A photoinitiator and a method for preparing the same

Abstract

The application relates to the field of organic photocuring materials, and particularly relates to a photoinitiator and a preparation method thereof. The photoinitiator proposes an innovative glycosyl-quaternary ammonium salt double modification strategy based on a TPO-L photoinitiator, glycosyl modification units and quaternary ammonium salt groups are simultaneously introduced into the molecular structure of the TPO-L photoinitiator, the glycosyl part improves water solubility and biocompatibility, the quaternary ammonium salt group significantly improves antibacterial performance and reduces the migration rate of the photoinitiator, a synergistic effect is formed, and the comprehensive performance of the photoinitiator is comprehensively optimized.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic photocuring materials, and in particular to a photoinitiator and a preparation method thereof. BACKGROUND

[0002] Photoinitiators play an important role in water-based photocuring applications such as UV-curable coatings, inks, 3D printing, etc. Methyl-substituted benzoyl phenyl phosphonate (TPO-L) photoinitiators are widely used in various photocuring systems due to their high light absorption characteristics and initiation ability. However, TPO-L itself has strong hydrophobicity, low solubility in water-based systems, and poor dispersibility, which leads to insufficient photoinitiation efficiency and limits its application range in water-based photocuring systems. At the same time, TPO-L and some of its derivatives have high migration rates in cured coatings, which poses certain biological safety risks and makes it difficult to meet the application requirements of high safety fields such as medical materials and food packaging.

[0003] To address the above problems, existing technologies mainly focus on introducing hydrophilic groups or using glycosylation strategies to improve the water solubility of TPO-L and other photoinitiators. For example, some studies have used glycosylation to modify small molecule photoinitiators such as Irgacure 2959

Liska, R., Knaus, S., Gruber, H. et al. Carbohydrate modified photoinitiators. Surface Coatings International 83, 297–303 (2000). https: / / doi.org / 10.1007 / BF02692730

Huang X, Zhang Y, Li F, et al. Highly efficient alginate-based macromolecular photoinitiator for crosslinking and toughening gelatin hydrogels. J Polym Sci. 2020; 58: 1439–1449. https: / / doi.org / 10.1002 / pol.20200138

[0004] However, the existing glycosylation photoinitiators and their macromolecular modification systems still have the following shortcomings and deficiencies:

[0005] (1) The photo-initiation efficiency is still limited: although the sugar-modified photo-initiator has certain hydrophilicity, the photo-polymerization rate in aqueous system is still low, which cannot meet the industrial demand of efficient and rapid curing;

[0006] (2) Lack of antibacterial function: neither sugar-modification nor Alg-2959 modification involves or significantly improves the antibacterial activity, which cannot meet the strict requirement of antibacterial property for medical dressings, food packaging, etc.;

[0007] (3) Migration control is still insufficient: some macromolecular modified initiators still have a migration risk of >1%, which cannot completely meet the low migration requirement of sensitive environment (such as food contact materials);

[0008] (4) Limited improvement of biocompatibility: although sugar glycosylation can improve biocompatibility, in actual application with various additives and complex formulations, the overall system biocompatibility and environmental friendliness still need to be further improved. SUMMARY

[0009] In view of the above deficiencies of the existing photo-initiator, the present application provides a photo-initiator and a preparation method thereof.

[0010] The technical scheme of the present application is realized by providing a photo-initiator with the following molecular structure:

[0011]

[0012] wherein R is a sugar group, X- is an anion, R1, R2 and R3 are the same or different C1-C8 straight chain or branched alkyl, benzyl, hydroxyalkyl or substituted benzyl.

[0013] In a preferred embodiment of the present application, the sugar group is a monosaccharide, disaccharide or polysaccharide, and the monosaccharide is glucose, arabinose, galactose or xylose.

[0014] In a preferred embodiment of the present application, R is selected from one of the following groups:

[0015] .

[0016] In a preferred embodiment of the present application, X- is a halide anion, sulfonate ion, carboxylate ion or other inorganic acid ion.

[0017] In a preferred embodiment of the present application, the molecular formula of the photo-initiator is selected from the following:

[0018]

[0019]

[0020]

[0021] .

[0022] In another aspect, the present application also provides a preparation method of the photoinitiator, and the preparation process is as follows:

[0023]

[0024] Specifically, the method comprises the following steps:

[0025] S1, adding NaI into a solvent in which TPO-L is dissolved, and performing a de-ethylation reaction to generate compound 2, and then performing a reaction of the obtained compound 2 and bromoethane to generate intermediate 3;

[0026] S2, performing a reaction of the obtained intermediate 3 and bromoacetylated sugar 4 under the condition of an alkaline catalyst, and then performing purification to obtain TPO-L derivative 5 substituted with acetylated sugar groups;

[0027] S3, dissolving the obtained TPO-L derivative 5 substituted with acetylated sugar groups, and then adding an appropriate amount of an acidic ion exchange resin to hydrolyze and remove acetyl protecting groups, so as to obtain sugar-modified TPO-L derivative 6;

[0028] S4, performing a reaction of the obtained sugar-modified TPO-L derivative 6 and N-bromosuccinimide to generate bromine-containing derivative 7;

[0029] S5, performing a reaction of the obtained bromine-containing derivative 7 and a tri-substituted amine, and then performing purification to obtain quaternary ammonium salt and sugar group substituted derivative 9.

[0030] In a preferred embodiment of the present application, the obtained quaternary ammonium salt and sugar group substituted derivative 9 is further subjected to ion exchange with an ammonium salt containing anions in an aqueous solution to obtain target compound T containing anions.

[0031] Specifically, in a preferred embodiment of the present application, the synthesis method is as follows:

[0032] First step: dissolving TPO-L in a suitable solvent, adding NaI (1 equivalent), and stirring at a suitable temperature. The reaction is carried out at 65°C, and after the reaction is completed, a yellow precipitate is generated. The precipitate is collected by filtration, washed with an appropriate amount of n-hexane to remove unreacted substances, and the washed product is dried at 60°C under vacuum for 24 hours to obtain an intermediate. The yield of this step reaches 90.1%. The obtained intermediate is directly used in the next step reaction.

[0033] Second step: Compound 2 is mixed with bromoethane (1 equivalent) in an appropriate ratio in acetone and stirred at room temperature overnight. After the reaction is complete, the product is isolated by column chromatography, and the appropriate solvent is used to wash and ensure purity.

[0034] Third step: Intermediate 3 is dissolved in acetone in an equivalent ratio with bromoacetyl sugar (1 equivalent), and potassium carbonate (1 equivalent) is added as a basic catalyst. The reaction is continued to stir at room temperature until the reaction is complete. After the reaction is complete, the reaction is dissolved in dichloromethane by solvent extraction, and washed with pure water to remove impurities such as bromide. Then, anhydrous sodium sulfate is used for drying treatment, and finally the solution is concentrated. In the concentrated solution, further purification is carried out by dichloromethane / petroleum ether column chromatography to obtain a TPO-L derivative substituted with a fully acetylated sugar group.

[0035] Fourth step: The resulting TPO-L derivative substituted with a fully acetylated sugar group is dissolved in dichloromethane, an appropriate amount of acidic ion exchange resin is added, and stirred overnight. This reaction causes the acetyl protecting group to hydrolyze and remove the protecting group. After the reaction is complete, the ion exchange resin is removed by filtration to obtain the target product, a sugar-modified TPO-L photoinitiator.

