Highly water permeable crystal extending adhesive composition, and preparation method and application thereof

Abstract

The application provides a high-water-permeable crystal extension glue composition and a preparation method and application thereof, the high-water-permeable crystal extension glue is prepared by photo-initiated polymerization of polyethylene glycol polyurethane polyacrylate, acrylated gelatin (GelMA) and acryl-polylysine-polyphenylalanine polypeptide; and the polymer after photo-curing polymerization of the high-water-permeable crystal extension glue comprises a polymer shown in formula I. The high-water-permeable crystal extension glue is prepared by photo-initiated polymerization of polyethylene glycol polyurethane polyacrylate, acrylated gelatin (GelMA) and acryl-polylysine-polyphenylalanine polypeptide, and after polymerization, polyurethane segments, gelatin segments and polylysine-polyphenylalanine segments are formed, the biocompatibility and water solubility of gelatin are retained, and the flexibility, air permeability and biological safety performance of the high-water-permeable crystal extension glue are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nail polish, in particular to a high-permeability crystal nail extender composition, a preparation method and application thereof. BACKGROUND

[0002] Polyurethane ultraviolet curing nail polish is widely used due to its good strength and flexibility. However, the poor air permeability of the polyurethane ultraviolet curing nail polish easily leads to nail dehydration, brittleness and yellowing, and the modification of the polyurethane ultraviolet curing nail polish has a negative impact on the strength and flexibility of the polyurethane ultraviolet curing nail polish. SUMMARY

[0003] The present application aims to overcome the shortcomings of the prior art and provide a high-permeability crystal nail extender composition, a preparation method and application thereof.

[0004] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows: a high-permeability crystal nail extender, the polymer after photopolymerization of the high-permeability crystal nail extender 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 segment of polyether glycol, 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 containing hydroxyl acrylate, Gelatin represents a molecular segment of gelatin, and PEG is a polyethylene glycol segment.

[0008] The high-permeability crystal nail extender is formed by photopolymerization of polyethylene glycolized polyurethane polyacrylate, acrylated gelatin (GelMA), acryl-polylysine-polyphenylalanine polypeptide, and includes a polyurethane segment, a gelatin segment and a polylysine-polyphenylalanine segment after polymerization, thereby retaining the biocompatibility and water solubility of gelatin and synergistically improving the flexibility, air permeability and biological safety of the high-permeability crystal nail extender.

[0009] Preferably, the segment of 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 water permeable crystal extension glue is prepared by acrylation of gelatin (GelMA) through acryl-polylysine-polyphenylalanine polypeptide photoinitiated polymerization.

[0011] The structural diagram of the acrylated gelatin (GelMA) is shown in Formula II,

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

[0013] The application also provides a high water permeable crystal extension glue composition, the high water permeable crystal extension glue composition comprising the following components:

[0014] 60-90 parts by weight of acryl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of polyglycolated polyurethane acrylate, 50-80 parts by weight of acrylated gelatin (GelMA), 0.2-1 part 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 the acrylated gelatin (GelMA) is shown in Formula II,

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

[0017] The chemical structure of the polyglycolated polyurethane acrylate is shown in Formula III;

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

[0019] ;

[0020] Wherein, 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 segment of polyether glycol, 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 containing a hydroxyl acrylate; the segment of the polyether glycol is , 3≤a≤10 or -O-CO-R-CO-O-, R is a fatty carbon chain or an aromatic ring; R3 is -CH2CH2- or -CH2CH2CH2- or -CH2CH2CH2CH2-, PEG is a polyethylene glycol segment;

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

[0024] The light-induced polymerization component of the composition of the high-water-permeable crystal extension glue is a polyglycolated polyurethane polyacrylate, acrylated gelatin (GelMA), and acryl-polylysine-polyphenylalanine polypeptide, which, after polymerization, forms a polyurethane segment, a gelatin segment, and a polylysine-polyphenylalanine segment, retains the biocompatibility and water solubility of gelatin, and synergistically improves the flexibility, air permeability, and biological safety performance of the high-water-permeable crystal extension glue. The acryl-polylysine-polyphenylalanine polypeptide has undergone molecular denaturation, and the acryl-polylysine-polyphenylalanine polypeptide microcapsule forms a microcapsule wall material of a polymer containing a coumarin group to protect the acryl-polylysine-polyphenylalanine polypeptide, and in the process of light-induced polymerization, the microcapsule wall material is cracked to release the acryl-polylysine-polyphenylalanine polypeptide, which not only avoids the influence of the deformation of the acryl-polylysine-polyphenylalanine polypeptide on the performance of the high-water-permeable crystal extension glue after polymerization, but also does not affect the process of light-induced polymerization.

