CN110746523A - Lignin-based macromolecular photoinitiator and preparation method and application thereof - Google Patents
Lignin-based macromolecular photoinitiator and preparation method and application thereof Download PDFInfo
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- CN110746523A CN110746523A CN201810810727.4A CN201810810727A CN110746523A CN 110746523 A CN110746523 A CN 110746523A CN 201810810727 A CN201810810727 A CN 201810810727A CN 110746523 A CN110746523 A CN 110746523A
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- lignin
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 47
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- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
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- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 13
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 12
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- 230000003165 hydrotropic effect Effects 0.000 claims 1
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 claims 1
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- OIFAHDAXIUURLN-UHFFFAOYSA-N 2-(fluoromethyl)oxirane Chemical compound FCC1CO1 OIFAHDAXIUURLN-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a lignin-based macromolecular photoinitiator and a preparation method and application thereof. The invention firstly discloses a lignin-based macromolecular photoinitiator, which has a structural formula shown as the following formula I:wherein the content of the first and second substances,
Description
Technical Field
The invention relates to the technical field of photocuring. More particularly, relates to a lignin-based macromolecular photoinitiator and a preparation method and application thereof.
Background
The photocuring technology is a high-efficiency, energy-saving, environment-friendly and high-quality material surface treatment technology, and is praised as a new technology facing the green industry of the 21 st century. The method is widely applied to various industries such as printing, packaging, advertising, building materials and the like. The product mainly comprises UV printing ink, UV adhesive, photosensitive printing plate, photoresist, illumination rapid forming material and the like. In recent years, with the expansion of the demand of high-end users for customized products, especially with great application prospects in life science, 3D printing based on optical technology has gained wide attention by people due to the characteristics of high printing precision, high printing speed, high z-axis strength and the like. However, the existing light-cured materials often have a plurality of problems, which limits the application of the technology in high-end fields.
The photocuring system mainly comprises a photopolymerization monomer, a photoinitiator and an additive. The photoinitiator is an important component in the formula of a photocuring system, and determines the curing speed and the curing degree of the system, thereby determining a series of macroscopic properties of a cured material. At present, the photocuring products in the market mainly adopt organic small-molecule photoinitiators, and have the main advantages of definite chemical structures and high initiation efficiency. However, there are also problems in use, such as poor compatibility with monomers or oligomers in the photocurable system; after curing, the photoinitiator and photolysis products are easy to migrate to cause toxicity and yellowing; and part of the small-molecule photoinitiator is volatile, has a strong smell and the like. Thus, the use of the photo-curing technique in hygiene and food packaging materials is limited.
In order to overcome the above disadvantages of small molecule photoinitiators, the preparation of macromolecular photoinitiators has become an important research direction in the field of photocuring research, and the most common technical solution is to hang small molecule photoinitiators onto polymer chains, for example, ① small molecule photoinitiators substituted with hydroxyl groups and monomers or polymers containing isocyanate groups and epoxy groups undergo condensation polymerization to obtain target products, ② introduces unsaturated groups (usually vinyl groups and acryloxy groups) onto small molecule photoinitiators, and then obtains target products by homopolymerization or copolymerization with other monomers, ③ obtains target products by chemically modifying and grafting photoinitiator groups onto side chains of main polymers, however, macromolecular photoinitiators often have the problems of high viscosity and low photoinitiation activity, and are limited in large-scale application, for example, macromolecule photoinitiators such as esackip 150 from ningford corporation and SR1130 from sandoman corporation, compared with corresponding small molecule initiators, the migration of which is obviously reduced, but the initiation efficiency is also obviously reduced, KIP150 in structural formula is equivalent to linking small molecule photoinitiators 1173 onto methyl ethylene oligomer, the molecular photoinitiator is obviously reduced in migration resistance, and the advantages of high molecular weight, such as high viscosity, high molecular weight, low molecular weight, high molecular weight, low molecular weight, high molecular weight, and low molecular weight, high molecular.
Therefore, there is a need to provide a new idea or scheme to construct and optimize the structure and properties of the macro-photoinitiators to meet the practical needs of the photo-curing industry.
Disclosure of Invention
The first purpose of the invention is to provide a lignin-based macro-molecular photoinitiator with high photoinitiation activity, good thermal stability, good storage performance, low viscosity, low mobility, low toxicity and no volatilization.
The second purpose of the invention is to provide a preparation method of the lignin-based macro-molecular photoinitiator.
The third purpose of the invention is to provide an application of the lignin-based macro-molecular photoinitiator.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a lignin-based macromolecular photoinitiator, which has a structural formula shown as the following formula I:
wherein,
the lignin does not contain a molecular skeleton of a terminal hydroxyl group, M1 is a molecular skeleton of epoxy halogenated alkane which does not contain a terminal hydroxyl group and a halogen atom after an epoxy ring-opening reaction, M2 is a molecular skeleton of an cosolvent compound which does not contain a hydroxyl group, and M3 is a molecular skeleton of a cracking type photoinitiator which does not contain a hydroxyl group;
n1, n2, x1, x2, y1 and y2 are integers not less than 0 and x1+ x2 is 1; n3 is a natural number not less than 1, n1+ n2+ n3 is the number of terminal hydroxyl groups of lignin, and y1+ x2+ n2 is not less than 1.
