CN109867760B - Cardanol-based photosensitive resin for 3D printing and preparation method thereof - Google Patents
Cardanol-based photosensitive resin for 3D printing and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cardanol-based photosensitive resin for 3D printing and a preparation method thereof, wherein the preparation method comprises the steps of mixing cardanol and hexamethylenetetramine serving as raw materials, adding dimethylbenzene serving as a solvent, and mixing to obtain a cardanol formaldehyde condensation polymer; then, adding toluenesulfonic acid serving as a catalyst, 1, 4-hydroquinone serving as a polymerization inhibitor and dimethylbenzene serving as a solvent into a mixture of the cardanol formaldehyde condensation polymer and the monomer with the photosensitive group to prepare a cardanol-based photocuring prepolymer; then evaporating the solvent, and mixing the cardanol-based photocuring prepolymer and the photoinitiator in a mass ratio of 100: 0.1-10, and fully stirring to obtain the cardanol-based photosensitive resin for 3D printing.
Description
Technical Field
The invention relates to the field of photosensitive resin, in particular to cardanol-based photosensitive resin for 3D printing and a preparation method thereof.
Background
Three-Dimensional rapid prototyping technology of 3D Printing (Three Dimensional Printing) has been remarkably developed in recent years. The product is manufactured by using materials such as metal, ceramic, polymer and the like in a multilayer overlapping printing mode. At present, the use of the three-dimensional rapid prototyping technology has spread to a plurality of fields of industry, medical treatment, cultural originality and the like, and the application prospect is wide. The 3D printing industry has become a hot spot for many developers and capital investments. The photocuring 3D printing and molding technology is a hot spot of current research, and one of the core problems lies in the development of photosensitive resin. The photocuring system generally consists of an oligomer, a reactive diluent, a photoinitiator and various additives. As for the molding material free radical type ultraviolet photosensitive resin used for photo-curing, acrylic ester and polyurethane acrylic ester are mainly used as prepolymers, most of the prepolymers in the market use petrochemical products as main raw materials, and the products inevitably bring harm to the environment and human bodies while consuming a large amount of petroleum resources. The development of the biomass light-cured resin by replacing petrochemical resources with renewable resources is one of the major development directions of the industry, meets the requirement of green sustainable development, and has become a necessary development trend.
Cardanol (Cardanol) is the main component of Cashew Nut Shell Liquid (Cashew Nut Shell Liquid), and Cashew Nut Shell Liquid is a tawny viscous Liquid, is extracted from shells of fruits of Cashew trees planted in tropical or subtropical zones, is a byproduct of Cashew nuts in the processing process, is rich in source and low in price, and is a renewable natural green resource. The cardanol molecule structure not only contains phenolic hydroxyl, but also contains unsaturated alkyl long chain on the side chain, and can perform photo-curing polymerization reaction under the excitation of ultraviolet light, and the cardanol molecule structure becomes a hotspot for research and attention in the fields of coatings and materials. In recent years, the reports on the research on the light curing of cardanol are increasing, and mainly include the research on direct ultraviolet light curing of cardanol, acrylation, epoxy acrylation, vinylation, phenolic resination, isocyanate grafting modification, blending compounding, nano-compounding modification and the like. The cardanol photocuring materials mainly use a cardanol monomer phenolic hydroxyl group and a side chain unsaturated double bond as reactive active sites, and methacryloxy or acryloxy is introduced into a molecular structure through etherification or esterification reaction to prepare photocuring monomers and oligomers, but the cardanol photocuring materials are often limited in further utilization of cardanol-based photocuring due to high ultraviolet light power and long curing time during curing.
Therefore, the cardanol resin capable of being directly printed in 3D mode is researched and developed, the requirement of green sustainable development is met, and meanwhile the cost of 3D photo-curing photosensitive resin can be reduced.
And 3D printing curing after modification with formaldehyde condensation polymer of cardanol has not been reported so far.
Disclosure of Invention
In view of the situations and defects of the prior art, the invention aims to provide a cardanol-based photosensitive resin for 3D printing, which is controllable in curing and crosslinking, short in curing time and reliable in implementation, and a preparation method thereof.
In order to achieve the technical purpose, the invention adopts the technical scheme that:
a preparation method of cardanol-based photosensitive resin for 3D printing comprises the steps of mixing cardanol and hexamethylenetetramine serving as raw materials, adding dimethylbenzene serving as a solvent, and mixing to obtain a cardanol formaldehyde condensation polymer; then, adding toluenesulfonic acid serving as a catalyst, 1, 4-hydroquinone serving as a polymerization inhibitor and dimethylbenzene serving as a solvent into a mixture of the cardanol formaldehyde condensation polymer and the monomer with the photosensitive group to prepare a cardanol-based photocuring prepolymer; then evaporating the solvent, and mixing the cardanol-based photocuring prepolymer and the photoinitiator in a mass ratio of 100: and mixing the components in a ratio of 0.1-10, and fully stirring to obtain the cardanol-based photosensitive resin for 3D printing.
