CN115746226A - Plant oil-based ultraviolet curing resin oligomer, preparation method thereof and ultraviolet curing composition - Google Patents
Plant oil-based ultraviolet curing resin oligomer, preparation method thereof and ultraviolet curing composition Download PDFInfo
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Abstract
The invention discloses a preparation method of a vegetable oil-based ultraviolet curing resin oligomer, which adopts epoxidized soybean oil as a substrate, and adds acrylic acid or methacrylic acid to perform a catalytic ring-opening reaction under the action of a catalyst to obtain the vegetable oil-based ultraviolet curing resin oligomer. The synthetic composition of the vegetable oil-based uv curable resin oligomer, the reactive diluent and the photoinitiator was further used for photocuring 3D printing. The plant oil-based ultraviolet curing resin oligomer with the specific structure disclosed by the invention is green and environment-friendly and belongs to renewable energy, so that an object obtained by photocuring 3D has high toughness, high hydrophobicity and good thermal stability. Moreover, the synthesized vegetable oil-based ultraviolet curing resin oligomer has good compatibility with the reactive diluent, and the crosslinking density of each compound in the photocuring 3D process can be improved, so that the firmware printed by the photocuring 3D has higher precision.
Description
Technical Field
The invention belongs to the technical field of photosensitive resin, and particularly relates to a green and environment-friendly vegetable oil-based ultraviolet curing resin oligomer, a preparation method thereof and an ultraviolet curing composition.
Background
The ultraviolet curing technology is an industrial technology with the 5E characteristic, namely has the characteristics of high efficiency (efficiency), economy (Economic), energy conservation (Energy saving), wide adaptability (Enabling) and Environmental friendliness (Environmental friendliness), is a very ideal curing mode, is developed rapidly since the appearance of the technology in the 20 th century and 60 th era, and is mainly applied to the technical fields of coatings, printing ink, adhesives and the like.
Currently, the number of photosensitive resin varieties available on the market for 3D printing is relatively small, and most are produced based on a free radical photocuring mechanism. These cured resins harden and become brittle, resulting in poor bending and tensile properties. At the same time, the printed firmware is less accurate and shrinks, which severely limits their applications. Most of the traditional light-cured resins are produced by petroleum-based raw materials, and with the continuously developing concept of being more and more interesting and the continuous popularization of the green environmental protection concept, the seeking of alternative raw materials with high efficiency, low cost and reproducibility to prepare green polymer materials is urgent. With the development of the world green polymer materials, the development of the vegetable oil-based polymers has rapidly entered the field of researchers. Soybean Oil (Epoxidized Soybean Oil) is one of the most common renewable green resources in human society, epoxidized Soybean Oil (Epoxidized Soybean Oil) can be rapidly synthesized by epoxidizing Soybean Oil and an oxidant, the process is simple, the yield is high, and the Epoxidized Soybean Oil has important research significance in the field of resin synthesis due to non-volatility, excellent thermal stability and light stability and good intersolubility with resin materials. Compared with other light-cured resins, the resin prepared and synthesized by the epoxy soybean oil has the advantages of low price, environmental protection, low viscosity and good flexibility. In conclusion, the development of a green, environment-friendly and reproducible plant oil-based resin for photocuring 3D printing is urgently needed.
Disclosure of Invention
The invention provides a plant oil-based light-cured resin oligomer, a preparation method thereof and an ultraviolet light-cured composition, aiming at solving the defects of poor mechanical property, large shrinkage rate, poor printing precision and the like of printing firmware in the traditional light-cured system and saving energy and being renewable.
