Preparation and application of linear acrylate monomer and retardation film thereof

Abstract

The invention relates to a linear acrylate monomer and preparation thereof. The linear acrylate monomer is an acrylate-terminated monomer containing an alkynyl side chain; aryl of an alkynyl side chain contains at least one of phenyl, naphthyl, benzofuryl, benzothienyl and benzothiazolyl; the terminal group forming the alkynyl side chain is alkyl, alkyl ether or ester group, and the method for preparing the retardation film from the linear acrylate monomer comprises the following steps: forming a film under the condition of at least containing an ultraviolet initiator, and then polymerizing to form the film under the condition of light exposure.

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 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. Flat displays with these new functions require that the screen-matching optical film has properties such as high transmittance, thinner weight, and 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 substitutions of 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 for regulating polarization states. The existing preparation process for delay films is relatively complex and has a low success rate. Summary of the invention

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

[0004]

[0005] The linear acrylate monomer is a monomer terminated by an acrylate containing an alkynyl side chain, wherein the aromatic group of the alkynyl side chain contains at least one of a phenyl group, a naphthyl group, a benzofuranyl group, a benzothiophenyl group, and a benzothiazolyl group;

[0006] The terminal group constituting the alkynyl side chain is an alkyl group, an alkyl ether group or an ester group;

[0007] Wherein, A is a carbon atom bonding part, A is CH2 or C=O;

[0008] Wherein, Ar is an aromatic substituent, Ar is one of phenyl, substituted phenyl, biphenyl, naphthyl, 4-tert-butylnaphthyl, benzothiazole, benzoxazole, and benzofuran;

[0009] Among them, G is an alkyl group or an ester group, the alkyl group includes alkyl and alkoxy groups, the alkyl group includes methyl, ethyl, propyl, butyl, fluorine-substituted alkyl, alkoxy-substituted alkyl, the alkoxy group includes methoxy, ethoxy, propoxy, butoxy, methoxyethoxy, fluorine-substituted alkyl, aryl-substituted alkyl; the ester group includes acetate, acrylate, methacrylate, and propionate.

[0010] Preferably, the linear acrylate monomer includes but is not limited to the following molecules: molecules 1, 2 and 3 having two acrylate polymerization groups; molecule 4 having a hydroxyl-terminated side chain and molecule 5 containing three acrylate groups.

[0011]

[0012]

[0013] Preferably, a linear acrylate monomer is prepared into a solution with a solid content of 10% in ethyl acetate, and the polymerization of the acrylate monomer and the acrylate derivative is initiated under the radiation energy of ultraviolet light absorbed by the photosensitive initiator, and then filtered, spin-coated or scraped, and then heated, baked and irradiated with ultraviolet light.

[0014] Preferably, the exposure corresponding wavelength is 250-450nm.

[0015] Preferably, when preparing the retardation film, the film is prepared under heating conditions of 10-150 degrees Celsius.

[0016] Preferably, the organic solution is a mixture of dichloromethane, ethyl acetate, ethyl formate, methyl acetate, dichloroethane, cyclohexanone and acetone.

[0017] Preferably, the retardation film is adapted for use in a display device.

[0018] Preferably, the thickness of the retardation film is less than 10 microns.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The linear acrylate monomer has a T-shaped alkyl chain containing an alkynyl group and an aryl group as a side chain. The side chain containing an alkynyl group with good solubility is constructed to prepare an optical film with a phase retardation effect that is inverse to the optical wavelength effect;

[0021] (2) The process for preparing the delay film is simple, the operation is relatively easy and the success rate is high.

[0022] The present invention will be further described below in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic diagram of the delayed wavelength dispersion of the forward / reverse dispersion characteristics of the present invention.

[0024] Figure 2 It is a photograph of the molecular formula 2 after spin coating and heating in a specific embodiment of the present invention.

[0025] Figure 3 1 is a wavelength-refractive index difference diagram of a molecularly prepared thin film in a specific embodiment of the present invention.