[0025] Preferably, 70-80 parts by weight of acryl-polylysine-polyphenylalanine polypeptide microcapsule, 100 parts by weight of polyglycolated polyurethane acrylate, 60-70 parts by weight of acrylated gelatin (GelMA), 0.2-1 part by weight of isobornyl acrylate, 1-5 parts by weight of a photoinitiator, and 50-80 parts by weight of a diluent.

[0026] The above weight ratio of polyglycolated polyurethane acrylate, acrylated gelatin (GelMA), and acryl-polylysine-polyphenylalanine polypeptide can better synergistically improve the flexibility, air permeability, and biological safety performance of the high-water-permeable crystal extension glue.

[0027] Preferably, the capsule wall material of the acryl-polylysine-polyphenylalanine polypeptide microcapsule is polyazobenzyl acrylate containing a coumarin group, the photoinitiator is 1173 photoinitiator or TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

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

[0029] (1) 1-5 mg / mL acryl-polylysine-polyphenylalanine polypeptide phosphate buffer solution, the pH of the phosphate buffer is 6.5-7.0, 4%-6% polyazo benzyl methacrylate ethyl acetate solution containing coumarin groups as a wall material oil phase solution, 1 part by weight of the acryl-polylysine-polyphenylalanine polypeptide phosphate buffer solution is slowly added to 3.5-5 parts by weight of the wall material oil phase solution, and the preliminary mixed solution is formed by premixing while adding and stirring magnetically;

[0030] (2) 7000-10000 rpm of high-speed shearing emulsifier, shearing for 15-30 minutes, 25℃±2, ice water bath cooling, avoiding polypeptide denaturation caused by shearing heat, forming an emulsion;

[0031] (3) the emulsion is slowly evaporated by rotary evaporation to obtain a suspension, the temperature is ≤30℃, and the vacuum degree is -0.01 MPa to 0.10 MPa;

[0032] (4) the suspension is centrifuged at 4000-6000 rpm for 12-20 minutes at 3-5℃, the supernatant is discarded, and then PBS buffer solution with a pH of 6.5-7.0 is added to resuspend, and the polypeptide microcapsule powder is obtained by repeating the steps of ultrasonic dispersion at 80-120 W for 2.5-5 minutes, centrifugation and freeze-drying.

[0033] The dried polypeptide microcapsule powder is sealed, stored in the dark, and refrigerated at 4℃ for standby use.

[0034] Preferably, the preparation method of the acryl-polylysine-polyphenylalanine polypeptide comprises the following steps: methacrylating polylysine (PLMA) and phenylalanine are subjected to a peptide bond condensation reaction.

[0035] Preferably, the weight average molecular weight of the polyethylene glycolized polyurethane acrylate is 15-100 kDa.

[0036] The application also provides a photopolymerization method of the composition of any one of the high-water-permeable crystal extending adhesives, and the method comprises the following steps: the high-water-permeable crystal extending adhesive is irradiated at a light intensity of 360-370 nm for 30-60 mW / cm 2 for 30-90 seconds to obtain the high-water-permeable crystal extending adhesive.

[0037] The application has the beneficial effects that the application provides a high-water-permeable crystal extension glue composition, a preparation method and application thereof. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 It is a structure diagram of the polymer of the high-water-permeable crystal extension glue after photopolymerization in the high-water-permeable crystal extension glue composition of the application.

[0039] Figure 2 It is a dynamic light scattering (DLS) test result diagram of the acryl-polylysine-polyphenylalanine polypeptide microcapsule in the high-water-permeable crystal extension glue composition of the application.

