Preparation of linear acrylate monomer with side chain and delay film of linear acrylate monomer

Abstract

The invention relates to preparation of a retardation film of a linear acrylate monomer with a side chain. The linear acrylate monomer with the side chain is an acrylate-terminated monomer containing a side chain group, and the ester group or amide side chain group contains at least one of naphthyl, benzofuryl, benzothienyl, benzothiazolyl and glycol ether. The polyphenyl ester derivative monomer containing the multi-substituted benzyne side chain group and different components are polymerized to obtain the phase difference delay film composition. The polysubstituted benzyne side chain in the linear acrylate monomer with the side chain has abundant substituent groups, so that the properties and characteristics of light transmission, solubility, film-forming property, refractivity and insulativity of the film are effectively regulated and controlled.

Description

Technical Field

[0001] The invention relates to the technical field of compounds, in particular to a linear acrylate monomer with a side chain and the preparation of 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. The key monomers are designed and improved through various substitutions of the side chains to improve film-forming properties, transparency, and birefringence performance, and to establish the relationship between wavelength dispersion and optical delay effects to meet the application needs of various optical films to regulate polarization states. Acrylate-terminated benzoate oligomers have excellent properties such as transparency, good solubility, easy film formation, good refractive properties, and good insulation, and are therefore often used to prepare various optical films. Polymer films with birefringence effects are achieved through the directional arrangement of molecules. Summary of the invention

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

[0004]

[0005] The linear acrylate monomer with a -COXA2A3 side chain of formula I is a monomer terminated by an acrylate containing a side chain group, and the side chain -COXA2A3 is composed of an ester group or an amide group, wherein the ester group or the amide group contains at least one of a naphthyl group, a benzofuranyl group, a benzothiophenyl group, a benzothiazolyl group, and a glycol ether group,

[0006] Wherein, A1 is a bonding part of a carbon atom, and A1 is CH2 or C=O;

[0007] X is O, N, or CH2 bonding; when X is O, A2 is an aryl or alkyl group, and A3 does not exist; when X is N, A2 is an aryl or alkyl group, and A3 is an alkyl group; when X is CH2O, A2 is an aryl or alkyl group, and A3 does not exist;

[0008] A2 is selected from aryl or substituted aryl, including naphthyl, 4-tert-butylnaphthyl, benzothiazole, benzoxazole, benzofuran and substituted aryl,

[0009] A3 is selected from substituted alkyl groups, and the substituents include alkyl and alkoxy substituted alkyl groups; alkyl groups include methyl, ethyl, propyl, butyl, fluorine substituted alkyl groups, aryl substituted alkyl groups, and alkoxy substituted alkyl groups; alkoxy substituted alkyl groups include methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, and methoxyethoxyethyl.

[0010] Preferably, it is characterized in that the linear acrylic ester monomer with a side chain includes but is not limited to the following molecules: molecules 1, 2, 3 whose side chains are ester groups and molecules 4, 5, 6 whose side chains are amide groups,

[0011]

[0012]

[0013]

[0014] The second object of the present invention is to provide a method for preparing a delay film based on a linear acrylate monomer with a side chain, wherein the linear acrylate monomer with a side chain is prepared into a solution with a solid content of 10% with an acrylate derivative in an organic solvent, and the polymerization of the acrylate monomer and the acrylate derivative is initiated when a photosensitive initiator absorbs the radiation energy of ultraviolet light, and then the solution is filtered, spin-coated or scraped, and then heated, baked and irradiated with ultraviolet light.

[0015] Preferably, the corresponding wavelength of the ultraviolet light irradiation is 250-450nm.

[0016] Preferably, when preparing the retardation film, the film is prepared under heating conditions of 10-150 degrees Celsius.

[0017] Preferably, the organic solution is a mixture of dichloromethane, ethyl acetate, ethyl formate, methyl acetate, ethylene dichloride, cyclohexanone and acetone.

[0018] Preferably, the retardation film is suitable for a display device, and the thickness of the retardation film is less than 10 microns.

[0019] The present invention also provides an application of the prepared phase retardation film, which is suitable for display devices, and the thickness of the retardation film is less than 10 microns;

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The polysubstituted phenylacetyl side chains in the linear acrylate monomers with side chains have abundant substituent groups, which can effectively control the light transmittance, solubility, film-forming properties, refractive properties, and insulation properties of the film;

[0022] (2) The polymer film achieves optical dispersion and phase inverse wavelength delay effects by changing the optical isotropy within the film plane. Specifically, the anisotropic effect is achieved by stretching or designing the orderly arrangement of polymer molecules.