In order to solve the problems, the invention is realized by the following technical scheme:
the invention firstly provides a preparation method of a vegetable oil-based ultraviolet curing resin oligomer, which comprises the following steps:
(1) Under inert atmosphere, mixing a certain amount of epoxidized soybean oil with a polymerization inhibitor, and dispersing (mechanically stirring at 180-250 r/min) under the condition of 80-100 ℃ (oil bath) to form a uniform solution A;
(2) Adding a certain amount of catalyst into the monomer, and dispersing at 20-40 ℃ to form a uniform solution B;
(3) And slowly dripping the solution B into the solution A in an inert atmosphere, after the solution B is completely dripped, adjusting the temperature of a reaction system to 110-130 ℃, uniformly dispersing (adjusting the mechanical stirring speed to 400-500 r/min), and reacting for 5-6 hours to obtain the plant oil-based ultraviolet curing resin oligomer.
Further, the chemical structure of the epoxidized soybean oil is shown in the formula (A)
) Shown in the figure:
formula (A), (B) and
）。
further, in the step (1), the amount of the polymerization inhibitor is 0.1-0.2 wt% of the amount of the epoxidized soybean oil.
Further, in the step (1), the polymerization inhibitor is selected from at least one of hydroquinone, p-methoxyphenol, o-methylhydroquinone and 2, 6-di-tert-butyl-4-methylphenol; in the step (2), the catalyst is at least one selected from phosphine, triphenylphosphine, palladium bis (triphenylphosphine) diacetate, iodine and potassium iodide.
Further, in the step (2), the monomer is at least one of acrylic acid and methacrylic acid.
Further, in the step (2), the amount of the catalyst is 1-2 wt% of the amount of the epoxidized soybean oil used in the step (1); the molar ratio of carboxyl in the monomer used to epoxy in the epoxidized soybean oil used in step (1) is 1:1.05-1.25.
Another object of the present invention is to provide the vegetable oil-based uv curable resin oligomer prepared by the above method.
The invention also provides an ultraviolet curing composition which comprises the vegetable oil-based ultraviolet curing resin oligomer, a reactive diluent and a photoinitiator.
Further, the material comprises the following raw materials in percentage by weight: 45-50% of the vegetable oil-based ultraviolet curing resin oligomer, 48-53% of the reactive diluent and 1-3% of the photoinitiator.
Further, the reactive diluent is selected from at least one of acryloyl morpholine (ACMO), trimethylolpropane triacrylate (TMPTA) and 1, 6-hexanediol diacrylate (HDDA), polyethylene glycol diacrylate (PEGDA), isobornyl acrylate (IBOA), pentaerythritol triacrylate (PETA); the photoinitiator is at least one selected from Irgacure 819, irgacure 261 and TPO.
Since triglyceride in the vegetable oil-based uv-curable resin oligomer increases the viscosity of the oligomer, a greater proportion of acrylate monomer or other monomer in the choice of the photocurable reactive diluent is required. In the photocuring process, triglyceride in the epoxidized soybean oil reacts with acrylate of the reactive diluent in the photocuring system to form thermosetting crosslinking, and a resin material with better flexibility, thermal stability, light stability and printing precision is formed in a light-heat dual-curing mode.
The invention has the following positive and beneficial effects:
(1) The vegetable oil-based ultraviolet curing resin is vegetable oil-based acrylate synthesized by open-chain reaction of acrylic acid or methacrylic acid serving as a monomer and epoxy soybean oil, can be used as main resin, and can generate cross-linking reaction between triglyceride and other acrylate reactive diluents by heat release and temperature rise in the curing and cross-linking process in the photocuring process to finally form a compact cross-linking structure, so that the flexibility, the photo-thermal stability and the printing resolution of the material are greatly improved.
(2) The plant oil-based ultraviolet curing resin can be directly used as a prepolymer of the photocuring resin, and after the prepolymer is reacted with an active diluent, the mechanical properties of the photocuring 3D printing resin can be improved, the defects of high shrinkage rate, fragile and breakable printing firmware, poor printing precision and the like of the existing resin are overcome, so that a 3D printing material is easier to obtain, and meanwhile, the plant oil-based ultraviolet curing resin can gradually replace the traditional petroleum-based photocuring resin, so that the cost of the 3D printing material is reduced, and the waste of energy is reduced.