[0040] Figure 3 It is an infrared spectrum diagram of the polymer of the high-water-permeable crystal extension glue after photopolymerization in the application. DETAILED DESCRIPTION

[0041] For the purpose, technical scheme and advantages of the application, the application will be further described below in combination with specific embodiments.

[0042] Embodiment 1

[0043] (1) As a high-water-permeable crystal extension glue of the application, the polymer of the high-water-permeable crystal extension glue after photopolymerization includes a polymer as shown in formula I,

[0044] ; Formula I, wherein 20≤x≤30, 5≤y≤20, 3≤z≤8, 2≤l≤5,

[0045] 15≤m≤30, 15≤n≤30, 15≤k≤30, and 45≤m+n+k≤80;

[0046] R1 is , 3≤a≤10; R2 is a benzene ring structure of toluene diisocyanate, and R3 is -CH2CH2CH2-.

[0047] Gelatin represents a molecular chain segment of gelatin, and a structure diagram of acrylated gelatin (GelMA) is as shown in formula II,

[0048] Formula II, the molecular weight of acrylated gelatin is 8000-12000 Da, and the acrylated gelatin has an acrylated substitution degree of 8%-15%.

[0049] (II) Preparation of the high-water-permeable crystal extension glue of the embodiment

[0050] 1. Preparation of acrylated gelatin (GelMA)

[0051] (1) Preparation of 8000 Da-12000 Da small molecular gelatin

[0052] The macromolecular gelatin was magnetically stirred in a constant-temperature water bath at 55°C until the gelatin was completely dissolved to obtain a 10% (w / v) gelatin solution. The gelatin solution was cooled to 37°C, and the pH was adjusted to 8.0 with 1M NaOH or 1M HCl. Then, 0.1M PBS buffer (1:1 by volume ratio with the gelatin solution, pH 8.0) was added. The trypsin powder was added at an enzyme-to-substrate mass ratio (E / S) of 1:100, and the enzyme was completely dissolved by magnetic stirring.

[0053] The enzyme reaction was kept at a constant temperature of 37°C, and the reaction was magnetically stirred for 4 hours. The 8000 Da-12000 Da small molecular gelatin was collected by using a dialysis bag with a molecular weight cutoff of 8000 Da and a dialysis bag with a molecular weight cutoff of 12000 Da.

[0054] (2) Preparation of acrylated gelatin

[0055] The above-mentioned 8000 Da-12000 Da small molecular gelatin was dissolved in 0.1M PBS buffer (pH 7.4) in a constant-temperature water bath at 40°C by magnetic stirring until it was completely dissolved to obtain a 5% (w / v) gelatin solution. The pH of the gelatin solution was adjusted to 8.5. MAA (methyl acrylate) was added at 10% of the mass of the gelatin, and the MAA was slowly dropped into the gelatin solution through a constant-pressure dropping funnel (dropping speed of 1 drop per second) while being magnetically stirred (300 rpm) to ensure uniform dispersion of the MAA. After the dropping was completed under the conditions of a 40°C water bath and pH 8.5, the reaction was continued for 1.5 hours under the conditions of a 40°C water bath and pH 8.5. Then, 1M HCl solution was added to adjust the pH of the system to 7.0 (neutral) to terminate the reaction. Deionized water was added to dilute the solution, and the 8000 Da-12000 Da acrylated gelatin was collected by using a dialysis bag with a molecular weight cutoff of 8000 Da and a dialysis bag with a molecular weight cutoff of 12000 Da. The acrylated gelatin was detected by 1H NMR method. 10 mg of the freeze-dried acrylated gelatin was dissolved in 0.5 mL of D2O (heavy water), and the test was performed on a 400 MHz nuclear magnetic resonance instrument. The characteristic peak area at 4.5 ppm±0.5 was S1. The substitution degree DS=(S1 / 2)×100%=9.7%.

[0056] 2. Preparation of acryl-polylysine-polyphenylalanine polypeptide microcapsules

[0057] (1) Preparation of acryloyl-polylysine-polyphenylalanine polypeptide

[0058] Methacrylated polylysine (20%~30% degree of substitution, 5000 Da,) was reacted with phenylalanine (Phe) at a weight ratio of 5:2.