[0023] The present invention will be further described below in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of delay wavelength dispersion.

[0025] Figure 2 This is a diagram of the molecular formula 5 after spin coating and heating in a specific embodiment of the present invention.

[0026] Figure 3 1 is a wavelength-refractive index difference diagram of a molecularly prepared thin film in a specific embodiment of the present invention.

[0027] Figure 4 Graph showing wavelength-dispersion characteristics of a thin film prepared by molecules in a specific embodiment of the present invention.

[0028] Figure 5 is the specific embodiment of the present invention molecule 1 1 H NMR spectra.

[0029] Figure 6 is the specific embodiment of the present invention molecule 2 1 H NMR spectra.

[0030] Figure 7 is the specific embodiment of the present invention molecule 3 1 H NMR spectra.

[0031] Figure 8 is the specific embodiment of the present invention molecule 4 1 H NMR spectra.

[0032] Fig. 9 It is the synthesis route diagram of specific embodiment 1 of the present invention.

[0033] Fig.10 It is the synthesis route diagram of specific embodiment 2 of the present invention.

[0034] Fig.11 It is the synthesis route diagram of specific embodiment 3 of the present invention.

[0035] Fig.12 It is the synthesis route diagram of specific embodiment 4 of the present invention.

[0036] Fig.13 This is the synthesis route diagram of specific embodiment 5 of the present invention.

[0037] Fig.14 This is the synthesis route diagram of specific embodiment 6 of the present invention. DETAILED DESCRIPTION

[0038] A linear acrylic ester monomer with a side chain is a monomer terminated by an acrylic ester containing a side chain group, constituting the ester group or amide side chain group, and containing at least one of a naphthyl group, a benzofuranyl group, a benzothiophenyl group, a benzothiazolyl group, and a glycol ether group. A phase difference delay film composition is obtained by polymerizing an oligophenyl ester derivative monomer containing a multi-substituted phenyl alkynyl side chain group with different components;

[0039] As shown in formula 1,

[0040]

[0041] In the general formula, A1 is a carbon atom bonding part, A1 is CH2 or C=O;

[0042] Wherein, X is O, N, CH2 bonding;

[0043] Wherein, when X is O, A2 is an aryl group or an alkyl group, and A3 does not exist;

[0044] Wherein, when X is N, A2 is an aryl group or an alkyl group, and A3 is an alkyl chain;

[0045] Wherein, when X is CH2O, A2 is an aryl group or an alkyl group, and A3 does not exist;

[0046] wherein A2 is selected from aryl or substituted aryl, naphthyl, 4-tert-butylnaphthyl, benzothiazole, benzoxazole, benzofuran aryl substituent;

[0047] Among them, A3 is selected from substituted alkyl, and the substituents include alkyl and alkoxy; alkyl includes methyl, ethyl, propyl, butyl, fluorine-substituted alkyl, and alkoxy-substituted alkyl; alkoxy includes methoxy, ethoxy, propoxy, butoxy, methoxyethoxy, and fluorine-substituted alkylaryl substituted alkyl.

[0048] The linear acrylic ester monomer with a side chain includes but is not limited to the following molecules: molecules 1, 2, and 3 whose side chains are ester groups and molecules 4, 5, and 6 whose side chains are amide groups.

[0049]

[0050]

[0051]

[0052] 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 performing ultraviolet light exposure after film formation. The corresponding exposure wavelength is 250-450nm. 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.

[0053] The film formed by the polymerization is a phase difference delay film, which is suitable for use in display devices, and the thickness of the delay film is less than 10 microns; a quarter-wavelength phase difference delay film, the thickness of the delay film is less than 5 microns.

[0054] The polysubstituted phenylacetyl side chains in the linear acrylate monomers with side chains have abundant substituent groups, which can effectively regulate the light transmittance, solubility, film-forming properties, refractive properties and insulation properties of the film.