Further, the cardanol is derived from cashew nut shell liquid.
Preferably, the method specifically comprises the following steps:
(1) adding 100 parts of cashew nut shell liquid and 4 parts of hexamethylenetetramine into dimethylbenzene serving as a solvent, then adding distilled water, mixing and reacting at 80-90 ℃ for 1-3 hours, and then heating to 130-140 ℃ for reflux treatment for 1-2 hours to obtain a cardanol formaldehyde condensation polymer;
(2) taking 0.8 part of p-toluenesulfonic acid as a catalyst, 1 part of 1, 4-hydroquinone as a polymerization inhibitor and 30 parts of xylene as a solvent, mixing, then adding 25-50 parts of the cardanol formaldehyde condensation polymer prepared in the step (2) and 50-75 parts of a monomer with a photosensitive group, mixing, performing reflux treatment at 80-90 ℃ for 6 hours, heating to 100-110 ℃, and continuing to react for 5-6 hours to prepare a cardanol-based photocuring prepolymer;
(3) and (3) after the solvent in the cardanol-based photocuring prepolymer prepared in the step (2) is subjected to rotary evaporation, mixing the cardanol-based photocuring prepolymer with a photoinitiator in a mass ratio of 100: and fully stirring and mixing the components in a ratio of 0.1-10 to obtain the cardanol-based photosensitive resin for 3D printing.
Preferably, the photosensitive monomer in step (2) is one of acrylic acid, methacrylic acid, acryloyl chloride and glycidyl methacrylate.
Preferably, the photoinitiator in step (3) comprises one of 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-trimethylbenzoyl-diphenyl phosphine oxide and ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate.
Preferably, the viscosity of the cardanol-based photocuring prepolymer prepared in the step (2) is 1132-1711 mPas.
Preferably, the cardanol-based photosensitive resin for 3D printing prepared in the step (3) has an ultraviolet wavelength of 365-405 nm and an ultraviolet power of 100-133 mW/cm2The ultraviolet curing time of the illumination treatment under the condition (1) is 1-100 s.
The application of the cardanol-based photosensitive resin for 3D printing prepared by the preparation method is to load the cardanol-based photosensitive resin into 3D printing equipment to perform 3D printing on products.
Further, the photocuring three-dimensional printing technology adopted by the 3D printing equipment is one of a three-dimensional photocuring molding technology, a digital light projection technology and a laser cladding deposition technology.
The cardanol resin cardanol for three-dimensional printing and formaldehyde form a condensation polymer, and the forming shrinkage rate, the bending performance and the like of the cardanol resin can be regulated and controlled. Meanwhile, the content of carbon-carbon double bonds (C ═ C) in the cardanol resin is controlled and regulated through the control of the using amount of the monomers with photosensitive groups, so that the ultraviolet free radical crosslinking and curing of the cardanol resin can be controlled and regulated, the three-dimensional printing performance is further regulated and regulated, and the cardanol resin for 3D printing can be suitable for various three-dimensional photocuring forming technologies.
The scheme relates to a partial reaction formula as follows:
by adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that: the cardanol-based photosensitive resin for 3D printing prepared by the scheme of the invention can change the content of carbon-carbon double bonds (C ═ C) in the resin by using the amount of the monomers with photosensitive groups under the irradiation of ultraviolet light of 355-405 nm, namely, the content of free radicals is controlled to realize the controllable ultraviolet free radical crosslinking polymerization of the cardanol resin. Moreover, tests show that the crosslinking rate of the cardanol resin is improved and controllable, namely the ultraviolet curing time can be shortened to 10-180s from 600s, and in addition, the cardanol-based photosensitive resin for 3D printing can regulate and control the use performance of the cardanol resin by regulating and controlling the use amount of monomers with photosensitive groups, including glossiness, flexibility, adhesive force, hardness and impact resistance; with the increase of the content of the photosensitive group monomer, the glossiness, flexibility, adhesive force, hardness and impact strength of the cardanol photosensitive resin are improved. Furthermore, the cardanol-based photosensitive resin for 3D printing has the excellent performances of cardanol resin, such as thermal oxidation stability, electrical insulation performance, weather resistance and the like; the cardanol resin is rapidly cured by ultraviolet light, so that the cardanol resin has potential application capability in the fields of paint process automation technology and additive manufacturing technology; meanwhile, the use performance of the resin and the ultraviolet free radical crosslinking polymerization can be finely adjusted through regulating and controlling the type and the using amount of the photosensitive groups, and the application cost of the cardanol resin can be reduced.