[0036] Fifth step: The sugar-modified TPO-L derivative (compound 6) is dissolved in an appropriate amount of chloroform, and an equimolar amount of N-bromosuccinimide (NBS) is slowly added, and the reaction is stirred at room temperature to generate a bromine-containing derivative (compound 7). After the reaction is complete, the completion of the reaction is confirmed by TLC detection, and the solvent is removed by rotary evaporation. The crude product can be further purified by dichloromethane / petroleum ether column chromatography to obtain a high-purity bromine-containing derivative (compound 7).

[0037] Sixth step: The resulting bromine-containing and sugar-substituted derivative (compound 7) is dissolved in anhydrous ethanol, and an equivalent amount of a tri-substituted amine (such as tributylamine, dimethyl-benzylamine, etc.) is added, and the reaction is stirred at room temperature overnight. After the reaction is complete, the solvent is removed by rotary evaporation to obtain a preliminary quaternary ammonium salt and sugar-substituted derivative (compound 9).

[0038] Seventh step (ion exchange): Compound 9 is dissolved in an appropriate amount of aqueous solution, and various ammonium salt solutions (such as ammonium chloride, ammonium iodide, etc.) are added for ion exchange reaction to generate the target compound T containing different anions. After the ion exchange is complete, the water is removed by freeze-drying or rotary evaporation to obtain the pure product of the target compound T.

[0039] The compound prepared by the present application can be applied as a photoinitiator in the fields of green and environmentally friendly materials, medical coatings, degradable coatings, drug delivery systems, etc.

[0040] The beneficial effects are as follows: the present application first proposes a molecular design strategy for sugar-quinolinol double-modified methyl-substituted benzoyl phenyl phosphonate photoinitiators, which fully utilizes the synergistic effect of sugar modification and quaternary ammonium salt introduction, and brings the following important technical breakthroughs:

[0041] (1) Synergistic innovation of double modification

[0042] Sugar modification unit: improve the solubility and dispersibility of photoinitiators in water-based photocuring system, significantly improve the water solubility and biocompatibility.

[0043] Quaternary ammonium salt group: give the photoinitiator good antibacterial activity, and effectively reduce the migration rate of the photoinitiator through cation exchange, improve the application safety of the photoinitiator in medical, food contact and other high safety fields.

[0044] Synergistic effect of the two: breaking the limitation of single modification initiator in existing technology, which is difficult to balance water solubility, photoinitiation efficiency, low migration and antibacterial property, realizing the synergistic improvement of water solubility, photoinitiation efficiency, low migration and antibacterial property in multiple dimensions.

[0045] (2) Construction of representative compounds and diversity

[0046] A variety of representative compounds are provided, which have structural and functional diversity to meet the specific application needs of different fields (such as medical dressings, food packaging, environmental protection coatings, etc.), significantly improving the scalability and applicability of photoinitiators.

[0047] (3) Excellent multi-dimensional performance

[0048] The photoinitiation efficiency, water solubility, curing rate, film optical quality, migration rate, antibacterial activity and biocompatibility of the representative compounds are systematically evaluated.

[0049] The performance data show that the initiator of the present application exhibits fast curing (curing within 56s), high photoinitiation efficiency (>76%), low migration rate (<1%), antibacterial circle diameter 6-7mm, cell proliferation rate >95% in water-based photocuring system, which is much better than the commercially available TPO-L and the control products such as Alg-2959 reported in the literature. DETAILED DESCRIPTION

[0050] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme of the present application will be described clearly and completely in combination with specific embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0051] The application will be further described in detail below in connection with examples.

[0052] On the basis of compound synthesis, the performance of the glycosyl-quaternary ammonium salt bifunctional modified methyl-substituted benzoyl phenyl phosphonate photoinitiator is tested by the following evaluation methods:

[0053] 1 Water solubility test

[0054] The synthesized photoinitiator sample (10 mg each) is added to 10 mL of deionized water, and after ultrasonic assisted dispersion for 10 min, it is left to stand for 1 h. After filtration with a 0.45 μm filter membrane, the absorbance is measured by a UV-Vis spectrophotometer, and the water solubility is calculated by combining the standard curve, and the average value of three parallel experiments is taken.

[0055] 2 Photoinitiation efficiency test

[0056] In a typical aqueous acrylate photocuring formula (hydroxyethyl acrylate: polyurethane acrylate = 1:1, containing 1.0wt% photoinitiator), the photoinitiator is uniformly mixed and spin-coated on a KBr sheet (thickness about 20 μm). Using 365 nm ultraviolet light (50 mW / cm²) irradiation, the infrared spectrum change of C = C double bond is recorded in real time (RT-FTIR), the double bond conversion rate (DBC) at 60 s and the maximum reaction rate are calculated, and the average value of three parallel experiments is taken.

[0057] 3 UV curing effect test

[0058] The same formula is spin-coated on a PET film (thickness 30 μm), and 365 nm ultraviolet light (50 mW / cm²) is used for irradiation, and the time required for complete curing is recorded, and the optical quality of the film layer is observed, including film surface flatness, uniformity, etc.

[0059] 4 Migration test

[0060] A cured film piece (1x1cm) is prepared, and immersed in deionized water at 37°C for 7 days (water is replaced daily). The concentration of the migrated substance is analyzed by UV-Vis, and the migration rate is calculated, and the average value of three parallel experiments is taken.

[0061] 5 Antibacterial performance test

[0062] Staphylococcus aureus and Escherichia coli are inoculated on agar plates, and a cured photoinitiator film piece (diameter 6 mm) is placed on the surface of the culture medium, and the diameter of the inhibition zone is measured after 24 h of culture at 37°C, and the average value of three parallel experiments is taken.

[0063] 6 Biocompatibility test

[0064] L929 cells were inoculated in 96-well plates, and after 24 h of culture, the membrane pieces were added, and the culture was continued for 24 h. The relative proliferation rate of the cells was determined using the CCK-8 method, and the average value of three parallel experiments was taken.

[0065] Through the above multi-dimensional performance test, the application verifies the comprehensive advantages of the sugar group-quaternary ammonium salt bifunctional modified methyl-substituted benzoyl phenyl phosphonate photoinitiator in water solubility, photoinitiation efficiency, antibacterial activity, low migration and biocompatibility, and proves that the material has broad prospects and practical application value in water-based photocuring application.

[0066] Example 1: Synthesis of TPO-L photoinitiator B-1 modified by β-D-glucosyl and tri-n-butyl quaternary ammonium salt

[0067]

[0068] TPO-L (B-1-1, molecular weight 316.12, 10 g, 31.61 mmol) was dissolved in 50 mL of acetone, and NaI (B-1-2, 10 g, 31.61 mmol) was added. The reaction was stirred at 65°C for 15 minutes, and then the stirring was continued until completion. After the reaction was completed, a yellow precipitate was formed, which was collected by filtration and washed twice with 10 mL of n-hexane to remove unreacted substances. The washed product was dried at 60°C under vacuum for 24 hours to obtain the B-1-2 intermediate.