[0055] In an embodiment, the structure of the acrylate end-capping group is

[0056] Example 1

[0057] The synthesis process of molecular formula 1 is as follows Fig. 9 As shown. At 0°C, the acid intermediate 1 (70g, 75.51mmol, 1eq), the intermediate naphthol (13.06g, 90.61mmol, 37.32mL, 1.2eq) and 4-dimethylaminopyridine (DMAP, 922.44mg, 7.55mmol, 0.1eq) were added to the flask. 1-acetyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI, 17.37g, 90.61mmol, 1.2eq) was added to the solution in dichloromethane (DCM, 700mL). The mixture was stirred at 20°C for 4 hours. The mixture system was added to 3L of water, stirred for 10 minutes, and the acidity was adjusted to PH = 6 by dilute hydrochloric acid. Then the aqueous phase solution was extracted with dichloromethane (1L×3), the organic phase was separated and extracted, and the combined organic phase was washed with brine (2L), 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 a white solid. The target product molecule 1 (white solid, 41.5 g, 49.84% yield) was obtained. MS: [M+H2O+H] + =1070.8m / z. Figure 5 , 1HNMR(CD3Cl,400MHz)δ7.96-7.81(m,3H),7.69(d,J=1.6Hz,1H),7.58(d,J=3.2Hz,1H),7.5 4-7.44(m,2H),7.40-7.33(m,1H),7.18-7.08(m,1H),7.03-6.79(m,9H),6.41(d,J=17.2Hz, 2H),6.20-6.05(m,2H),5.83(d,J=10.4Hz,2H),4.28-4.14(m,4H),4.01-3.76(m,8H),2.61 -2.34(m,2H),2.29-2.13(m,4H),2.13-2.02(m,4H),1.87-1.37(m,22H),1.34-1.15(m,4H).

[0058] Example 2

[0059] The synthesis process of molecular formula 2 is as follows Fig.10 As shown. Acid intermediate 1 (70g, 75.51mmol, 1eq), intermediate methoxyethoxyethanol (10.89g, 90.6mmol, 10.67mL, 1.3eq), DMAP (0.922g, 7.55mmol, 0.1eq) and DCM (500mL) were added to the flask at 0°C, and EDCI (12.92g, 67.42mmol, 1.25eq) was added to the solution. The mixture was stirred at 20°C for 24 hours. The mixture system was added to 6L water, stirred for 10 minutes, and the acidity was adjusted to PH = 6 by dilute hydrochloric acid. Then the aqueous phase solution was extracted with dichloromethane (1.5L×4), the organic phase was separated and extracted, and the combined organic phase was washed with saturated brine (2L×2), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (SiO2, DCM:EA=10:1-5:1) and concentrated under reduced pressure to give a white solid. The target product molecule 2 (white solid, 51.8 g, 48.44 mmol, 64.16% yield) was obtained. MS: [M+H2O+H] + =1046.9. Combined Figure 6 , 1HNMR (CDCl3, 400MHz): δ = 7.35 (d, J = 3.2Hz, 1H), 7.03-6.95 (m, 5H), 6.92-6.85 (m, 5H), 6.46-6.36 (m, 2 H),6.19-6.07(m,2H),5.86-5.79(m,2H),4.48(t,J=5.2Hz,2H),4.18(t,J=6.4Hz,4H),3.94(t,J=6.4 Hz,4H),3.88-3.81(m,4H),3.78(d,J=6.0Hz,2H),3.72-3.65(m,2H),3.61-3.54(m,2H),2.63-2.48(m ,2H),2.29-2.16(m,4H),2.12-2.00(m,4H),1.88-1.60(m,14H),1.53-1.42(m,8H),1.28-1.11(m,4H).