[0026] Figure 4 Graph showing wavelength-dispersion characteristics of a thin film prepared by molecules in a specific embodiment of the present invention.

[0027] Figure 5 is the molecular formula 2 of the specific embodiment of the present invention 1 HNMR spectrum.

[0028] Figure 6 is the molecular formula 5 of the specific embodiment of the present invention 1 HNMR spectrum.

[0029] Figure 7 This is a birefringence characteristic diagram of the 1 / 4 wavelength delay effect prepared by the present invention.

[0030] Figure 8 This is a graph showing the dispersion characteristics of a thin film having a quarter wavelength retardation effect prepared by the present invention.

[0031] Fig. 9 This is a specific anti-reflection application of the retardation film of the present invention.

[0032] Fig.10 It is the synthesis route diagram of specific embodiment 1 of the present invention.

[0033] Fig.11 It is the synthetic route of hydrazine 2 in specific embodiment 2 of the present invention.

[0034] Fig.12 It is the synthesis route diagram of specific embodiment 2 of the present invention.

[0035] Fig.13 It is the synthesis route diagram of specific embodiment 3 of the present invention.

[0036] Fig.14 It is the synthesis route diagram of specific embodiment 4 of the present invention.

[0037] Fig.15 This is the synthesis route diagram of specific embodiment 5 of the present invention. DETAILED DESCRIPTION

[0038] A linear acrylate monomer, which is a monomer terminated by acrylate containing an alkynyl side chain; the aromatic group of the alkynyl side chain contains at least one of phenyl, naphthyl, benzofuranyl, benzothiophenyl and benzothiazolyl; the terminal group constituting the alkynyl side chain is an alkyl, alkyl ether or ester group; a phase difference delay film composition is obtained by polymerizing the acrylate terminated monomer containing an alkynyl side chain with other components.

[0039] As shown in formula 1,

[0040]

[0041] As shown in Formula 1, in the general formula, A is a carbon atom bonding part, A can be CH2 or C=O; Ar is an aryl substituent, selected from phenyl, substituted phenyl, biphenyl, naphthyl, 4-tert-butyl naphthyl, benzothiazole, benzoxazole, benzofuran, etc. G can be selected from alkyl or hydrogen, can be selected from substituted alkyl, substituents include alkyl and alkoxy; alkyl includes methyl, ethyl, propyl, butyl, fluorine-substituted alkyl, alkoxy-substituted alkyl; alkoxy includes methoxy, ethoxy, propoxy, butoxy, methoxy, ethoxy, fluorine-substituted alkyl, aryl-substituted alkyl.

[0042] The ester group of the linear acrylate monomer includes acetate, acrylate, methacrylate, propionate, and the like.

[0043] The linear acrylate monomers include but are not limited to the following molecules: molecules 1, 2 and 3 having two acrylate polymerization groups; molecule 4 having a hydroxyl-terminated side chain; and molecule 5 containing three acrylate groups.

[0044]

[0045]

[0046] A method for preparing a delay film based on a linear acrylate monomer, wherein polymerization is carried out under light exposure conditions after film formation under conditions containing at least an ultraviolet initiator, ultraviolet exposure is carried out after film formation, and the corresponding exposure wavelength is 250-450nm. When preparing the delay film, the linear acrylate monomer and a variety of acrylate derivatives need to be polymerized by a photosensitizer in an organic solution, and a film is prepared under heating conditions of 10-150 degrees Celsius, and the organic solution is a mixture of dichloromethane, ethyl acetate, ethyl formate, methyl acetate, dichloroethane, cyclohexanone, and acetone.

[0047] The film formed by the polymerization is a phase difference delay film, which has an inverse wavelength effect and is suitable for use in display devices. It is prepared using Formula 1, and the thickness of the polymer delay film is less than 10 microns; in particular, when it is a quarter-wavelength phase difference delay film, it is suitable for use in display devices. It is prepared using Formula 1, and the thickness of the polymer delay film is less than 5 microns.