[0059] Phenylalanine was dissolved with the aid of DMF dropwise from 0.1 mol / L MES buffer (pH 5.5), magnetically stirred to clarify, Phe: 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC): N-hydroxysuccinimide (NHS) molar ratio = 1:1.2:1.2, stirred at room temperature (25°C) for 2 hours in the dark;

[0060] Methacrylated polylysine was dissolved in 0.1 M PBS buffer (pH 7.4), stirred in a 40°C water bath until the solution was completely dissolved, and the above-mentioned activated Phe-NHS solution system was slowly added dropwise into the methacrylated polylysine solution. After the dropwise addition was completed, the pH of the system was adjusted to 7.4 with 1 M NaOH, and the system was stirred at room temperature for 12 hours in the dark.

[0061] Acryloyl-polylysine-polyphenylalanine polypeptide with a molecular weight of 5000 Da~6000 Da was collected using a dialysis bag with a molecular weight of 5000 Da and a dialysis bag with a molecular weight of 6000 Da.

[0062] (2) Preparation of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules includes the following steps:

[0063] (1) 3 mg / mL acryloyl-polylysine-polyphenylalanine polypeptide phosphate buffer solution, the pH of the phosphate buffer solution is 6.7, and 5% polyazobenzyl acrylate ethyl acetate solution containing coumarin groups as wall material oil phase solution. 1 part by weight of acryloyl-polylysine-polyphenylalanine polypeptide phosphate buffer solution was slowly added to 4 parts by weight of wall material oil phase solution, and the preliminary mixture was formed by pre-mixing while stirring with a magnetic stirrer.

[0064] (2) High-speed shearing emulsifier speed 8000 rpm, shearing for 20 minutes, 25°C±2, ice water bath cooling to avoid denaturation of polypeptide caused by shearing heat, forming an emulsion;

[0065] (3) The emulsion was slowly evaporated by rotary evaporation to obtain a suspension, the temperature was ≤30°C, and the vacuum degree was -0.01 MPa~0.10 MPa;

[0066] (4) Centrifuge the suspension at 5000 rpm for 15 minutes at 3-5 °C, discard the supernatant, resuspend with PBS buffer at pH 6.7, disperse by ultrasonic treatment at 100 W for 3 minutes, centrifuge again at 5000 rpm for 15 minutes at 3-5 °C, repeat the washing, freeze-dry to obtain the dry polypeptide microcapsule powder (store in a sealed and light-proof container, refrigerate at 4 °C).

[0067] Malvern Zetasizer Nano ZS dynamic light scattering (DLS) test, such as Figure 2 The average particle size of the acryl-polylysine-polyphenylalanine polypeptide microcapsule was 2991 nm, and the PDI was 0.202.

[0068] 3. Preparation of polyethylene glycol polyurethane acrylate includes the following steps:

[0069]

[0070] (1) Preparation of PEG-polyurethane prepolymer

[0071] Dehydration treatment: add 65 g of PEG-6000 to a flask, dehydrate at 120 °C for 2 hours under vacuum (vacuum degree -0.09 MPa), and cool to 60 °C.

[0072] Prepolymerization: protect with nitrogen, add 13.0 g of TDI and 0.1 g of DBTDL, stir at a rate of 200 rpm, heat to 80 °C in an oil bath, and react for 3 hours. During the reaction, monitor the intensity of the 2270 cm -1 - NCO peak by FTIR, and when the peak area decreases to less than 10% of the initial value, the prepolymerization is complete.

[0073] Chain extension reaction: cool to 60 °C, add 8 g of DMPA (previously dissolved in 20 mL of N,N-dimethylformamide), heat to 75 °C, and react for 2 hours to allow the carboxyl groups to fully react with the remaining -NCO.

[0074] (2) Acrylation end-capping and copolymerization

[0075] End-capping reaction: cool the prepolymer to 50 °C, add 14.5 g of HPMA (containing 0.05 g of hydroquinone polymerization inhibitor) dropwise at a rate of 1 drop per second, and after the addition is complete, heat to 65 °C and react for 3 hours.