(3) The vegetable oil-based ultraviolet curing resin has higher viscosity due to the addition of the triglyceride, is more suitable for being diluted and mixed by adding the active diluent with better dilution performance, has very good compatibility with various resins or monomers, and has excellent performances of a cured part.
Drawings
FIG. 1 is a FTIR spectrum analysis of example 1 and comparative example 1;
FIG. 2 is an SEM image of the epoxidized soybean oil acrylate vegetable oil-based resin composition of example 1;
FIG. 3 is a contact angle plot of the epoxidized soybean oil acrylate vegetable oil-based resin composition of example 1;
fig. 4 is a picture of a photo-cured 3D printed sample of the epoxidized soybean oil acrylate vegetable oil-based resin composition of example 1.
Detailed Description
The present invention is described in further detail with reference to the following examples, but the embodiments of the present invention are not limited to these examples. The reagents used in the examples of the present invention are conventional raw materials or reagents unless otherwise specified, and the experimental methods used are conventional in the art unless otherwise specified.
Example 1
Will be represented by the formula (
) 50.00g of epoxidized soybean oil with the structure shown and 0.1g of hydroquinone as a polymerization inhibitor are put into a four-neck flask provided with a thermometer, a condenser tube, a dropping funnel and a stirring paddle, and mixed and stirred for 15min under the conditions of 90 ℃ oil bath and 200 r/min mechanical stirring until the solution A is completely and uniformly formed. 12.87g of acrylic acid was weighed into a beaker, 0.75 g of triphenylphosphine catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and magnetically stirred to form a homogeneous solution B. And then slowly dripping the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dripping is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in the acrylic acid to epoxy in the epoxidized soybean oil is 1:1.05 oligomeric epoxidized soy oil acrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil acrylate vegetable oil-based resin to prepare the epoxidized soybean oil acrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is: 48% of the epoxy soybean oil acrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of a photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 2
Will be represented by the formula (
) 50.00g of epoxidized soybean oil with the structure shown in the specification and 0.1g of hydroquinone as a polymerization inhibitor are added into a kettle which is provided with a thermometer, a condenser tube, a dropping funnel and stirringIn a paddle four-neck flask, the mixture was stirred for 15min under 90 ℃ oil bath and 200 r/min mechanical stirring until solution A was completely homogeneous. 12.28g of acrylic acid was weighed into a beaker, 0.75 g of triphenylphosphine catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and magnetically stirred to form a homogeneous solution B. And then slowly dropwise adding the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dropwise adding is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in the obtained acrylic acid to epoxy in the epoxidized soybean oil is 1:1.10 oligomeric epoxidized soybean oil acrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil acrylate vegetable oil-based resin to prepare the epoxidized soybean oil acrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is: 48% of the epoxy soybean oil acrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 3
Will be represented by the formula (A)
) 50.00g of epoxidized soybean oil having the structure shown in the specification and 0.1g of hydroquinone as a polymerization inhibitor were put in a four-necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirring paddle, and mixed and stirred for 15 minutes under a condition of 90 ℃ oil bath and mechanical stirring at 200 r/min until a solution A was completely and uniformly formed. 11.75g of acrylic acid was weighed into a beaker, 0.75 g of triphenylphosphine catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and magnetically stirred to form a homogeneous solution B. And then slowly dropwise adding the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dropwise adding is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in the obtained acrylic acid to epoxy in the epoxidized soybean oil is 1:1.15 oligomeric epoxidized soybean oil acrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil acrylate vegetable oil-based resin to prepare the epoxidized soybean oil acrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is as follows: 48% of the epoxy soybean oil acrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 4
Will be represented by the formula (