The invention also provides a preparation method of the lignin-based macromolecular photoinitiator, which comprises the following steps:
dissolving or melting a solubilizing compound containing hydroxyl, adding a catalyst, adding epoxy halogenated alkane for reaction, and removing unreacted epoxy halogenated alkane after the reaction is finished to obtain an intermediate product A;
dissolving lignin in an alkaline aqueous solution, heating to reflux, adding the intermediate product A for reaction, cooling after the reaction is finished, adjusting the pH value to 7, and purifying and drying to obtain an intermediate product B;
dissolving a cracking type photoinitiator containing hydroxyl, adding a catalyst, adding epoxy halogenated alkane for reaction, and removing unreacted epoxy halogenated alkane after the reaction is finished to obtain an intermediate product C;
and dissolving the intermediate product B and the intermediate product C, reacting under an alkaline condition, cooling after the reaction is finished, adjusting the pH value to 7, purifying and drying to obtain the lignin-based macroinitiator with the structural formula shown in the formula I.
Further, the structural formula of the intermediate product A is shown as formula II:
wherein M1 is a molecular skeleton of epoxy haloalkane which does not contain terminal hydroxyl and halogen after epoxy ring-opening reaction, M2 is a molecular skeleton of cosolvent compound which does not contain hydroxyl, X is halogen atom, and y3 is an integer more than or equal to 0.
Further, the structural formula of the intermediate product B is shown as a formula III:
wherein,
the lignin is a molecular skeleton without terminal hydroxyl, M1 is a molecular skeleton without terminal hydroxyl and halogen after epoxy ring-opening reaction of epoxy haloalkane, M2 is a molecular skeleton without hydroxyl of the solubilizing compound, n4 is a natural number not less than 1, n5 is an integer not less than 0, and n4+ n5 is the number of terminal hydroxyl of the lignin.
Further, the structural formula of the intermediate product C is shown as a formula IV:
wherein M1 is a molecular skeleton of epoxy haloalkane which does not contain terminal hydroxyl and halogen after epoxy ring-opening reaction, M3 is a molecular skeleton of cracking type photoinitiator which does not contain hydroxyl, and X is halogen atom.
Further, the lignin includes but is not limited to one or more of kraft lignin, alkali lignin, sodium lignin sulfonate and organic solvent-soluble lignin, preferably alkali lignin;
furthermore, the molecular weight of the lignin is 5000-50000, and the hydroxyl content is 2.0-5.0 mmol/g.
Further, the halogenated alkylene oxide includes but is not limited to one or more of epichlorohydrin, epifluorohydrin, epibromohydrin, methylepichlorohydrin, 4-bromo-1, 2-epoxybutane, and 6-bromo-1, 2-epoxyhexane.
Further, the solubilizing compound containing hydroxyl includes, but is not limited to, polyethylene glycol and derivatives thereof, polyvinyl alcohol and derivatives thereof, polymaleic acid and derivatives thereof, waterborne polyurethane and derivatives thereof, polyvinylpyrrolidone and derivatives thereof, water-soluble starch and derivatives thereof, sodium alginate and derivatives thereof, hyaluronic acid and derivatives thereof; preferably, the degree of polymerization of the solubilizing compound containing a hydroxyl group is 5 to 7500, more preferably 5 to 500.
Further, the hydroxyl group-containing cleavage type photoinitiators include, but are not limited to, α -hydroxyketone derivatives, α -aminoketone derivatives, benzoyl formates, and acylphosphine oxides, and preferably:
further, the catalyst includes but is not limited to boron trifluoride ethyl ether, aluminum trichloride, triethylamine, sodium hydroxide, ferric trichloride, titanium tetrachloride, preferably boron trifluoride ethyl ether, triethylamine, sodium hydroxide.
Further, the solvent used for dissolving includes but is not limited to one or more of alkaline aqueous solution, ethanol, dioxane, tetrahydrofuran and dimethyl sulfoxide.
Further, the reaction molar ratio of the intermediate product C to the intermediate product B is 2: 1-10: 1.
Furthermore, the mass fraction of the molecular skeleton of the solubilizing compound in the lignin-based macromolecular photoinitiator is 10-70 wt%, the mass fraction of the molecular skeleton of the cracking type photoinitiator is 5-20 wt%, and the solubility of the lignin-based macromolecular photoinitiator in water and/or an organic solvent is more than or equal to 5 wt%.
The invention further provides an application of the lignin-based macromolecular photoinitiator in a photocuring system.
Further, the photocuring system comprises 0.1-20 parts of lignin-based macromolecular photoinitiator with a structural formula shown as a formula I, 10-90 parts of solvent and 20-90 parts of photopolymerizable monomer.
The photopolymerizable monomer is selected from polymerizable monomers with the functional group number of at least 1, and comprises micromolecule and/or macromolecule polymerizable monomers containing monofunctional group, bifunctional group and polyfunctional group; preferably, selected from the group consisting of water-soluble photopolymerizable monomers, biomacromonomers selectively modifying polymerizable groups, and ester-soluble photopolymerizable monomers; more preferably, the water-soluble photopolymerizable monomers include, but are not limited to, one or more of epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, acrylated poly (meth) acrylates; the biomacromonomer comprises one or more of but not limited to gelatin derivatives, hyaluronic acid derivatives, chitin derivatives, sodium alginate derivatives, cellulose derivatives and xanthan gum derivatives; the ester-soluble photopolymerizable monomers include, but are not limited to, one or more of (meth) acrylates, vinyls, vinyl ethers, epoxies.
