Linear acrylate monomer with side chain and preparation and application of delay film of linear acrylate monomer

Abstract

The invention relates to preparation and application of a linear acrylate monomer with a side chain and a retardation film of the linear acrylate monomer. The linear acrylate monomer with the side chain is an acrylate-terminated monomer containing a side chain group. The side chain group is a polyfluorophenyl side chain group, and the polyfluorophenyl side chain group contains at least one of a polyfluorobenzene methoxy group, a polyfluorophenoxy group and a polymethoxyphenyl group; a linear acrylate monomer and a plurality of acrylate derivatives are polymerized to obtain the phase difference delay film. The delay mode is applicable to a display.

Description

Technical Field

[0001] The invention relates to the technical field of compounds, in particular to the preparation and application of a linear acrylate monomer with a side chain and a retardation film thereof. Background Art

[0002] In recent years, new display technologies represented by light-emitting diode displays (OLED Display) have achieved flexible, large-angle bendable, foldable, and transparent displays. These new functional flat displays require that the screen-matching optical film has high transmittance, is thinner, and has good bendability. Based on this requirement, people use various strategies to design and synthesize key monomers of resins with positive birefringence characteristics. Key monomers can be designed and improved through various substituents in the side chains to improve film-forming properties, transparency, birefringence, and other properties, and establish the relationship between wavelength dispersion and optical delay effects to meet the application needs of various optical films to regulate polarization states. However, there are currently few types of resins with positive wavelength dispersion, such as polycarbonate, cellulose ester, fluoropolymers and polyimides, and corresponding multi-component polymer resins, and their structure-activity relationships are not clear. Summary of the invention

[0003] The object of the present invention is to provide a linear acrylate monomer with a side chain having a structure shown in Formula I:

[0004] Formula I The linear acrylic ester monomer with a side chain is a monomer terminated by acrylic ester containing a side chain group, the side chain group is a polyfluorophenyl side chain group, and the polyfluorophenyl side chain group contains at least one of polyfluorobenzyloxy, polyfluorophenoxy, and polymethoxyphenyl. Wherein, A1 is a bonding part of a carbon atom, and A1 is CH2 or C=O; Wherein, A2--A3 is a bonding part of two atoms in space, -- is at least one of a triple bond, a double bond and a single bond, and A2--A3 is but not limited to C≡C, CH=CH, CH=CCH3, CH3C=CH, CH3C=CCH3, CH2O, OCH2 or CH2CH2; Among them, R1, R2, and R3 are selected from single-atom substituents or polyatomic substituents with strong electronegativity; the single-atom substituent refers to a fluorine atom; the polyatomic substituent includes alkyl and alkoxy groups, and the alkyl group includes methyl, ethyl, propyl, butyl, fluorine-substituted alkyl, and alkoxy-substituted alkyl; the alkoxy group includes methoxy, ethoxy, propoxy, butoxy, methoxyethoxy, fluorine-substituted alkyl, and aryl-substituted alkyl.

[0005] Preferably, the linear acrylate monomer with a side chain includes but is not limited to the following molecules: side chain trifluorophenyl substituted molecules 1, 2 and 3; side chain trimethoxyphenyl substituted molecules 4, 5 and 6:

[0006] Molecule 1 Molecule 2

[0007] Molecule 3

[0008] Molecule 4

[0009] Molecule 5

[0010] Molecule 6.

[0011] The second object of the present invention is to provide a method for preparing a delayed film of a linear acrylate monomer with a side chain, wherein a solution of the linear acrylate monomer with a solid content of 10% and an acrylate derivative is prepared in an organic solvent, and polymerization of the acrylate monomer and the acrylate derivative is initiated when a photosensitive initiator absorbs the radiation energy of ultraviolet light, and the solution is filtered, spin-coated or scraped, and then heated, baked and irradiated with ultraviolet light.

[0012] Preferably, the corresponding wavelength of the ultraviolet light irradiation is 250-450 nm.

[0013] Preferably, when preparing the retardation film, the film is prepared under heating conditions of 10-150 degrees Celsius.

[0014] Preferably, the organic solution is a mixture of dichloromethane, ethyl acetate, ethyl formate, methyl acetate, ethylene dichloride, cyclohexanone and acetone.

[0015] A third object of the present invention is to provide an application of a retardation film, wherein the retardation film is suitable for use in a display device.

