High-transmittance crystal extension glue composition as well as preparation method and application thereof

Abstract

The invention provides a high-transmittance crystal extension glue composition as well as a preparation method and application thereof. The high-transmittance crystal extension glue composition is prepared from pegylated polyurethane polyacrylate, acryloylated gelatin (GelMA) and acryloyl-polylysine-polyphenylalanine polypeptide through photo-initiation polymerization. A polymer obtained after photocuring polymerization of the high-transmittance crystal extension glue comprises a polymer as shown in a formula I in the specification. The high-transmittance crystal extension glue provided by the invention is formed by photo-initiation polymerization of pegylated polyurethane polyacrylate, acryloylated gelatin (GelMA) and acryloyl-polylysine-polyphenylalanine polypeptide, and a polyurethane chain segment, a gelatin chain segment and a polylysine-polyphenylalanine chain segment are formed after polymerization, so that the biocompatibility and water solubility of the gelatin are retained; the flexibility, the air permeability and the biological safety performance of the high-transmittance crystal extension glue are synergistically improved.

Description

Technical Field

[0001] The present invention relates to the technical field of nail polish, and in particular to a high-transparency crystal extension glue composition, a preparation method and an application thereof. Background Art

[0002] Polyurethane UV-curing nail polish is widely used due to its excellent strength and flexibility. However, its poor air permeability can easily lead to nail dehydration, brittleness, and yellowing. Furthermore, the modification process of polyurethane UV-curing nail polish can negatively impact its strength and flexibility. Summary of the Invention

[0003] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a high-transmittance crystal extension glue composition and its preparation method and application.

[0004] To achieve the above object, the technical solution adopted by the present invention is: a high-transmittance crystal extension glue, the polymer after the high-transmittance crystal extension glue is photocured and polymerized includes a polymer as shown in Formula I,

[0005] Formula I, wherein 20≤x≤30, 5≤y≤20, 3≤z≤8, 2≤l≤5,

[0006] 15≤m≤30, 15≤n≤30, 15≤k≤30, and 30≤m+n+k≤80;

[0007] R1 is a chain segment of polyether diol, R2 is a benzene ring structure of toluene diisocyanate or an alicyclic structure of isophorone diisocyanate or a straight-chain aliphatic carbon chain, R3 is a carbon chain of hydroxyl-containing acrylate, Gelatin represents a molecular chain segment of gelatin, and PEG is a polyvinyl alcohol chain segment.

[0008] The above-mentioned highly transparent crystal extension glue is composed of polyethylene glycol-modified polyurethane polyacrylate, acrylated gelatin (GelMA), and acryloyl-polylysine-polyphenylalanine polypeptide photoinitiated polymerization. After polymerization, polyurethane segments, gelatin segments, and polylysine-polyphenylalanine segments are formed, retaining the biocompatibility and water solubility of gelatin, and synergistically improving the flexibility, breathability, and biosafety of the highly transparent crystal extension glue.

[0009] Preferably, the chain segment of the polyether glycol is , 3≤a≤10 or -O-CO-R-CO-O-, R is an aliphatic carbon chain or an aromatic ring; R3 is -CH2CH2- or -CH2CH2CH2- or -CH2CH2CH2CH2-.

[0010] Preferably, the high-transmittance crystal extension glue is made of polyethylene glycol polyurethane polyacrylate, acryloyl gelatin (GelMA), and acryloyl-polylysine-polyphenylalanine polypeptide photoinitiated polymerization;

[0011] The structural diagram of acryloyl gelatin (GelMA) is shown in Formula II.

[0012] Formula II, the molecular weight of the acryloyl gelatin is 8000~15000Da, and the degree of acryloyl substitution of the acryloyl gelatin is 8%~15%.

[0013] The present invention also provides a composition of a highly transparent crystal extension adhesive, the composition of the highly transparent crystal extension adhesive comprising the following components:

[0014] 60-90 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 50-80 parts by weight of acryloyl gelatin (GelMA), 0.2-1 parts by weight of isobornyl acrylate, 1-5 parts by weight of a photoinitiator, and 50-80 parts by weight of a diluent;

[0015] The structural diagram of acryloyl gelatin (GelMA) is shown in Formula II.