Further, the solvent includes, but is not limited to, one or more of deionized water, ethanol, acetone, butanone, dimethyl sulfoxide, dimethylformamide, dichloromethane, chloroform, hexane, heptane.
The invention has the following beneficial effects:
1. the lignin-based macromolecular photoinitiator simultaneously modifies and articulates the solubilizing group and the cracking photoinitiator group on lignin molecules to endow the lignin with new structure and performance, so that the lignin-based macromolecular photoinitiator has sufficient solubility in water and conventional organic solvents and higher photoinitiation activity, can initiate monomers, oligomers and (or) unsaturated double bond modified macromonomers containing unsaturated double bonds to perform free radical polymerization or crosslinking reaction under the exposure of an ultraviolet-visible light source, is used for preparing photocureable coatings, printing ink, adhesives, photoresists, printed circuit boards, optical fibers, 3D printing, biomedical hydrogel and other fields, and has good application prospect in the photocuring industry.
2. The lignin-based macromolecular photoinitiator has a hyperbranched structure, has low viscosity compared with linear polymers with the same molecular weight, cannot cause obvious influence on the viscosity of a photocuring formula, and is favorable for the basic requirements of a coating process or 3D printing rheological parameters.
3. The lignin-based macromolecular photoinitiator is introduced into a photocuring formula as a photoinitiator and can also be used as a modified filler due to the multi-benzene ring and three-dimensional cross-linked network structure of lignin, so that the macroscopic properties of the photocuring material, such as mechanical properties, thermal properties, storage properties and the like, are modified.
4. Compared with the micromolecule photoinitiator, the lignin-based macromolecule photoinitiator has the advantages of large molecular weight, small mobility in photocuring materials, no volatilization, low toxicity and improved safety of the photocuring materials, and is more suitable for application in the field with higher safety.
5. The lignin-based macromolecular photoinitiator has the characteristics of simple synthetic route, easy quantitative synthesis, high yield and the like.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a one-dimensional nuclear magnetic hydrogen spectrum of the lignin-based macrophotoinitiator L-PEG-2959 of example 2.
FIG. 2 shows an infrared spectroscopic characterization of the lignin-based macrophotoinitiator L-PEG-2959 of example 2.
FIG. 3 shows the UV absorption spectrum of the lignin-based macrophotoinitiator L-PEG-2959 of example 2.
FIG. 4 shows the thermogravimetric analysis spectrum of the lignin-based macro-photoinitiator L-PEG-2959 of example 2.
FIG. 5 shows a gel permeation chromatogram of lignin-based macrophotoinitiator L-PEG-2959 in example 2.
FIG. 6 shows the photocurable formulation of example 7 containing a lignin-based macrophotoinitiator L-PEG-2959 and its photoinitiating properties.
FIG. 7 shows the migration test of the lignin-based macrophotoinitiator L-PEG-2959 in example 7 in the cured product.
FIG. 8 shows the mechanical strength test of lignin-based macrophotoinitiator L-PEG-2959 on gelatin hydrogel in example 7.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, biomaterials, etc. used in the following examples are commercially available unless otherwise specified. The methods and equipment used are conventional in the art.
In the following examples, lignin was purchased from national chemical agents, and the amount of hydroxyl groups was 2.0 to 5.0mmol/g, as measured by nuclear magnetic resonance.
Example 1
The embodiment provides an ester water amphiphilic lignin-based macromolecular photoinitiator L-PEG-2959, which is prepared according to the following steps:
1) 100g (0.1mol) of polyethylene glycol (PEG) with the molecular weight of 1000 is added into a 500mL three-necked flask, the temperature is raised to 55 ℃ until the polyethylene glycol is completely melted, 0.8g (0.005mol) of boron trifluoride diethyl etherate is added under the stirring condition, 4.626g (0.05mol) of Epichlorohydrin (ECH) is added into the reaction flask, and the reaction temperature is maintained at 55-60 ℃. After the addition was complete, the reaction was allowed to react for a further 4 hours in this temperature range. Then, unreacted epichlorohydrin was removed by rotary evaporation to obtain polyethylene glycol having a terminal group having a chlorine active group (PEG-ECH), and the yield of the obtained product was about 80 wt%.
2) Dissolving 20g of alkaline lignin in 1mol/L sodium hydroxide aqueous solution to ensure that the content of the lignin is 25% (w/w), dropwise adding the product obtained in the step 1) into the system, and reacting for 4 hours at 80 ℃. Adjusting the pH of the obtained reaction liquid to 7 by using hydrochloric acid, extracting unreacted polyethylene glycol by using butanone to obtain a product, pouring the rest reaction liquid into a large amount of ethanol, stirring for 1 hour to separate out a small amount of brownish black solids, removing the precipitate by filtering, adding a proper amount of ethyl acetate into the rest liquid to separate out a large amount of brown products, filtering and drying to obtain a crude product L-PEG, wherein the yield is about 70 wt%.
Wherein is n4Natural number not less than 1, n5Is a natural number not less than 0 and n4+n5Lignin has a number of terminal hydroxyl groups.
