysis before and after thermal reversible self-healing for the hybrid films of Examples 1 to 4, (a) and (b) show physical properties before scratch, (c) and (d) It shows the physical properties after scratching.
11 is a graph showing the results of FT-IR analysis before (Before UV-Curing) and after the first photocuring (After UV-Curing) for the hybrid films of Examples 12 to 14, (a) Example 12 , (b) Example 13 and (c) Example 14 are shown.
FIG. 12 shows FT- of primary hybridization of Examples 12 to 14 after primary photocuring (After UV-Curing), after DA crosslinking (After UV-Curing & DA), and after rDA (After UV-Curing & rDA). As a graph showing the results of the IR analysis, (a) Example 12, (b) Example 13, and (c) Example 14 are shown.
13 is an image showing the scratch test results of (ac) before and after (df) thermal reversibility of the film after the primary photocuring for the hybrid films of Examples 12 to 14.
FIG. 14 shows nanoindentation analysis of Examples 12 to 14 hybrid films before (As Cast), after primary photocuring (After UV-Curing), and after secondary thermal reversible self-healing (After UV-Curing & DA). It is a graph showing the results.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

According to an aspect of the present invention, there is provided a polysilsesquioxane copolymer having a self-healing function represented by Chemical Formula 1 below.

[Formula 1]

(However, in Formula 1, R ₁ to R ₆ are different from each other, and each independently hydrogen or -R ₇ R ₈ ,

R ₇ is hydrogen or an alkyl group having 1 to 6 carbon atoms,

R ₈ is selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms, -OR ₉ , an organic functional group containing diene, and an organic functional group containing dienophyl,

R ₉ is selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an acrylic group, an epoxy group, and an epoxycyclohexyl,

X = 1-10,000, y = 1-10,000, and z = 1-10,000.)

More preferably, R ₁ and R ₂ are the same as each other and an organic functional group containing diene, R ₃ and R ₄ are the same as each other and an organic functional group containing dienophyl, and R ₅ and R ₆ are -R _{It is 7} R ₈ . Even more preferably, R ₇ is an alkyl group having 1 to 6 carbon atoms, R ₈ is an alkyl group having 1 to 6 carbon atoms or -OR ₉ , and R ₉ is an acrylic group, an epoxy group, or an epoxycyclohexyl.

The diene (diene) or dieneophil (dienophile) containing an organic functional group when the heat is applied to the polysilsesquioxane copolymer dies-Elder reaction (Diels-Alder reaction) occurs. The Diels-Elder reaction occurs as shown in Reaction Scheme 1 below, and due to this reaction, serves to have thermal reversibility in the polysilsesquioxane copolymer.

[Scheme 1]

That is, in the polysilsesquioxane copolymer, the organic functional group containing diene and the organic functional group containing dienophil form a dies-elder reaction to form a crosslinked copolymer at a constant temperature range. The dieneophil group in the diene group in the silsesquioxane copolymer forms crosslinking due to the Diels-Elder reaction, and crosslinks due to the reversible reaction Retro Diels-Alder reaction. This can be solved.

Specifically, the organic functional group containing the diene is represented by the following formula (2), and the organic functional group containing the dienophyl is preferably represented by the following formula (3).

[Formula 2]

[Formula 3]

In Formulas 2 to 3, R ₁ to R ₆ are the same or different from each other, and each independently hydrogen, a branched or pulverized substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, Substitution is substituted with a functional group of an amine group or hydroxyl group. R ₁ to R ₆ of Formula 2 to 3 At least one of them is preferably substituted with a trialkoxysilane group and used as a silsesquioxane polymerization monomer.

More preferably, in Formulas 2 to 3, R ₁ to R ₆ are the same or different from each other, and are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, which rapidly accelerates the self-healing function to cause reaction within minutes. It was confirmed that it is effective and the self-healing function is significantly slowed over several hours in the case of other types than the above functional groups.

It is preferable that the polysilsesquioxane copolymer has a number average molecular weight (Mn) of 100 to 100,000, and when it is outside the above range, the copolymer exhibits physical properties that are difficult to film and is not preferable.

In particular, it is preferable that the polysilsesquioxane copolymer has a ladder type polysilsesquioxane (LPSQ), and this structure is structurally stable, so that it has high thermal stability, and exhibits high compatibility with organic solvents, which is organic-inorganic. It has advantages as a composite material.

If, when the polysilsesquioxane copolymer is a basket type (POSS, polyhedral silsesquioxane), it has a low molecular form and has crystallinity, so it is difficult to film and exhibits deteriorated physical properties. Does not.

More specifically, the polysilsquioxane copolymer preferably has one structure in the following formula (1a-1g).