[0016] Preferably, the thickness of the retardation film is less than 2 microns.

[0017] Compared with the prior art, the present invention has the following beneficial effects: The polysubstituted phenylacetyl side chain in the monomer has abundant substituent groups, which can effectively control the light transmittance, solubility, film-forming property, refractive property, insulation property and other properties of the film; Polymer films can achieve optical dispersion and phase retardation effects by changing the optical isotropy within the film plane. Specifically, the anisotropic effect can be achieved by stretching or designing the orderly arrangement of polymer molecules.

[0018] The present invention will be further described below in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a photograph of the molecular formula 5 after spin coating and heating in a specific embodiment of the present invention.

[0020] Figure 2 is the specific embodiment of the present invention molecule 1 1 H NMR spectra.

[0021] Figure 3 is the specific embodiment of the present invention molecule 2 1 H NMR spectra.

[0022] Figure 4 is the specific embodiment of the present invention molecule 2 19 F NMR spectrum.

[0023] Figure 5 is the specific embodiment of the present invention molecule 4 1 H NMR spectra.

[0024] Figure 6 is the specific embodiment of the present invention molecule 5 1 H NMR spectra.

[0025] Figure 7 It is the synthesis route diagram of specific embodiment 1 of the present invention.

[0026] Figure 8 It is the synthesis route diagram of specific embodiment 2 of the present invention.

[0027] Fig. 9 It is the synthesis route diagram of specific embodiment 3 of the present invention.

[0028] Fig.10 It is the synthesis route diagram of specific embodiment 4 of the present invention.

[0029] Fig.11 This is the synthesis route diagram of specific embodiment 5 of the present invention.

[0030] Fig.12 This is the synthesis route diagram of specific embodiment 6 of the present invention. DETAILED DESCRIPTION

[0031] The present invention provides a linear acrylate monomer with a side chain, wherein the linear acrylate monomer with a side chain is a monomer terminated by an acrylate containing a side chain group, and the side chain group is a polyfluorophenyl side chain group. The polyfluorophenyl side chain group contains at least one of a polyfluorobenzyloxy group, a polyfluorophenoxy group, and a polymethoxyphenyl group. A phase difference delay film composition is obtained by polymerizing an oligophenyl ester derivative monomer containing a polysubstituted phenyl alkynyl side chain group with different components;

[0032] Formula 1 As shown in Formula 1, in the general formula, A1 is a bonding part of a carbon atom, and A1 can be CH2 or C=O. A2--A3 is a bonding part of two atoms in space, and can be a triple bond, a double bond, and a single bond; A2--A3 can be, but not limited to, C≡C, CH=CH, CH=CCH3, CH3C=CH, CH3C=CCH3, CH2O, OCH2, CH2CH2. Among them, R1, R2, and R3 are selected from single-atom substituents or polyatomic substituents with strong electronegativity; the single-atom substituent refers to a fluorine atom; the polyatomic substituent includes an alkyl group and an alkoxy group, and the alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a fluorine-substituted alkyl group, and an alkoxy-substituted alkyl group, and the alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxy group, an ethoxy group, a fluorine-substituted alkyl group, and an aryl-substituted alkyl group.

[0033] The linear acrylic ester monomer with a side chain includes but is not limited to the following molecules: side chain trifluorophenyl substituted molecules 1, 2 and 3; side chain trimethoxyphenyl substituted molecules 4, 5 and 6:

[0034] Molecule 1 Molecule 2

[0035] Molecule 3

[0036] Molecule 4

[0037] Molecule 5

[0038] Molecule 6.

[0039] A method for preparing a delay film of a linear acrylate monomer with a side chain, which comprises polymerizing under the condition of at least containing an ultraviolet initiator, and exposing to ultraviolet light after film formation. The corresponding wavelength of exposure is 250-450 nm. When preparing the delay film, the linear acrylate monomer with a side chain and a plurality of acrylate derivatives need to be polymerized by a photosensitizer in an organic solution. The film is prepared under heating conditions of 10-150 degrees Celsius. The organic solution is a mixture of dichloromethane, ethyl acetate, ethyl formate, methyl acetate, dichloroethane, cyclohexanone, and acetone.

[0040] The film formed by the polymerization is a phase difference delay film, which has reverse wavelength and anti-reflection effects, is suitable for display devices, and is prepared using Formula 1. The thickness of the polymer delay film is less than 5 microns. In particular, when it is a quarter-wavelength phase difference delay film, it is suitable for display devices. The thickness of the polymer delay film prepared using Formula 1 is less than 2 microns.