[0069] B-1-2 (intermediate 31.61 mmol) was mixed with bromoethane (1 equivalent, 5.0 g, 31.61 mmol) in acetone and stirred at room temperature overnight. After the reaction, the key intermediate B-1-3 was obtained by column chromatography. HRMS (ESI+) Calcd for C18H21O4P [M+H]+: 332.1189, Found: 332.1192

[0070] B-1-3 (10 g, 30.12 mmol) was dissolved in 50 mL of acetone with 1-bromo-2, 3, 4, 6-tetra-O-acetyl-α-D-glucose (B-1-4, 10 g, 30.12 mmol) at an equivalent ratio of 1:1, and potassium carbonate (1 equivalent, 4.3 g, 31.61 mmol) was added as a catalyst and stirred at room temperature for 12 hours. After the reaction was completed, the reaction was dissolved in dichloromethane and washed with deionized water to remove impurities. Anhydrous sodium sulfate was used for drying, and finally further separation and purification by dichloromethane / petroleum ether column chromatography was performed to obtain B-1-5 (2, 3, 4, 6-tetra-O-acetyl-α-D-glucose substituted TPO-L derivative). Yield 85%.1 H NMR (500MHz) δ 6.80 (s,1H), 5.70 (s,1H), 5.07 (d, J = 5.5, 2.6 Hz, 1H), 4.68 (ddd, J = 22.9,11.9, 8.4Hz, 1H), 4.16 (dd, J = 24.1, 12.5Hz, 1H), 3.90 (dd, J = 24.6, 12.5Hz,1H), 3.68–3.42 (m,1H), 2.27 (s,1H), 2.22 (s,1H), 2.03 (d, J = 10.1Hz, 2H). HRMS(ESI⁺) Calcd for C31H37O13P [M+H]⁺: 648.2013, Found: 648.2009

[0071] The resulting B-1-5 (6.48 g, 10 mmol) was dissolved in 10 mL of anhydrous dichloromethane, and an appropriate amount of acidic ion exchange resin was added to remove the acetyl protecting group. The reaction solution was stirred at room temperature overnight under nitrogen protection. After the reaction was completed, the ion exchange resin was removed by filtration to obtain the target product B-1 (β-D-glucosyl modified TPO-L photoinitiator). The filtered solution was removed by solvent evaporation dichloromethane, and washed with cold ether several times, and the white solid product B-1-6 was collected. The final product was a white solid with a yield of 82%. 1 H NMR (500MHz) δ 6.80 (s,1H), 5.70 (s,1H), 5.07 (d, J = 14.6Hz,1H), 4.28 (dd, J = 14.7, 7.1Hz, 1H), 4.02 (t, J = 7.0 Hz,1H), 3.84–3.33 (m,4H), 2.43 (s,1H), 2.27 (s,2H), 2.22 (s,3H), 1.86(d, J =18.5Hz,1H).HRMS (ESI⁺) Calcd for C23H29O9P [M+H]⁺: 480.1523, Found: 480.1519

[0072] The purified B-1-7 (0.05 mol, 28.67 g) was dissolved in an appropriate amount of anhydrous ethanol and stirred uniformly. An equimolar amount of tributylamine (0.05 mol, 9.26 g) was added to the solution, and the reaction was stirred at room temperature overnight. After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, cooled to room temperature by standing, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target compound: a β-D-glucosyl and tri-n-butyl quaternary ammonium salt modified TPO-L photoinitiator B-1, which appeared as a white or light yellow solid. 1 H NMR (500 MHz, Chloroform) δ 7.54 - 7.17 (m, 5H), 6.95 (s, 2H), 5.76 (s, 1H), 5.52 (d, J = 6.6Hz, 1H), 4.66 (s,2H), 4.32 - 4.00 (m, 2H), 3.92 - 3.18 (m, 8H), 2.23 (s, 1H), 2.22 (s, 6H), 2.15(s, 1H), 1.25 (s, 1H).

[0073] The purified B-1-7 (0.05 mol, 28.67 g) was dissolved in an appropriate amount of anhydrous ethanol and stirred uniformly. An equimolar amount of tributylamine (0.05 mol, 9.26 g) was added to the solution, and the reaction was stirred at room temperature overnight. After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, cooled to room temperature by standing, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target compound: a β-D-glucosyl and tri-n-butyl quaternary ammonium salt modified TPO-L photoinitiator B-1, which appeared as a white or light yellow solid. 1 HNMR (500 MHz, Chloroform) δ 7.54 - 7.17 (m, 5H), 6.95 (s, 2H), 5.76 (s, 1H), 5.52 (d, J = 4.8Hz, 1H), 4.98 (s, 2H), 4.28 - 3.25 (m, 16H), 2.30 (s, 1H), 2.22 (s, 6H),1.93 - 1.70 (m, 6H), 1.55 (s, 1H), 1.38 (s, 1H), 1.34 - 1.11 (m, 6H), 0.89 (dd, J = 13.4, 12.8Hz, 9H).

[0074] Example 2: Synthesis of β-D-glucosyl and di-n-butyl and isobutyl quaternary ammonium salt modified TPO-L photoinitiator B-2

[0075]

[0076] The bromine and β-D-glucosyl substituted derivative (B-1-7, molecular weight 573.37 g / mol, 0.05 mol, 28.67 g) obtained in Example 1 was dissolved in an appropriate amount of absolute ethanol and stirred until uniform. To this solution, an equimolar amount of di-n-butyl-isobutyl amine B-2-1 (molecular weight 185.21 g / mol, 0.05 mol, 9.26 g) was added and the reaction was stirred at room temperature overnight.

[0077] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, allowed to cool to room temperature, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum suction filtration and washed with cold ethanol to obtain the target compound: β-D-glucosyl and di-n-butyl-isobutyl quaternary ammonium salt modified TPO-L photoinitiator B-2. 1 H NMR (500 MHz, Chloroform) δ 7.58 - 7.16 (m, 5H), 6.83 (s, 2H), 5.42 - 5.13 (m, 1H), 4.93 (s, 2H), 4.25 - 3.93 (m, 2H), 3.92 - 3.06 (m, 14H), 2.66 - 2.35 (m, 2H), 2.24 (d, J = 19.2 Hz, 7H), 2.02 (s, 1H), 1.91 - 1.69 (m, 4H), 1.53 (s, 1H), 1.39 - 1.08 (m, 4H), 1.02 - 0.72 (m, 12H).

[0078] Example 3: Synthesis of β-D-glucosyl and dimethyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-3

[0079]

[0080] The bromine and β-D-glucosyl substituted derivative (B-1-7, molecular weight 573.37 g / mol, 0.05 mol, 28.67 g) obtained in Example 1 was dissolved in an appropriate amount of absolute ethanol and stirred until uniform. To this solution, an equimolar amount of dimethyl-benzyl amine (B-3-1) (molecular weight 135.10 g / mol, 0.05 mol, 6.76 g) was added and the reaction was stirred at room temperature overnight.

[0081] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved with warm ethanol, cooled to room temperature, and then placed in an ice bath to promote the crystallization of the crystals. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target compound: β-D-glucosyl and dimethyl-benzyl quaternary ammonium salt modified TPO-L photoinitiator B-3. 1 H NMR (500MHz, Chloroform) δ7.50–7.09 (m, 10H), 6.83 (s,2H), 5.19 (d, J = 12.6Hz, 1H), 4.86 (s, 2H), 4.66 (s, 2H), 4.16–3.81 (m, 3H), 3.79–3.35 (m, 7H), 3.27 (s, 6H), 2.46 (d, J = 17.6Hz, 2H), 2.27 (s, 1H), 2.22 (s,6H), 1.35 (s, 1H).