3) A500 mL three-neck flask was charged with 22.4g (0.1mol) of a small molecule photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (Irgacure 2959) and 250mL of ethanol, sufficiently stirred to be dissolved uniformly, and then 0.8g (0.005mol) of boron trifluoride diethyl etherate was added with a needle, followed by slowly adding 9.25g (0.1mol) of epichlorohydrin dropwise thereto. After the completion of the dropwise addition, the reaction was continued at 55 ℃ for 2 hours to stop the reaction. Then, the reaction solution is subjected to rotary evaporation to remove the unreacted epichlorohydrin and the ethanol solvent, so as to obtain a crude product 2959-ECH.
4) Adding 5g of the product obtained in the step 2), 5.6g of the product obtained in the step 3) and 100mL of ethanol into a 250mL three-neck flask, fully stirring to mix uniformly, dropwise adding 1mol/L of sodium hydroxide into the solution to adjust the pH value to be 8-9, heating to 80 ℃, and continuing to react for 4 hours at the temperature. And after the reaction is finished, naturally cooling, regulating the pH of the reaction solution to 7 by using hydrochloric acid, removing the ethanol solvent by rotary evaporation, extracting the obtained product by using a small amount of water, filtering out unreacted micromolecule photoinitiator which is not dissolved in water, retaining the filtered brown water solution, and dialyzing for 7 days by using a dialysis membrane with the molecular weight cutoff of 5kDa to remove residual micromolecule photoinitiator, generated salt and other impurities. The resulting brown aqueous solution from the dialysis membrane was poured into a large petri dish and dried under vacuum at 30 ℃ for 7 days to give the pure final product L-PEG-2959.
Wherein n1, n2, x1, x2, y1 and y2 are integers not less than 0, and x1+ x2 is 1, and y1+ y2 is 1; n3 is a natural number not less than 1, n1+ n2+ n3 is the number of terminal hydroxyl groups of lignin, and y1+ x2+ n2 is not less than 1.
Thermogravimetric analysis of the product L-PEG-2959 shows that the mass ratio of the molecular skeleton of lignin, the molecular skeleton of PEG cosolvent compound and the molecular skeleton of Irgacure2959 micromolecule photoinitiator in the macromolecular photoinitiator is 22.4: 65.3: 12.3.
example 2
Similar to step 4) in example 1, 5g of the product obtained in step 2) above, 10g of the product obtained in step 3) above and 200mL of ethanol were added to a 500mL three-necked flask, sufficiently stirred to mix them uniformly, 1mol/L sodium hydroxide solution was added dropwise thereto, the pH was adjusted to 8 to 9, the mixture was heated to 80 ℃ and the reaction was continued at this temperature for 4 hours. And after the reaction is finished, naturally cooling, regulating the pH of the reaction solution to 7 by using hydrochloric acid, removing the ethanol solvent by rotary evaporation, extracting the product by using a small amount of water, filtering out unreacted micromolecule photoinitiator which is not dissolved in water, retaining the filtered brown water solution, and dialyzing for 7 days by using a dialysis membrane with the molecular weight cutoff of 5kDa to remove residual micromolecule photoinitiator, generated salt and other impurities. The resulting brown aqueous solution from the dialysis membrane was poured into a large petri dish and dried under vacuum at 30 ℃ for 7 days to give the pure final product L-PEG-2959. The product L-PEG-2959 is subjected to thermogravimetric analysis, wherein the mass ratio of the molecular skeleton of lignin, the molecular skeleton of a PEG cosolvent compound and the molecular skeleton of an Irgacure2959 micromolecule photoinitiator to the macromolecular photoinitiator is 21.5: 60.9: 17.6.
FIG. 1 shows a one-dimensional nuclear magnetic hydrogen spectrum of the macromolecular photoinitiator L-PEG-2959 prepared in the example, and FIG. 2 shows an infrared spectrum characterization of the macromolecular photoinitiator L-PEG-2959 prepared in the example. As can be seen from FIGS. 1 and 2, the L-PEG-2959 macrophotoinitiator was successfully prepared by the method of the present invention.
FIG. 3 shows the UV spectrum test characterization of the macromolecular photoinitiator L-PEG-2959 prepared in this example. As can be seen from FIG. 3, the prepared L-PEG-2959 has an obvious new absorption peak at 250-300 nm besides the original ultraviolet absorption peak of lignin, and the peak is similar to the spectral property of Irgacure2959, which indicates that the photoinitiation active group is successfully introduced into the lignin molecular skeleton.
FIG. 4 shows the thermogravimetric analysis spectrum of the macromolecular photoinitiator L-PEG-2959 prepared in this example. As can be seen from FIG. 4, a decomposition platform capable of clearly distinguishing different components of the material appears in FIG. 4, so that the composition of the macroinitiator can be obtained, wherein the mass fraction of the photoinitiating groups is 17.6 wt%, and the high initiation activity of the macroinitiator is ensured due to the considerable grafting amount.
FIG. 5 shows a gel permeation chromatogram of the macromolecular photoinitiator L-PEG-2959 prepared in this example. As can be seen from fig. 5, the prepared lignin-based macro-molecular photoinitiator has a relatively high molecular weight, meets the requirement of low macro-molecular mobility, has a typical hyperbranched molecular structure, and is easy to realize the characteristics of effective photoinitiation performance and low viscosity.