[0016] Formula II, the molecular weight of the acryloyl gelatin is 8000~15000Da, and the degree of acryloyl substitution of the acryloyl gelatin is 8%~15%;

[0017] The chemical structure of PEGylated polyurethane polyacrylate is shown in Formula III;

[0018] Formula III; the chemical structure of the acryloyl-polylysine-polyphenylalanine polypeptide is as shown in Formula IV;

[0019] ;

[0020] Among them, 20≤x≤30, 5≤y≤20,

[0021] 15≤m≤30, 15≤n≤30, 15≤k≤30, and 30≤m+n+k≤80;

[0022] R1 is a chain segment of polyether diol, R2 is a benzene ring structure of toluene diisocyanate or an alicyclic structure of isophorone diisocyanate or a straight-chain aliphatic carbon chain, and R3 is a carbon chain of hydroxyl-containing acrylate; the chain segment of polyether diol is , 3≤a≤10 or -O-CO-R-CO-O-, R is an aliphatic carbon chain or an aromatic ring; R3 is -CH2CH2- or -CH2CH2CH2- or -CH2CH2CH2CH2-, PEG is a polyvinyl alcohol segment;

[0023] The particle size of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is 1-8 μm, and the capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is a polymer containing a coumarin group.

[0024] The photopolymerization components of the highly transparent crystal extension glue are polyethylene glycolized polyurethane polyacrylate, acryloylated gelatin (GelMA), and acryloyl-polylysine-polyphenylalanine peptide. After polymerization, polyurethane segments, gelatin segments, and polylysine-polyphenylalanine segments are formed, retaining the biocompatibility and water solubility of gelatin, synergistically improving the flexibility, breathability, and biosafety of the highly transparent crystal extension glue. The acryloyl-polylysine-polyphenylalanine peptide has undergone molecular denaturation. The acryloyl-polylysine-polyphenylalanine peptide microcapsules are protected by a coumarin-containing polymer as the microcapsule wall. During the photopolymerization process, the microcapsule wall cleaves, releasing the acryloyl-polylysine-polyphenylalanine peptide. This prevents the impact of acryloyl-polylysine-polyphenylalanine peptide deformation on the post-polymerization properties of the highly transparent crystal extension glue and does not affect the photopolymerization process.

[0025] Preferably, 70 to 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 60 to 70 parts by weight of acryloyl gelatin (GelMA), 0.2 to 1 parts by weight of isobornyl acrylate, 1 to 5 parts by weight of photoinitiator, and 50 to 80 parts by weight of diluent.

[0026] The above weight ratio of polyethylene glycolated polyurethane acrylate, acryloylated gelatin (GelMA), and acryloyl-polylysine-polyphenylalanine polypeptide can better synergistically improve the flexibility, air permeability and biosafety of the highly transparent crystal extension glue.

[0027] Preferably, the capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is 1173 photoinitiator or TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0028] Preferably, the preparation method of acrylamide-polylysine-polyphenylalanine polypeptide microcapsules comprises the following steps:

[0029] (1) A phosphate buffer solution of 1-5 mg / mL acrylamide-polylysine-polyphenylalanine polypeptide, a pH of 6.5-7.0, and a 4%-6% by mass polyazobenzene methyl acrylate ethyl acetate solution as the wall material oil phase solution. 1 part by weight of the phosphate buffer solution of acrylamide-polylysine-polyphenylalanine polypeptide is slowly added dropwise to 3.5-5 parts by weight of the wall material oil phase solution, and premixed by magnetic stirring to form a preliminary mixed solution while adding dropwise;

[0030] (2) The speed of the high-speed shear emulsifier is 7000 rpm~10000 rpm, and the shearing time is 15~30 minutes. The temperature is 25℃±2, and the temperature is cooled in an ice water bath to avoid shear heat generation that may cause polypeptide denaturation and form a water-in-oil (W / O) emulsion.

[0031] (3) Rotate the oil-in-water (W / O) emulsion to slowly evaporate ethyl acetate to obtain a suspension at a temperature of ≤30°C and a vacuum degree of -0.01 MPa to 0.10 MPa;

[0032] (4) Centrifuge the suspension at 4000 rpm to 6000 rpm for 12 to 20 minutes at 3 to 5°C, discard the supernatant, and resuspend in PBS buffer at pH 6.5 to 7.0. Disperse the suspension by ultrasonic treatment at 80 to 120 W for 2.5 to 5 minutes, then centrifuge again. Repeat the washing and freeze-drying to obtain dry polypeptide microcapsule powder (storage in a sealed container away from light and refrigerate at 4°C).

[0033] Preferably, the method for preparing the acryloyl-polylysine-polyphenylalanine polypeptide comprises the following steps: performing a peptide bond condensation reaction between methacryloylated polylysine (PLMA) and phenylalanine.

[0034] Preferably, the weight average molecular weight of the PEGylated polyurethane acrylate is 15 kDa to 100 kDa.

[0035] The present invention also provides a method for photoinitiated polymerization of any of the above-mentioned high-transmittance crystal extension glue compositions, the method comprising the following steps: subjecting any of the above-mentioned high-transmittance crystal extension glue compositions to light irradiation at 360-370 nm with an intensity of 30-60 mW / cm 2 Irradiate for 30 to 90 seconds to obtain any of the above-mentioned high-transmittance crystal extension glues.

