CN112251241A - Liquid crystal type epoxy material and preparation method and application thereof - Google Patents
Liquid crystal type epoxy material and preparation method and application thereof Download PDFInfo
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- CN112251241A CN112251241A CN202011131933.6A CN202011131933A CN112251241A CN 112251241 A CN112251241 A CN 112251241A CN 202011131933 A CN202011131933 A CN 202011131933A CN 112251241 A CN112251241 A CN 112251241A
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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Abstract
The invention provides a liquid crystal type epoxy material and a preparation method and application thereof, belonging to the technical field of epoxy resin materials. The liquid crystal epoxy material provided by the invention is prepared from the following raw materials in parts by mass: 400 parts of liquid crystal epoxy monomer, 91.8-157.9 parts of curing agent, 9.5-11.2 parts of photoinitiator, 4.9-5.5 parts of photosensitizer and 2620-2808 parts of organic solvent; the curing agent is m-xylylenediamine; the photoinitiator is diaryl iodonium salt; the photosensitizer is ferrocenium salt. In the liquid crystal epoxy material provided by the invention, the ferrocenium salt is used as a photosensitizer, the diaryl iodonium salt is used as a photoinitiator, and the synergistic effect of the ferrocenium salt and the photoinitiator can shorten the curing time of the liquid crystal epoxy monomer; meanwhile, compared with epoxy resin E51, the liquid crystal epoxy material provided by the invention has improved toughness; the liquid crystal epoxy material can be applied to the fields of aerospace, intelligent robots and 4D printing.
Description
Technical Field
The invention relates to the technical field of epoxy resin materials, in particular to a liquid crystal type epoxy material and a preparation method and application thereof.
Background
Epoxy resin (EP) is a high molecular polymer having two or more epoxy groups in a molecular structural formula, and has good mechanical properties and chemical stability, and thus has been widely used as a thermosetting resin. However, the conventional epoxy resin has poor toughness and long curing time.
The liquid crystal epoxy monomer prepared by combining the epoxy group with the liquid crystal can be used as a toughening agent to be added into a traditional epoxy resin system, and the problem of poor toughness of the traditional epoxy resin system can be solved. However, the liquid crystal epoxy material has a long curing time, which limits the application of the liquid crystal epoxy material.
Disclosure of Invention
In view of the above, the present invention provides a liquid crystal epoxy material, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a liquid crystal type epoxy material which is prepared from the following raw materials in parts by mass: 400 parts of liquid crystal epoxy monomer, 91.8-157.9 parts of curing agent, 9.5-11.2 parts of photoinitiator, 4.9-5.5 parts of photosensitizer and 2620-2808 parts of organic solvent; the curing agent is m-xylylenediamine; the photoinitiator is diaryl iodonium salt; the photosensitizer is ferrocenium salt.
Preferably, the liquid crystal type epoxy material is prepared from the following raw materials in parts by mass: 400 parts of liquid crystal epoxy monomer, 124.9 parts of curing agent, 10 parts of photoinitiator, 5 parts of photosensitizer and 2620-2808 parts of organic solvent.
Preferably, the diaryliodonium salt is 4, 4-dimethyldiphenyliodonium hexafluorophosphate or 4, 4-diphenyliodonium hexafluorophosphate.
Preferably, the ferrocenium salt is cumyl cyclopentadienyl iron hexafluorophosphate or phenyl cyclopentadienyl iron hexafluorophosphate.
Preferably, the organic solvent is N, N-dimethylacetamide or dimethylsulfoxide.
Preferably, the curing mode of the liquid crystal type epoxy material is ultraviolet curing.
Preferably, the wavelength of the ultraviolet light for ultraviolet light curing is 365nm, and the time is 10-20 minutes.
The invention also provides a preparation method of the liquid crystal type epoxy material, which comprises the following steps:
and mixing the liquid crystal epoxy monomer with a solvent, and then adding a curing agent, a photoinitiator and a photosensitizer for mixing to obtain the liquid crystal epoxy material.
The invention also provides application of the liquid crystal epoxy material in the technical scheme in the fields of aerospace, intelligent robots and 4D printing.
The invention provides a liquid crystal type epoxy material which is prepared from the following raw materials in parts by mass: 400 parts of liquid crystal epoxy monomer, 91.8-157.9 parts of curing agent, 9.5-11.2 parts of photoinitiator, 4.9-5.5 parts of photosensitizer and 2620-2808 parts of organic solvent; the curing agent is m-xylylenediamine; the photoinitiator is diaryl iodonium salt; the photosensitizer is ferrocenium salt. In the liquid crystal epoxy material provided by the invention, the ferrocenium salt is used as a photosensitizer, the diaryl iodonium salt is used as a photoinitiator, and the synergistic effect of the ferrocenium salt and the photoinitiator can shorten the curing time of the liquid crystal epoxy monomer; meanwhile, compared with epoxy resin E51, the liquid crystal epoxy material provided by the invention has improved toughness; the liquid crystal epoxy material can be applied to the fields of aerospace, intelligent robots and 4D printing.