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

Thus, the above-mentioned ladder-type polysilsesquioxane copolymer is self-healing within a few minutes at a temperature of 100 to 120 ° C after a crosslinking reaction at a temperature of 80 to 100 ° C, which is described later. It was confirmed through the examples and FIGS. 9 and 10.

According to an embodiment for preparing the ladder-type polysilsesquioxane copolymer, as shown in Reaction Scheme 2 below, a trialkoxysiloxane monomer, an organic functional material containing diene, and an organic functional group comprising dienophyl 20 After reacting for 50 to 150 hours at a temperature of 30 ℃ may be prepared by purification.

[Scheme 2]

Further, according to another embodiment, a trialkoxysiloxane monomer, an organic solvent, a water-containing organic solution including a catalyst and a method of adjusting the amount or water content of the organic solvent in the water-containing organic solution is not a ladder type. It may be selectively synthesized from other structural forms of polysilsesquioxane copolymer, but is not limited thereto.

According to another aspect of the present invention, a hybrid film comprising the polysilsesquioxane copolymer is disclosed. The hybrid film (thickness 1 nm to 500 μm) preferably has an 80 to 100% light transmittance at a wavelength of 500 to 800 nm, which shows that it can be widely applied as a coating material for displays or automobiles as a hybrid material.

In addition, among the polysilsesquioxane copolymers, a hybrid film containing an organic functional group capable of photocuring may be prepared as a high-strength thermosetting hybrid film through a primary photocuring process.

According to another aspect of the present invention, a gas separation membrane comprising the polysilsesquioxane copolymer is disclosed.

Hereinafter, the present invention will be described in more detail through examples and the like, but the scope and content of the present invention may be reduced or limited by the following examples and the like and cannot be interpreted. In addition, if it is based on the disclosure of the present invention including the following examples, it is obvious that a person skilled in the art can easily carry out the present invention in which experimental results are not specifically presented, and patents to which such modifications and corrections are attached Naturally, it is within the scope of the claims.

In addition, the experimental results presented below are only representative of experimental results of the examples and comparative examples, and the effects of various embodiments of the present invention, which are not explicitly presented below, will be described in detail in the corresponding parts.

(Example 1: Synthesis of ladder-type polysilsesquioxane (LPCSQ55))

a) Prepared by dissolving 0.01 g of potassium carbonate as a catalyst in 1.2 g of distilled water in advance and uniformly stirring with 2 g of tetrahydrofuran for 20 minutes.

b) 0.04 mol of N- (3-trimethoxysilylpropyl) pyrrole (N- (3-Trimethoxysilylpropyl) pyrrole, Abcr, 95%) as an organic functional material containing diene and 2 as an organic functional material containing dienophyll 0.04 mol of-(3-cyclohexenyl) ethyltrimethoxysilane (2- (3-Cyclohexenyl) ethyltrimethoxysilane, Abcr, 97%) was added dropwise to the solution of a) previously prepared and stirred. After the dropwise addition is completed, the mixture is reacted at a temperature of 25 ° C. for 96 hours, and the purification method is not mixed with water such as chloroform, methylene chloride, toluene, or xylene, and fractionated using solvents capable of dissolving polysilsesquioxane-based materials. By purification by distillation, a ladder type polysilsesquioxane represented by the following formula 1a was synthesized (however, Mw = 13,000 (based on polystyrene), yield = 95%).

[Formula 1a]

(Example 2: Synthesis of ladder-type polysilsesquioxane (LPrPCSQ244))

a) It was carried out in the same manner as in Example 1.

b) 0.016 mol of propyltrimethoxysilane, 0.032 mol of N- (3-trimethoxysilylpropyl) pyrrole, and 0.032 mol of 2- (3-cyclohexenyl) ethyl trimethoxysilane prepared in advance The a) was added dropwise to the solution and stirred. After the dropwise addition was completed, the reaction was carried out for 96 hours at a temperature of 25 ° C., and after the reaction was completed, a solvent capable of dissolving the polysilsesquioxane-based material was not mixed with water such as chloroform, methylene chloride, toluene, and xylene. It was synthesized using a fractional distillation method to synthesize a ladder type polysilsesquioxane represented by the following formula 1b (however, Mw = 23,000 (based on polystyrene), yield = 95%).