[0048] The alkynyl side chain of the linear acrylate monomer has a dinitrogen hydrazone structure, in which one nitrogen is connected to the main chain through a double bond, and the other nitrogen is linked to the side chain and another aromatic substituent, where the aromatic group can be a heteroaryl group or a substituted alkyl group and other rich substituent groups, which can effectively regulate the light transmittance, solubility, film-forming properties, refractive properties, insulation properties and other properties of the film.

[0049] In an embodiment, the structure of the acrylate end-capping group is

[0050] Example 1

[0051] The synthesis process of molecular formula 1 is as follows Fig.10 As shown. Aldehyde intermediate 1 (12.0 g, 13 mmol, 1.00 eq), N-([1,1'-biphenyl]-4-yl)-N-(4-methoxy-2-butyn-1-yl)hydrazine (3.9 g, 13.8 mmol, 1.05 eq) and DL-10-camphorsulfonic acid (611 mg, 2.63 mmol, 0.20 eq) and tetrahydrofuran (THF, 120 mL) were added to a flask at room temperature, and the solution was stirred at 20°C for 2 hours. The mixture system was concentrated under reduced pressure, and the solid mixture was separated by column chromatography. (SiO2, petroleum ether:ethyl acetate = 1:0 to 5:1, TLC: petroleum ether:ethyl acetate = 1:1, P1:Rf = 0.4) Separation and concentration gave molecule 1 as an off-white solid (13.8 g, 11.8 mmol, 90% yield, 98.5% purity) MS: [M+H]+ = 1159.8 m / z. 1HNMR: (400MHz, CDCl3) δ8.04 (s, 1H), 7.56-7.65 (m, 5H), 7.50-7.55 (m, 2H), 7.43 (t, J = 7.60Hz, 2H), 7.28-7.34 (m, 1H), 6.94-7.04 (m ,4H),6.75-6.92(m,6H),6.41(dd,J=17.2,1.60Hz,2H),6.08-6.18(m,2H),5.83(d,J=10.4Hz,2H),4.18(s,2H),3.95(t,J=5.60Hz,4H ),3.77-3.89(m,6H),3.68(s,2H),3.56(dd,J=3.20,2.40Hz,2H),3.38(s,3H),2.46-2.62(m,2H),2.24(d,J=13.2Hz,4H),2.04-2.14( m,4H),1.90(dt,J=8.40,3.20Hz,2H),1.77-1.84(m,4H),1.69-1.75(m,4H),1.59-1.67(m,4H),1.42-1.55(m,8H),1.17-1.31(m,4H).

[0052] Example 2

[0053] The synthesis process of molecular formula 2 is as follows Fig.11As shown. At 0°C, t-BuOK (2.69 g, 23.9 mmol, 1.10 eq) was added to a DMF (36.0 mL) solution of intermediate 2 (3.60 g, 21.7 mmol, 1.00 eq), and the mixture was stirred at 0°C for 10 min. A DMF (36 mL) solution of 2-hydrazinobenzothiazole (4.99 g, 19.6 mmol, 0.90 eq) was added to the system, and the resulting mixed system was stirred at 25°C for 30 minutes. The mixture was diluted with 200 mL of water, extracted three times with EtOAc (100 mL × 3), and the organic phases were combined. The organic phase was washed with saturated brine (100 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (SiO2, petroleum ether: ethyl acetate = 1: 0 to 5: 1, TLC: petroleum ether: ethyl acetate = 2: 1, P1: Rf = 0.3), and concentrated under reduced pressure to give the product hydrazine (3.80 g, 15.3 mmol, 70.5% yield) MS (M+1): 248.21H NMR: (400 MHz, CDCl3) δ 7.57-7.68 (m, 2H), 7.31 (t, J = 7.60 Hz, 1H), 7.08-7.18 (m, 1H), 4.68 (s, 2H), 4.38 (s, 2H), 4.12 (s, 2H), 3.37 (s, 3H).