Example 3
Similar to the step 4) in the example 1, 5g of the product obtained in the step 2), 15g of the product obtained in the step 3) and 200mL of ethanol are added into a 500mL three-neck flask, the mixture is stirred sufficiently and mixed uniformly, 1mol/L sodium hydroxide solution is added dropwise, the pH is adjusted to 8-9, the mixture is heated to 80 ℃, and the reaction is continued for 4 hours at the temperature, so that the crude product of the final product is obtained. And after the reaction is finished, naturally cooling, regulating the pH of the reaction solution to 7 by using hydrochloric acid, removing the ethanol solvent by rotary evaporation, extracting the product by using a small amount of water, filtering out most unreacted micromolecule photoinitiator which is insoluble in water, retaining the filtered brown water solution, and dialyzing for 7 days by using a dialysis membrane with the molecular weight cutoff of 5kDa to remove residual micromolecule photoinitiator, generated salt and other impurities. The resulting brown aqueous solution from the dialysis membrane was poured into a large petri dish and dried under vacuum at 30 ℃ for 7 days to give the pure final product L-PEG-2959.
The product L-PEG-2959 is subjected to thermogravimetric analysis, wherein the mass ratio of the molecular skeleton of lignin, the molecular skeleton of a PEG cosolvent compound and the molecular skeleton of an Irgacure2959 micromolecule photoinitiator in the macromolecular photoinitiator is 24.5: 55.7: 19.8.
example 4
1) 27.6g (0.1mol) of hydroxyl group-containing TPO-OH and 200mL of dimethyl sulfoxide (DMSO) were put into a 500mL three-necked flask, sufficiently stirred to mix them uniformly, 0.8g (0.005mol) of boron trifluoride diethyl ether was added through a needle, and 9.25g (0.1mol) of epichlorohydrin was slowly added dropwise to the mixture. After the completion of the dropwise addition, the reaction was continued for 2 hours while maintaining 55 ℃. After the reaction is finished, removing unreacted epichlorohydrin by rotary evaporation, washing with a large amount of water, precipitating, and filtering to obtain a crude product TPO-ECH.
2) 5g of the product obtained in the step 2) of the example 1, 5.6g of the product obtained in the step 1) and 100mL of a mixed solution of dimethyl sulfoxide and water are added into a 250mL three-neck flask, the mixture is stirred sufficiently and uniformly mixed, 1mol/L of an aqueous sodium hydroxide solution is added dropwise into the solution to adjust the pH value to be between 8 and 9, the solution is heated to 80 ℃, and the reaction is continued for 4 hours at the temperature. And after the reaction is finished, naturally cooling, adjusting the pH of the reaction solution to 7 by using hydrochloric acid, washing the reaction solution by using a small amount of water, filtering, retaining a brown water solution, and dialyzing for 7 days by using a dialysis membrane with the molecular weight cutoff of 5kDa to remove residual small-molecular photoinitiator, solvent, generated salt and other impurities. The resulting brown aqueous solution from the dialysis membrane was poured into a large petri dish and dried under vacuum at 30 ℃ for 48 hours to give the final pure product L-PEG-TPO.
Wherein n1, n2, x1, x2, y1 and y2 are integers not less than 0, and x1+ x2 is 1, and y1+ y2 is 1; n3 is a natural number not less than 1, n1+ n2+ n3 is the number of terminal hydroxyl groups of lignin, and y1+ x2+ n2 is not less than 1.
Thermogravimetric analysis is carried out on the product L-PEG-TPO, wherein the mass ratio of a molecular framework of lignin, a molecular framework of a PEG cosolvent compound and a molecular framework of a TPO micromolecule photoinitiator in the macromolecular photoinitiator is 31.5: 56.7: 11.8.
example 5
The embodiment provides a water-soluble lignin-based macro-photoinitiator L-PVA-2959, which is prepared according to the following steps:
1) 15g of low molecular weight 13,000-23,000, 86-89% hydrolyzed polyvinyl alcohol (PVA) and 300mL of water are added into a 500mL three-necked flask, the temperature is raised to 70 ℃, the mixture is fully dissolved by high-speed mechanical stirring, 0.008g (0.00005mol) of boron trifluoride ethyl ether complex is added into the three-necked flask by a needle tube under the temperature condition as a catalyst, and 0.04626g (0.0005mol) of Epichlorohydrin (ECH) is slowly dropped into the reaction flask. After the addition was complete, the reaction was continued for 4 hours. After the reaction is finished, unreacted epichlorohydrin is removed by rotary evaporation to obtain a crude product PVA-ECH with the yield of about 90 wt%.
Wherein n is6Is a natural number not less than 1, and n6+n7The hydroxyl number of polyvinyl alcohol.
2) Dissolving 5g of alkaline lignin in 1mol/L sodium hydroxide aqueous solution to ensure that the content of the lignin is 25% (w/w), adding the product obtained in the step 1) and the alkaline lignin aqueous solution into a 500mL three-necked bottle, heating to 80 ℃, fully dissolving the product by high-speed mechanical stirring, and then reacting for 4 hours under the conditions. After the reaction was completed, the pH of the obtained reaction solution was adjusted to 7 with hydrochloric acid. Then, repeatedly extracting for 3 days by using a Soxhlet extractor under the condition of using water as a solvent and heating, and finally drying for 48 hours in a vacuum drying oven to obtain a pure L-PVA copolymerization product with the yield of about 70 percent.