[0082] Example 4: Synthesis of β-D-glucosyl and di-n-butyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-4

[0083]

[0084] The bromine and β-D-glucosyl substituted derivative (B-1-7, molecular weight 573.37 g / mol, 0.05 mol, 28.67 g) obtained in Example 1 was dissolved in an appropriate amount of anhydrous ethanol and stirred uniformly. To this solution, an equimolar amount of di-n-butyl-benzyl amine (B-4-1, molecular weight 219.20 g / mol, 0.05 mol, 10.96 g) was added and stirred at room temperature overnight.

[0085] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved with warm ethanol, cooled to room temperature, and then placed in an ice bath to promote the crystallization of the crystals. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target compound: β-D-glucosyl and di-n-butyl-benzyl quaternary ammonium salt modified TPO-L photoinitiator B-4, which appeared as a white or light yellow solid. 1 H NMR (500MHz, Chloroform) δ7.50–7.09 (m, 10H), 6.83 (s,2H), 5.19 (d, J= 12.8Hz, 1H), 4.84 (s, 1H), 4.73 (s, 2H), 4.53 (s, 2H), 4.34–3.95 (m, 2H), 3.96–3.22 (m, 13H), 2.22 (s, 6H), 2.01–1.54 (m, 5H), 1.47–1.10(m, 5H), 1.03–0.60 (m, 6H).

[0086] Example 5: Synthesis of β-D-galactosyl and tri-n-butyl quaternary ammonium salt modified TPO-L photoinitiator A-5

[0087]

[0088]

[0089] B-1-3 (10 g, 30.12 mmol) and 1-bromo-2, 3, 4, 6-tetra-O-acetyl-a-D-galactose (B-5-1, 10 g, 24.39 mmol) were dissolved in 50 mL of acetone in an equivalent ratio of 1:1, potassium carbonate (1 equivalent, 4.3 g, 31.61 mmol) was added as a catalyst, and the reaction was stirred at room temperature for 12 hours. After the reaction was completed, the progress of the reaction was monitored by thin layer chromatography (TLC), and it was confirmed that the reaction had been completely converted. After the reaction was completed, it was cooled to room temperature, and the reaction solution was poured into ice water, and the solution was adjusted to pH ~ 3 with 1M hydrochloric acid, and the solid product was precipitated. The precipitated solid was collected by filtration and washed with deionized water until it was neutral, and the excess hydrochloric acid and solvent were removed. The solid intermediate after the reaction was dissolved in dichloromethane, dried with anhydrous sodium sulfate, and after further filtration, the solution was concentrated to dryness. Purification by column chromatography with dichloromethane / petroleum ether gave B-5-2 (2, 3, 4, 6-tetra-O-acetyl-a-D-galactose-substituted TPO-L derivative) with a yield of 80%. 1 HNMR (500MHz, Chloroform) δ7.45–7.17 (m, 5H), 6.80 (s, 2H), 6.03–5.77 (m, 2H), 5.32 (dd, J =5.6, 2.5Hz,1H), 4.68 (ddd, J =22.8, 11.9, 8.2Hz, 2H), 4.16 (dd, J =24.1, 12.5Hz, 1H), 3.90(dd, J= 24.6, 12.5Hz, 1H), 3.69–3.48 (m, 4H), 2.27 (s, 3H), 2.22 (s, 6H), 2.03(d, J = 10.1Hz, 12H).HRMS (ESI⁺) Calcd for C32H39O13P [M+H]⁺: 662.2153, Found: 662.2149.

[0090] B-5-2 was dissolved in 10 mL of anhydrous dichloromethane, and an appropriate amount of acidic ion exchange resin was added to remove the acetyl protecting group. The reaction solution was stirred at room temperature overnight under nitrogen protection. After the reaction was completed, the ion exchange resin was removed by filtration to obtain the target product B-5-3 (β-D-galactosyl modified TPO-L photoinitiator). The filtered solution was removed by solvent evaporation dichloromethane, and washed with cold ether several times, and the white solid product B-2 was collected. The final product was a white solid with a yield of 75%. 1 HNMR (500MHz, Chloroform) δ7.47–7.18 (m, 5H), 6.80 (s,2H), 5.50 (s, 1H), 4.66 (d, J = 15.2Hz, 1H), 4.07 (dd, J = 16.7, 15.3Hz, 1H),3.82–3.49 (m, 7H), 3.44 (dd, J = 24.7, 10.3Hz, 1H), 3.24 (dt, J = 18.6, 10.4Hz,1H), 2.27 (s, 3H), 2.22 (s, 6H), 2.13 (s, 1H), 2.03 (s, 1H), 1.92 (s, 1H).HRMS (ESI⁺) Calcd for C24H31O9P [M+H]⁺: 494.1785, Found: 494.1779.

[0091] The purified B-5-4 (molecular weight 573.37 g / mol, 0.05 mol, 28.67 g) was dissolved in an appropriate amount of anhydrous ethanol and stirred uniformly. An equimolar amount of tributylamine (B-5-5, molecular weight 185.21 g / mol, 0.05 mol, 9.26 g) was added to the solution, and the reaction was stirred at room temperature overnight. After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, cooled to room temperature after standing, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target product: a β-D-galactosyl and tri-n-butyl quaternary ammonium salt modified TPO-L photoinitiator A-5, which appeared as a white or light yellow solid.

[0092] The purified B-5-4 (molecular weight 573.37 g / mol, 0.05 mol, 28.67 g) was dissolved in an appropriate amount of anhydrous ethanol and stirred uniformly. An equimolar amount of tributylamine (B-5-5, molecular weight 185.21 g / mol, 0.05 mol, 9.26 g) was added to the solution, and the reaction was stirred at room temperature overnight. After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, cooled to room temperature after standing, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target product: a β-D-galactosyl and tri-n-butyl quaternary ammonium salt modified TPO-L photoinitiator A-5, which appeared as a white or light yellow solid. 1 HNMR (500MHz, Chloroform) δ7.47–7.17 (m, 5H),6.83 (s, 2H), 4.92 (s, 2H), 4.56 (d, J = 15.4Hz, 1H), 4.04 (dd, J = 17.4, 15.4Hz,1H), 3.87–3.03 (m, 15H), 2.22 (s, 6H), 2.01 (d,J = 10.4Hz, 2H), 1.82 (dq, J =30.5, 15.3Hz, 7H), 1.45–1.14 (m, 6H), 1.02 (s, 1H), 0.89 (dd, J = 13.4, 12.8Hz,9H).

[0093] Example 6: Synthesis of β-D-galactosyl and di-n-butyl and isobutyl quaternary ammonium salt modified TPO-L photoinitiator B-6

[0094]

[0095] The bromine and β-D-galactosyl substituted derivative (B-5-4, molecular weight 573.37 g / mol, 0.05 mol, 28.67 g) obtained in Example 5 was dissolved in an appropriate amount of anhydrous ethanol and stirred until uniform. To this solution, an equimolar amount of di-n-butyl-isobutyl amine B-6-1 (molecular weight 185.21 g / mol, 0.05 mol, 9.26 g) was added and the reaction was stirred at room temperature overnight.

