Preparation process of fluorosilicone acrylate emulsion containing LAP

Abstract

The invention specifically discloses a preparation process of a fluorosilicone acrylate emulsion containing LAP, and relates to the technical field of acrylate materials. The fluorosilicone acrylate emulsion provided by the invention has the advantages of high curing speed, complete crosslinking, no devitrification and no turbidity, and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of acrylate materials, and particularly relates to a preparation process of fluorosilicone acrylate emulsion containing LAP. BACKGROUND

[0002] LAP is a blue light curing photoinitiator, which can rapidly initiate the curing of photosensitive hydrogel materials under the action of blue light. The application field of LAP is quite wide, especially in biological 3D printing containing cells, since the damage of blue light to cells is smaller, LAP becomes a more ideal choice.

[0003] LAP (Lithium phenyl-2,4,6-trimethylbenzoylphosphinate) is easily soluble in hydrogel systems (PBS, HAMA / GelMA, etc.), but it is seriously incompatible with hydrophobic monomers (especially fluorine-containing and silicon-containing acrylates), resulting in turbidity and phase separation when directly added, and it is difficult to obtain a clear homogeneous resin; the oil-soluble azo / phosphine oxide photoinitiator is commonly used in fluorosilicone systems in the existing literature, but the hydrophilicity of LAP determines that it is difficult to be directly replaced; if the homogeneous dispersion of LAP in fluorosilicone monomers can be realized by a mild and low-residue process, the advantages of LAP in the 405 nm waveband activity, low yellowing and good toxicological properties will be combined, which will provide a new choice for the medical / optical field. SUMMARY

[0004] (I) Technical problems solved In view of this, one of the main purposes of the present application is to provide a preparation process of fluorosilicone acrylate emulsion containing LAP. The fluorosilicone acrylate emulsion provided by the present application has the advantages of fast curing speed, complete crosslinking, no crystallization and no turbidity, and has a broad application prospect.

[0005] (II) Technical solutions In order to achieve the above-mentioned purpose, the present application provides a preparation process of fluorosilicone acrylate emulsion containing LAP, comprising: S1: mixing polyethylene glycol diacrylate and lithium phenyl (2,4,6-trimethylbenzoyl) phosphate solution to prepare a pre-solution; S2: mixing the pre-solution with fluorosilicone acrylate to obtain the fluorosilicone acrylate emulsion.

[0006] In one embodiment, by mass fraction, polyethylene glycol diacrylate (PEG-DA, 0.5-5 parts), lithium phenyl (2,4,6-trimethylbenzoyl) phosphate (LAP, 0.1-1 parts) and fluorosilicone acrylate (9-27 parts).

[0007] In one embodiment, the polyethylene glycol diacrylate is 1 part, the lithium phenyl (2,4,6-trimethylbenzoyl) phosphate is 0.2 parts, and the fluoro-silicone acrylate is 18 parts by mass.

[0008] In one embodiment, the fluoro-silicone acrylate comprises perfluorodecyl methacrylate, dodecafluoroheptyl-2-methyl acrylate, nonafluoro-hexyl acrylate, hexafluorobutyl-2-methyl acrylate, tridecafluoro-octyl methacrylate, and / or 3-(trimethoxysilyl)propyl methacrylate.

[0009] In one embodiment, the fluoro-silicone acrylate is tridecafluoro-octyl methacrylate (TFMA) and 3-(trimethoxysilyl)propyl methacrylate (TMSPMA).

[0010] In one embodiment, the mass ratio of the tridecafluoro-octyl methacrylate and 3-(trimethoxysilyl)propyl methacrylate is (1-5): 1.

[0011] In one embodiment, the mass ratio of the tridecafluoro-octyl methacrylate and 3-(trimethoxysilyl)propyl methacrylate is 3: 1.

[0012] In one embodiment, the mass ratio of the polyethylene glycol diacrylate: lithium phenyl (2,4,6-trimethylbenzoyl) phosphate: fluoro-silicone acrylate is (0.5-5):(0.1-1):(9-27).

[0013] In one embodiment, the mass ratio of the polyethylene glycol diacrylate: lithium phenyl (2,4,6-trimethylbenzoyl) phosphate: fluoro-silicone acrylate is (1):(0.2):(18).

[0014] In one embodiment, the polyethylene glycol diacrylate, lithium phenyl (2,4,6-trimethylbenzoyl) phosphate, and fluoro-silicone acrylate are used in amounts of 1 g, 0.2 g, and 18 g, respectively.