Wherein n8, n9 and n10 are integers of 0 or more, and n6Is a natural number not less than 1, and n6+ n8+ n9 is the number of hydroxyl groups of polyvinyl alcohol, and n8+ n10 is the number of terminal hydroxyl groups of lignin;
3) 5g of the product obtained in 2) above, 2959-ECH1.0g of the product obtained in step 3) described in example 1, and 200mL of a 1mol/L aqueous solution of sodium hydroxide were charged into a 500mL three-necked flask, heated to 80 ℃ and reacted under these conditions for 4 hours. After the reaction is finished, naturally cooling, adjusting the pH of the reaction solution to 7 by using hydrochloric acid, repeatedly extracting for 3 days by using a Soxhlet extractor under the condition of heating reflux, dialyzing for 7 days by using a dialysis membrane with molecular weight cutoff molecular weight of 5kDa, and finally drying for 48 hours in a vacuum drying oven to obtain the final pure product L-PVA-2959.
Wherein n1, n2, n9, x1, x2, y1, y2, z1 and z2 are integers not less than 0, x1+ x2 is 1, z1+ z2 is 1, y1+ y2+ n9+1 is the hydroxyl number of the raw material polyvinyl alcohol; n3 is a natural number not less than 1, n1+ n2+ n3 is the number of terminal hydroxyl groups of lignin, and y1+ x2+ + z2+ n2 is not less than 1.
The product L-PVA-2959 is subjected to thermogravimetric analysis, wherein the mass ratio of the molecular framework of lignin, the molecular framework of a PVA solubilizing compound and the molecular framework of an Irgacure2959 micromolecule photoinitiator in the macromolecular photoinitiator is 27.8: 63.5: 8.7.
example 6
Similar to step 3) in example 5), 5g of the product obtained in step 2) above, 2g of the product obtained in step 3) in example 1 and 200mL of ethanol were added to a 500mL three-necked flask, and the mixture was heated and stirred sufficiently to mix them uniformly, then 1mol/L aqueous sodium hydroxide solution was added dropwise thereto, the pH was adjusted to 8 to 9, the mixture was heated to 80 ℃ and the reaction was continued at this temperature for 4 hours. And after the reaction is finished, naturally cooling, adjusting the pH of the reaction solution to 7 by using hydrochloric acid, repeatedly extracting for 3 days by using a Soxhlet extractor under the conditions of using water as a solvent and heating reflux, dialyzing for 7 days by using a dialysis membrane with the molecular weight cutoff molecular weight of 5kDa, and finally drying for 48 hours in a vacuum drying oven to obtain the final pure product L-PVA-2959.
The product L-PVA-2959 is subjected to thermogravimetric analysis, wherein the mass ratio of the molecular framework of lignin, the molecular framework of a PVA solubilizing compound and the molecular framework of an Irgacure2959 micromolecule photoinitiator in the macromolecular photoinitiator is 30.9: 56.8: 12.3.
in the above examples, the above experimental contents were repeated to replace the "alkali lignin" with another one selected from kraft lignin, alkali lignin, sodium lignosulfonate and organic solvent-soluble lignin, without affecting the properties of the finally obtained lignin-based macro-photoinitiator.
In the above examples, the above experimental contents were repeated to replace "epichlorohydrin" with another one selected from the group consisting of epifluorohydrin, epibromohydrin, methylepichlorohydrin, 4-bromo-1, 2-epoxybutane, and 6-bromo-1, 2-epoxyhexane, without affecting the properties of the finally obtained lignin-based macrophotoinitiator.
In the above examples, the above experimental contents were repeated to replace "polyethylene glycol" or "polyvinyl alcohol" with another one selected from polymaleic acid and its derivatives, aqueous polyurethane and its derivatives, polyvinylpyrrolidone and its derivatives, water-soluble starch and its derivatives, sodium alginate and its derivatives, hyaluronic acid and its derivatives, without affecting the performance of the finally obtained lignin-based macrophotoinitiator.
In the above examples, the above experimental contents were repeated to replace "2959" or "TPO-OH" with another one selected from α -hydroxyketone derivatives, α -aminoketone derivatives, benzoyl formates and acylphosphorus oxides, without affecting the performance of the finally obtained lignin-based macrophotoinitiator.
Example 7: lignin-based macromolecular photoinitiator L-PEG-2959 for preparing biological composite hydrogel by photoinitiating gelatin derivatives
Taking gelatin (Gel-GMA) modified by glycidyl methacrylate as a water-soluble macromonomer (with double bond grafting rate of 74%), dissolving the gelatin in hot water and keeping the content of the gelatin at 20 wt%, adding a macromolecular photoinitiator L-PEG-2959 (the content of the photoinitiator component in the formula is about 5 wt%, 10 wt% and 15 wt% relative to the monomer), synthesized in example 2, and then adding the gelatin with the maximum absorption wavelength of 365nm and the light intensity of 20mw/cm2The lignin-gelatin composite hydrogel is obtained by initiating polymerization for 10 minutes under the irradiation of an ultraviolet light source. As a reference sample, Irgacure2959, a small molecule photoinitiator, was added in an amount of 1 wt% (relative to the monomer) and was photopolymerized under the same experimental conditions to obtain a homopolymeric gelatin hydrogel. The prepared sample is subjected to ultrasonic extraction of unreacted photoinitiator or cracking residues thereof in a certain amount of ethanol, and the extraction amount of the unreacted photoinitiator or the cracking residues is measured through high pressure liquid chromatography and ultraviolet spectroscopy to quantitatively measure the mobility of the photoinitiator in the photocuring material. Table 1 shows the formulation of a photocuring system containing the macrophotoinitiator L-PEG-2959 obtained in example 2, a gelatin derivative macromonomer and water as a solvent.