Detailed Description
Example 1
A preparation method of cardanol-based photosensitive resin for 3D printing comprises the following steps:
1) adding 100g of Cashew Nut Shell Liquid (CNSL) and 4g of hexamethylenetetramine (H powder) into xylene serving as a solvent, then adding a certain amount of distilled water, reacting the mixed system at the temperature of 80-90 ℃ for 1-3 hours, and then heating to the temperature of 130-140 ℃ for reflux treatment for 1-2 hours to obtain a cardanol formaldehyde condensation Polymer (PCF);
2) taking 0.8g of p-toluenesulfonic acid as a catalyst, 1g of 1, 4-hydroquinone as a polymerization inhibitor and 30g of xylene as a solvent, mixing, adding 50g of cardanol formaldehyde Polycondensate (PCF) and 50g of Acryloyl Chloride (AC), performing reflux treatment at 80-90 ℃ for 6 hours, heating to 100-110 ℃, and reacting for 5-6 hours again to obtain acryloyl chloride cardanol photosensitive resin (MPCF), namely a cardanol-based photocuring prepolymer; wherein the viscosity of the acryloyl chloride cashew phenol aldehyde photosensitive resin is 1132mPa & s;
3) and (3) after the solvent in the cardanol-based photocuring prepolymer prepared in the step (2) is subjected to rotary evaporation, adding 50g of acryloyl chloride cardanol aldehyde photosensitive resin into a photoinitiator 1-hydroxycyclohexyl phenyl ketone (184) with the mass ratio of 3%, and fully stirring to obtain the cardanol-based photosensitive resin for 3D printing.
Performance testing
Uniformly coating the prepared cardanol-based photosensitive resin for 3D printing on a clean tinplate (the thickness is 100 mu m), and then putting the cardanol-based photosensitive resin on 365nm ultraviolet light (100 mW/cm)2) And (3) irradiating in an ultraviolet curing box under irradiation, wherein the photocuring time of the cardanol-based photosensitive resin for 3D printing is 40s, the film is completely cured, and the surface is smooth. The resin film had a bending property of 2mm and no cracks, a hardness of 4B, an adhesion of grade 2, and an impact resistance of the cured film of 60 kg/cm. The molded article was printed in a shape using SLA printer of Form2 and had a molding shrinkage of 0.3%.
Example 2
1) Adding 100g of Cashew Nut Shell Liquid (CNSL) and 4g of hexamethylenetetramine (H powder) into xylene serving as a solvent, and then adding a certain amount of distilled water; reacting the mixed system at 80-90 ℃ for 1-3 hours, and then heating to 130-140 ℃ for reflux treatment for 1-2 hours to obtain a cardanol formaldehyde condensation Polymer (PCF);
2) mixing 0.8g of p-toluenesulfonic acid serving as a catalyst, 1g of 1, 4-hydroquinone serving as a polymerization inhibitor and 30g of xylene serving as a solvent, adding 34g of cardanol formaldehyde Polycondensate (PCF) and 66g of methacrylic acid (MAA), carrying out reflux treatment at the temperature of 80-90 ℃ for 6 hours, then heating to 100-110 ℃, and carrying out reaction for 5-6 hours to obtain methacrylic acid cardanol photosensitive resin, wherein the viscosity of the methacrylic acid cardanol photosensitive resin is 1352mPa & s;
3) and (3) after the solvent in the methacrylic acid cardanol aldehyde photosensitive resin prepared in the step (2) is subjected to rotary evaporation, adding 50g of the methacrylic acid cardanol aldehyde photosensitive resin into 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) of a photoinitiator with the mass ratio of 3%, mixing, and fully stirring to obtain the cardanol-based photosensitive resin for 3D printing.
Performance testing
Uniformly coating the prepared cardanol-based photosensitive resin for 3D printing on a clean tinplate (the thickness is 100 mu m), and then putting the cardanol-based photosensitive resin on 365nm ultraviolet light (100 mW/cm)2) And (5) irradiating in an ultraviolet curing box under irradiation. The light curing time of the cardanol-based photosensitive resin for 3D printing is 15s, the film is completely cured, and the surface is smooth. The resin film has a bending property of 2mm, no crack, a hardness of 3B, an adhesion force of 2 grades, and an impact resistance of the cured film of 75kg cm. The molded product was printed into a sample tape using SLA 3D printer of form2, and the molding shrinkage of the sample tape was 0.2%.