) 50.00g of epoxidized soybean oil with the structure shown and 0.1g of hydroquinone as a polymerization inhibitor are put into a four-neck flask provided with a thermometer, a condenser tube, a dropping funnel and a stirring paddle, and mixed and stirred for 15min under the conditions of 90 ℃ oil bath and 200 r/min mechanical stirring until the solution A is completely and uniformly formed. 11.26g of acrylic acid was weighed into a beaker, 0.75 g of triphenylphosphine catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and magnetically stirred to form a homogeneous solution B. And then slowly dripping the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dripping is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in the obtained acrylic acid to epoxy in the epoxidized soybean oil is 1:1.20 oligomeric epoxidized soybean oil acrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil acrylate vegetable oil-based resin to prepare the epoxidized soybean oil acrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is: 48% of the epoxy soybean oil acrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of a photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 5
Will be represented by the formula (A)
) What is needed is50.00g of epoxidized soybean oil having the structure shown in the figure and 0.1g of hydroquinone as a polymerization inhibitor were put in a four-necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirring paddle, and mixed and stirred for 15 minutes under a condition of 90 ℃ oil bath and mechanical stirring at 200 r/min until a solution A was completely and uniformly formed. 10.81g of acrylic acid was weighed into a beaker, 0.75 g of triphenylphosphine catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and magnetically stirred to form a homogeneous solution B. And then slowly dripping the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dripping is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in the acrylic acid to epoxy in the epoxidized soybean oil is 1:1.25 oligomeric epoxidized soybean oil acrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil acrylate vegetable oil-based resin to prepare the epoxidized soybean oil acrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is as follows: 48% of the epoxy soybean oil acrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 6
50.00g of epoxidized soybean oil with the structure shown in the formula (I) and 0.1g of hydroquinone as a polymerization inhibitor are put into a four-neck flask provided with a thermometer, a condenser tube, a dropping funnel and a stirring paddle, and are mixed and stirred for 15min under the conditions of 90 ℃ oil bath and 200 r/min mechanical stirring until the solution A is completely and uniformly formed. 15.37g of methacrylic acid was weighed into a beaker, 0.75 g of triphenylphosphine as a catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and stirred magnetically to form a homogeneous solution B. And then slowly dripping the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dripping is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in the methacrylic acid to epoxy in the epoxidized soybean oil is 1:1.05 oligomeric epoxidized soy oil methacrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil methacrylate vegetable oil-based resin to prepare the epoxidized soybean oil methacrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is: 48% of the epoxidized soybean oil methacrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 7
50.00g of epoxidized soybean oil with the structure shown in the formula (I) and 0.1g of hydroquinone as a polymerization inhibitor are put into a four-neck flask provided with a thermometer, a condenser tube, a dropping funnel and a stirring paddle, and are mixed and stirred for 15min under the conditions of 90 ℃ oil bath and 200 r/min mechanical stirring until the solution A is completely and uniformly formed. 14.67g of methacrylic acid were weighed in a beaker, 0.75 g of triphenylphosphine as a catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and stirred magnetically to form a homogeneous solution B. And then slowly dropwise adding the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dropwise adding is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in methacrylic acid to epoxy in epoxidized soybean oil is 1:1.10 oligomeric epoxidized soy oil methacrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil methacrylate vegetable oil-based resin to prepare the epoxidized soybean oil methacrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is as follows: 48% of the epoxy soybean oil methacrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of a photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 8