TABLE 1 photocurable System formulation
FIG. 6, panel A, shows a photocurable formulation of different formulation compositions containing varying amounts of L-PEG-2959. As can be seen from the figure, the L-PEG-2959 can be well mixed with the gelatin derivative in a larger addition range (5-15 wt%) under the condition of deionized water;
in fig. 6, B is the lignin-gelatin composite hydrogel obtained after ultraviolet light curing. As can be seen from the figure, L-PEG-2959 can initiate photopolymerization of water-soluble bio-based macromonomers (gelatin derivatives), demonstrating its photoinitiating capability. The compatibility of the two is good in the composition range, and the color of the mixed hydrogel gradually becomes darker along with the increase of the lignin content.
Fig. 7 shows the test characterization results of the permeation amount of the photoinitiator remaining after ethanol ultrasonic extraction or the cleavage residue after photoinitiation in the photo-cured composite hydrogel. As can be seen from the figure, the amount of the photoinitiator extractable by the macromolecular photoinitiator L-PEG-2959 is obviously less than that of the corresponding micromolecular photoinitiator Irgacure2959, which shows that the mobility of the photoinitiator in a curing system is obviously reduced, and the safety of the cured material is increased.
FIG. 8 shows the results of the test for the effect of L-PEG-2959 as a filler on the mechanical strength of gelatin hydrogel. As can be seen from the figure, the mechanical strength of the homopolygelatin hydrogel is weak, the Young's modulus of the homopolygelatin hydrogel can be obviously improved after the lignin is introduced, and the modulus of the mixed hydrogel is obviously increased along with the increase of the content of the lignin.
Example 8: lignin-based macromolecular photoinitiator L-PEG-2959 used for photo-initiating commercial acrylate monomers to prepare 3D products
Under the condition of keeping out of the sun, polyethylene glycol diacrylate (PEGDA) with the molecular weight of 1000 is taken as a photopolymerization monomer to be dissolved in dimethyl sulfoxide (DMSO), then a certain amount of macromolecular photoinitiator L-PEG-2959 is added, and the mixture is fully stirred to be completely dissolved; wherein, the formula of the photocuring system containing the macrophotoinitiator L-PEG-2959 obtained in any one of examples 1-3, PEGDA oligomer monomer and DMSO as solvents is shown in Table 2. Then, the photocuring formula is placed in a machine gun of a 3D printer, certain instrument parameters are set, and then the 3D printing material with certain shape and specification is obtained under the exposure of an ultraviolet-visible light source.
TABLE 2 light-curing System formulation
Example 9: lignin-based macromolecular photoinitiator L-PEG-2959 used for aqueous photocureable coating
50-70 parts of commercial waterborne polyurethane acrylate (Bayer U54), 10-15 parts of tripropylene glycol diacrylate (TPGDA) emulsion, 5-40 parts of deionized water, 0.05-1 part of macromolecular photoinitiator L-PEG-2959 and 5-20 parts of solid powdery substances such as pigments, fillers and auxiliaries which may be contained are connected, ground and dispersed to form a slurry-like dispersion, the slurry-like dispersion is coated on a base material, the slurry-like dispersion is dried and fixed, and then ultraviolet light curing is carried out to obtain a photocuring coating, a formula of a photocuring system containing the macromolecular photoinitiator L-PEG-2959 obtained in any one of examples 1-3, waterborne polyurethane acrylate oligomer and TPGDA as an active diluent is given in Table 3, and the water-based photocuring coating can be obtained through the formula of the table.
TABLE 3 light-curing System formulation
Example 10: lignin-based macromolecular photoinitiator L-PEG-TPO for preparing 3D product by photoinitiating commercial acrylate monomer
Under the condition of keeping out of the sun, polyethylene glycol diacrylate (PEGDA) with the molecular weight of 1000 is taken as a photopolymerization monomer to be dissolved in dimethyl sulfoxide (DMSO), then a certain amount of the macromolecular photoinitiator L-PEG-TPO prepared in the embodiment 4 is added, and the mixture is fully stirred to be completely dissolved; wherein, the formula of the photocuring system containing the macromolecular photoinitiator L-PEG-TPO, PEGDA oligomer monomer and DMSO as solvents is given in Table 4. Then, the photocuring formula is placed in a machine gun of a 3D printer, certain instrument parameters are set, and then the 3D printing material with certain shape and specification is obtained under the exposure of an ultraviolet-visible light source.