[0036] The present invention provides a highly transparent crystal extension glue composition, its preparation method, and its application. The highly transparent crystal extension glue is prepared by photoinitiated polymerization of PEGylated polyurethane polyacrylate, acrylated gelatin (GelMA), and acryloyl-polylysine-polyphenylalanine polypeptide. Polymerization forms polyurethane segments, gelatin segments, and polylysine-polyphenylalanine segments, while retaining the biocompatibility and water solubility of gelatin. This synergistically improves the flexibility, breathability, and biosafety of the highly transparent crystal extension glue. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic structural diagram of the polymer after photocuring polymerization of the high-transmittance crystal extension glue in the high-transmittance crystal extension glue composition of the present invention.

[0038] Figure 2 This is a dynamic light scattering (DLS) test result of the acrylamide-polylysine-polyphenylalanine polypeptide microcapsules in the high-transmittance crystal extension glue composition of the present invention.

[0039] Figure 3 This is the infrared spectrum of the polymer after light-curing polymerization of the high-transmittance crystal extension glue of the present invention. DETAILED DESCRIPTION

[0040] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0041] Example 1

[0042] (1) As a high-transmittance crystal extension glue of an embodiment of the present invention, the polymer after light-curing polymerization of the high-transmittance crystal extension glue includes a polymer as shown in Formula I,

[0043] Formula I, wherein 20≤x≤30, 5≤y≤20, 3≤z≤8, 2≤l≤5,

[0044] 15≤m≤30, 15≤n≤30, 15≤k≤30, and 45≤m+n+k≤80;

[0045] R1 is , 3≤a≤10; R2 is a benzene ring structure of toluene diisocyanate, and R3 is -CH2CH2CH2-.

[0046] Gelatin represents the molecular chain segment of gelatin. The structural diagram of acryloyl gelatin (GelMA) is shown in Formula II.

[0047] Formula II, the molecular weight of the acryloyl gelatin is 8000~12000Da, and the degree of acryloyl substitution of the acryloyl gelatin is 8%~15%.

[0048] (2) Preparation of the High-Transparency Crystal Extension Glue of this Example

[0049] 1. Preparation of acryloyl gelatin (GelMA)

[0050] (1) Preparation of 8000Da~12000Da small molecule gelatin

[0051] Place macromolecular gelatin in deionized water at 55°C under magnetic stirring until the gelatin is completely dissolved, to obtain a 10% (w / v) gelatin solution. Cool the gelatin solution to 37°C, adjust the pH to 8.0 with 1M NaOH or 1M HCl, and add 0.1M PBS buffer (1:1 volume ratio with the gelatin solution, pH 8.0). Add trypsin powder at an enzyme-to-substrate mass ratio (E / S) of 1:100 and magnetically stir until the enzyme is completely dissolved.

[0052] The enzymatic hydrolysis reaction was carried out at a constant temperature of 37°C and magnetic stirring was performed for 4 hours; small molecule gelatin of 8000Da to 12000Da was collected using 8000Da and 12000Da dialysis bags.

[0053] (2) Preparation of acryloyl gelatin

[0054] The above-mentioned 8000Da-12000Da small molecule gelatin was dissolved in 0.1 M PBS buffer (pH 7.4) in a constant temperature water bath at 40°C and magnetically stirred until completely dissolved to obtain a 5% (w / v) gelatin solution. The pH of the gelatin solution was adjusted to 8.5 by adding MAA (methacrylic anhydride) at a rate of 10% of the gelatin mass. MAA was slowly dripped into the gelatin solution through a constant pressure dropping funnel (dropping rate of 1 drop / second) while magnetically stirring (300 rpm) to ensure uniform dispersion of MAA. The reaction was maintained at 40°C in a water bath at pH 8.5. After the addition was complete, the reaction was continued at 40°C in a water bath at pH 8.5 for 1.5 hours. 1M HCl solution was added to adjust the pH of the system to 7.0 (neutral) to terminate the reaction. Add deionized water to dilute the solution. Use 8000 Da and 12000 Da dialysis bags to collect 8000 Da to 12000 Da acryloyl gelatin. Analyze by 1H NMR. Dissolve 10 mg of freeze-dried acryloyl gelatin in 0.5 mL of D2O (heavy water) on a 400 MHz NMR spectrometer. The characteristic peak area of ​​4.5 ppm ± 0.5 is S1. The degree of substitution (DS) = (S1 / 2) × 100% = 9.7%.