[0060] Example 3

[0061] The synthesis process of molecular formula 3 is as follows Fig.11 As shown. Acid intermediate 1 (70g, 75.51mmol, 1eq), intermediate 2-(2-hydroxyethoxy)ethyl acrylate (13.64g, 83mmol, 1.1eq), DMAP (0.922g, 7.55mmol, 0.1eq) and DCM (700mL) were added to the flask at 0°C, and EDCI (18.8g, 98.16mmol, 1.3eq) was added to the solution. The mixture was stirred at 20°C for 24 hours. The mixture system was added to 6L water, stirred for 10 minutes, and the acidity was adjusted to PH = 6 by dilute hydrochloric acid. Then the aqueous phase solution was extracted with dichloromethane (1.5L×4), the organic phase was separated and extracted, and the combined organic phase was washed with saturated brine (2L×2), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (SiO2, DCM:EA=30:1-5:1) and concentrated under reduced pressure to obtain the target product molecule 3 as a white solid (35 g, 29.36 mmol, 54.4% yield). MS: [M+H2O+H] + =1086.7. Combined Figure 7 , 1H NMR (CDCl3, 400MHz): δ7.34 (d, J = 3.2Hz, 1H), 7.06-6.93 (m, 5H), 6.93-6.81 (m, 5H), 6.51 -6.34(m,3H),6.23-6.08(m,3H),5.90-5.75(m,3H),4.57-4.44(m,2H),4.39-4.28(m,2H ),4.18(t,J=6.8Hz,4H),3.95(t,J=6.4Hz,4H),3.88-3.75(m,8H),2.52(s,2H),2.30-2. 17(m,4H),2.12-1.96(m,4H),1.90-1.56(m,14H),1.56-1.38(m,8H),1.30-1.12(m,4H).

[0062] Example 4

[0063] The synthesis process of molecular formula 4 is as follows Fig.12 As shown. Acid intermediate 1 (70g, 75.51mmol, 1eq), intermediate N-methylbenzothiazole-2-amine (13.64g, 83mmol, 1.1eq) and DMAP (0.922g, 7.55mmol, 0.1eq) and DCM (700mL) were added to the flask at 0°C, and EDCI (18.8g, 98.16mmol, 1.3eq) was added to the solution. The mixture was stirred at 20°C for 24 hours. The mixture system was added to 6L water, stirred for 10 minutes, and the acidity was adjusted to PH = 6 by dilute hydrochloric acid. Then the aqueous phase solution was extracted with dichloromethane (1.5L×4), the organic phase was separated and extracted, and the combined organic phase was washed with saturated brine (2L×2), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (SiO2, DCM:EA=10:1-5:1) and concentrated under reduced pressure to give a white solid. The target product molecule 4 was obtained as a white solid (49 g, 43.37 mmol, 57.44% yield). MS: [M+H] + =1073.8. Combined Figure 8 , 1H NMR (CDCl3, 400MHz): δ=7.96-7.84(m,2H),7.50-7.41(m,1H),7.37-7.31(m,1H),7.01 -6.81(m,11H),6.47-6.34(m,2H),6.24-6.07(m,2H),5.89-5.76(m,2H),4.21-4.13(m ,4H),4.01-3.90(m,4H),3.85-3.73(m,4H),3.67(s,3H),2.58-2.46(m,1H),2.34-2.1 6(m,3H),2.12-2.01(m,4H),1.89-1.59(m,16H),1.51-1.44(m,8H),1.27-1.00(m,4H).

[0064] Example 5

[0065] The synthesis process of molecular formula 5 is as follows Fig.13 As shown. Acid intermediate 1 (70g, 75.51mmol, 1eq), intermediate 2-methoxyethoxyethyl-benzothiophene-2-amine (10.89g, 90.6mmol, 10.67mL, 1.3eq) and DMAP (0.922g, 7.55mmol, 0.1eq) and DCM (900mL) were added to the flask at 0°C, and EDCI (18.8g, 98.16mmol, 1.3eq) was added to the solution. The mixture was stirred at 20°C for 48 hours. The mixture system was added to 6L water, stirred for 10 minutes, and the acidity was adjusted to PH = 6 by dilute hydrochloric acid. Then the aqueous phase solution was extracted with dichloromethane (1.5L×4), the organic phase was separated and extracted, and the combined organic phase was washed with saturated brine (2L×2), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (SiO2, DCM:EA=10:1-3:1) and concentrated under reduced pressure to give a white solid. The target product molecule 5 was obtained as a white solid (46.2 g, 39.8 mmol, 52.7% yield). MS: [M+H] + =1161.8.