TABLE 4 light-curing System formulation
Example 11: lignin-based macromolecular photoinitiator L-PVA-2959 used for aqueous photocureable coating
50-70 parts of commercial waterborne polyurethane acrylate (Bayer U54), 10-15 parts of tripropylene glycol diacrylate (TPGDA) emulsion, 5-40 parts of deionized water, 0.05-1 part of macromolecular photoinitiator L-PVA-2959 prepared in example 5 and 5-20 parts of solid powdery substances such as pigments, fillers and auxiliaries which may be contained are connected together, ground and dispersed to form a slurry-like dispersion, the slurry-like dispersion is coated on a substrate in construction, dried and fixed, and then ultraviolet light curing is performed to obtain a light-cured coating, a light-cured system formula containing the macromolecular photoinitiator L-PVA-2959, waterborne polyurethane acrylate oligomer and TPGDA as active diluents is given in Table 5, and the water-based light-cured coating can be obtained through the formula in the table.
TABLE 5 light-curing System formulation
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A lignin-based macro-molecular photoinitiator is characterized in that the structural formula of the photoinitiator is shown as the following formula I:
wherein,
is a molecular skeleton of lignin without terminal hydroxyl,
m1 is a molecular skeleton of epoxy halogenated alkane which does not contain terminal hydroxyl and halogen atom after epoxy ring-opening reaction,
m2 is a molecular skeleton in which the hydrotropic compound does not contain hydroxyl groups,
m3 is a molecular skeleton of a cleavage type photoinitiator containing no hydroxyl group;
n1, n2, x1, x2, y1 and y2 are integers not less than 0 and x1+ x2 is 1;
n3 is a natural number of 1 or more,
n1+ n2+ n3 is the number of terminal hydroxyl groups of lignin and y1+ x2+ n2 is not less than 1.
2. The method for preparing the lignin-based macro-photoinitiator according to claim 1, comprising the steps of:
dissolving or melting a solubilizing compound containing hydroxyl, adding a catalyst, adding epoxy halogenated alkane for reaction, and removing unreacted epoxy halogenated alkane after the reaction is finished to obtain an intermediate product A; the structural formula of the intermediate product A is shown as a formula II:
wherein X is a halogen atom, and y3 is an integer of 0 or more;
dissolving lignin in an alkaline aqueous solution, heating to reflux, adding the intermediate product A for reaction, cooling after the reaction is finished, adjusting the pH value to 7, and reacting to obtain an intermediate product B; the structural formula of the intermediate product B is shown as a formula III:
wherein n4 is a natural number not less than 1, n5 is an integer not less than 0, and n4+ n5 is the number of terminal hydroxyl groups of lignin;
dissolving a cracking type photoinitiator containing hydroxyl, adding a catalyst, adding epoxy halogenated alkane for reaction, and removing unreacted epoxy halogenated alkane after the reaction is finished to obtain an intermediate product C; the structural formula of the intermediate product C is shown as a formula IV:
and dissolving the intermediate product B and the intermediate product C, reacting under an alkaline condition, cooling after the reaction is finished, adjusting the pH value to 7, purifying, and reacting to obtain the lignin-based macromolecular photoinitiator.
3. The method of claim 2, wherein the lignin comprises one or more of kraft lignin, alkali lignin, sodium lignosulfonate and organic solvent-soluble lignin, preferably alkali lignin; more preferably, the molecular weight of the lignin is 5000-50000, and the hydroxyl content is 2.0-5.0 mmol/g.
4. The preparation method according to claim 2, wherein the epihalohydrin comprises one or more of epichlorohydrin, epifluoropropane, epibromohydrin, methylepichlorohydrin, 4-bromo-1, 2-epoxybutane and 6-bromo-1, 2-epoxyhexane; the catalyst comprises boron trifluoride diethyl etherate, aluminum trichloride, triethylamine, sodium hydroxide, ferric trichloride and titanium tetrachloride, and preferably boron trifluoride diethyl etherate, triethylamine and sodium hydroxide.
5. The preparation method according to claim 2, wherein the solubilizing compound containing a hydroxyl group comprises polyethylene glycol and derivatives thereof, polyvinyl alcohol and derivatives thereof, polymaleic acid and derivatives thereof, aqueous polyurethane and derivatives thereof, polyvinylpyrrolidone and derivatives thereof, water-soluble starch and derivatives thereof, sodium alginate and derivatives thereof, hyaluronic acid and derivatives thereof; preferably, the degree of polymerization of the solubilizing compound containing a hydroxyl group is 5 to 7500, more preferably 5 to 500.
6. The method of claim 2, wherein the hydroxyl-containing cleavage type photoinitiator comprises α -hydroxyketone derivative, α -aminoketone derivative, benzoylformate and acylphosphine oxide, preferably:
7. the preparation method according to claim 2, wherein the reaction molar ratio of the intermediate product C to the intermediate product B is 2: 1-10: 1.
8. The preparation method according to claim 2, wherein the mass fraction of the molecular skeleton of the co-soluble compound in the lignin-based macro-molecular photoinitiator is 10 to 70 wt%, the mass fraction of the molecular skeleton of the cleavage-type photoinitiator is 5 to 20 wt%, and the solubility of the lignin-based macro-molecular photoinitiator in water and/or an organic solvent is not less than 5 wt%.
9. Use of the lignin-based macrophotoinitiator according to claim 1 in a photocuring system.
10. The application of claim 9, wherein the photo-curing system comprises 0.1-20 parts of lignin-based macro-photoinitiator represented by formula I, 10-90 parts of solvent, and 20-90 parts of photopolymerizable monomer.
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