[0055] 2. Preparation of Acryloyl-Polylysine-Polyphenylalanine Polypeptide Microcapsules

[0056] (1) Preparation of acryloyl-polylysine-polyphenylalanine peptide

[0057] Methacryl-modified polylysine (20%-30% substitution degree, 5000 Da) was reacted with phenylalanine (Phe) in a weight ratio of 5:2.

[0058] Phenylalanine was dissolved in 0.1 mol / L MES buffer (pH 5.5) with the aid of DMF dropwise addition and magnetic stirring until clear. Phe: 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC): N-hydroxysuccinimide (NHS) was dissolved in a molar ratio of 1:1.2:1.2 and stirred at room temperature (25°C) in the dark for 2 h.

[0059] Dissolve methacryloyl polylysine in 0.1 M PBS buffer (pH 7.4) and stir in a 40°C water bath until the solution is completely dissolved. Slowly drop the above-mentioned activated Phe-NHS solution system into the methacryloyl polylysine solution. After the addition is complete, adjust the pH of the system to 7.4 with 1 M NaOH and stir at room temperature in the dark for 12 hours.

[0060] Use 5000Da and 6000Da dialysis bags to collect 5000Da~6000Da acrylamide-polylysine-polyphenylalanine polypeptides.

[0061] (2) The preparation of acrylamide-polylysine-polyphenylalanine polypeptide microcapsules includes the following steps:

[0062] (1) A phosphate buffer solution of 3 mg / mL acrylamide-polylysine-polyphenylalanine polypeptide, the pH of the phosphate buffer solution is 6.7, and a 5% by weight polyazobenzene methyl acrylate ethyl acetate solution is used as the wall material oil phase solution. 1 part by weight of the phosphate buffer solution of acrylamide-polylysine-polyphenylalanine polypeptide is slowly added dropwise to 4 parts by weight of the wall material oil phase solution, and premixed with magnetic stirring to form a preliminary mixed solution while adding dropwise;

[0063] (2) The high-speed shear emulsifier was operated at 8000 rpm for 20 minutes at 25°C ± 2, and then cooled in an ice water bath to avoid heat generation due to shearing and thus denaturation of the polypeptide, thereby forming an oil-in-water (W / O) emulsion.

[0064] (3) Rotate the oil-in-water (W / O) emulsion to slowly evaporate ethyl acetate to obtain a suspension at a temperature of ≤30°C and a vacuum degree of -0.01 MPa to 0.10 MPa;

[0065] (4) The suspension was centrifuged at 5000 rpm for 15 minutes at 3-5°C, the supernatant was discarded, and pH 6.7 PBS buffer was added for re-suspending. Ultrasonic dispersion was performed at 100W for 3 minutes, and the suspension was centrifuged again at 5000 rpm for 15 minutes at 3-5°C. The suspension was washed repeatedly and freeze-dried to obtain dry polypeptide microcapsule powder (sealed and stored in the dark, refrigerated at 4°C).

[0066] Malvern Zetasizer Nano ZS Dynamic Light Scattering (DLS) test, such as Figure 2 The average particle size of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is 2991 nm and PDI is 0.202.

[0067] 3. The preparation of polyethylene glycol polyurethane acrylate comprises the following steps: Table 1 Raw material parameters for the preparation of polyethylene glycol polyurethane acrylate

[0068] Raw material name Specifications / Molecular weight Dosage (g) Molar ratio / functional group Polyethylene glycol (PEG-6000) Analytical grade, Mn=6000 65 -OH: 0.0108 mol Toluene diisocyanate (TDI) Industrial grade, purity ≥99% 13.0 -NCO: 0.0119 mol Dimethylolpropionic acid (DMPA) Analytical grade, purity ≥99% 8 -OH: 0.0615 mol Hydroxypropyl methacrylate (HPMA) Analytical grade, containing inhibitor 16.0 -OH: 0.113 mol Dibutyltin dilaurate (DBTDL) analytically pure 0.1 0.05 wt% Triethylamine (TEA) analytically pure 4.8 Neutralization degree 100% Ethyl acetate Analytical grade, anhydrous 80 solvent Deionized water Resistivity ≥18MΩ・cm 120 -

[0069] (1) Preparation of PEG-polyurethane prepolymer

[0070] Dehydration treatment: 65 g of PEG-6000 was added to the flask and vacuum dehydrated at 120 °C for 2 h (vacuum degree -0.09 MPa), and then cooled to 60 °C.

[0071] Prepolymerization: nitrogen was passed through, 13.0 g TDI and 0.1 g DBTDL were added, the stirring rate was 200 rpm, the oil bath temperature was raised to 80 ° C, and the reaction was carried out for 3 hours. During this period, the FTIR was monitored at 2270 cm -1 When the peak area drops below 10% of the initial value, the prepolymerization is completed.