[Formula 1b]

(Example 3: Synthesis of ladder-type polysilsesquioxane (LHPCSQ244))

The same procedure as in Example 2 was carried out, but instead of propyl trimethoxysilane, hexyltrimethoxysilane was used to synthesize ladder-type polysilsesquioxane represented by the following Chemical Formula 1c (however, Mw = 11,000 (based on polystyrene), yield = 95%)

[Formula 1c]

(Example 4: Synthesis of ladder-type polysilsesquioxane (LDPCSQ244))

Ladder-type polysilsesquioxane represented by the following Chemical Formula 1d was synthesized in the same manner as in Example 2, using dodecyltrimethoxysilane instead of propyltrimethoxysilane (however, Mw). = 11,000 (based on polystyrene), yield = 95%)

[Formula 1d]

(Example 5: Synthesis of ladder-type polysilsesquioxane (LPAPCSQ244))

The same procedure as in Example 2 was carried out, but instead of propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane was used to synthesize ladder-type polysilsesquioxane represented by the following Chemical Formula 1e. . (However, Mw = 13,000 (based on polystyrene), yield = 95%)

[Formula 1e]

(Example 6: Synthesis of ladder-type polysilsesquioxane (LPGPCSQ244))

The same procedure as in Example 2 was carried out, but instead of propyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane was used to synthesize ladder-type polysilsesquioxane represented by Chemical Formula 1f. (However, Mw = 12,000 (based on polystyrene), yield = 95%)

[Formula 1f]

(Example 7: Synthesis of ladder-type polysilsesquioxane (LPCEPCSQ244))

Performed in the same manner as in Example 2, using a 2-3-cyclohexyl epoxyethyltrimethoxysilane (2-3-cyclohexylepoxyethyltrimethoxysilane) instead of propyltrimethoxysilane, ladder-type polysilses represented by the following Chemical Formula 1g Quioxane was synthesized (however, Mw = 10,000 (based on polystyrene), yield = 95%).

[Formula 1g]

(Examples 8 to 11: Hybrid film production using ladder-type polysilsesquioxane)

After the polysilsesquioxane copolymers of Examples 1 to 4 were dissolved in tetrahydrofuran at 50 wt% to make a transparent solution, the solution was drop-casted onto a glass substrate and dried at room temperature for one day. , A hybrid film having a thickness of 50 μm was prepared by performing vacuum drying at a temperature of 40 ° C. for an additional 2 hours.

(Examples 12 to 14: Preparation of photocurable / thermal self-healing hybrid film capable of curing system)

(a) Self-healing silsesquioxane introduced in Examples 5 to 7 capable of double curing was dissolved in tetrahydrofuran at 50 wt%, respectively, to prepare a transparent solution, and Example 5 (LPAPCSQ244) was a photoinitiator 1- Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 / Basf) is 1 wt% of polymer, Example 6 (LPGPCSQ244) and Example 7 (LPCEPCSQ244) are photoinitiators (4-Methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate (Irgacure 250 / Basf) was added 3 wt% of the polymer to prepare a transparent coating solution.

(b) The solution was drop-casted onto a glass substrate, dried at room temperature for one day, and then vacuum dried at a temperature of 40 ° C. for 2 hours to obtain a hybrid film having a thickness of 50 μm 500 mJ. / cm ² UV cured to prepare a photocurable / thermal self-healing hybrid film capable of a dual curing system.

(Test Example 1: NMR, FT-IR and XRD analysis)

The ladder-type polysilsesquioxane copolymers of Examples 1 to 7 were subjected to ¹ H NMR, ²⁹ Si NMR and FT-IR analysis, and the results are shown in FIGS. 1 to 3 and 8.

1 is a graph showing the results of ¹ H NMR analysis, FIG. 2 is a graph showing the results of ²⁹ Si NMR analysis, FIG. 3 is a graph showing the results of FT-IR analysis, and FIG. 8 is a graph showing the results of XRD.

Referring to Figure 1, it can be seen the peak of each structure indicated by ag as showing the polysilsesquioxane copolymer structure of the embodiment, and referring to Figure 2 of the alkyl-Si (OSi-) ₃ having a ladder structure The peak can be confirmed.

In addition, referring to FIG. 3, when the chemical functional groups of the ladder-type silsesquioxanes of Examples 1 to 7 are shown, a peak showing a typical double Si-O-Si bond peak and an n-pyrrole / cyclohexenyl group of the ladder-type silsesquioxane Showed. FIG. 8 shows the results of XRD analysis, showing the interval between the ladder-type silsesquioxane polymers or the intramolecular interval, and the longer the propyl, hexyl, and dodecyl groups of LPrPCSQ244, LHPCSQ244 and LDPCSQ244, the longer the interval between ladder-type silsesquioxane polymers. Prove that it grows.

(Test Example 2: TGA and DSC analysis)

The hybrid films of Examples 8 to 11 were analyzed by TGA and DSC, and the results are shown in FIGS. 4 and 5, respectively.

4 is a graph showing the results of the TGA analysis, and the weight loss at 500 ° C or higher was found to be 70 to 80% below, and it can be seen that the weight loss of about 40% or more was maintained up to a temperature of 800 ° C.

In addition, according to FIG. 5, which is a graph showing DSC analysis results, it was confirmed that Tg was maintained at a temperature of -50 to -25 ° C.