[0096] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, cooled to room temperature, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target compound: β-D-galactosyl and di-n-butyl and isobutyl quaternary ammonium salt modified TPO-L photoinitiator B-6. 1 HNMR (500 MHz, Chloroform) δ 7.56–7.09 (m, 5H), 6.82 (s, 2H), 4.74 (s, 2H), 4.55 (d, J = 15.4Hz, 1H), 4.25–3.03 (m, 16H), 2.53–2.25 (m, 1H), 2.22 (s, 6H), 2.01 (d, J = 10.4Hz, 2H), 1.93–1.63 (m, 5H), 1.48–1.12 (m, 4H), 0.93 (dt, J = 26.1,18.7Hz, 13H).

[0097] Example 7: Synthesis of β-D-galactosyl and dimethyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-7

[0098]

[0099] The bromine and β-D-galactosyl substituted derivative (B-5-4, molecular weight 573.37 g / mol, 0.05 mol, 28.67 g) obtained in Example 5 was dissolved in an appropriate amount of absolute ethanol and stirred well. To this solution, an equimolar amount of dimethyl-benzylamine (B-7-1) (molecular weight 135.10 g / mol, 0.05 mol, 6.76 g) was added and the reaction was stirred at room temperature overnight.

[0100] After completion of the reaction, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, allowed to cool to room temperature, and then placed in an ice bath to promote crystallization. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target compound: β-D-galactosyl and dimethyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-7. 1 H NMR (500 MHz, Chloroform) δ 7.55 - 7.08 (m, 5H), 6.83 (s, 1H), 5.02 (d, J = 15.4 Hz, 1H), 4.61 (s, 2H), 4.23 (dd, J = 16.9, 15.6 Hz, 1H), 3.91 (dd, J = 18.9, 17.1 Hz, 1H), 3.79 - 3.36 (m, 4H), 3.33 - 3.09 (m, 3H), 2.22 (s, 3H), 2.13 (s, 1H), 1.75 - 1.11 (m, 2H).

[0101] Example 8: Synthesis of β-D-galactosyl and di-n-butyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-8

[0102]

[0103] The bromine and β-D-galactosyl substituted derivative (B-5-4, molecular weight 573.37 g / mol, 0.05 mol, 28.67 g) obtained in Example 5 was dissolved in an appropriate amount of absolute ethanol and stirred well. To this solution, an equimolar amount of dimethyl-benzylamine (B-7-1) (molecular weight 135.10 g / mol, 0.05 mol, 6.76 g) was added and the reaction was stirred at room temperature overnight.

[0104] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain the crude product. The crude product was dissolved with warm ethanol, cooled to room temperature, and then placed in an ice bath to promote the crystallization of the crystals. The crystals were collected by vacuum suction filtration and washed with cold ethanol to obtain the target compound: β-D-galactosyl and di-n-butyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-8, which appeared as a white or light yellow solid. 1 H NMR (500MHz, Chloroform) δ7.63–7.02 (m, 10H), 6.82 (s,2H), 4.79 (s, 2H), 4.70 (s, 2H), 4.57 (d, J = 15.4Hz, 1H), 4.04 (dd, J = 17.3,15.4Hz, 1H), 3.89–2.95 (m, 13H), 2.22 (s, 6H), 2.01 (d, J = 10.4Hz, 2H), 1.81(dq, J = 30.5, 15.3Hz, 5H), 1.44–1.13 (m, 4H), 1.02 (s, 1H), 0.89 (dd, J = 13.4,12.8Hz, 6H).

[0105] Example 9: Synthesis of β-D-xylosyl and tri-n-butyl quaternary ammonium salt modified TPO-L photoinitiator B-9

[0106]

[0107] B-1-3 (10 g, 30.12 mmol) and 1-bromo-2, 3, 4-tri-O-acetyl-α-D-xylose (B-9-1, 10 g, 29.59 mmol) were dissolved in 50 mL of acetone at an equivalent ratio of 1:1, potassium carbonate (1 equivalent, 4.3 g, 31.61 mmol) was added as a catalyst, and the reaction was stirred at room temperature for 12 hours. After the reaction was completed, the progress of the reaction was monitored by thin layer chromatography (TLC), and it was confirmed that the reaction had been completely converted. After the reaction was completed, it was cooled to room temperature, and the reaction solution was poured into ice water, and the pH of the solution was adjusted to pH ≈ 3 with 1M hydrochloric acid, and the solid product was precipitated. The precipitated solid was collected by filtration and washed with deionized water until it was neutral, and the excess hydrochloric acid and solvent were removed.

[0108] The reacted solid intermediate was dissolved in dichloromethane, dried with anhydrous sodium sulfate, further filtered, and the solution was concentrated to dryness. Purification by column chromatography with dichloromethane / petroleum ether yielded B-9-2 (2, 3, 4-tri-O-acetyl-a-D-xylose substituted TPO-L derivative) with a yield of 80%. 1 HNMR (500MHz, Chloroform) δ7.41–7.11 (m, 5H),6.78 (s, 2H), 5.54–5.38 (m, 1H), 5.35 (d, J = 9.6Hz, 1H), 5.25 (td, J = 5.2,3.6Hz, 1H), 5.00 (dd, J = 10.3, 3.7Hz, 1H), 3.99 (dd, J = 24.8, 5.2Hz, 1H), 3.80–3.44 (m, 5H), 2.26 (s, 3H), 2.21 (s, 6H), 2.01 (s, 9H).

[0109] HRMS (ESI⁺) Calcd for C29H35O11P [M+H]⁺: 590.1993, Found: 590.1991.

[0110] The 5.90 g of B-9-2 was dissolved in 10 mL of anhydrous dichloromethane, and an appropriate amount of acidic ion exchange resin was added to remove the acetyl protecting group. The reaction solution was stirred at room temperature overnight under nitrogen protection. After the reaction was completed, the ion exchange resin was removed by filtration to obtain the target product B-3 (β-D-xylosyl modified TPO-L photoinitiator). The filtered solution was removed by solvent evaporation dichloromethane, and washed with cold ether several times, and the white solid product B-9-3 was collected. The final product was a white solid with a yield of 75%. 1 HNMR (500MHz, Chloroform) δ7.47–7.15 (m, 5H), 6.80 (s, 2H),5.08 (d, J = 7.2Hz, 1H), 4.17–3.78 (m, 5H), 3.70–3.52 (m, 4H), 3.28 (dd, J= 24.7, 4.9Hz, 1H), 2.27 (s, 3H), 2.22 (s, 6H), 2.15 (s, 1H), 1.73 (s, 1H). HRMS (ESI+) Calcd for C23H29O8P [M+H]+: 464.1673, Found: 464.1669.