[0054] like Fig.12As shown. Aldehyde intermediate 1 (12.0 g, 13 mmol, 1.00 eq), hydrazine 2 (3.4 g, 13.8 mmol, 1.05 eq) and DL-10-camphorsulfonic acid (611 mg, 2.63 mmol, 0.20 eq) and tetrahydrofuran (THF, 120 mL) were added to the flask at room temperature, and the solution was stirred at 20 ° C for 0.5 hours. 50 mL of methanol was added to the phase system, and a precipitate was precipitated by stirring. The suspension system was stirred for 0.5 hours, filtered to obtain a solid, and the solid was washed with water. After drying, molecule 2 was obtained as a white solid (13.0 g, 10.9 mmol, 83% yield, purity 96.1%). MS (M+1): 1140.8. 1H NMR: (400 MHz, CDCl3) δ 8.34 (s, 1H), 7.70 (dd, J = 7.60, 4.63 Hz, 2H), 7.56 (d, J = 4.00 Hz, 1H), 7.33-7.40 (m, 1H), 7.14-7.21 (m, 1H), 6.95-7.02 (m, 4H), 6.85-6.94 (m, 6H), 6.41 (dd, J = 17.6, 1.20 Hz, 2H), 6.06-6.19 (m, 2H), 5. 83(dd,J=10.4,1.20Hz,2H),5.21(s,2H),4.18(t,J=6.80Hz,4H),4.09(s ,2H),3.95(t,J=6.40Hz,4H),3.87(t,J=6.40Hz,4H),3.32(s,3H),2.49- 2.62(m,2H),2.20-2.31(m,4H),2.10(t,J=9.60Hz,4H),1.92(dd,J=8.00 ,3.20Hz,2H),1.63-1.85(m,12H),1.41-1.55(m,8H),1.20-1.33(m,4H).

[0055] Example 3

[0056] The synthesis process of molecular formula 3 is as follows Fig.13 As shown. Aldehyde intermediate 1 (12.5 g, 13 mmol, 1.00 eq), hydrazine 2 (3.4 g, 13.8 mmol, 1.05 eq) and DL-10-camphorsulfonic acid (611 mg, 2.63 mmol, 0.20 eq) and tetrahydrofuran (THF, 120 mL) were added to a flask at room temperature, and the solution was stirred at 20 ° C for 0.5 hours. 50 mL of methanol was added to the phase system, and a precipitate was precipitated after stirring. The suspension system was stirred for 0.5 hours, filtered to obtain a solid, and the solid was washed with water. After drying, a white solid of molecule 4 was obtained (13.0 g, 11.1 mmol, 85% yield, purity 98.8%) MS (M+1): 1168.4.

[0057] Example 4

[0058] The synthesis process of molecular formula 4 is as follows Fig.14 As shown. Aldehyde intermediate 1 (26.6 g, 29.2 mmol, 0.9 eq), hydrazine 3 (9.0 g, 32.4 mmol, 1.00 eq) and DL-10-camphorsulfonic acid (1.51 g, 6.49 mmol, 0.20 eq) and tetrahydrofuran (THF, 260 mL) were added to the flask at room temperature, and the solution was stirred at 25 ° C for 1 hour. The reaction system was poured into methanol (1.3 L) and stirred to precipitate. The suspension system was stirred for 2.5 hours, filtered to obtain a solid, and the solid was washed with water. After drying, molecule 3 was obtained as a white solid (28.0 g, 23.5 mmol, 72.4% yield, purity 98.3%). MS (M+1): 1170.8. 1H NMR (CDCl3, 400 MHz): δ 8.33 (s, 1H), 7.70 (dd, J = 7.60, 4.40 Hz, 2H), 7.55 (d, J = 3.20 Hz, 1H), 7.36 (t, J = 7.20 Hz, 1H), 7.14-7.21 (m, 1H), 6.95-7.01 (m, 4H), 6.85-6.94 (m, 6H), 6.41 (dd, J = 17.60, 1.20 Hz, 2H), 6.08-6.18 (m, 2H), 5.83 (dd, J = 10. 20,1.20Hz,2H),5.20(s,2H),4.14-4.23(m,6H),3.95(t,J=6.20Hz,4H),3.87 (t,J=5.40Hz,4H),3.67(brs,2H),3.53-3.59(m,2H),2.55(ddd,J=15.20,8.80 ,3.00Hz,2H),2.25(brd,J=11.20Hz,4H),2.04-2.15(m,4H),1.88-1.97(m,2H ),1.77-1.85(m,4H),1.64-1.75(m,8H),1.42-1.55(m,8H),1.19-1.34(m,4H).