[0066] Example 6

[0067] The synthesis process of molecular formula 6 is as follows Fig.14As shown. Acid intermediate 1 (70g, 75.51mmol, 1eq), intermediate 2 (21.64g, 83mmol, 1.1eq), DMAP (0.922g, 7.55mmol, 0.1eq) and DCM (900mL) were added to the flask at 0°C, and EDCI (18.8g, 98.16mmol, 1.3eq) was added to the solution. The mixture was stirred at 20°C for 24 hours. The mixture system was added to 6L water, stirred for 10 minutes, and the acidity was adjusted to PH = 6 by dilute hydrochloric acid. Then the aqueous phase solution was extracted with dichloromethane (1.5L×4), the organic phase was separated and extracted, and the combined organic phase was washed with saturated brine (2L×2), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (SiO2, DCM:EA=1:0~3:1) and concentrated under reduced pressure to obtain a white solid. The target product molecule 6 was obtained as a white solid (53.3 g, 44.37 mmol, 58.77% yield). MS: [M+H] + =1202.5.

[0068] Demonstration Example 7

[0069] In this embodiment, the molecules described in the above six embodiments are prepared into a solution in ethyl acetate with a solid content of 10%, and 1 wt% of a photosensitive initiator is added. After conventional filtration, the solution is spin-coated or scraped on the oriented film and then heated and baked at 100°C to remove the solvent. The obtained film exhibits obvious light and dark states when irradiated with 365nm ultraviolet light, and is peeled off and used to make a phase delay film. The thickness of the test film is within 0.9 to 1.1 microns. Axostep tests the phase difference of the optical film, which shows that the phase difference of the optical film has demonstration characteristics within -50.00° to +50.00°. The thickness of the obtained film, 450nm to 650nm R0 and Δn values ​​are shown in the following table:

[0070]

[0071] Combination Figure 1-4 ,The test results show that after the molecular orientation coating is photocured, all films have obvious light and dark phases; Figure 2 , the prepared film has anisotropy. Figure 3The delay per unit thickness of molecules 1, 4, 5, and 6 in the x-axis and y-axis directions increases with the increase of wavelength, indicating that the films prepared by molecules 1, 4, 5, and 6 have the characteristics of reverse wavelength dispersion; molecules 2, 3, and the demonstration example have the characteristics of positive wavelength dispersion. By adjusting the film thickness, a film with a thickness of about 2.5 microns was prepared. The Ro@550nm of the corresponding films of molecules 1, 4, 5, 2, 3, and 6 were 137.5nm, 141.5nm, 141.5nm, 135.2nm, 132.8nm, and 146.5nm, respectively, with a 1 / 4 wavelength phase difference delay effect, which can be used to manufacture a 1 / 4 wavelength circularly polarized optical delay film.

Claims

1. A linear acrylic ester monomer with a side chain, characterized in that: It has the structure shown in formula I: The linear acrylate monomer with a -COXA2A3 side chain of formula I is a monomer terminated by an acrylate containing a side chain group, and the side chain -COXA2A3 is composed of an ester group or an amide group, wherein the ester group or the amide group contains at least one of a naphthyl group, a benzofuranyl group, a benzothiophenyl group, a benzothiazolyl group, and a glycol ether group, Wherein, A1 is a bonding part of a carbon atom, and A1 is CH2 or C=O; X is O, N, or CH2 bonding; when X is O, A2 is an aryl or alkyl group, and A3 does not exist; when X is N, A2 is an aryl or alkyl group, and A3 is an alkyl group; when X is CH2O, A2 is an aryl or alkyl group, and A3 does not exist; A2 is selected from aryl or substituted aryl, including naphthyl, 4-tert-butylnaphthyl, benzothiazole, benzoxazole, benzofuran and substituted aryl, A3 is selected from substituted alkyl groups, and the substituents include alkyl and alkoxy substituted alkyl groups; alkyl groups include methyl, ethyl, propyl, butyl, fluorine substituted alkyl groups, aryl substituted alkyl groups, and alkoxy substituted alkyl groups; alkoxy substituted alkyl groups include methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, and methoxyethoxyethyl.

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: molecules 1, 2, 3 whose side chains are ester groups and molecules 4, 5, 6 whose side chains are amide groups, 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 side chain is prepared into a solution with a solid content of 10% and an acrylate derivative in an organic solvent, and the polymerization of the acrylate monomer and the acrylate derivative is initiated 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 method for preparing a retardation film according to claim 3, characterized in that: The corresponding wavelength of UV light irradiation is 250-450nm.

5. The method for preparing a retardation film according to claim 3, characterized in that: When preparing the retardation film, the film is prepared under heating conditions of 10-150 degrees Celsius.

6. The method for preparing a retardation film 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 display devices, and the thickness of the retardation film is less than 10 microns.

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