[0072] Chain extension reaction: cool to 60°C, add 8g DMPA (pre-dissolved in 20mL N,N-dimethylformamide), and heat to 75°C for 2 hours to allow the carboxyl groups to fully react with the remaining -NCO groups.

[0073] (2) Acrylation end-capping and copolymerization

[0074] End-capping reaction: cool the prepolymer to 50°C, add 14.5g HPMA (containing 0.05g hydroquinone inhibitor) dropwise at a rate of 1 drop / second, and after the addition is complete, heat to 65°C and react for 3 hours.

[0075] Neutralization and emulsification: After the reaction is completed, add 4.8g of triethylamine to neutralize the carboxyl group (pH = 7.5-8.0), then slowly add 120g of deionized water under high-speed stirring (1000rpm) to form a stable emulsion;

[0076] After dialysis with a 30,000 Da dialysis bag and a 40,000 Da dialysis bag, 30,000-40,000 Da of dialysate was collected and 120 g of deionized water was added to form a stable emulsion.

[0077] (3) A composition of a high-transmittance crystal extension glue, wherein the composition of the high-transmittance crystal extension glue comprises the following components:

[0078] 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate (calculated by dry weight), 70 parts by weight of acryloyl gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of photoinitiator and 60 parts by weight of diluent. The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0079] The method for photoinitiated polymerization of a composition of a high-transmittance crystal extension glue comprises the following steps: uniformly mixing the composition of the high-transmittance crystal extension glue, and irradiating the composition under a light intensity of 40 mW / cm at 365 nm. 2 Irradiate for 60 seconds.

[0080] After the composition of the high-transmittance crystal extension glue is mixed according to the weight ratio, the formed photoinitiated polymer is subjected to infrared detection, and the results are as follows Figure 3 As shown by Figure 3 It was found that double bond polymerization occurred among acryloyl-polylysine-polyphenylalanine polypeptide, PEGylated polyurethane acrylate, and acryloyl gelatin.

[0081] Example 2

[0082] As a high-transmittance crystal extension glue of an embodiment of the present invention, the only difference between this embodiment and Example 1 is that the weight ratio of the acrylamide-polylysine-polyphenylalanine polypeptide microcapsules in the high-transmittance crystal extension glue composition is different:

[0083] 60 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 70 parts by weight of acryloyl gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of photoinitiator and 60 parts by weight of diluent. The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0084] Example 3

[0085] As a high-transmittance crystal extension glue of an embodiment of the present invention, the only difference between this embodiment and Example 1 is that the weight ratio of the acrylamide-polylysine-polyphenylalanine polypeptide microcapsules in the high-transmittance crystal extension glue composition is different:

[0086] 70 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 70 parts by weight of acryloyl gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of photoinitiator and 60 parts by weight of diluent. The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0087] Example 4

[0088] As a high-transmittance crystal extension glue of an embodiment of the present invention, the only difference between this embodiment and Example 1 is that the weight ratio of the acrylamide-polylysine-polyphenylalanine polypeptide microcapsules in the high-transmittance crystal extension glue composition is different:

[0089] 90 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 70 parts by weight of acryloyl gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of photoinitiator and 60 parts by weight of diluent. The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0090] Example 5

[0091] As a high-transmittance crystal extension glue of an embodiment of the present invention, the only difference between this embodiment and Example 1 is that the weight of acryloyl gelatin (GelMA) in the high-transmittance crystal extension glue composition is different:

[0092] 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 60 parts by weight of acryloyl gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of photoinitiator and 60 parts by weight of diluent. The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0093] Comparative Example 1

[0094] As a comparative example, a highly transparent crystal extension glue is prepared. The only difference between this comparative example and Example 1 is that 80 parts by weight of acrylyl-polylysine is used to replace 80 parts by weight of acrylyl-polylysine-polyphenylalanine polypeptide microcapsules.

[0095] The preparation method is as in Example 1.

[0096] High-transparency crystal extension glue polymer is as shown in Formula V:

[0097] .

[0098] Comparative Example 2

[0099] As a comparative example, a high-transmittance crystal extension glue is used. The only difference between this comparative example and Example 1 is:

[0100] The high-transmittance crystal extension glue composition includes: 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of polyethylene glycol polyurethane acrylate, 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of photoinitiator and 60 parts by weight of diluent. The capsule wall material of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0101] High-transparency crystal extension glue polymer is as shown in Formula VI:

[0102] .

[0103] Comparative Example 3

[0104] As a comparative example, a high-transmittance crystal extension glue is used. The only difference between this comparative example and Example 1 is:

[0105] 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide, 100 parts by weight of PEGylated polyurethane acrylate, 70 parts by weight of acryloylated gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of a photoinitiator (TPO-L) and 60 parts by weight of a diluent (hydroxypropyl methacrylate (HPMA)). This means that the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules in Example 1 were replaced with the acryloyl-polylysine-polyphenylalanine polypeptide.