[0041] In an embodiment, the structure of the acrylate end-capping group is .

[0042] Example 1, the synthesis process of molecular formula 1 is as follows Figure 7 As shown. 1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (11.1 g, 57.8 mmol, 2.50 eq) was added to a solution of intermediate acid 1 (12.6 g, 23.1 mmol, 1.00 eq), intermediate phenol 2 (12.2 g, 46.2 mmol, 2.00 eq) and DMAP (282 mg, 2.31 mmol, 0.100 eq) in dichloromethane DCM (126 mL) at 0 °C. The mixture was stirred at 20 °C for 1 hour. 150 mL of saturated brine was added to the mixture system, and the organic phase was extracted by separation; the aqueous phase solution was extracted with dichloromethane (150 mL×3); the combined organic phase was washed with brine (300 mL), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography and concentrated under reduced pressure to obtain as shown. Figure 1 The target product molecule 1 is a white solid (14.8 g, 60.3% yield, 97.9% purity). The thin-layer chromatography conditions are [n-hexane: (dichloromethane: ethyl acetate = 10:1) = 1:1], and the Rf of the desired product is 0.40. Figure 2 , 1 H NMR: DMSO- d 6 , 400 MHz δ 7.48 (dd, J= 8.30, 6.80 Hz, 2 H), 6.90 - 7.08 (m, 11 H), 6.27 - 6.35 (m, 2 H), 6.12 - 6.22 (m, 2 H), 5.93 (dd, J = 10.2, 1.60 Hz, 2 H), 4.11 (t, J = 6.60 Hz, 4 H), 3.94 (t, J = 6.40 Hz, 4H), 3.73 - 3.88 (m, 4H), 2.10 (d, J = 10.8 Hz, 4 H), 1.88 - 2.02 (m, 4 H), 1.57 - 1.86 (m, 11 H), 1.34 - 1.56 (m, 13 H), 1.12 - 1.30 (m, 4 H).

[0043] Example 2, the synthesis process of molecular formula 2 is as follows Figure 8 As shown. To a solution of intermediate acid 11 (12.0 g, 21.8 mmol, 1.00 eq), intermediate phenol 2 (11.5 g, 43.5 mmol, 2.00 eq) and DMAP (266 mg 2.18 mmol, 0.100 eq) in dichloromethane DCM (120 mL) was added 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (10.4 g, 54.4 mmol, 2.50 eq) at 0 °C. The mixture was stirred at 20 °C for 1 hour. The mixture was poured into H2O (200 mL) and then extracted with ethyl acetate (300 mL×3). The combined organic phases were washed with brine (300 mL), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography and concentrated under reduced pressure to give a white solid of formula 2 (18.9 g, 18.1 mmol, 60.7% yield). Combined Figure 3 , 1 H NMR: DMSO- d 6, 400 MHz. δ 6.80 -7.14 (m, 13 H), 6.25 - 6.37 (m, 2 H), 6.11 - 6.21 (m, 2 H), 5.92 (dd, J =10.4, 1.60 Hz, 2 H), 5.03 (s, 2 H), 4.11 (t, J = 6.80 Hz, 4 H), 3.94 (t, J=6.40 Hz, 4 H), 3.77 (dd, J = 16.0, 6.00 Hz, 4 H), 2.51 - 2.56 (m, 1 H), 2.39(t, J = 12.0 Hz, 1 H), 1.98 - 2.15 (m, 4 H), 1.80 - 1.97 (m, 4 H), 1.58 -1.77 (m, 10 H), 1.30 - 1.53 (m, 12 H), 1.03 - 1.25 (m, 4 H). combine Figure 4 , 19 F NMR:DMSO- d 6, 376 MHz. δ -134.68 (d, J = 22.4 Hz, 2 F), -172.65 - -172.02 (m, 1F).