[0111] The β-D-xylosyl modified TPO-L derivative (B-9-3, molecular weight 464.16 g / mol, 0.05 mol, 23.21 g) was dissolved in an appropriate amount of chloroform and stirred uniformly. An equimolar amount of N-bromosuccinimide (NBS, molecular weight 177.98 g / mol, 0.05 mol, 8.90 g) was slowly added and the reaction was stirred at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC) until the completion of the reaction was confirmed. After the completion of the reaction, the chloroform solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain the bromine and β-D-xylosyl substituted TPO-L (B-9-4, molecular weight 543.35 g / mol) in high purity. 1 HNMR (500MHz, Chloroform) δ 7.48 - 7.14 (m, 5H), 6.95 (s, 2H), 4.75 (s, 2H), 4.39 (d, J = 7.1Hz, 1H), 4.17 (dd, J = 9.7, 7.2Hz, 1H), 3.98(q, J = 5.3Hz, 1H), 3.85 (ddd, J = 30.2, 17.3, 5.2Hz, 2H), 3.66 - 3.45 (m, 4H), 3.34 (dd, J = 24.8, 5.4Hz, 1H), 3.09 (s, 1H), 2.47 (s, 1H), 2.22 (s, 6H), 1.49 (s, 1H).

[0112] The purified B-9-4 (molecular weight 543.35 g / mol, 0.05 mol, 27.17 g) was dissolved in an appropriate amount of absolute ethanol and stirred uniformly. An equimolar amount of tributylamine (B-9-5, molecular weight 185.21 g / mol, 0.05 mol, 9.26 g) was added to the solution and stirred at room temperature overnight. After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, cooled to room temperature by standing, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target product: a β-D-xylosyl and tri-n-butyl quaternary ammonium salt modified TPO-L photoinitiator B-9, which appeared as a white or light yellow solid. 1 HNMR (500MHz, Chloroform) δ 7.52 - 7.21 (m, 5H), 6.82 (s, 2H), 5.14 (d, J = 7.1Hz, 1H), 4.75 (s, 2H), 4.34 - 3.74 (m, 4H), 3.72 - 3.21 (m, 11H), 2.98 (s, 1H), 2.24 (d, J = 20.0Hz, 7H), 1.91 - 1.65 (m, 6H), 1.43 (s, 1H), 1.36 - 1.03 (m, 6H), 0.89 (dd, J = 13.4, 12.8Hz, 9H).

[0113] Example 10: Synthesis of a β-D-xylosyl and di-n-butyl and isobutyl quaternary ammonium salt modified TPO-L photoinitiator B-10

[0114]

[0115] The bromine and β-D-xylosyl substituted TPO-L (B-9-4, molecular weight 543.35 g / mol, 0.05 mol, 27.17 g) obtained in Example 9 was dissolved in an appropriate amount of absolute ethanol and stirred uniformly. An equimolar amount of di-n-butyl-isobutylamine (B-10-1, molecular weight 185.21 g / mol, 0.05 mol, 9.26 g) was added to the solution and stirred at room temperature overnight.

[0116] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, cooled to room temperature by standing, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target product: a β-D-xylosyl and di-n-butyl-isobutyl quaternary ammonium salt modified TPO-L photoinitiator B-10. 1H NMR (500 MHz, Chloroform) δ 7.54 - 7.18 (m, 5H), 6.83 (s, 2H), 5.06 (d, J = 12.1 Hz, 1H), 4.73 (s, 2H), 4.28 - 3.00 (m, 16H), 2.87 (s, 1H), 2.38 (dtd, J = 22.8, 12.7, 2.7 Hz, 1H), 2.20 (d, J = 19.6 Hz, 7H), 1.82 (p, J = 15.3 Hz, 4H), 1.39 - 1.08 (m, 4H), 1.08 - 0.64 (m, 12H).

[0117] Example 11: Synthesis of β-D-xylosyl and dimethyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-11

[0118]

[0119] The bromine and β-D-xylosyl substituted TPO-L (B-9-4, molecular weight 543.35 g / mol, 0.05 mol, 27.17 g) obtained in Example 9 was dissolved in an appropriate amount of anhydrous ethanol and stirred uniformly. To this solution, an equimolar amount of dimethyl-benzyl amine (B-11-1, molecular weight 135.10 g / mol, 0.05 mol, 6.76 g) was added and the reaction was stirred at room temperature overnight.

[0120] After the completion of the reaction, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, allowed to cool to room temperature, and then placed in an ice bath to promote the crystallization of the crystals. The crystals were collected by vacuum suction filtration and washed with cold ethanol to obtain the target compound: β-D-xylosyl and dimethyl-benzyl quaternary ammonium salt modified TPO-L photoinitiator B-11, which appeared as a white or light yellow solid.1H NMR (500 MHz, Chloroform) δ 7.57 - 7.13 (m, 10H), 6.83 (s, 2H), 5.33 (d, J = 9.0 Hz, 1H), 4.65 (s, 2H), 4.61 (s, 2H), 4.22 - 3.16 (m, 15H), 2.54 (d, J = 34.8 Hz, 2H), 2.22 (s, 6H), 1.78 (s, 1H).

[0121] Example 12: Synthesis of β-D-xylosyl and di-n-butyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-12

[0122]

[0123] The bromine and β-D-xylosyl substituted TPO-L (B-9-4, Mw 543.35 g / mol, 0.05 mol, 27.17 g) obtained in Example 9 was dissolved in an appropriate amount of anhydrous ethanol and stirred uniformly. To this solution, an equimolar amount of di-n-butyl-benzylamine (B-8-1, Mw 219.20 g / mol, 0.05 mol, 10.96 g) was added and the reaction was stirred at room temperature overnight.

[0124] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, allowed to cool to room temperature, and then placed in an ice bath to promote crystallization. The crystals were collected by vacuum suction filtration and washed with cold ethanol to obtain the target product: β-D-xylosyl and di-n-butyl-benzyl quaternary ammonium salt modified TPO-L photoinitiator B-12, which appeared as a white or light yellow solid.1H NMR (500 MHz, Chloroform) δ 7.58 - 7.04 (m, 10H), 6.83 (s, 2H), 5.35 (d, J = 8.9 Hz, 1H), 4.71 (s, 2H), 4.62 (s, 2H), 4.22 - 3.24 (m, 13H), 2.50 (d, J = 26.6 Hz, 2H), 2.22 (s, 6H), 2.02 - 1.57 (m, 5H), 1.41 - 1.10 (m, 4H), 0.89 (t, J = 13.1 Hz, 6H).

[0125] Example 13: Synthesis of β-D-Arabinosyl and tri-n-butyl quaternary ammonium salt modified TPO-L photoinitiator B-13

[0126]

[0127] B-1-3 (10 g, 30.12 mmol) and 1-bromo-2, 3, 4-tri-O-acetyl-α-D-arabinose (B-13-1, 10 g, 29.59 mmol) were dissolved in 50 mL of acetone at an equivalent ratio of 1:1, and potassium carbonate (1 equivalent, 4.3 g, 31.61 mmol) was added as a catalyst and the reaction was stirred at room temperature for 12 hours. After the reaction was completed, the progress of the reaction was monitored by thin layer chromatography (TLC) and it was confirmed that the reaction had been completely converted. After the reaction was completed, it was cooled to room temperature, and the reaction solution was poured into ice water, and the pH of the solution was adjusted to pH ≈ 3 with 1M hydrochloric acid to precipitate the solid product. The precipitated solid was collected by filtration and washed with deionized water until it was neutral to remove excess hydrochloric acid and solvent.1 HNMR (500MHz, Chloroform) δ7.64–7.03 (m, 5H), 6.83 (s,2H), 5.31 (d, J = 11.5Hz, 1H), 4.89 (s, 2H), 4.38–3.74 (m, 4H), 3.67–3.17 (m,12H), 2.22 (s, 6H), 2.09 (s, 1H), 1.82 (p, J = 15.4Hz, 6H), 1.54 (s, 1H), 1.36–1.06 (m, 6H), 0.89 (dd, J = 13.4, 12.7Hz, 9H).