[0015] In one embodiment, the fluoro-silicone acrylate comprises perfluorodecyl methacrylate, dodecafluoroheptyl-2-methyl acrylate, nonafluoro-hexyl acrylate, hexafluorobutyl-2-methyl acrylate, tridecafluoro-octyl methacrylate, and / or 3-(trimethoxysilyl)propyl methacrylate.

[0016] In one embodiment, the fluoro-silicone acrylate is tridecafluoro-octyl methacrylate and 3-(trimethoxysilyl)propyl methacrylate.

[0017] In one embodiment, the mass ratio of the tridecafluoro-octyl methacrylate and 3-(trimethoxysilyl)propyl methacrylate is (1-5): 1.

[0018] In one embodiment, the mass ratio of the tridecafluoro-octyl methacrylate and 3- (trimethoxysilyl)propyl methacrylate is 3:1.

[0019] In one embodiment, the tridecafluoro-octyl methacrylate and 3- (trimethoxysilyl)propyl methacrylate are used in an amount of 13.5g and 4.5g respectively.

[0020] In one embodiment, the solvent of the lithium phenyl (2,4,6-trimethylbenzoyl) phosphate solution is an organic solvent.

[0021] In one embodiment, the organic solvent comprises methanol, ethanol, acetone, acetonitrile, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), tetrahydrofuran (THF), ethyl acetate, diethyl ether, chloroform, dichloromethane, toluene, benzene, cyclohexane, n-hexane and / or petroleum ether.

[0022] In one embodiment, the organic solvent is dimethyl sulfoxide.

[0023] In one embodiment, the concentration of the lithium phenyl (2,4,6-trimethylbenzoyl) phosphate solution is 10-50wt%; preferably, the concentration is 20wt%.

[0024] In one embodiment, the mixing method in S2 is: dropping the pre-solution into the fluorosilicone acrylate.

[0025] In one embodiment, the preparation process further comprises: heating the fluorosilicone acrylate to 30-40℃.

[0026] In one embodiment, the fluorosilicone acrylate is heated to 35℃.

[0027] In one embodiment, the preparation process specifically comprises: S1: mixing polyethylene glycol diacrylate and lithium phenyl (2,4,6-trimethylbenzoyl) phosphate solution to prepare a pre-solution; S2: mixing the pre-solution with the fluorosilicone acrylate heated to 30-40℃ to obtain the fluorosilicone acrylate emulsion.

[0028] In one embodiment, the preparation process specifically comprises: S1: mixing polyethylene glycol diacrylate and lithium phenyl (2,4,6-trimethylbenzoyl) phosphate solution to prepare a pre-solution; S2: mixing the pre-solution with the fluorosilicone acrylate heated to 30-40℃ to obtain the fluorosilicone acrylate emulsion.

[0029] In another aspect, the present invention also provides a fluorosilicone acrylate emulsion, which is obtained by the above-described preparation process.

[0030] In another aspect, the present invention also provides the application of the above-mentioned fluorosilicone acrylate emulsion in the preparation of cured materials.

[0031] (III) Beneficial Effects This invention provides a process for preparing fluorosilicone acrylate emulsions containing LAP. Compared with existing technologies, it has the following advantages: 1. Fast curing speed, 405nm LED, light intensity 20mW / cm² -2 The surface is dry to the touch after 10 seconds of irradiation.

[0032] 2. Complete cross-linking, does not soften at 120℃ hot table for 1 hour.

[0033] 3. The sample showed no crystallization or turbidity after standing at 25℃ for 7 days. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 After DMSO removal 1 H-NMR spectrum.

[0036] Figure 2 Before and after DMSO removal 1 H-NMR spectrum.

[0037] Figure 3 It is a process flow diagram. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] Terms and Definitions As used herein, “containing,” “having,” or “including” includes “comprising,” “consisting essentially of,” “consisting of,” and “made of”; “consisting essentially of,” “consisting of,” and “made of” are subsumed into “containing,” “having,” or “including.”

[0040] The experimental methods used in the following examples are conventional methods, and the reagents, methods, and equipment used are conventional reagents, methods, and equipment in the art unless otherwise specified.

[0041] Example 1 Preparation of fluorosilicone acrylate emulsion #1: 1. Preparation of LAP stock solution: After mixing 2.00 g of LAP with 8.00 g of anhydrous DMSO, a completely clear dark yellow solution was obtained by ultrasonic treatment at 50 °C for 10 min. Then, a 20 wt% LAP stock solution was obtained by 0.22 µm PTFE filtration and stored in the dark.

