CN109929065B - Sulfydryl-containing castor oil based deep light curing material and preparation method and application thereof - Google Patents
Sulfydryl-containing castor oil based deep light curing material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of bio-based UV curing materials, and particularly relates to a castor oil based deep light curing material containing sulfydryl, and a preparation method and application thereof. The castor oil-based deep light curing material containing sulfydryl comprises the following raw material components: castor oil, castor oil mercapto and a photoinitiator; the preparation method has simple steps: and uniformly mixing the castor oil, the mercaptocastor oil and the photoinitiator under the complete dark condition, and storing the obtained prepolymer solution in the dark. The invention introduces sulfydryl into a biomass UV curing material system, constructs a sulfydryl-alkene photopolymerization material system, replaces the traditional acrylate single alkene photopolymerization material system, the double bonds of the prepared UV curing material are all from castor oil, and the prepared UV curing material does not contain acrylate double bonds, and simultaneously, due to the unique gradual polymerization mechanism of the sulfydryl-alkene photopolymerization system, the sulfydryl-alkene photopolymerization system effectively delays gel points, overcomes the phenomenon of oxygen inhibition, reduces volume shrinkage, improves the double bond conversion rate, and simultaneously enables a polymerization network to be more uniform.
Description
Technical Field
The invention belongs to the technical field of bio-based UV curing materials, and particularly relates to a castor oil based deep light curing material containing sulfydryl, and a preparation method and application thereof.
Background
The traditional UV curing polymer mainly depends on double bonds in acrylate monomers from petrochemical resources to perform polymerization reaction under the action of a free radical photoinitiator to form a high polymer, and the high polymer is widely applied to the fields of coatings, printing ink, adhesives, 3D printing and the like at present due to excellent performance, energy conservation and environmental protection. The raw materials of the conventional UV curable material mainly consist of a UV curable prepolymer, a reactive diluent and a photoinitiator. At present, the UV curing prepolymer is mainly petrochemical prepolymer, and has a plurality of defects on application, thereby limiting the application range to a certain extent. For example, oxygen inhibition is more severe and cure shrinkage is higher; since the UV curable coating requires light irradiation, it is also limited by the shape of the cured object and the curing depth, and it is difficult to apply it to a colored system and a shaded portion. Because the viscosity of the UV curing prepolymer is often high, a reactive diluent is needed to adjust the viscosity of the UV curing prepolymer in the construction process, and most of the reactive diluents are easy to volatilize and have pungent odor, so that certain harm can be caused to the environment and the body of a constructor. Meanwhile, the introduction of the active diluent as a micromolecule can also have some adverse effects on the performance of the high polymer cured film. The raw materials of the traditional UV curing material mainly come from petrochemical resources and are more and more limited by resources and environmental factors. The vegetable oil molecular structure contains unsaturated double bonds, and many of the vegetable oil molecular structure also contain active reaction groups such as hydroxyl groups and the like, so that the vegetable oil molecular structure has a structural foundation for building a UV curing material system, but the vegetable oil double bonds have very low photocuring activity, and the vegetable oil can not be cured into a film under the action of a free radical photoinitiator. Based on this, there is a need to provide a new photocurable material to solve the problems of the prior art.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a castor oil based deep light curing material containing sulfydryl.
The invention also aims to provide a preparation method of the castor oil based deep light curing material containing sulfydryl.
The invention further aims to provide application of the castor oil based deep light curing material containing sulfydryl in the fields of coatings, printing ink, adhesives and the like.
The purpose of the invention is realized by the following scheme:
a sulfydryl-containing castor oil based deep light curing material comprises the following raw material components: castor oil, castor oil mercapto and a photoinitiator.
Preferably, the mass ratio of the castor oil to the mercaptocastor oil is (0-60): (100-40), wherein the dosage of the photoinitiator is 1-5% of the total mass of the castor oil and the mercapto castor oil.
The photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone (907), 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide (TPO), 2,4, 6-trimethylbenzoylphenylphosphonic acid ethyl ester (TPO-L), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (659), bis-2, 6-difluoro-3-pyrrol-ylphenyltitanocene (784), benzoin dimethyl ether (DMPA).