Example 3
1) Adding 100g of Cashew Nut Shell Liquid (CNSL) and 4g of hexamethylenetetramine (H powder) into xylene serving as a solvent, adding a certain amount of distilled water to enable the mixed system to react for 1-3 hours at the temperature of 80-90 ℃, and then heating to 130-140 ℃ for reflux treatment for 1-2 hours to obtain a cardanol formaldehyde condensation Polymer (PCF);
2) mixing 0.8g of p-toluenesulfonic acid serving as a catalyst, 1g of 1, 4-hydroquinone serving as a polymerization inhibitor and 30g of xylene serving as a solvent, adding 50g of cardanol formaldehyde Polycondensate (PCF) and 50g of Acrylic Acid (AA), performing reflux treatment at the temperature of 80-90 ℃ for 6 hours, then heating to 100-110 ℃, and reacting for 5-6 hours to obtain acrylic cashew phenol aldehyde photosensitive resin, wherein the viscosity of the acrylic cashew phenol aldehyde photosensitive resin is 1710mPa & s;
3) after the solvent in the acrylic acid cardanol aldehyde photosensitive resin prepared in the step (2) is subjected to rotary evaporation, 50g of acrylic acid cardanol aldehyde photosensitive resin is added into 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) of a photoinitiator with the mass ratio of 3%, and the mixture is fully stirred to prepare cardanol base photosensitive resin for 3D printing;
performance testing
Uniformly coating the prepared cardanol-based photosensitive resin for 3D printing on a clean tinplate (the thickness is 100 mu m), and then putting the cardanol-based photosensitive resin on 365nm ultraviolet light (100 mW/cm)2) Irradiating in an ultraviolet curing box under irradiation; the light curing time of the cardanol-based photosensitive resin for 3D printing is 10s, the film is completely cured, and the surface is smooth. The resin film has the bending property of 2mm and no crack, the hardness of 3B and the adhesive force of 2 grades,the impact resistance of the cured film was 75 kg/cm. The molded product was printed into a sample tape using SLA 3D printer of form2, and the molding shrinkage of the sample tape was 0.2%.
Example 4
1) Adding 100g of Cashew Nut Shell Liquid (CNSL) and 4g of hexamethylenetetramine (H powder) into xylene serving as a solvent, adding a certain amount of distilled water to enable the mixed system to react for 1-3 hours at the temperature of 80-90 ℃, and then heating to 130-140 ℃ for reflux treatment for 1-2 hours to obtain a cardanol formaldehyde condensation Polymer (PCF);
2) mixing 0.8g of p-toluenesulfonic acid serving as a catalyst, 1g of 1, 4-hydroquinone serving as a polymerization inhibitor and 30g of xylene serving as a solvent, adding 25g of cardanol formaldehyde Polycondensate (PCF) and 75g of methacrylic acid (MAA), performing reflux treatment at the temperature of 80-90 ℃ for 6 hours, heating to 100-110 ℃, and continuing to react for 5-6 hours to obtain methacrylic acid cardanol phenolic photosensitive resin, wherein the viscosity of the methacrylic acid cardanol phenolic resin is 1711 mPas;
3) and (3) after the solvent in the methacrylic acid cardanol photosensitive resin prepared in the step (2) is subjected to rotary evaporation, adding 50g of methacrylic acid cardanol photosensitive resin into a photoinitiator 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone with the mass ratio of 3%, mixing, and fully stirring to prepare the cardanol-based photosensitive resin for 3D printing.
Performance testing
Uniformly coating the prepared cardanol-based photosensitive resin for 3D printing on a clean tinplate (the thickness is 100 mu m), and then putting the cardanol-based photosensitive resin on 365nm ultraviolet light (100 mW/cm)2) Carrying out irradiation treatment in an ultraviolet curing box under irradiation; the light curing time of the cardanol-based photosensitive resin for 3D printing is 10s, the film is completely cured, and the surface is smooth. The resin film has a bending property of 2mm, no crack, a hardness of 3B, an adhesion force of 2 grades, and an impact resistance of the cured film of 55kg cm. The molded product was printed into a sample tape using SLA 3D printer of form2, and the molding shrinkage of the sample tape was 0.5%.