[0042] 2. Preparation of pre-solution: After mixing 2 g of the above-prepared LAP stock solution with 2 g of PEGDA 400, a uniform, transparent, and low-viscosity pre-solution was obtained by magnetic stirring at 25 °C for 30 min.

[0043] 3. Preparation of fluorosilicone acrylate emulsion: After preheating the mixture of 13.5 g of tridecafluorooctyl methacrylate and 4.5 g of 3-(trimethoxysilyl)propyl methacrylate to reduce the viscosity at 35 °C in an oil bath, the above-prepared pre-solution was slowly added dropwise while stirring at 600 rpm; about 5 min for 2 g of pre-solution to be added dropwise, and then stirring for 10 min to obtain a clear and transparent homogeneous system.

[0044] The residual DMSO was completely removed by vacuum rotary evaporation at 35 °C for 15 min (vacuum degree ≤ 50 mbar) (less than 0.1 wt% confirmed by ¹H-NMR as shown in Figure 1 and Figure 2 ).

[0045] Oxygen was removed by nitrogen bubbling for 5 min, and then immediately used for UV curing (405 nm LED, light intensity 20 mW cm -2 under the conditions, and the process flow is shown in Figure 3 .

[0046] The surface was dry to the touch after 10 s of irradiation.

[0047] No softening was observed at 120 °C hot stage for 1 h, indicating complete crosslinking.

[0048] No crystallization or turbidity was observed after standing at 25 °C for 7 days, and some samples had crystallization within 48 h at 22 °C.

[0049] Viscosity: 250 mPa-s at 25 °C.

[0050] Transmittance: 91% in the 400-800 nm range.

[0051] DMSO residue: The resulting system is transparent; 1 H-NMR (400 MHz, CDC13) no DMSO residue peak at 2.50 ppm (within noise), methyl methacrylate at 1.95 ppm, olefinic H at 5.60 / 6.10 ppm, PEGDA-CH2-0 at 3.65 ppm, TMSPMA-OCH3 at 3.60 ppm, weak aromatic region (LAP) at 6.9-7.2 ppm; Example 2 Preparation of fluorosilicone acrylate emulsion #2: 1. Preparation of LAP stock solution: After mixing 2.00 g of LAP with 8.00 g of anhydrous DMSO, a completely clear dark yellow solution was obtained at 50 °C for 10 min. Then a 20 wt% LAP stock solution was obtained by 0.22 pm PTFE filtration and stored in the dark.

[0052] 2. Preparation of pre-solution: After mixing 2 g of the above prepared LAP stock solution with 3 g of PEGDA 400, a uniform, transparent, low viscosity pre-solution was obtained by magnetic stirring at 25 °C for 30 min.

[0053] 3. Preparation of fluorosilicone acrylate emulsion: After preheating the mixture of 13.5 g of tridecafluorooctyl methacrylate and 4.5 g of 3-(trimethoxysilyl)propyl methacrylate to reduce the viscosity at 35 °C, the above prepared pre-solution was slowly added dropwise while stirring at 600 rpm. About 5 min for 2 g of pre-solution to be added dropwise, and continue stirring for 10 min to obtain a clear, transparent homogeneous system.

[0054] Remove DMSO residue completely (<0.1 wt% confirmed by 1H-NMR) by vacuum rotary evaporation at 35 °C for 15 min (vacuum degree < 50 mbar).

[0055] Deoxidize by nitrogen bubbling for 5 min, and immediately use for UV curing (405 nm LED, light intensity 20 mW cm -2 under the condition of irradiation).

[0056] The surface is dry to the touch after 10 s of irradiation.

[0057] No softening at 120 °C hot stage for 1 h, indicating complete crosslinking.

[0058] No crystallization and no turbidity at 25 °C for 7 days, the sample has partial state crystallization within 48 hours at 22 °C.

[0059] Viscosity: 320 mPa-s at 25 °C.

[0060] Transmittance: 94% in the 400-800 nm band.

[0061] DMSO residue: GC-MS detection signal intensity lower than Example 1.

[0062] Example 3 Preparation of fluorosilicone acrylate emulsion #3: 1. Preparation of LAP stock solution: After mixing 2.00 g of LAP with 8.00 g of anhydrous DMSO, a completely clear dark yellow solution was obtained by ultrasonic treatment at 50 °C for 10 min. Then a 30 wt% LAP stock solution was obtained by 0.22 pm PTFE filtration and stored in the dark.