50.00g of epoxy soybean oil with the structure shown in formula (I) and 0.1g of polymerization inhibitor hydroquinone are put into a four-neck flask provided with a thermometer, a condenser tube, a dropping funnel and a stirring paddle, and mixed and stirred for 15min under the conditions of 90 ℃ oil bath and 200 r/min mechanical stirring until the solution A is completely and uniformly formed. 14.03g of methacrylic acid was weighed in a beaker, 0.75 g of triphenylphosphine as a catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and stirred magnetically to form a homogeneous solution B. And then slowly dripping the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dripping is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in methacrylic acid to epoxy in epoxidized soybean oil is 1:1.15 oligomeric epoxidized soy oil methacrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil methacrylate vegetable oil-based resin to prepare the epoxidized soybean oil methacrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is: 48% of the epoxy soybean oil methacrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of a photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 9
50.00g of epoxy soybean oil with the structure shown in formula (I) and 0.1g of polymerization inhibitor hydroquinone are put into a four-neck flask provided with a thermometer, a condenser tube, a dropping funnel and a stirring paddle, and mixed and stirred for 15min under the conditions of 90 ℃ oil bath and 200 r/min mechanical stirring until the solution A is completely and uniformly formed. 13.45g of methacrylic acid was weighed in a beaker, 0.75 g of triphenylphosphine catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and stirred magnetically to form a homogeneous solution B. And then slowly dropwise adding the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dropwise adding is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in methacrylic acid to epoxy in epoxidized soybean oil is 1:1.20 oligomeric epoxidized soya oil methacrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil methacrylate vegetable oil-based resin to prepare the epoxidized soybean oil methacrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is: 48% of the epoxidized soybean oil methacrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
Example 10
50.00g of epoxy soybean oil with the structure shown in formula (I) and 0.1g of polymerization inhibitor hydroquinone are put into a four-neck flask provided with a thermometer, a condenser tube, a dropping funnel and a stirring paddle, and mixed and stirred for 15min under the conditions of 90 ℃ oil bath and 200 r/min mechanical stirring until the solution A is completely and uniformly formed. 12.91g of methacrylic acid was weighed into a beaker, 0.75 g of triphenylphosphine catalyst was added, and the beaker was placed in a thermostatic water bath at 60 ℃ and stirred magnetically to form a homogeneous solution B. And then slowly dripping the solution B into the solution A, raising the reaction temperature to 120 ℃ after the dripping is finished, and increasing the mechanical stirring speed to 450 r/min. After 5.5 h of reaction, the molar ratio of carboxyl in methacrylic acid to epoxy in epoxidized soybean oil is 1:1.25 oligomeric epoxidized soybean oil methacrylate.
And adding a reactive diluent, a reactive diluent and a photoinitiator into the obtained epoxidized soybean oil methacrylate vegetable oil-based resin to prepare the epoxidized soybean oil methacrylate vegetable oil-based photocuring composition. The concrete weight percentage ratio is as follows: 48% of the epoxy soybean oil methacrylate vegetable oil-based light-cured resin, 30% of acryloyl morpholine (ACMO), 20% of 1, 6 hexanediol diacrylate (HDDA) and 819% of a photoinitiator; the raw materials are stirred and mixed uniformly, and the material for photocuring 3D printing can be obtained.
The materials obtained in the above examples were subjected to performance tests:
(1) And (3) viscosity testing: the viscosity of the synthesized epoxidized soybean oil-based acrylate synthetic product was measured using a NDJ-5S rotational viscometer equipped with a constant temperature water bath at a measuring temperature of 25 ℃ using a number 2 spindle.
(2) And (3) testing the esterification rate: the determination of the esterification rate of the monomers is carried out according to the standard GB 2895-1982, c being the concentration of ethanol solution of KOHDegree, V is the volume of KOH in ethanol solution consumed and the mass of the sample taken is recorded as m 1 The amount of monomer species added for the reaction is recorded as n and the total mass of reactants is recorded as m 0 Then, the esterification rate of the monomers in the reaction system is calculated by the formula: ES (%) = (1- (c × V × m) 1 ×m 0 )/(n×1000))×100%。
(3) And (3) testing the gel rate: irradiating the liquid resin solution in the sample tank with 405nm LED ultraviolet UV curing lamp, collecting cured resin sample 0.8-1.0g, and recording the weight of the sample as W 1 Putting the sample into a Soxhlet extractor, extracting for 12h by using acetone, taking out the residual cured resin after extraction is finished, putting the residual cured resin into a drying oven, and drying until the sample is constant in weight, wherein the mass of the sample is recorded as W 2 . The gel fraction (GC) of the resin is calculated as: GC (%) = W 2 /W 1 ×100%。
(4) And (3) infrared testing: and (3) characterizing the infrared absorption peak of the resin by using an AVATAR 360ESP Fourier infrared spectrometer.