Preferably, the castor oil mercapto is prepared by the following steps: adding castor oil, catalyst p-toluenesulfonic acid and solvent into a reactor, then filling a water separator, uniformly stirring, heating, adding mercaptofatty acid, and reacting to obtain the mercaptocastor oil.
The preparation method of the sulfhydryl castor oil comprises the following steps:
heating to 110-120 ℃, then adding a mercapto fatty acid for reaction, wherein the reaction temperature is 110-120 ℃, and the reaction time is 9-11 h;
the mercapto fatty acid is preferably at least one of thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptobutyric acid, 2-mercaptoisobutyric acid, 3-mercaptoisobutyric acid and 4-mercaptobutyric acid;
the molar ratio of the castor oil to the mercapto fatty acid is 1: 5-1: 7;
the dosage of the catalyst p-toluenesulfonic acid is 3-6% of the mass of the castor oil;
the solvent is preferably cyclohexane, the dosage of the solvent is determined according to the dosage of the castor oil, and 4-6 ml of cyclohexane is needed when 1g of the castor oil is used;
after the reaction is finished, the method also comprises a separation and purification step, wherein the separation and purification step comprises the following steps: pouring the reaction solution into a separating funnel, adding water to wash and remove redundant sulfhydryl fatty acid, adding an organic solvent to stand and stratify, taking the upper layer into a three-necked bottle, adding a drying agent to dry, and finally carrying out reduced pressure distillation at 60-70 ℃.
The preparation method of the castor oil base deep light curing material containing sulfydryl comprises the following steps: and uniformly mixing the castor oil, the mercaptocastor oil and the photoinitiator under the complete dark condition to obtain a prepolymer solution, namely the mercaptocastor oil-based deep light curing material, and storing the prepolymer solution in the dark.
The invention also provides application of the castor oil based deep light curing material containing sulfydryl in the fields of materials such as coating, printing ink, adhesive and the like.
The application method of the mercapto castor oil-based deep light curing material comprises the following steps: uniformly coating the castor oil-based deep light curing material containing sulfydryl on a base material, and irradiating for a certain time under a light source to cure into a film; the light source is an LED lamp light source with the wavelength of 350-440 nm or a mercury lamp light source with the wavelength of 245-405 nm; the curing time is 10-60 s.
Except for using a small amount of thioglycollic acid, all raw materials of the sulfhydryl-containing castor oil based deep light curing material are castor oil, and the content of the castor oil in the final material is more than 80 percent, so that the material is a bio-based material with high biomass content; in addition, the mercapto-alkene photopolymerization material system overcomes the problem of insufficient curing depth of the traditional UV curing material, and can ensure that the curing depth reaches 10 cm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, castor oil which is a natural renewable resource is introduced into a UV curing material system to prepare the castor oil based deep light curing material containing sulfydryl, so that the use amount of the traditional petrochemical raw materials in the UV curing material is greatly reduced, and can be reduced by more than 80%; on one hand, the method opens up a new application field for natural materials, improves the use value of the natural materials, has excellent popularization significance for the development of forestry economy, and on the other hand, greatly relieves the pressure of petrochemical industry.
(2) According to the invention, sulfydryl is introduced into a biomass UV curing material system, a sulfydryl-alkene photopolymerization material system is constructed, the traditional acrylate simple alkene photopolymerization material system is replaced, gel points are effectively delayed, the phenomenon of oxygen inhibition is overcome, volume shrinkage is reduced, the double bond conversion rate is improved, and a polymerization network is more uniform. More importantly, the sulfydryl-alkene photopolymerization material system overcomes the problem that the curing depth of the traditional UV curing material is not enough, and can enable the curing depth to reach 10 cm.
Drawings
FIG. 1 is a chemical reaction scheme for the synthesis of mercaptocastor oil in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
(1) Sequentially adding castor oil, p-toluenesulfonic acid and cyclohexane into a reactor, then filling a water separator, uniformly stirring, heating to 120 ℃, adding thioglycollic acid, reacting for 11 hours, pouring the reaction solution into a separating funnel, adding water, washing to remove redundant thioglycollic acid, adding cyclohexane, standing for layering, taking the upper layer into a three-necked bottle, adding anhydrous magnesium sulfate, drying, and finally distilling at 70 ℃ under reduced pressure to obtain the sulfhydryl castor oil. Wherein, the molar ratio of the castor oil to the thioglycollic acid is 1:5, the dosage of the p-toluenesulfonic acid is 6 percent of the mass of the castor oil, and 4ml of cyclohexane is needed when the dosage of the cyclohexane is 1g of the castor oil.