[0063] 2. Preparation of pre-solution: After mixing 2 g of the above-prepared LAP stock solution with 3 g of PEGDA 400, a uniform, transparent, and low-viscosity pre-solution was obtained by magnetic stirring at 25 °C for 30 min.

[0064] 3. Preparation of fluorosilicone acrylate emulsion: After preheating the mixture of 13.5 g of tridecafluorooctyl methacrylate and 4.5 g of 3-(trimethoxysilyl)propyl methacrylate at 35 °C in an oil bath to reduce the viscosity, the above-prepared pre-solution was slowly added dropwise while stirring at 600 rpm. About 5 min for 2 g of pre-solution to be added dropwise, and continue stirring for 10 min to obtain a clear and transparent homogeneous system.

[0065] Remove DMSO residue completely (<0.1 wt% confirmed by ¹H-NMR) by vacuum rotary evaporation at 35 °C for 15 min (vacuum degree < 50 mbar).

[0066] Deoxidize by nitrogen bubbling for 5 min, and immediately use for UV curing (405 nm LED, light intensity 20 mW cm -2 under the condition of irradiation).

[0067] The surface is dry to the touch after 10 s of irradiation.

[0068] No softening at 120 °C hot stage for 1 h, indicating complete crosslinking.

[0069] No crystallization and no turbidity at 25 °C for 7 days, the sample has partial state crystallization within 48 hours at 22 °C.

[0070] Viscosity: 302 mPa-s at 25 °C.

[0071] Transmittance: 92% in the range of 400~800 nm.

[0072] DMSO residue: GC-MS signal intensity slightly lower than Example 1.

[0073] Example 4 Preparation of fluorosilicone acrylate emulsion #4: 1. Preparation of LAP stock solution: After mixing 2.00 g of LAP with 8.00 g of anhydrous DMSO, a completely clear dark yellow solution was obtained by ultrasonic treatment at 50 °C for 10 min. Then a 20 wt% LAP stock solution was obtained by 0.22 µm PTFE filtration and stored in the dark.

[0074] 2. Preparation of pre-solution: After mixing 2 g of the above-prepared LAP stock solution with 3 g of PEGDA 400, a uniform, transparent, and low-viscosity pre-solution was obtained by magnetic stirring at 25 °C for 30 min.

[0075] 3. Preparation of fluorosilicone acrylate emulsion: After preheating the mixture of 10.8 g of tridecafluoro-1-octyl methacrylate and 7.2 g of 3-(trimethoxysilyl)propyl methacrylate to reduce the viscosity at 35 °C in an oil bath, the above-prepared pre-solution was slowly added dropwise while stirring at 600 rpm. About 5 min for 2 g of pre-solution to be added dropwise, and continue stirring for 10 min to obtain a clear and transparent homogeneous system.

[0076] Remove DMSO residue (<0.1 wt% confirmed by ¹H-NMR) completely by vacuum rotary evaporation at 35 °C for 15 min (vacuum degree ≤ 50 mbar).

[0077] Deoxidize by nitrogen bubbling for 5 min and immediately use for UV curing (405 nm LED, light intensity 20 mW cm -2 under the condition of irradiation).

[0078] The surface is dry to the touch after 10 s of irradiation.

[0079] No softening at 120 °C hot stage for 1 h, indicating complete crosslinking.

[0080] No crystallization and no turbidity after standing at 25 °C for 7 days, but some samples have crystallization within 48 h at 22 °C.

[0081] Viscosity: 280 mPa·s at 25 °C.

[0082] Transmittance: 91% in the range of 400~800 nm.

[0083] Example 5 Preparation of fluorosilicone acrylate emulsion #5: 1. Preparation of LAP stock solution: After mixing 2.00 g of LAP with 8.00 g of anhydrous DMSO, a completely clear dark yellow solution was obtained by ultrasonic treatment at 50 °C for 10 min. Then a 20 wt% LAP stock solution was obtained by 0.22 µm PTFE filtration and stored in the dark.

[0084] 2. Preparation of the pre-solution: After mixing 2 g of the LAP stock solution prepared above with 3 g of PEGDA 700, a homogeneous, transparent, low viscosity pre-solution was obtained by magnetic stirring at 25 °C for 30 min.