[0106] Comparative Example 4

[0107] As a comparative example, a high-transmittance crystal extension glue is used. The only difference between this comparative example and Example 1 is:

[0108] 100 parts by weight of polyethylene glycolated polyurethane acrylate, 70 parts by weight of acryloylated gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of photoinitiator and 60 parts by weight of diluent. The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0109] High-transparency crystal extension glue polymer is as shown in Formula VII:

[0110]

[0111] Comparative Example 5

[0112] As a comparative example, a high-transmittance crystal extension glue is prepared. The only difference between this comparative example and Example 1 is that the composition of the high-transmittance crystal extension glue includes the following components:

[0113] 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 70 parts by weight of acryloyl gelatin (GelMA), 3 parts by weight of photoinitiator and 60 parts by weight of diluent. The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0114] Performance test experimental method:

[0115] The samples to be tested are the high-transmittance crystal extension glue after photoinitiated polymerization of Examples 1 to 5 and Comparative Examples 1 to 5.

[0116] 1. Wear resistance test

[0117] This experiment uses the P-228 abrasion tester produced by Fu Chien Company for testing. Three parallel groups are set up and the average value is taken.

[0118] The prepared raw material was evenly coated on a PS substrate using a wire rod coater, with the film thickness controlled at 20 μm. The film was then photocured. After 24 hours, 0000# steel wool was used as the wear test material. The wool was tied to the wiping head of an automatic abrader with a load of one kilogram. The paint film was rubbed back and forth until it was completely worn through. The number of rubs was recorded as the wear resistance test result. The number of wear-throughs was recorded.

[0119] Test environment conditions: temperature 25±2℃, humidity 40%~50%RH;

[0120] Judgment requirements: The sample must not expose the base material within the standard number of revolutions.

[0121] Polyethylene glycol polyurethane acrylate was used as a blank control.

[0122] 2. Flexibility test

[0123] Apply the prepared high-transparency crystal extension adhesive to an A4 sheet to a thickness of 30μm. Curing with a lamp for 30 seconds, cut into dumbbell-shaped strips (Type 5, GB / T 1040.2) with a total length of 75mm, a parallel section length of 25mm, a width of 4mm, and a transition radius of 10mm. Fold the strip 180° along the centerline and bond it flat. Fold the A4 sheet inward 20 times, then fold the high-transparency crystal extension adhesive inward 20 times. Set up three parallel strips and take the average value.

[0124] After folding in half, place the sample in an environment with a temperature of (23 ± 2)°C and a relative humidity of (50 ± 5)% for 4 hours before testing. Calculate the tensile strength (σ) of each sample using a tensile speed of 50 mm / min, as per GB / T 1040.1-2018.

[0125] The sample that was not folded in half in Example 1 was used as a control to obtain σ0.

[0126] Flexibility ratio = σ / σ0 × 100%.

[0127] Pegylated polyurethane acrylate was used as a control.

[0128] 3. Air permeability test

[0129] Detailed test method based on GB / T 1038-2000 "Plastic film and sheeting gas permeability test method pressure difference method"

[0130] 1. Sample size: 100 mm square, thickness: use a screw micrometer to measure 5 points at different positions of the sample and take the average value (accurate to 0.001 mm). The thickness unevenness should be ≤5%.

[0131] Remove oil and dust from the sample surface. Before testing, condition the sample in an environment of (23±2)℃ and relative humidity of (50±5)% for 48 hours.

[0132] 2. Test method steps (differential pressure method)

[0133] (1) Instrument and parameter settings

[0134] Equipment: Gas permeability tester (e.g., differential pressure gas permeability tester), equipped with: Test chamber: divided into a high-pressure side (upstream) and a low-pressure side (downstream), sealed in between by a sample clamping device; Vacuum system: capable of pumping the downstream pressure to ≤10⁻³Pa; Gas source: Test gas N2 purity ≥99.99%, pressure control accuracy ±0.1 kPa; Constant temperature system: Temperature control range (23±0.5)°C, humidity control (if required) ±2% RH.

[0135] (1) Testing process

[0136] Sample installation: Clamp the sample between the test chambers to ensure there is no air leakage at the edges. Apply vacuum grease to seal the test surface to avoid contamination. Check the sealing (the pressure drop rate after vacuuming should be ≤0.1 Pa / min).

[0137] Vacuuming: Evacuate the downstream side (low-pressure chamber) to ≤10⁻³ Pa and maintain for 30 minutes to remove residual gas and moisture. Temporarily seal the upstream side. Introducing test gas: Introduce test gas into the upstream side (high-pressure chamber) until the set pressure (0.1 MPa absolute) is reached. Meanwhile, continue evacuating the downstream side.