Comparative example
1) Adding 100g of Cashew Nut Shell Liquid (CNSL) and 4g of hexamethylenetetramine (H powder) into xylene serving as a solvent, and then adding a certain amount of distilled water; reacting the mixed system at 80-90 ℃ for 1-3 hours, heating to 130-140 ℃ and performing reflux treatment for 1-2 hours to obtain a cardanol formaldehyde condensation Polymer (PCF), wherein the viscosity of the PCF is 2536mPa & s;
2) according to the weight, 50g of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide of a photoinitiator with the mass ratio of PCF to PCF being 5% is fully stirred to obtain cardanol-based resin in the comparative example;
3) the cardanol-based resin of the comparative example was uniformly coated on a clean tinplate (thickness 100 μm), and placed in an ultraviolet curing box under 365nm ultraviolet light (100mW/cm2) for irradiation, while the cardanol-based resin of the comparative example was uncured. Printed with SLA 3D printer of form2, unprinted and molded.
By comparing examples 1-4 with comparative example 1, it can be seen that introducing a photosensitive group into PCF can effectively improve the uv curing ability of cardanol-based resin and shorten the uv curing time.
The foregoing is merely illustrative of the present invention, and it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of cardanol-based photosensitive resin for 3D printing is characterized by comprising the following steps: mixing cardanol and hexamethylenetetramine serving as raw materials, adding dimethylbenzene serving as a solvent, and mixing to obtain a cardanol formaldehyde condensation polymer; then, adding toluenesulfonic acid serving as a catalyst, 1, 4-hydroquinone serving as a polymerization inhibitor and dimethylbenzene serving as a solvent into a mixture of the cardanol formaldehyde condensation polymer and the monomer with the photosensitive group to prepare a cardanol-based photocuring prepolymer; then evaporating the solvent, and mixing the cardanol-based photocuring prepolymer and the photoinitiator in a mass ratio of 100: 0.1-10, and fully stirring to obtain the cardanol-based photosensitive resin for 3D printing, which specifically comprises the following steps:
(1) adding 100 parts of cashew nut shell liquid and 4 parts of hexamethylenetetramine into dimethylbenzene serving as a solvent, then adding distilled water, mixing and reacting at 80-90 ℃ for 1-3 hours, and then heating to 130-140 ℃ for reflux treatment for 1-2 hours to obtain a cardanol formaldehyde condensation polymer;
(2) taking 0.8 part of p-toluenesulfonic acid as a catalyst, 1 part of 1, 4-hydroquinone as a polymerization inhibitor and 30 parts of xylene as a solvent, mixing, then adding 25-50 parts of the cardanol formaldehyde condensation polymer prepared in the step (2) and 50-75 parts of a monomer with a photosensitive group, mixing, performing reflux treatment at 80-90 ℃ for 6 hours, heating to 100-110 ℃, and continuing to react for 5-6 hours to prepare a cardanol-based photocuring prepolymer;
the photosensitive monomer is one of acrylic acid, methacrylic acid, acryloyl chloride and glycidyl methacrylate;
(3) and (3) after the solvent in the cardanol-based photocuring prepolymer prepared in the step (2) is subjected to rotary evaporation, mixing the cardanol-based photocuring prepolymer with a photoinitiator in a mass ratio of 100: and fully stirring and mixing the components in a ratio of 0.1-10 to obtain the cardanol-based photosensitive resin for 3D printing.
2. The preparation method of the cardanol-based photosensitive resin for 3D printing according to claim 1, wherein the cardanol-based photosensitive resin comprises the following steps: the cardanol is derived from cashew nut shell liquid.
3. The preparation method of the cardanol-based photosensitive resin for 3D printing according to claim 1, wherein the cardanol-based photosensitive resin comprises the following steps: the photoinitiator in the step (3) comprises one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate.
4. The preparation method of the cardanol-based photosensitive resin for 3D printing according to claim 1, wherein the cardanol-based photosensitive resin comprises the following steps: the viscosity of the cardanol-based photocuring prepolymer prepared in the step (2) is 1132-1711 mPa.s.
5. The preparation method of the cardanol-based photosensitive resin for 3D printing according to claim 1, wherein the cardanol-based photosensitive resin comprises the following steps: the cardanol-based photosensitive resin for 3D printing prepared in the step (3) has an ultraviolet wavelength of 365-405 nm and an ultraviolet power of 100-133 mW/cm2The ultraviolet curing time of the illumination treatment under the condition (1) is 1-100 s.
6. Use of the cardanol-based photosensitive resin for 3D printing prepared by the preparation method according to any one of claims 1 to 5, characterized in that: the printing paper is loaded in a 3D printing device to perform 3D printing on products.
7. Use according to claim 6, characterized in that: the photocuring three-dimensional printing technology adopted by the 3D printing equipment is one of a three-dimensional photocuring forming technology, a digital light projection technology and a laser cladding deposition technology.
8. The utility model provides a 3D prints uses cardanol base photosensitive resin which characterized in that: which is obtained by the production process according to any one of claims 1 to 5.
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