(2) And (3) uniformly mixing the mercaptocastor oil and the photoinitiator 1173 under the complete light-proof condition to obtain a prepolymer solution, namely the needed mercaptocastor oil-based deep light curing material. Wherein the dosage of the photoinitiator is 5 percent of the mass of the sulfhydryl castor oil.
(3) And (3) rapidly and uniformly coating the prepared castor oil-based deep light curing material containing sulfydryl on a base material by using a film coater, and irradiating for 60 seconds to form a film under an LED lamp light source with the wavelength of 440 nm.
Example 2
(1) Sequentially adding castor oil, p-toluenesulfonic acid and cyclohexane into a reactor, then filling a water separator, uniformly stirring, heating to 110 ℃, adding 3-mercaptopropionic acid, reacting for 10 hours, pouring the reaction liquid into a separating funnel, adding water, washing to remove redundant 3-mercaptopropionic acid, adding cyclohexane, standing for layering, taking the upper layer into a three-necked bottle, adding anhydrous magnesium sulfate, drying, and finally distilling at 65 ℃ under reduced pressure to obtain the mercaptocastor oil. Wherein, the molar ratio of the castor oil to the 3-mercaptopropionic acid is 1:6, the dosage of the catalyst p-toluenesulfonic acid is 5 percent of the mass of the castor oil, and the dosage of the cyclohexane is 5ml for 1g of the castor oil.
(2) The castor oil, the mercapto castor oil and the photoinitiator 184 are mixed evenly under the condition of complete light shielding to obtain prepolymer solution, namely the needed mercapto castor oil based deep light curing material. Wherein the mass ratio of the castor oil to the mercapto castor oil is 40:60, and the dosage of the photoinitiator is 5% of the total mass of the castor oil and the mercapto castor oil.
(3) The obtained castor oil-based deep light curing material containing sulfydryl is quickly and uniformly coated on a base material by a film coater, and is irradiated for 60 seconds to form a film under the light source of a mercury lamp with the wavelength of 245 nm.
Example 3
(1) Sequentially adding castor oil, p-toluenesulfonic acid and cyclohexane into a reactor, then filling a water separator, uniformly stirring, heating to 110 ℃, adding 2-mercaptobutyric acid, reacting for 9 hours, pouring the reaction solution into a separating funnel, adding water, washing to remove redundant 2-mercaptobutyric acid, adding cyclohexane, standing for layering, taking the upper layer into a three-necked bottle, adding anhydrous magnesium sulfate, drying, and finally carrying out reduced pressure distillation at 60 ℃ to obtain the mercaptocastor oil. Wherein the molar ratio of the castor oil to the 2-mercaptobutyric acid is 1:7, the dosage of the catalyst p-toluenesulfonic acid is 3 percent of the mass of the castor oil, and the dosage of the cyclohexane is 6ml for 1g of the castor oil.
(2) The castor oil, the mercapto castor oil and the photoinitiator 907 are mixed evenly under the complete dark condition, and the obtained prepolymer solution is the needed mercapto castor oil based deep light curing material. Wherein the mass ratio of the castor oil to the mercapto castor oil is 60:40, and the dosage of the photoinitiator is 1 percent of the total mass of the castor oil and the mercapto castor oil.
(3) And (3) rapidly and uniformly coating the prepared castor oil-based deep light curing material containing sulfydryl on a base material by using a film coater, and irradiating for 50 seconds to form a film under an LED lamp light source with the wavelength of 350 nm.
Example 4
(1) Sequentially adding castor oil, p-toluenesulfonic acid and cyclohexane into a reactor, then filling a water separator, uniformly stirring, heating to 115 ℃, adding 2-mercaptoisobutyric acid, reacting for 9-11 h, pouring the reaction solution into a separating funnel, adding water to wash and remove redundant 2-mercaptoisobutyric acid, adding cyclohexane, standing and layering, taking the upper layer into a three-necked bottle, adding anhydrous magnesium sulfate, drying, and finally distilling at 65 ℃ under reduced pressure to obtain the mercaptocastor oil. Wherein, the molar ratio of the castor oil to the 2-mercapto isobutyric acid is 1:5, the dosage of the p-toluenesulfonic acid is 5 percent of the mass of the castor oil, and 4ml of cyclohexane is needed for 1g of the castor oil.