[0138] Data collection: When the downstream pressure changes linearly with time, record the pressure-time curve (collect at least 5 data points, and the linear correlation coefficient R² ≥ 0.99).

[0139] Calculate the air permeability coefficient:

[0140] Gas permeability , Unit: Common

[0141] (Where: Δp is the downstream pressure change (Pa), V is the downstream volume (m³), L is the sample thickness (m), A is the effective area (m²), Δt is the time interval (s), is standard atmospheric pressure (101325 Pa), is the upstream and downstream pressure difference (Pa)

[0142] 4. Biosafety Test (Cytotoxicity Test)

[0143] Test samples: Highly transparent crystal extension glue after photoinitiated polymerization from Examples 1-5 and Comparative Examples 1-5. Serum-containing MEM cell culture medium (10 mL for 1 g of extension glue) was ultrasonically extracted for 20 minutes, and the extract was collected for testing.

[0144] Cell line: L929 mouse fibroblasts (adherent growth).

[0145] Method: MTT method (tetrazolium colorimetric method)

[0146] Cell seeding: 96-well plate, density 5×10 4 cells / mL, cultured for 24 h;

[0147] Exposure treatment: Add sample extract (100 μL / well), set the extract as a negative control, and continue culturing for 48 h.

[0148] Pegylated polyurethane acrylate served as a positive control.

[0149] Detection: Add MTT solution (5 mg / mL), incubate for 4 h, discard the supernatant, add DMSO to dissolve formazan, and measure the absorbance (OD value) at 570 nm with a microplate reader.

[0150] Relative cell proliferation rate (RGR) = (mean OD of sample group / mean OD of negative control group) × 100%;

[0151] Table 2 Performance of high-transparency crystal extension glue

[0152] sample Wear resistance (times) Flexibility (ratio %) <![CDATA[Gas permeability Q (10 -15 cm²·s·Pa)]]> Relative cell proliferation rate (RGR)% Example 1 370 87.9 13.80 99.9 Example 2 374 83.6 13.10 99.9 Example 3 378 86.5 13.86 99.9 Example 4 379 82.8 13.21 99.9 Example 5 378 85.4 13.58 99.9 Comparative Example 1 375 66.4 10.34 94.1 Comparative Example 2 374 58.4 9.50 93.8 Comparative Example 3 372 74.9 11.93 94.4 Comparative Example 4 372 57.6 9.26 92.6 Comparative Example 5 379 78.7 12.66 95.3 Reference substances 383 50.5 7.83 87.6

[0153] The highly transparent crystal extension glue of the present invention is formed by photoinitiated polymerization of polyethylene glycol-modified polyurethane polyacrylate, acrylated gelatin (GelMA), and acryloyl-polylysine-polyphenylalanine polypeptide. After polymerization, polyurethane segments, gelatin segments, and polylysine-polyphenylalanine segments are formed, retaining the biocompatibility and water solubility of gelatin, and synergistically improving the flexibility, air permeability, and biosafety of the highly transparent crystal extension glue.

[0154] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A high-transmittance crystal extension glue, characterized in that: The polymer after light-curing polymerization of the high-transmittance crystal extension glue includes a polymer as shown in Formula I, Formula I, wherein 20≤x≤30, 5≤y≤20, 3≤z≤8, 2≤l≤5, 15≤m≤30, 15≤n≤30, 15≤k≤30, and 45≤m+n+k≤80; R1 is a chain segment of polyether diol, R2 is a benzene ring structure of toluene diisocyanate or an alicyclic structure of isophorone diisocyanate or a straight-chain aliphatic carbon chain, R3 is a carbon chain of hydroxyl-containing acrylate, Gelatin represents a molecular chain segment of gelatin, and PEG is a polyvinyl alcohol chain segment.

2. The high-transmittance crystal extension glue according to claim 1, characterized in that: The chain segment of the polyether diol is , 3≤a≤10 or -O-CO-R-CO-O-, R is an aliphatic carbon chain or an aromatic ring; R3 is -CH2CH2- or -CH2CH2CH2- or -CH2CH2CH2CH2-.

3. The high-transmittance crystal extension glue according to claim 1, characterized in that: High-transparency crystal extension glue is made of polyethylene glycol polyurethane polyacrylate, acryloyl gelatin (GelMA), and acryloyl-polylysine-polyphenylalanine polypeptide photoinitiated polymerization; The structural diagram of acryloyl gelatin (GelMA) is shown in Formula II. Formula II, the molecular weight of the acryloyl gelatin is 8000~15000Da, and the degree of acryloyl substitution of the acryloyl gelatin is 8%~15%.