[0059] Example 5

[0060] The synthesis process of molecular formula 5 is as follows Fig.15As shown. Molecule 5 (25.0 g, 21.3 mmol, 1.00 eq) and N,N-diisopropylethylamine (DIEA, 8.28 g, 64.0 mmol, 11.1 mL, 3.00 eq) and DCM (250 mL) were added to the reaction bottle, the solution was cooled to 0°C, prop-2-enoyl chloride (3.87 g, 42.7 mmol, 3.47 mL, 2.0 eq) was slowly added to the mixture, and the mixture was stirred at 10°C for 0.1 hour. H2O (100 mL) was added to the mixture, the pH value of the mixture was adjusted to 5-6 with 1M HCl, extracted with ethyl acetate (50 mL×4), the combined organic phase was washed with brine (100 mL×1), dried over anhydrous Na2SO4, filtered and concentrated, and the residue was obtained under reduced pressure at 45°C. The residue was purified by column chromatography (SiO2, petroleum ether:ethyl acetate = 1:0 to 3:1, TLC: petroleum ether:ethyl acetate = 2:1, product Rf = 0.5) and concentrated under reduced pressure to give molecule 5 as a white solid (18.0 g, 18.3 mmol) in a yield of 85.7%. MS(M+1)+: 1224.8. 1HNMRCDCl3,400MHzδ8.33(s,1H),7.70(t,J=6.80Hz,2H),7.55(d,J=3.00Hz,1H),7.32-7.39(m,1H),7.14- 7.22(m,1H),6.95-7.02(m,4H),6.85-6.94(m,6H),6.33-6.46(m,3H),6.04-6.18(m,3H),5.74-5.86(m,3H),5.21(s,2H),4.15 -4.25(m,8H),3.95(t,J=6.40Hz,4H),3.87(t,J=6.40Hz,4H),3.66-3.73(m,2H),2.48-2.62(m,2H),2.25(brd,J=11.2Hz,4H), 2.09(brt,J=10.8Hz,4H),1.87-1.97(m,2H),1.77-1.85(m,4H),1.64-1.76(m,8H),1.43-1.56(m,8H),1.26(q,J=12.8Hz,4H).

[0061] Example 7

[0062] like Figure 1-9 As shown, in this embodiment, the molecules described in the above five embodiments are prepared into a solution in ethyl acetate with a solid content of 10%, 1 wt% of a photosensitive initiator is added, and the solution is conventionally filtered, spin-coated or scraped on an oriented film, and then heated and baked at 100°C to remove the solvent; when irradiated with 365nm ultraviolet light, the obtained film exhibits obvious light and dark states, and can be peeled off and used to manufacture a phase delay film. Figure 2The display shows obvious full brightness and full transparency at a 90° angle difference. Figure 3 and Figure 4 The curves of Δn and R0 changing with wavelength after the molecules 1 and 5 were prepared into thin films, where the film thicknesses of molecules 1 and 2 were 1.5 and 1.38 microns, respectively. The test curves show that the in-situ oriented polymerized films of molecules 1 and 5 both have the effect of reverse wavelength dispersion, where molecule 5 has a higher birefringence difference, and the films with the same effect can be made thinner. The optical film phase difference was tested using Axostep, which showed that the optical film phase difference had demonstration characteristics within -50.00o to +50.00o. The film thickness, 450nm to 650nm R0 and Δn values ​​are shown in the following table:

[0063]

[0064] Test results combined Figure 4 The delay per unit thickness in the x-axis and y-axis directions of the films prepared by molecules 1, 2, 3, 4 and 5 increases with the increase of wavelength, indicating that this series of films have the characteristics of reverse wavelength dispersion. By adjusting the film thickness, a film with a thickness of about 2.5 microns was prepared. Figure 7 To prepare the birefringence wavelength characteristic diagram of 1 / 4 wavelength delay effect; at the same time, the phase difference Ro@550nm of the corresponding films of molecules 1, 2, 3, 4, and 5 are 141.6nm, 146.6nm, 130.9nm, 137.7nm and 142.1nm respectively. Figure 8 It shows that the film prepared by this type of molecules has a 1 / 4 wavelength phase difference delay effect and can be used to manufacture 1 / 4 wavelength circularly polarized optical delay film.

[0065] Superimposing a film with a 1 / 4 wavelength phase difference reverse dispersion delay effect and a polarizer can have the effect of suppressing the reflection of transmitted visible light. The reflectivity at each angle is less than 10%, which can achieve the application effect of suppressing strong light reflection in the display. Fig. 9 Specular reflection test of the anti-reflection film applied and prepared for molecules 1 and 5, reflection effect pictures taken from the front and at 45o angles at four angles.

Claims

1. A linear acrylate monomer, characterized in that: It has the structure shown in formula I: The linear acrylate monomer is a monomer terminated by an acrylate containing an alkynyl side chain, wherein the aromatic group of the alkynyl side chain contains at least one of a phenyl group, a naphthyl group, a benzofuranyl group, a benzothiophenyl group, and a benzothiazolyl group; The terminal group constituting the alkynyl side chain is an alkyl group, an alkyl ether group or an ester group; Wherein, A is a carbon atom bonding part, A is CH2 or C=O; Wherein, Ar is an aromatic substituent, Ar is one of phenyl, substituted phenyl, biphenyl, naphthyl, 4-tert-butylnaphthyl, benzothiazole, benzoxazole, and benzofuran; Among them, G is an alkyl group or an ester group; the alkyl group includes alkyl and alkoxy groups, the alkyl group includes methyl, ethyl, propyl, butyl, fluorine-substituted alkyl, alkoxy-substituted alkyl, the alkoxy group includes methoxy, ethoxy, propoxy, butoxy, methoxyethoxy, fluorine-substituted alkyl, aryl-substituted alkyl; the ester group includes acetate, acrylate, methacrylate, and propionate.

2. The linear acrylate monomer according to claim 1, characterized in that The linear acrylate monomers include but are not limited to the following molecules: molecules 1, 2 and 3 having two acrylate polymerization groups; molecule 4 having a hydroxyl-terminated side chain; and molecule 5 containing three acrylate groups.

3. A method for preparing a retardation film based on the linear acrylate monomer according to claim 1 or 2, characterized in that: A linear acrylate monomer is prepared into a solution in ethyl acetate with a solid content of 10%, and the linear acrylate monomer and the acrylate derivative are polymerized under the radiation energy of ultraviolet light absorbed by a photosensitive initiator, and then the solution is filtered, spin-coated or scraped, and then heated, baked and irradiated with ultraviolet light.

4. The preparation method according to claim 3, characterized in that: The exposure corresponding wavelength is 250-450nm.

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

6. The preparation method according to claim 3, 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 3 to 6, characterized in that: The retardation film is suitable for use in display devices.

8. The use of the retardation film according to claim 7, characterized in that: The thickness of the retardation film is less than 10 micrometers.

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