(Test Example 3: Analysis of the transparency of the hybrid film)

The transparency of the hybrid films of Examples 8 to 11 was analyzed by UV-vis spectroscopy, and the results are shown in FIG. 6.

Referring to Figure 6, it can be seen that the light transmittance of about 80 to 100% at 500 to 800 nm.

(Test Example 4: Analysis of self-healing of hybrid film through scratch test)

In order to confirm the possibility of self-healing reaction for the hybrid films of Examples 8 to 11, the hybrid film was cured through a Diels-Elder reaction for 2 hours at a temperature of 90 ° C., and then scratched to a size of ˜100 μm. Gave out. And, self-healing was analyzed by an optical microscope, and the results are shown in FIGS. 9 and 10. In addition, the cured hybrid film was analyzed by FT-IR, and the results are shown in FIG. 7.

Referring to FIG. 9, it can be confirmed that the hybrid films of Examples 8 to 11 were self-healing within 5 minutes of the scratch through a retro dies-elder reaction at a temperature of 110 ° C.

In addition, the hybrid films of Examples 12 to 14 were cured at a temperature of 100 ° C. for 30 minutes to show that DA (Diels-Alder reaction) crosslinking was possible, after which an intentional scratch was performed at a temperature of 120 ° C. After heat treatment for 10 minutes, rDA (Retro Diels-Alder reaction) effectively occurred and the phenomenon of crosslinking being solved was analyzed by FT-IR, and the results are shown in FIG. 12. Figure 13 is the result of the image confirmed by the optical microscope that scratches disappeared after DA crosslinking under the self-healing heat treatment conditions.

Therefore, according to various embodiments of the present invention, a polysilsesquioxane copolymer capable of self-healing within a few minutes at a temperature of 100 to 120 ° C. after a crosslinking reaction at a temperature of 80 to 100 ° C. In the polysilsesquioxane copolymer, diene and dienophyl are introduced together in the copolymer, and thus can be applied as a single material.

In addition, when the polysilsesquioxane copolymer having a self-healing function is applied to a hybrid material such as a film, the physical properties of heat resistance, mechanical strength, light transmittance, solubility and processability are significantly improved, and thus display or It can be widely applied as a coating material for automobiles.

Claims (9)

A polysilsesquioxane copolymer having a self-healing function represented by the following Chemical Formula 1,
[Formula 1]

(In Formula 1, R ₁ to R ₄ are -R ₇ -R ₈ , R ₅ and R ₆ are each independently hydrogen or -R ₇ -R ₈ ,
R ₇ is an alkyl group having 1 to 6 carbon atoms,
R ₈ of R ₁ and R ₂ is an organic functional group containing dienophyl,
R ₈ of R ₃ and R ₄ is an organic functional group containing diene,
R ₈ of R ₅ and R ₆ is selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms, and -OR ₉ ,
R ₉ is selected from the group consisting of an acrylic group, an epoxy group and an epoxy cyclohexyl,
X = 1-10,000, y = 1-10,000, and z = 1-10,000.)
The organic functional group containing the diene is selected from the group consisting of compounds represented by the following Chemical Formulas 2-1 to 2-6,
The organic functional group containing the dienophyl is a polysilsesquioxane copolymer having a self-healing function, characterized in that the compound represented by the following formula 3-1 or 3-2.
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 3-1]

[Formula 3-2]

(In Formulas 2-1 to 2-6 and in Formulas 3-1 and 3-2, R ₁ to R ₆ are the same or different from each other, and each independently hydrogen, a side chain of 1 to 30 carbon atoms, or a substituted or pulverized type. A substituted alkyl group or a cycloalkyl group having 3 to 10 carbon atoms,
The said substitution is substituted by the functional group of an amine group or a hydroxyl group.)
delete According to claim 1,
The polysilsesquioxane copolymer is a polysilsesquioxane copolymer having a self-healing function, characterized in that the number average molecular weight (Mn) is 100 to 100,000.
According to claim 1,
The polysilsquioxane copolymer is a polysilsesquioxane copolymer having a self-healing function characterized by having one structure in the following formula:
[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

According to claim 1,
The polysilsesquioxane copolymer is polysilses having a self-healing function, characterized in that it is self-healing at a temperature of 100 to 120 ° C after a crosslinking reaction occurs at a temperature of 80 to 100 ° C. Quioxane copolymer.
Hybrid film comprising the polysilsesquioxane copolymer according to any one of claims 1 and 3 to 5.
The method of claim 6,
The hybrid film is a hybrid film characterized in that it has a light transmittance of 80 to 100% at a wavelength of 500 to 800 nm.
The method of claim 6,
The hybrid film has a thickness of 1 nm to 500 μm.
A gas separation membrane comprising the polysilsesquioxane copolymer according to any one of claims 1 and 3 to 5.

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