4. A composition of high-transmittance crystal extension glue, characterized in that: The composition of the high-transmittance crystal extension glue includes the following components: 60-90 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 50-80 parts by weight of acryloyl gelatin (GelMA), 0.2-1 parts by weight of isobornyl acrylate, 1-5 parts by weight of a photoinitiator, and 50-80 parts by weight of a diluent; The structural diagram of acryloyl gelatin (GelMA) is shown in Formula II. Formula II, the molecular weight of the acryloyl gelatin is 8000~15000Da, and the degree of acryloyl substitution of the acryloyl gelatin is 8%~15%; The chemical structure of PEGylated polyurethane polyacrylate is shown in Formula III; Formula III; the chemical structure of the acryloyl-polylysine-polyphenylalanine polypeptide is as shown in Formula IV; ； Among them, 20≤x≤30, 5≤y≤20, 15≤m≤30, 15≤n≤30, 15≤k≤30, and 45≤m+n+k≤80; R1 is a chain segment of polyether diol, R2 is a benzene ring structure of toluene diisocyanate or an alicyclic structure of isophorone diisocyanate or a straight-chain aliphatic carbon chain, and R3 is a carbon chain of hydroxyl-containing acrylate; the chain segment of polyether diol is , 3≤a≤10 or -O-CO-R-CO-O-, R is an aliphatic carbon chain or an aromatic ring; R3 is -CH2CH2- or -CH2CH2CH2- or -CH2CH2CH2CH2-; PEG is a polyvinyl alcohol segment; The particle size of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is 1-8 μm, and the capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is a polymer containing a coumarin group.

5. The composition according to claim 4, characterized in that The composition of the high-transmittance crystal extension glue includes the following components: 70-80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of pegylated polyurethane acrylate, 60-70 parts by weight of acryloyl gelatin (GelMA), 0.2-1 parts by weight of isobornyl acrylate, 1-5 parts by weight of a photoinitiator, and 50-80 parts by weight of a diluent.

6. The composition according to claim 5, characterized in that The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate, the photoinitiator is 1173 photoinitiator or TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

7. The composition according to claim 4, characterized in that The preparation method of acrylamide-polylysine-polyphenylalanine polypeptide microcapsules comprises the following steps: (1) A phosphate buffer solution of 1-5 mg / mL acrylamide-polylysine-polyphenylalanine polypeptide, a pH of 6.5-7.0, and a 4%-6% by mass polyazobenzene methyl acrylate ethyl acetate solution as the wall material oil phase solution. 1 part by weight of the phosphate buffer solution of acrylamide-polylysine-polyphenylalanine polypeptide is slowly added dropwise to 3.5-5 parts by weight of the wall material oil phase solution, and premixed by magnetic stirring to form a preliminary mixed solution while adding dropwise; (2) The speed of the high-speed shear emulsifier is 7000 rpm~10000 rpm, and the shearing time is 15~30 minutes. The temperature is 25℃±2, and the temperature is cooled in an ice water bath to avoid shear heat generation that may cause polypeptide denaturation and form a water-in-oil (W / O) emulsion. (3) Rotate the oil-in-water (W / O) emulsion to slowly evaporate ethyl acetate to obtain a suspension at a temperature of ≤30°C and a vacuum degree of -0.01 MPa to 0.10 MPa; (4) Centrifuge the suspension at 4000 rpm to 6000 rpm for 12 to 20 minutes at 3 to 5°C, discard the supernatant, and resuspend in PBS buffer at pH 6.5 to 7.

0. Disperse the suspension by ultrasonic treatment at 80 to 120 W for 2.5 to 5 minutes, then centrifuge again. Repeat the washing and freeze-drying to obtain dry polypeptide microcapsule powder (storage in a sealed container away from light and refrigerate at 4°C).

8. The composition according to claim 4, characterized in that The preparation method of the acryloyl-polylysine-polyphenylalanine polypeptide comprises the following steps: carrying out peptide bond condensation reaction between methacrylylated polylysine (PLMA) and phenylalanine.

9. The composition according to claim 4, characterized in that The weight average molecular weight of the polyethylene glycol polyurethane acrylate is 15 kDa~100 kDa.

10. The method for photoinitiated polymerization of the composition of the high-transmittance crystal extension adhesive according to any one of claims 4 to 9, characterized in that: The method comprises the following steps: applying the high-transmittance crystal extension glue as claimed in any one of claims 4 to 8 under a light intensity of 30 to 60 mW / cm at 360 to 370 nm; 2 Irradiate for 30 to 90 seconds to obtain the high-transmittance crystal extension glue as described in any one of claims 1 to 3.

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