[0085] 3. Preparation of the fluoro-silicon acrylate emulsion: After pre-heating the mixture of 13.5 g of tridecafluoro-octyl methacrylate and 4.5 g of 3-(trimethoxysilyl)propyl methacrylate at 35 °C in an oil bath to reduce the viscosity, the pre-solution prepared above was added dropwise slowly while stirring at 600 rpm. About 5 min for 2 g of the pre-solution was added dropwise, and the stirring was continued for 10 min to obtain a clear, transparent and homogeneous system.

[0086] The residual DMSO was removed completely by vacuum rotary evaporation at 35 °C for 15 min (vacuum degree ≤ 50 mbar) (<0.1 wt% confirmed by ¹H-NMR).

[0087] Oxygen was removed by nitrogen bubbling for 5 min, and then the system was used for UV curing immediately (405 nm LED, light intensity 20 mW cm -2 under the condition of irradiation).

[0088] The surface was dry to the touch after 10 s of irradiation.

[0089] No softening was observed at 120 °C hot stage for 1 h, indicating complete crosslinking.

[0090] No crystallization and no turbidity were observed after standing at 25 °C for 7 days, but some samples had crystallization after 48 h at 22 °C.

[0091] Viscosity: 200 mPa·s at 25 °C.

[0092] Transmittance: 85% in the wavelength range of 400-800 nm.

[0093] It is to be noted that, in the present text, relational terms such as first and second and the like can be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can also include other elements not expressly listed or inherent to such process, method, article, or apparatus. An element proceeded by "comprises... a" does not, without more constraints, exclude the existence of additional identical elements in the process, method, article, or apparatus that comprises the element.

[0094] The above examples are merely used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A process for preparing a fluorosilicone acrylate emulsion containing LAP, characterized in that, include: S1: A pre-solution was prepared by mixing polyethylene glycol diacrylate with a phenyl (2,4,6-trimethylbenzoyl) lithium phosphate solution; S2: The presol solution is mixed with fluorosilicone acrylate to obtain the fluorosilicone acrylate emulsion.

2. The preparation process according to claim 1, characterized in that, By weight, it contains 0.5 to 5 parts of polyethylene glycol diacrylate, 0.1 to 1 part of lithium phenyl (2,4,6-trimethylbenzoyl)phosphate, and 9 to 27 parts of fluorosilicone acrylate.

3. The preparation process according to claim 2, characterized in that, By weight, it contains 1 part polyethylene glycol diacrylate, 0.2 parts lithium phenyl (2,4,6-trimethylbenzoyl)phosphate, and 18 parts fluorosilicone acrylate.

4. The preparation process according to any one of claims 1-3, characterized in that, The fluorosilicone acrylates include undecyl perfluoromethacrylate, dodecafluoroheptyl-2-methacrylate, nonafluorohexyl acrylate, hexafluorobutyl-2-methacrylate, tridecylfluorooctyl methacrylate and / or 3-(trimethoxysilyl)propyl methacrylate; preferably, the fluorosilicone acrylates are tridecylfluorooctyl methacrylate and 3-(trimethoxysilyl)propyl methacrylate.

5. The preparation process according to claim 4, characterized in that, The mass ratio of tridecyl methacrylate to 3-(trimethoxysilyl)propyl methacrylate is (1~5):

1.

6. The preparation process according to claim 5, characterized in that, The mass ratio of tridecylfluorooctyl methacrylate to 3-(trimethoxysilyl)propyl methacrylate is 3:

1.

7. The preparation process according to claim 1, characterized in that, The solvent for the phenyl (2,4,6-trimethylbenzoyl)lithium phosphate solution is an organic solvent.

8. The preparation process according to claim 7, characterized in that, The organic solvent includes methanol, ethanol, acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, ethyl acetate, diethyl ether, chloroform, dichloromethane, toluene, benzene, cyclohexane, n-hexane, and / or petroleum ether; preferably, the organic solvent is dimethyl sulfoxide.

9. The preparation process according to claim 1, characterized in that, The concentration of the phenyl (2,4,6-trimethylbenzoyl) lithium phosphate solution is 10~50wt%; preferably, the concentration is 20wt%.

10. The preparation process according to claim 1, characterized in that, The mixing method in S2 is as follows: the pre-solution is added dropwise to the fluorosilicone acrylate.

11. The preparation process according to claim 1, characterized in that, The preparation process further includes heating the fluorosilicone acrylate to 30~40℃.

12. A fluorosilicone acrylate emulsion, characterized in that, The fluorosilicone acrylate emulsion is obtained by the preparation process described in any one of claims 1-11.

13. The use of the fluorosilicone acrylate emulsion of claim 12 in the preparation of cured materials.

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