[0076] Neutralization and emulsification: after the reaction is complete, neutralize the carboxyl groups by adding 4.8 g of triethylamine (pH = 7.5-8.0), and then slowly add 120 g of deionized water under high-speed stirring (1000 rpm) to form a stable emulsion;

[0077] Dialysis bag 30000 Da, dialysis bag 40000 Da dialysis collection 30000~40000 Da dialysate, add 120 g of deionized water, form stable emulsion.

[0078] (Three) high water permeable crystal extension glue composition, the high water permeable crystal extension glue composition includes the following components:

[0079] 80 parts by weight of acryl-polylysine-polyphenylalanine polypeptide microcapsule, 100 parts by weight of polyethylene glycol polyurethane acrylate (calculated as dry weight), 70 parts by weight of acrylated 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 acryl-polylysine-polyphenylalanine polypeptide microcapsule is polyazobenzyl acrylate containing coumarin group, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0080] The photopolymerization method of the high water permeable crystal extension glue composition includes the following steps: uniformly mixing the high water permeable crystal extension glue composition, irradiating under 365 nm light intensity of 40 mW / cm 2 Irradiate for 60 seconds.

[0081] After the high water permeable crystal extension glue composition is mixed according to the weight ratio, the formed photopolymer is subjected to infrared detection, and the results are shown in Figure 3 As shown in Figure 3 It can be seen that acryl-polylysine-polyphenylalanine polypeptide, polyethylene glycol polyurethane acrylate and acrylated gelatin occur double bond polymerization reaction.

[0082] Example 2

[0083] As a high water permeable crystal extension glue of an embodiment of the application, the only difference between this embodiment and example 1 is that the weight ratio of acryl-polylysine-polyphenylalanine polypeptide microcapsule in the high water permeable crystal extension glue composition is different:

[0084] 60 parts by weight of acryl-polylysine-polyphenylalanine polypeptide microcapsule, 100 parts by weight of polyethylene glycol polyurethane acrylate, 70 parts by weight of acrylated 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 acryl-polylysine-polyphenylalanine polypeptide microcapsule is polyazobenzyl acrylate containing coumarin group, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0085] Example 3

[0086] As a high water permeable crystal extension glue of an embodiment of the present application, the only difference between this embodiment and embodiment 1 is that the weight ratio of acryl-polylysine-polyphenylalanine polypeptide microcapsules in the high water permeable crystal extension glue composition is different:

[0087] 70 parts by weight of acryl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of polyethylene glycol polyurethane acrylate, 70 parts by weight of acrylated gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of a photoinitiator, and 60 parts by weight of a diluent, the capsule wall material of the acryl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzyl acrylate containing a coumarin group, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0088] Example 4

[0089] As a high water permeable crystal extension glue of an embodiment of the present application, the only difference between this embodiment and embodiment 1 is that the weight ratio of acryl-polylysine-polyphenylalanine polypeptide microcapsules in the high water permeable crystal extension glue composition is different:

[0090] 90 parts by weight of acryl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of polyethylene glycol polyurethane acrylate, 70 parts by weight of acrylated gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of a photoinitiator, and 60 parts by weight of a diluent, the capsule wall material of the acryl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzyl acrylate containing a coumarin group, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0091] Example 5

[0092] As a high water permeable crystal extension glue of an embodiment of the present application, the only difference between this embodiment and embodiment 1 is that the weight ratio of acryl-polylysine-polyphenylalanine polypeptide microcapsules in the high water permeable crystal extension glue composition is different:

[0093] 80 parts by weight of acryl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of polyethylene glycol polyurethane acrylate, 60 parts by weight of acrylated gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of a photoinitiator, and 60 parts by weight of a diluent, the capsule wall material of the acryl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzyl acrylate containing a coumarin group, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0094] Comparative Example 1

[0095] As a high water permeable crystal extender of a comparative example, the only difference between this comparative example and Example 1 is that 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is replaced with 80 parts by weight of acryloyl-polylysine.

[0096] The preparation method is referred to Example 1.