[0044] Example 3, the synthesis process of molecular formula 3 is as follows Fig. 9 As shown. To a solution of intermediate acid 15 (15.7 g, 27.3 mmol, 1.00 eq), intermediate phenol 2 (14.4 g, 54.6 mmol, 2.00 eq) and DMAP (333 mg, 2.73 mmol, 0.100 eq) in dichloromethane DCM (150 mL) was added 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (13.1 g, 68.2 mmol, 2.50 eq) at 0 °C. The mixture was stirred at 20 °C for 1 hour. The mixture was poured into saturated brine (300 mL) and then extracted with ethyl acetate (300 mL×3). The combined organic phases were washed with brine (300 mL), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography and concentrated under reduced pressure to give molecule 3 as a white solid (15.2 g, 52.0% yield). MS(ESI): 1167.4 [M+H + ].

[0045] Example 4, the synthesis of molecular formula 4 is as follows Fig.10As shown. To a solution of intermediate acid 2 (23.5 g, 40.4 mmol, 1.00 eq), intermediate phenol 2 (21.3 g, 80.9 mmol, 2.00 eq) and DMAP (494 mg, 4.05 mmol, 0.100 eq) in DCM (235 mL) was added 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDCI (19.4 g, 101 mmol, 2.50 eq) at 0 °C. The mixture was stirred at 20 °C for 1 hour. Brine (300 mL) was added to the reaction mixture, followed by extraction with ethyl acetate (120 mL) and DCM (160 mL×3). The combined organic layers were dried over Na2SO4, filtered and concentrated under reduced pressure to obtain a residue. The residue was purified by column chromatography and concentrated under reduced pressure to obtain a white solid of molecule 4 (15.0 g, 52.4% yield, 98.2% purity). The crude product was triturated with a mixture of MeCN:DCM = 5:1 (230 mL, 5 V) at 25 °C for 1 h, filtered and concentrated under reduced pressure. Figure 5 , 1 H NMR: DMSO - d 6 , 400 MHz, δ 6.87 - 7.08(m, 11 H), 6.79 (s, 2 H), 6.27 - 6.37 (m, 2 H), 6.11 - 6.23 (m, 2 H), 5.93(dd, J = 10.2, 1.60 Hz, 2 H), 4.11 (t, J = 6.60 Hz, 4 H), 3.94 (t, J = 6.40Hz, 4H), 3.75 - 3.89 (m, 10H), 3.68 (s, 3H), 1.88 - 2.18 (m, 8H), 1.05 -1.87 (m, 28H).

[0046] Example 5, the synthesis of molecular formula 5 is as follows Fig.11As shown. To a solution of intermediate acid 12 (12.9 g, 22.0 mmol, 1.00 eq), intermediate phenol 2 (11.7 g, 44.0 mmol, 2.00 eq) and DMAP (266 mg, 2.2 mmol, 0.100 eq) in dichloromethane DCM (120 mL) was added 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (10.5 g, 54.6 mmol, 2.50 eq) at 0 °C. The mixture was stirred at 20 °C for 1 hour. The mixture was poured into H2O (300 mL) and then extracted with ethyl acetate (300 mL×3). The combined organic phases were washed with brine (300 mL), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography and concentrated under reduced pressure to give molecule 5 as a white solid (17.8 g, 16.5 mmol, 97.7% purity, 75% yield). MS(ESI): 1079.8 [M+H + ]. Combined Figure 6 , 1 H NMR:DMSO - d 6 , 400 MHz, δ 7.05 (d, J = 1.60 Hz, 1 H), 6.93 - 7.00 (m, 4 H), 6.84 -6.90 (m, 4 H), 6.79 - 6.83 (m, 2 H), 6.43 (d, J = 1.60 Hz, 1 H), 6.39 (d, J =1.20 Hz, 1 H), 6.27 (s, 2 H), 6.08 - 6.18 (m, 2 H), 5.82 (dd, J = 12.0, 1.60Hz, 2 H), 5.07 (s, 2 H), 4.18 (t, J = 6.80 Hz, 4 H), 3.94 (t, J = 6.40 Hz, 4H), 3.80 - 3.87 (m, 9 H), 3.77 (d, J = 6.13 Hz, 2 H), 2.42 - 2.58 (m, 2 H), 2.20 (br t, J= 9.60 Hz, 4 H), 1.97 - 2.09 (m, 4 H), 1.68 - 1.91 (m, 10 H), 1.57 - 1.68 (m, 6 H), 1.41 - 1.55 (m, 8 H), 1.11 - 1.29 (m, 4 H).