[0128] The reacted solid intermediate was dissolved in dichloromethane, dried with anhydrous sodium sulfate, further filtered, and the solution was concentrated to dryness. Purification by column chromatography with dichloromethane / petroleum ether gave B-13-2 (2, 3, 4-tri-O-acetyl-a-D-arabinose substituted TPO-L derivative) with a yield of 80%. 1 HNMR (500MHz, Chloroform) δ7.42–7.07 (m,5H), 6.79 (s, 2H), 5.44 (s, 1H), 5.33 (d, J = 28.5Hz, 2H), 4.92 (s, 1H), 3.94(s, 1H), 3.60 (t, J = 22.2Hz, 5H), 2.27 (s, 3H), 2.22 (s, 6H), 2.02 (s, 9H).HRMS (ESI⁺) Calcd for C29H35O11P [M+H]⁺: 590.1993, Found: 590.1991.

[0129] The 5.90 g of B-13-3 was dissolved in 10 mL of anhydrous dichloromethane, and an appropriate amount of acidic ion exchange resin was added to remove the acetyl protecting group. The reaction solution was stirred at room temperature overnight under nitrogen protection. After the reaction was completed, the ion exchange resin was removed by filtration to obtain the target product B-4 (β-D-arabinosyl modified TPO-L photoinitiator). The filtered solution was removed by solvent evaporation dichloromethane, and washed with cold ether several times, and the white solid product B-4 was collected. The final product was a white solid with a yield of 75%. 1HNMR (500MHz, Chloroform) δ 7.50-7.12 (m, 5H), 6.80 (s, 2H), 5.02 (s, 1H), 4.09 (s, 1H), 4.01-3.73 (m, 4H), 3.70-3.37 (m, 5H), 2.27 (s, 3H), 2.22 (s, 6H), 1.51 (s, 1H), 1.39 (s, 1H). HRMS (ESI+) Calcd for C23H29O8P [M+H]+: 464.1673, Found: 464.1671.

[0130] The β-D-arabinosyl modified TPO-L derivative (B-13-3, molecular weight 464.16 g / mol, 0.05 mol, 23.21 g) was dissolved in an appropriate amount of chloroform and stirred uniformly. An equimolar amount of N-bromosuccinimide (NBS, molecular weight 177.98 g / mol, 0.05 mol, 8.90 g) was slowly added and the reaction was stirred at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC) until the completion of the reaction was confirmed. After the completion of the reaction, the chloroform solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by column chromatography using dichloromethane / petroleum ether as the eluent to obtain the bromine and β-D-arabinosyl substituted TPO-L (B-13-4, molecular weight 543.35 g / mol) with high purity. 1 HNMR (500MHz, Chloroform) δ 7.53-7.15 (m, 5H), 6.95 (s, 2H), 4.87 (s, 2H), 4.82 (d, J = 6.6Hz, 1H), 4.10-3.24 (m, 9H), 2.40-1.98 (m, 8H), 1.51 (s, 1H).

[0131] The purified B-13-4 (molecular weight 543.35 g / mol, 0.05 mol, 27.17 g) was dissolved in an appropriate amount of absolute ethanol and stirred uniformly. To this solution, an equimolar amount of tributylamine (B-13-5, molecular weight 185.21 g / mol, 0.05 mol, 9.26 g) was added and the reaction was stirred at room temperature overnight. After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, allowed to cool to room temperature, and then placed in an ice bath to promote crystallization. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target product: a β-D-arabinosyl and tri-n-butyl quaternary ammonium salt-modified TPO-L photoinitiator B-13, which appeared as a white or light yellow solid.1H NMR (500 MHz, Chloroform) δ 7.64 - 7.03 (m, 5H), 6.83 (s, 2H), 5.31 (d, J = 11.5 Hz, 1H), 4.89 (s, 2H), 4.38 - 3.74 (m, 4H), 3.67 - 3.17 (m, 12H), 2.22 (s, 6H), 2.09 (s, 1H), 1.82 (p, J = 15.4 Hz, 6H), 1.54 (s, 1H), 1.36 - 1.06 (m, 6H), 0.89 (dd, J = 13.4, 12.7 Hz, 9H).

[0132] Example 14: Synthesis of a β-D-arabinosyl and di-n-butyl and isobutyl quaternary ammonium salt-modified TPO-L photoinitiator B-14

[0133]

[0134] The bromine and β-D-arabinosyl substituted TPO-L (B-13-4, molecular weight 543.35 g / mol, 0.05 mol, 27.17 g) obtained in Example 9 was dissolved in an appropriate amount of absolute ethanol and stirred uniformly. To this solution, an equimolar amount of di-n-butyl-isobutylamine (B-14-1, molecular weight 185.21 g / mol, 0.05 mol, 9.26 g) was added and the reaction was stirred at room temperature overnight.

[0135] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, allowed to cool to room temperature, and then placed in an ice bath to promote crystallization. The crystals were collected by vacuum filtration and washed with cold ethanol to obtain the target product: a β-D-arabinosyl and di-n-butyl and isobutyl quaternary ammonium salt-modified TPO-L photoinitiator B-14. 1HNMR (500MHz, Chloroform) δ 7.57 - 7.05 (m, 5H), 6.83 (s, 2H), 4.86 (d, J = 6.8Hz, 1H), 4.75 (s, 2H), 4.21 - 3.03 (m, 15H), 2.93 (s, 1H), 2.39 (ddt, J = 15.4, 12.7, 6.4Hz, 1H), 2.19 (d, J = 26.0Hz, 7H), 1.83 (p, J = 15.3Hz, 4H), 1.42 - 0.71 (m, 17H).

[0136] Example 15: Synthesis of β-D-Arabinosyl and dimethyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-15

[0137]

[0138] The bromine and β-D-arabinosyl substituted TPO-L (B-13-4, molecular weight 543.35 g / mol, 0.05 mol, 27.17 g) obtained in Example 9 was dissolved in an appropriate amount of anhydrous ethanol and stirred until uniform. To this solution, an equimolar amount of dimethyl-benzyl amine (B-15-1, molecular weight 135.10 g / mol, 0.05 mol, 6.76 g) was added and the reaction was stirred at room temperature overnight.

[0139] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, allowed to cool to room temperature, and then placed in an ice bath to promote crystal precipitation. The crystals were collected by vacuum suction filtration and washed with cold ethanol to obtain the target compound: β-D-arabinosyl and dimethyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-15. 1 HNMR (500MHz, Chloroform) δ 7.57 - 7.05 (m, 5H), 6.83 (s, 2H), 4.86 (d, J = 9.0Hz,1H), 4.65 (s, 2H), 4.61 (s, 2H), 4.10 (dd, J = 13.1, 9.0Hz, 1H), 3.94 (ddd, J =19.2, 10.4, 3.8Hz, 2H), 3.77 (dd, J= 24.8, 7.6Hz, 1H), 3.59 (s, 4H), 3.50 (dd, J = 24.8, 7.6Hz, 1H), 3.30 (s, 6H), 2.58 (s, 1H), 2.51 (s, 1H), 2.22 (s, 6H),1.78 (s, 1H).