[0097] The high water permeable crystal extender polymer is as shown in Formula V:

[0098] .

[0099] Comparative Example 2

[0100] As a high water permeable crystal extender of a comparative example, the only difference between this comparative example and Example 1 is that:

[0101] The high water permeable crystal extender composition includes 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of polyethyleneglycolated 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 the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzyl acrylate containing coumarin groups, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0102] The high water permeable crystal extender polymer is as shown in Formula VI:

[0103] .

[0104] Comparative Example 3

[0105] As a high water permeable crystal extender of a comparative example, the only difference between this comparative example and Example 1 is that:

[0106] 80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide, 100 parts by weight of polyethyleneglycolated polyurethane acrylate, 70 parts by weight of acrylated gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of photoinitiator, and 60 parts by weight of diluent, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA). That is, the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules in Example 1 is replaced with acryloyl-polylysine-polyphenylalanine polypeptide.

[0107] Comparative Example 4

[0108] As a high water permeable crystal extender of a comparative example, the only difference between this comparative example and Example 1 is that:

[0109] 100 parts by weight of polyethylene glycol polyurethane acrylate, 70 parts by weight of acrylated gelatin (GelMA), 0.5 parts by weight of isobornyl acrylate, 3 parts by weight of a photoinitiator, and 60 parts by weight of a diluent, the capsule wall material of the acryl-polylysine-polyphenylalanine polypeptide microcapsule is polyazobenzyl acrylate containing a coumarin group, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0110] A high water permeable crystal extender polymer such as Formula VII:

[0111]

[0112] Comparative Example 5

[0113] As a high water permeable crystal extender of a comparative example, the only difference between this comparative example and Example 1 is that the composition of the high water permeable crystal extender includes the following components:

[0114] 80 parts by weight of acryl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of polyethylene glycol polyurethane acrylate, 70 parts by weight of acrylated gelatin (GelMA), 3 parts by weight of a photoinitiator, and 60 parts by weight of a diluent, the capsule wall material of the acryl-polylysine-polyphenylalanine polypeptide microcapsule is polyazobenzyl acrylate containing a coumarin group, the photoinitiator is TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

[0115] Performance test experimental method:

[0116] The high water permeable crystal extender after photopolymerization of the sample to be tested, Examples 1-5, Comparative Examples 1-5.

[0117] I. Abrasion resistance test

[0118] This experiment uses a P-228 abrasion tester from Fu Chien Company for testing, with three parallel groups set, and the average value is taken.

[0119] The prepared raw materials are uniformly coated on the PS substrate using a wire bar coater, with a film thickness of 20 μm, and are cured by photoinitiation. After 24 hours, 0000# steel wool is used as the abrasion test material, and the wool is tied to the wiping head of an automatic abrasion tester with a weight of one kilogram. The paint film is wiped back and forth until it is completely worn out, and the number of wipes is recorded as the abrasion resistance test result. The number of wear-outs is recorded.

[0120] Test environmental conditions: temperature 25±2℃, humidity 40%~50%RH;

[0121] Judgment requirements: the sample is required to be free of substrate within the standard number of revolutions.

[0122] PEG-PUA as a blank control.

[0123] II. Flexibility Test

[0124] The prepared high water permeable crystal extension adhesive was brushed on A4 paper pieces with a film thickness of 30 pm. After 30 seconds of lamp curing, it was cut into dumbbell-shaped samples (Type 5, GB / T 1040.2) with a total length of 75 mm, a parallel part length of 25 mm, a width of 4 mm, and a transition arc radius of 10 mm. Folded in half along the center line at 180°, the plane was fitted and pasted. The A4 paper was folded inward 20 times, and the high water permeable crystal extension adhesive was folded inward 20 times, with three groups of parallel, and the average value was taken.

[0125] After folding, the test was conducted after 4 h of storage in an environment of (23 ± 2) °C and relative humidity (50 ± 5) %. Referring to GB / T 1040.1-2018, the tensile speed was 50 mm / min; the tensile strength (σ) of each sample was calculated.

[0126] The sample of Example 1 without folding treatment was used as a control to obtain σ0.

[0127] Flexibility ratio = σ / σ0 x 100%.