(2) Uniformly mixing castor oil, mercaptocastor oil and a photoinitiator TPO under the complete dark condition to obtain a prepolymer solution, namely the needed mercaptocastor oil-based deep light curing material. Wherein the mass ratio of the castor oil to the mercapto castor oil is 50:50, and the dosage of the photoinitiator is 3 percent of the total mass of the castor oil and the mercapto castor oil.
(3) The obtained castor oil-based deep light curing material containing sulfydryl is quickly and uniformly coated on a base material by a film coater, and is irradiated for 30 seconds to be cured into a film under a mercury lamp light source with the wavelength of 405 nm.
Example 5
(1) Sequentially adding castor oil, p-toluenesulfonic acid and cyclohexane into a reactor, then filling a water separator, uniformly stirring, heating to 115 ℃, adding 3-mercaptoisobutyric acid, reacting for 10 hours, pouring the reaction solution into a separating funnel, adding water, washing to remove redundant 3-mercaptoisobutyric acid, adding cyclohexane, standing for layering, taking the upper layer into a three-neck bottle, adding anhydrous magnesium sulfate, drying, and finally carrying out reduced pressure distillation at 60 ℃ to obtain the mercaptocastor oil. Wherein, the molar ratio of the castor oil to the 3-mercapto isobutyric acid is 1:5, the dosage of the p-toluenesulfonic acid is 6 percent of the mass of the castor oil, and the dosage of the cyclohexane is 6ml for 1g of the castor oil.
(2) Uniformly mixing castor oil, castor oil mercapto and a photoinitiator DMPA under the condition of complete light shielding to obtain a prepolymer solution, namely the needed castor oil mercapto-containing deep light curing material. Wherein the mass ratio of the castor oil to the mercapto castor oil is 30:70, and the dosage of the photoinitiator is 5 percent of the total mass of the castor oil and the mercapto castor oil.
(3) And (3) rapidly and uniformly coating the prepared castor oil-based deep light curing material containing sulfydryl on a base material by using a film coater, and irradiating for 10 seconds to form a film under a 440nm LED lamp light source.
Example 6
(1) Sequentially adding castor oil, p-toluenesulfonic acid and cyclohexane into a reactor, then filling a water separator, uniformly stirring, heating to 120 ℃, adding 4-mercaptobutyric acid, reacting for 11 hours, pouring the reaction solution into a separating funnel, adding water, washing to remove redundant 4-mercaptobutyric acid, adding cyclohexane, standing for layering, taking the upper layer into a three-necked bottle, adding anhydrous magnesium sulfate, drying, and finally distilling at 70 ℃ under reduced pressure to obtain the mercaptocastor oil. Wherein the molar ratio of the castor oil to the 4-mercaptobutyric acid is 1:6, the dosage of the p-toluenesulfonic acid is 3 percent of the mass of the castor oil, and the dosage of the cyclohexane is 5ml for 1g of the castor oil.
(2) And uniformly mixing the castor oil, the mercapto castor oil and the photoinitiator 784 under the complete light-proof condition to obtain a prepolymer solution, namely the required mercapto castor oil-based deep light curing material. Wherein the mass ratio of the castor oil to the mercapto castor oil is 20:80, and the dosage of the photoinitiator is 5 percent of the total mass of the castor oil and the mercapto castor oil.
(3) The obtained castor oil-based deep light curing material containing sulfydryl is quickly and uniformly coated on a base material by a film coater, and is irradiated for 10 seconds to form a film under the light source of a mercury lamp with the wavelength of 365 nm.
Performance test example of deep light-cured material containing mercapto castor oil base
The castor oil-based deep light curing materials containing sulfydryl prepared in examples 1-6 were tested for the relevant properties of the cured film.