(5) Resin composition SEM test: and (3) freezing and brittle-breaking the plant oil-based ultraviolet curing resin 3D printed bending test sample bar in liquid nitrogen, drying and spraying gold, and observing the section morphology by adopting an EVO 18 scanning electron microscope. The test conditions are 25 ℃, the accelerating voltage is 20 kV, and the magnification is 1000 to 5000 times.
(6) Contact angle test: and (3) performing a contact angle test on the cured resin 3D printed wafer by using an OCA-20 contact angle measuring instrument at 25 ℃, wherein a wetting medium is deionized water, and a static dropping method is adopted.
TABLE 1 results of the related tests
As can be seen from the viscosity experiment results in table 1, the oligomer of the vegetable oil-based uv curable resin obtained in the above example has good viscosity, and is very suitable for uv curable 3D printing.
From the rest esterification rate and gel fraction test results in table 1, it can be known that the esterification rate of acrylic acid is gradually increased along with the increase of the molar ratio of epoxy group to carboxyl group, and the esterification rate is not changed too much after the molar ratio of epoxy group to carboxyl group is more than 1.15; and as the molar ratio of the epoxy group to the carboxyl group increases, the viscosity of the epoxidized soybean oil acrylate gradually increases and the growth rate gradually increases. The esterification rate and the gel rate of examples 1 to 5 were higher than those of examples 6 to 10, and the gel rate was increased as the molar ratio of epoxy groups in epoxidized soybean oil to carboxyl groups in acrylic acid was increased.
As can be seen from the FTIR spectrum analysis chart of the infrared test in FIG. 1, the curves (a) and (b) are the infrared spectra of acrylic acid and methacrylic acid, respectively, the curve (c) is the infrared spectrum of epoxidized soybean oil, and the curves (d) and (e) are the infrared spectra of the synthesized product using acrylic acid and methacrylic acid as the reaction monomers, respectively. In the curves (c) to (e), the length is 3000 to 2800 cm -1 There were multiple absorption peaks in the range, indicating the presence of significant methyl and methylene groups from the aliphatic structure, 1629cm -1 The peak is the stretching vibration peak of the carbon-carbon double bond, and the absorption peaks are obvious in the curves (a) and (b), and 1629cm can be observed in the curves (d) and (e) -1 Has an absorption peak of (c) to (e) at 1739 cm -1 The characteristic peak appearing nearby is a carbonyl absorption peak of the acrylate, which indicates that the epoxy soybean oil is acrylated by the successful reaction of the monomers, and the product contains an acrylate group, wherein the carbon-carbon double bond enables the reaction product to be also suitable for LCD3D printing based on free radical photocuring reaction.
From the SEM test results of fig. 2, it can be seen that a typical peak shape can be observed in the cross section of the vegetable oil-based photocurable resin sample, which shows the propagation and accelerated diffusion of the tensile crack, indicating that the energy is dispersed during the stretching process of the cured resin, and the cured resin has an obvious layered structure, indicating that the cured resin has a dense cured network and good toughness.
As can be seen from the contact angle test experiment results of fig. 3, the contact angle of the surface of the vegetable oil-based photocurable resin sample is 91 °, which indicates that the triglyceride groups provided in the uv vegetable oil-based oligomer synthesized in the present invention can provide better hydrophobic properties to the 3D printed firmware.
As can be seen from the printed sample diagram in FIG. 4, the two resins have high molding precision and high model resolution, which shows that the epoxy soybean oil-based light-cured resin of the system is also suitable for LCD printing of high-precision and high-complexity models, and can meet the material requirements of DLP or LCD printers in the market.