[0128] PEG-PUA as a blank control.

[0129] III. Air Permeability Test

[0130] Detailed test method based on GB / T 1038-2000 "Plastic film and sheet - Determination of gas transmission - Pressure difference method"

[0131] 1. Sample size: 100 mm square, thickness: measure 5 points at different positions of the sample using a screw micrometer, and take the average value (accurate to 0.001 mm), the thickness unevenness should be ≤5%.

[0132] Remove oil and dust from the surface of the sample, and adjust the state for 48 h in an environment of (23 ± 2) °C and relative humidity (50 ± 5) % before testing.

[0133] 2. Test method steps (pressure difference method)

[0134] (1) Instrument and parameter settings

[0135] Apparatus: gas permeability tester (e.g. pressure difference method gas permeability tester), equipped with: test chamber: divided into high pressure side (upstream) and low pressure side (downstream), sealed by sample clamping device in the middle; vacuum system: downstream pressure can be extracted to ≤10⁻³ Pa; gas source: test gas N2 purity ≥ 99.99%, pressure control accuracy ±0.1 kPa; constant temperature system: temperature control range (23±0.5) ℃, humidity control (if necessary) ±2% RH.

[0136] (1) Test procedure

[0137] Sample installation: clamp the sample between the test chambers, ensure that the edges are air-tight, apply vacuum grease to seal and avoid contamination of the test surface, check the sealing (pressure drop rate after vacuum extraction should be ≤0.1 Pa / min).

[0138] Vacuum extraction: extract the downstream side (low pressure chamber) to ≤ Pa, maintain for 30 min to remove residual gas and moisture; temporarily close the upstream side. Introduce test gas: introduce test gas to the upstream side (high pressure chamber) until the set pressure of 0.1 MPa (absolute pressure) is reached, while the downstream side continues to be vacuumed.

[0139] Data collection: when the downstream side pressure changes linearly with time, record the pressure-time curve (at least 5 data points are collected, linear correlation coefficient R²≥0.99).

[0140] Calculate the gas permeability coefficient:

[0141] Gas permeability , unit: commonly used

[0142] (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 the standard atmospheric pressure (101325 Pa), is the upstream and downstream pressure difference (Pa))

[0143] Four, biological safety test (cytotoxicity test)

[0144] Test sample: high water permeable crystal extension adhesive after photopolymerization of Examples 1-5, Comparative Examples 1-5. Serum-containing MEM cell culture solution (10 mL per 1 g of extension adhesive), ultrasonic extraction for 20 minutes, collect the extraction liquid for testing.

[0145] Cell line: L929 mouse fibroblast cells (adherent growth).

[0146] Method: MTT method (tetrazolium salt colorimetric method)

[0147] Cell inoculation: 96-well plate, density , culture for 24 h;

[0148] Exposure treatment: add sample extract (100 μL / well), set the extract as negative control, continue to culture for 48 h.

[0149] PEGylated polyurethane acrylate as positive control.

[0150] Detection: add MTT solution (5 mg / mL), incubate for 4 h, discard supernatant, dissolve formazan with DMSO, and measure absorbance (OD value) at 570 nm by microplate reader.

[0151] Cell relative growth rate (RGR) = (OD average of sample group / OD average of negative control group) x 100%;

[0152] Table 1 Performance of high-water-permeable crystal extending glue

[0153]

[0154] The high-water-permeable crystal extending glue of the present application is prepared by photoinitiated polymerization of polyethylene glycol polyurethane polyacrylate, acrylated gelatin (GelMA) and acryl-polylysine-polyphenylalanine polypeptide, and forms polyurethane segments, gelatin segments and polylysine-polyphenylalanine segments after polymerization, retains the biocompatibility and water solubility of gelatin, and synergistically improves the flexibility, air permeability and biological safety performance of the high-water-permeable crystal extending glue.