[0047] Example 6, the synthesis of molecular formula 6 is as follows Fig.12 As shown. To a solution of intermediate acid 16 (18.0 g, 29.5 mmol, 1.00 eq), intermediate phenol 2 (15.6 g, 59.0 mmol, 2.00 eq) and DMAP (360 mg, 2.95 mmol, 0.100 eq) in dichloromethane DCM (150 mL) was added 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (14.1 g, 73.4 mmol, 2.50 eq) at 0 °C. The mixture was stirred at 20 °C for 1 hour. The mixture was poured into saturated brine (300 mL) and then extracted with ethyl acetate (300 mL×3). The combined organic phases were washed with brine (300 mL), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography and concentrated under reduced pressure to give a white solid of molecule 6 (18.3 g, 16.6 mmol, 56.3% yield). MS(ESI): 1103.8 [M+H + ].

[0048] Example 7: In this example, the molecules described in the six examples above were prepared into a solution in ethyl acetate with a solid content of 10%, 1 wt% of a photoinitiator was added, and the solution was filtered and spin-coated or blade-coated for 100 min. o C heating and baking to remove the solvent; 365nm ultraviolet light irradiation, the obtained film shows obvious light and dark states, can be peeled off and used to make phase difference delay film. The optical film phase difference is tested using Axostep, which shows that the optical film phase difference is -50.00 o ~ +50.00 o The thickness of the film, 400~700nm R0 and Δn values ​​are shown in the following table:

[0049] The test results show that the oriented delay film prepared by the monomer molecules of the present invention has a large birefringence, Δn is comparable to that of existing commercial optical films, and can have a 1 / 4 wavelength phase difference delay effect below 2 microns in thickness, and can be used to manufacture thinner optical delay films.

Claims

1. A linear acrylic ester monomer with a side chain, characterized in that: It has the structure shown in formula I: ， The linear acrylic ester monomer with a side chain is a monomer terminated by acrylic ester containing a side chain group, the side chain group is a polyfluorophenyl side chain group, and the polyfluorophenyl side chain group contains at least one of polyfluorobenzyloxy, polyfluorophenoxy, and polymethoxyphenyl. Wherein, A1 is a bonding part of a carbon atom, A1 is CH2 or C=O, Wherein, A2--A3 is the bonding part of two atoms in space, -- is at least one of a triple bond, a double bond and a single bond, A2--A3 is but not limited to C≡C, CH=CH, CH=CCH3, CH3C=CH, CH3C=CCH3, CH2O, OCH2 or CH2CH2, Among them, R1, R2, and R3 are selected from single-atom substituents or polyatomic substituents with strong electronegativity; the single-atom substituent refers to a fluorine atom; the polyatomic substituent includes an alkyl group and an alkoxy group, and the alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a fluorine-substituted alkyl group, and an alkoxy-substituted alkyl group; the alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxy group, an ethoxy group, a fluorine-substituted alkyl group, and an aryl-substituted alkyl group.

2. The linear acrylate monomer with a side chain according to claim 1, characterized in that The linear acrylic ester monomer with a side chain includes but is not limited to the following molecules: side chain trifluorophenyl substituted molecules 1, 2 and 3; side chain trimethoxyphenyl substituted molecules 4, 5 and 6: Molecule 1, Molecule 2, Molecule 3, Molecule 4, Molecule 5, Molecule 6.

3. A method for preparing a retardation film based on the linear acrylate monomer with a side chain according to claim 1 or 2, characterized in that: A linear acrylate monomer with a solid content of 10% and an acrylate derivative are prepared in an organic solvent to prepare a solution, and the polymerization of the acrylate monomer and the acrylate derivative is initiated when the photosensitive initiator absorbs the radiation energy of ultraviolet light. After filtering, spin coating or scraping, the solution is heated, baked and irradiated with ultraviolet light.

4. The preparation method according to claim 3, characterized in that: The corresponding wavelength of the ultraviolet light irradiation is 250-450 nm.

5. The preparation method according to claim 4, characterized in that: When preparing the delay film, the film is prepared under heating conditions of 10-150 degrees Celsius.

6. The preparation method according to claim 5, characterized in that: The organic solution is a mixture of dichloromethane, ethyl acetate, ethyl formate, methyl acetate, dichloroethane, cyclohexanone and acetone.

7. An application of the retardation film according to any one of claims 4 to 6, characterized in that: The retardation film is suitable for use in display devices.

8. Use of the retardation film according to claim 7, characterized in that: The retardation film has a thickness of less than 2 μm.

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