Thus, it is demonstrated that acrylic acid as a monomer is more suitable for photo-curing 3D printing than methacrylic acid as a monomer in the reaction with epoxidized soybean oil, and as the molar ratio of epoxy groups in epoxidized soybean oil to carboxyl groups in acrylic acid is increased, the curing rate of the vegetable oil-based photo-curing resin is increased, because the more acrylate groups on epoxidized soybean oil, the better the curing and crosslinking degree of the resin under uv irradiation. Meanwhile, due to the characteristic that the epoxidized soybean oil contains triglyceride, the 3D printing firmware with high toughness, high hydrophobicity and good thermal stability can be obtained finally.
The above examples and comparative examples are intended to illustrate embodiments of the present invention without departing from the scope of the subject matter of the invention, and the scope of the invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Claims (10)
1. The preparation method of the plant oil-based ultraviolet curing resin oligomer is characterized by comprising the following steps of:
(1) Under inert atmosphere, mixing a certain amount of epoxidized soybean oil and a polymerization inhibitor, and dispersing at 80-100 ℃ to form a uniform solution A;
(2) Adding a certain amount of catalyst into the monomer, and dispersing at 20-40 ℃ to form a uniform solution B;
(3) Slowly dripping the solution B into the solution A under an inert atmosphere, after the solution B is completely dripped, adjusting the temperature of a reaction system to 110-130 ℃, uniformly dispersing, and reacting for 5-6 h to obtain the vegetable oil-based ultraviolet curing resin oligomer.
2. According toThe method of claim 1, wherein: the chemical structure of the epoxidized soybean oil is shown as the formula (
) Shown in the specification:
formula (A), (B) and
）。
3. the method of claim 1, wherein: in the step (1), the amount of the polymerization inhibitor is 0.1-0.2 wt% of the amount of the epoxidized soybean oil, and the polymerization inhibitor is selected from at least one of hydroquinone, p-methoxyphenol, o-methylhydroquinone and 2, 6-di-tert-butyl-4-methylphenol.
4. The method of claim 1, wherein: in the step (2), the catalyst is at least one selected from phosphine, triphenylphosphine, palladium bis (triphenylphosphine) diacetate, iodine and potassium iodide; the dosage of the catalyst is 1-2 wt% of the dosage of the epoxidized soybean oil used in the step (1).
5. The production method according to claim 1, characterized in that: in the step (2), the monomer is at least one of acrylic acid and methacrylic acid; the molar ratio of carboxyl in the monomer used to epoxy in the epoxidized soybean oil used in step (1) is 1:1.05-1.25.
6. The production method according to claim 1, characterized in that: mechanically stirring the dispersion in the step (1) at 180-250 r/min; and (4) the mechanical stirring speed is adjusted to 400-500 r/min in the dispersion in the step (3).
7. The vegetable oil-based ultraviolet-curable resin oligomer obtained by the production method according to any one of claims 1 to 6.
8. The ultraviolet curing composition is characterized by comprising the following raw materials in percentage by weight: 45-50% of the vegetable oil-based ultraviolet-curable resin oligomer as defined in claim 7, 48-53% of the reactive diluent, and 1-3% of the photoinitiator.
9. The uv curable composition according to claim 8, wherein: the reactive diluent is at least one selected from acryloyl morpholine, trimethylolpropane triacrylate and 1, 6-hexanediol diacrylate, polyethylene glycol diacrylate, isobornyl acrylate and pentaerythritol triacrylate.
10. The uv curable composition according to claim 8, wherein: the photoinitiator is at least one selected from Irgacure 819, irgacure 261 and TPO.
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| CN202211456954.4A CN115746226A (en) | 2022-11-21 | 2022-11-21 | Plant oil-based ultraviolet curing resin oligomer, preparation method thereof and ultraviolet curing composition |
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| CN202211456954.4A CN115746226A (en) | 2022-11-21 | 2022-11-21 | Plant oil-based ultraviolet curing resin oligomer, preparation method thereof and ultraviolet curing composition |
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