[0140] Example 16: Synthesis of β-D-Arabinosyl and di-n-butyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-16

[0141]

[0142] The bromine and β-D-arabinosyl substituted TPO-L (B-13-4, molecular weight 543.35 g / mol, 0.05 mol, 27.17 g) obtained in Example 9 was dissolved in an appropriate amount of anhydrous ethanol and stirred until uniform. To this solution, an equimolar amount of di-n-butyl-benzyl amine (B-16-1, molecular weight 219.20 g / mol, 0.05 mol, 10.96 g) was added and the reaction was stirred at room temperature overnight.

[0143] After the reaction was completed, the ethanol solvent was removed by rotary evaporation to obtain a crude product. The crude product was dissolved in warm ethanol, allowed to cool to room temperature, and then placed in an ice bath to promote crystallization. The crystals were collected by vacuum suction filtration and washed with cold ethanol to obtain the target product: β-D-arabinosyl and di-n-butyl and benzyl quaternary ammonium salt modified TPO-L photoinitiator B-16.1H NMR (500 MHz, Chloroform) δ 7.42 - 7.01 (m, 10H), 6.82 (s, 2H), 5.13 (d, J = 6.8 Hz, 1H), 4.77 (s, 2H), 4.69 (s, 2H), 3.92 (dddd, J = 22.4, 18.1, 11.2, 5.9 Hz, 4H), 3.64 - 3.53 (m, 4H), 3.44 (dt, J = 30.3, 10.1 Hz, 5H), 2.81 (s, 1H), 2.24 (d, J = 18.5 Hz, 7H), 1.81 (p, J = 15.3 Hz, 4H), 1.41 (s, 1H), 1.36 - 1.05 (m, 4H), 0.89 (dd, J = 13.4, 12.8 Hz, 6H).

[0144] Example 17: Performance Evaluation

[0145] To verify the comprehensive performance of the glycosyl-quaternary ammonium salt bifunctional modified TPO-L photoinitiator of the application, representative compounds B-1 to B-16 were selected and compared with commercially available Irgacure 2959, TPO-L and literature reported Alg-2959 as controls. The specific experimental process and data are as follows.

[0146] Water solubility test

[0147] Each photoinitiator sample (10 mg) was added to 10 mL of deionized water, and after ultrasonic treatment for 10 min, it was left to stand for 1 h. Filtration (0.45 μm filter membrane), and the absorbance was measured by UV-visible spectrophotometer, and the water solubility was calculated by combining the standard curve. The experiment was repeated 3 times, and the average value was taken.

[0148]

[0149] The water solubility of the experimental group was all above 3.0 mg / mL, which was significantly higher than that of commercially available Irgacure 2959 (0.5 mg / mL), TPO-L (<0.1 mg / mL) and literature Alg-2959 (3.5 mg / mL), showing good water solubility and being suitable for water-based photocuring applications.

[0150] Photoinitiation efficiency test

[0151] 1.0 wt% photoinitiator was uniformly mixed into a water-based acrylate formula (hydroxyethyl acrylate: polyurethane acrylate = 1:1), and spin-coated on a KBr sheet (20 μm). 365 nm ultraviolet light (50 mW / cm²) was irradiated, and the change in C = C double bond in the FTIR spectrum was recorded in real time. The DBC at 60 s and the maximum reaction rate were calculated, repeated 3 times, and the average value was taken.

[0152]

[0153] The initiation efficiency of the experimental group was above 70%, and the maximum reaction rate was 0.024~0.028 s-1, which was significantly better than the control group (Irgacure 2959 was only 53%, Alg-2959 was only 66%, and TPO-L was 48.2%), indicating that it had faster reaction rate and higher efficiency.

[0154] Ultraviolet light curing effect test

[0155] The photoinitiator formula was spin-coated on a quartz sheet, 365 nm ultraviolet light was irradiated, and the complete curing time was recorded. The flatness of the film layer was evaluated by optical microscope and naked eye observation.

[0156]

[0157] The complete curing time of the experimental groups B-1 to B-16 is in the range of 56 s, and the optical quality of the film layer is excellent (flat, no defects), which is better than that of the commercially available Irgacure 2959 (60 s, uneven surface), TPO-L (86 s, film layer has shrinkage hole, edge warping) and Alg-2959 (45 s, slight waviness).

[0158] Migration rate test

[0159] The film 37°C deionized water immersion 7 days, UV-Vis determination of migration, calculation of migration rate.

[0160]

[0161] The migration rate of B-1 to B-16 is less than 1%, which is significantly lower than that of the commercially available and literature control groups (6.5% and 4.8%), and has better low migration characteristics, which is suitable for food / medical field.

[0162] Antibacterial activity test

[0163] The cured film is placed on the surface of the Staphylococcus aureus and Escherichia coli culture medium, and cultured at 37°C for 24 hours, and the diameter of the inhibition zone (mm) is measured.

[0164]

[0165] The diameter of the inhibition zone of B-1 to B-16 samples is greater than 6 mm, and has good antibacterial performance; the antibacterial activity of the control groups Irgacure 2959 and TPO-L is 0, and that of Alg-2959 is only 12 mm, which is significantly lower than that of the samples of the application.

[0166] Biocompatibility test

[0167] L929 cells are co-cultured with the film for 24 hours, and the cell proliferation rate (%) is measured by CCK-8 method.

[0168]

[0169] The cell proliferation rate of B-1 to B-16 is more than 95%, which is significantly better than that of the commercially available Irgacure 2959 (62%), TPO-L (64.2%) and literature Alg-2959 (76%), and shows excellent biocompatibility, which meets the needs of medical and biological applications.

[0170] Through the detailed evaluation of the six dimensions of water solubility, photoinitiation efficiency and maximum reaction rate, complete curing time and optical quality of the film layer, migration rate, antibacterial activity and biocompatibility, B-1 to B-16 show the following outstanding advantages:

[0171] Water solubility: all 3.13.6 mg / mL, better than the control. Photoinitiation efficiency (DBC) and rate: both > 76%, much higher than the commercial and literature products. Curing speed and film layer quality: fast curing within 56s, film layer smooth and flat. Low migration: <1%, suitable for food and medical packaging. Antibacterial property: inhibition zone diameter up to 6-7mm, with antibacterial function. Biocompatibility: >95%, very suitable for high safety requirement field.

[0172] The glycosyl-quaternary ammonium salt double-modified TPO-L photoinitiator of the present application is superior to the control group in multiple performance dimensions, and exhibits good comprehensive application potential.

[0173] The above listed polymer structures are only part of the representatives, and other photoinitiator molecules containing the same idea are within the scope of this patent.

[0174] Although the embodiments of the present application have been shown and described above, it should be understood that the above embodiments are exemplary and should not be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application.

Claims

1. A photoinitiator, characterized in that, The general molecular formula is as follows: in, It is an anion. They can be the same or different C1–C8 straight-chain or branched alkyl or benzyl groups; R is selected from one of the following groups: 。 2. The photoinitiator according to claim 1, characterized in that, It can be a halide anion, sulfonate ion, carboxylate ion or other inorganic acid anion.

3. The photoinitiator according to claim 1, characterized in that, Selected from the following: 。

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