[0155] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A high-transparency crystal extension adhesive, characterized in that, The polymer after photopolymerization of high-transparency crystal extension adhesive includes polymers as shown in Formula I. ； Equation I, where 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 , 3≤a≤10 or -O-CO-R-CO-O-, R is an aliphatic carbon chain or an aromatic ring, R2 is the benzene ring structure of toluene diisocyanate or the aliphatic ring structure of isophorone diisocyanate or a straight-chain aliphatic carbon chain, R3 is -CH2CH2- or -CH2CH2CH2- or -CH2CH2CH2CH2-, Gelatin represents the molecular chain segment of gelatin, and PEG is the polyethylene glycol chain segment.

2. The high-transparency crystal extension adhesive according to claim 1, characterized in that, The high-transparency crystal extension adhesive is composed of polyethylene glycol polyurethane polyacrylate, acrylamide gelatin (GelMA), and acrylamide-polylysine-polyphenylalanine peptide photoinitiated polymerization. The structural diagram of acryloyl gelatin (GelMA) is shown in Formula II. Formula II, the molecular weight of acrylated gelatin is 8000~15000 Da, and the degree of acrylyl substitution of acrylated gelatin is 8%~15%.

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

4. The composition according to claim 3, characterized in that, The composition of the high-transparency crystal extension adhesive includes the following components: 70-80 parts by weight of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules, 100 parts by weight of polyethylene glycol-modified polyurethane acrylate, 60-70 parts by weight of acryloyl-modified gelatin (GelMA), 0.2-1 parts by weight of isoborneol acrylate, 1-5 parts by weight of photoinitiator, and 50-80 parts by weight of diluent.

5. The composition according to claim 4, characterized in that, The capsule wall material of the acryloyl-polylysine-polyphenylalanine polypeptide microcapsules is polyazobenzene methacrylate containing coumarin groups, the photoinitiator is 1173 photoinitiator or TPO-L photoinitiator, and the diluent is hydroxypropyl methacrylate (HPMA).

6. The composition according to claim 3, characterized in that, The preparation method of acryloyl-polylysine-polyphenylalanine polypeptide microcapsules includes the following steps: (1) A phosphate buffer solution of acryloyl-polylysine-polyphenylalanine polypeptide with a concentration of 1~5 mg / mL, the pH of the phosphate buffer solution is 6.5~7.0, and an ethyl acetate solution of coumarin-containing polyazobenzene methacrylate with a mass fraction of 4%~6% is used as the wall material oil phase solution. 1 part by weight of the phosphate buffer solution of acryloyl-polylysine-polyphenylalanine polypeptide is slowly added dropwise to 3.5~5 parts by weight of the wall material oil phase solution, and the mixture is premixed by magnetic stirring while being added dropwise to form a preliminary mixture. (2) The high-speed shear emulsifier operates at a speed of 7000rpm~10000rpm, shearing for 15~30 minutes, at 25℃±2, and is cooled in an ice water bath to avoid the denaturation of peptides caused by shear heat and to form an emulsion. (3) The emulsion was slowly evaporated by rotary evaporation to obtain a suspension at a temperature ≤30℃ and a vacuum of -0.01MPa~0.10MPa; (4) Centrifuge the suspension at 4000rpm~6000rpm for 12~20 minutes at 3~5℃, discard the supernatant, add PBS buffer at pH 6.5~7.0 to resuspend, sonicate at 80~120W for 2.5~5 minutes to disperse, centrifuge again, repeat washing and freeze drying to obtain dried polypeptide microcapsule powder.

7. The composition according to claim 3, characterized in that, The preparation method of the acryloyl-polylysine-polyphenylalanine polypeptide includes the following steps: methacryloyl-polylysine (PLMA) undergoes a peptide bond condensation reaction with phenylalanine.

8. The composition according to claim 3, characterized in that, The weight-average molecular weight of polyethylene glycol-modified polyurethane acrylate is 15kDa~100kDa.

9. A photoinitiated polymerization method for the composition of the high-transparency crystal extension adhesive as described in any one of claims 3 to 8, characterized in that, The method includes the following steps: subjecting the high-transparency crystal extension adhesive composition as described in any one of claims 3 to 8 to a light intensity of 30 to 60 mW / cm at 360 to 370 nm. 2 Irradiation for 30-90 seconds yields the high-transparency crystal extension resin as described in any one of claims 1-2.

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