The gel content was determined by extraction with acetone. The cured films prepared in the above examples were soaked in acetone at room temperature for 48h and then dried at 60 ℃ until the weight remained constant. And weighing the mass before and after soaking, and dividing the mass after soaking by the mass before soaking to obtain the gel fraction.
The glass transition temperature, Young's modulus and toughness were tested using dynamic thermomechanical analysis (DMA) in a NetzschDMA 242C dynamic mechanical analysis in a 1Hz film tension mode, all samples were 20mm x 6mm x 0.5mm in size and the heating rate was 3 ℃/min-80-150 ℃. The glass transition temperature (Tg) of the film results from the peak of the tan curve of the DMA test curve.
The tensile property test of the film adopts a Shimadzu AGS-X1 kN type universal tensile machine for testing, the tensile rate is 100mm/min, the sample is made into a film with the size of 50 multiplied by 10mm, each sample is tested in parallel for three times, and the tensile strength and the elongation at break are the average value of the three tests.
And (3) testing the curing depth, namely injecting the prepolymer solution into a flat-bottomed glass test tube with the length of 15cm, irradiating and curing the sample on the surface of the prepolymer solution from a test tube port by using a light source, and taking out a cured sample in the test tube after reaching the irradiation preset time to test the length of the cured sample, namely the curing depth.
Table 1 results of performance test of some examples
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The sulfydryl-containing castor oil based deep light curing material is characterized by comprising the following raw material components: castor oil, sulfhydryl castor oil and a photoinitiator, wherein the mass ratio of the castor oil to the sulfhydryl castor oil is (20-60): (100-40).
2. The castor oil based deep light curing material containing sulfydryl according to claim 1, wherein the amount of the photoinitiator is 1-5% of the total mass of castor oil and sulfydryl castor oil.
3. The castor oil based deep photocurable material with sulfydryl according to claim 1, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, ethyl 2,4, 6-trimethyl benzoyl phenyl phosphonate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis 2, 6-difluoro-3-pyrrolyl phenyl titanocene, bis (2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis (2, 6-difluoro-3-pyrrolyl) phenyl titanocene, bis (2-hydroxy-2-methyl, At least one of benzoin dimethyl ether.
4. The castor oil mercapto group-containing deep light curing material as claimed in any one of claims 1 to 3, wherein the castor oil mercapto group is prepared by the following steps: adding castor oil, catalyst p-toluenesulfonic acid and solvent into a reactor, then filling a water separator, uniformly stirring, heating, adding mercaptofatty acid, and reacting to obtain the mercaptocastor oil.
5. The castor oil based deep light curing material containing sulfydryl according to claim 4, wherein the temperature is increased to 110-120 ℃, and then sulfydryl fatty acid is added for reaction, the reaction temperature is 110-120 ℃, and the reaction time is 9-11 hours.
6. The castor oil based deep light curing material as claimed in claim 4, wherein the mercaptofatty acid is at least one of mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptobutyric acid, 2-mercaptoisobutyric acid, 3-mercaptoisobutyric acid, 4-mercaptobutyric acid.
7. The castor oil-based deep light curing material containing sulfydryl according to claim 4, wherein the molar ratio of castor oil to sulfydryl fatty acid is 1: 5-1: 7;
the dosage of the catalyst p-toluenesulfonic acid is 3-6% of the mass of the castor oil.
8. The method for preparing the castor oil based deep light curing material containing sulfydryl according to any one of claims 1 to 7, which is characterized by comprising the following steps: and uniformly mixing the castor oil, the mercaptocastor oil and the photoinitiator under the complete dark condition to obtain a prepolymer solution, namely the mercaptocastor oil-based deep light curing material, and storing the prepolymer solution in the dark.
9. Use of the castor oil based deep light curable material containing mercapto groups as claimed in any one of claims 1 to 7 in the fields of coatings, inks and adhesives.
10. The use method of the castor oil based deep light curing material containing sulfydryl according to any one of claims 1 to 7, which comprises the following steps: uniformly coating the sulfydryl-containing castor oil based deep light curing material on a base material, placing the base material under a light source for irradiation for a certain time, and curing to form a film;
the light source is an LED lamp light source with the wavelength of 350-440 nm or a mercury lamp light source with the wavelength of 245-405 nm; the curing time is 10-60 s.
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