Drawings
FIG. 1 is an infrared spectrum of a polymer film obtained in examples 1 to 3 and comparative example 1 and a liquid crystal type epoxy monomer powder obtained in example 1;
FIG. 2 is a stress-strain curve of the polymer films obtained in examples 1 to 3 and comparative example 2.
Detailed Description
The invention provides a liquid crystal type epoxy material which is prepared from the following raw materials in parts by mass: 400 parts of liquid crystal epoxy monomer, 91.8-157.9 parts of curing agent, 9.5-11.2 parts of photoinitiator, 4.9-5.5 parts of photosensitizer and 2620-2808 parts of organic solvent; the curing agent is m-xylylenediamine; the photoinitiator is diaryl iodonium salt; the photosensitizer is ferrocenium salt.
The raw materials for preparing the liquid crystal epoxy material comprise 400 parts by mass of liquid crystal epoxy monomers. In the present invention, the liquid crystal epoxy-based monomer is preferably prepared by a method comprising the steps of:
weighing 18.6g of biphenol, placing the biphenol in a 250mL three-neck flask, adding 62.7mL of epoxy chloropropane and 50mL of isopropanol, heating to 75 ℃, uniformly stirring, dropwise adding 30.6g of NaOH aqueous solution with the mass percent of 28.8% by using a constant-pressure funnel, heating to 95 ℃ after 6h of dropwise adding, carrying out reflux reaction for 4h, stopping heating, washing and filtering the obtained reaction liquid by using the isopropanol, drying the obtained filter cake for 24h, and then recrystallizing and drying the obtained filter cake by using toluene to obtain the liquid crystal epoxy monomer.
Based on the weight parts of the liquid crystal epoxy monomer, the liquid crystal epoxy material provided by the invention comprises 91.8-157.9 parts of curing agent by mass, preferably 124.9 parts; the curing agent is m-xylylenediamine.
Based on the weight parts of the liquid crystal epoxy monomer, the raw materials for preparing the liquid crystal epoxy material provided by the invention comprise 9.5-11.2 parts by weight of photoinitiator, preferably 10 parts by weight; the photoinitiator is diaryl iodonium salt; the diaryliodonium salt is preferably 4, 4-dimethyldiphenyliodonium hexafluorophosphate or 4, 4-diphenyliodonium hexafluorophosphate.
In the present invention, the 4, 4-dimethyldiphenyliodonium hexafluorophosphate is preferably prepared by a method comprising the steps of:
weighing 15.0g of potassium iodate and 12.88g of toluene, placing the potassium iodate and the toluene into a reaction bottle, sequentially dropwise adding 30mL of acetic anhydride, 10mL of glacial acetic acid and 8mL of concentrated sulfuric acid under the condition of ice-bath stirring, heating to room temperature after the dropwise addition of the concentrated sulfuric acid is finished, continuously stirring for reacting for 24 hours, slowly dropwise adding 50mL of deionized water, extracting the obtained solution for 2-3 times by using benzene, separating a water layer, combining and washing the benzene layer for 1 time, and then combining the water layers to obtain a water layer, namely the p-tolyl iodonium bisulfate aqueous solution;
weighing 26g of potassium hexafluorophosphate solid, adding the potassium hexafluorophosphate solid into the p-tolyliodonium bisulfate aqueous solution, carrying out ion exchange, adding deionized water under stirring, slowly separating out 4, 4-dimethyldiphenyliodonium hexafluorophosphate with the dissolution of potassium hexafluorophosphate, collecting precipitate, washing the obtained precipitate with deionized water, filtering, and drying the filter cake at 40 ℃ for 48 hours in vacuum to obtain the 4, 4-dimethyldiphenyliodonium hexafluorophosphate.
In the present invention, the 4, 4-diphenyliodonium hexafluorophosphate is preferably prepared by a method comprising the steps of:
weighing 15.0g of potassium iodate and 11g of benzene, placing the potassium iodate and 11g of benzene into a three-neck flask with a condensation reflux device, sequentially dropwise adding 30mL of acetic anhydride, 10mL of acetic acid and 8mL of concentrated sulfuric acid under the condition of ice-bath stirring, reacting for 24 hours at room temperature after dropwise adding of concentrated sulfuric acid, adding 100mL of deionized water into reaction liquid, stirring for 2 hours, carrying out suction filtration after a small amount of white solid is insoluble, collecting filtrate, extracting the filtrate for 3 times by using benzene, and collecting a water layer, wherein the obtained water layer is 4, 4-diphenyliodonium bisulfate aqueous solution;
adding 19g of potassium hexafluorophosphate solid to the 4, 4-diphenyliodonium hydrogen sulfate aqueous solution for ion exchange, precipitating white precipitate along with hydrolysis of potassium hexafluorophosphate, performing suction filtration, washing the obtained filter cake with deionized water and performing suction filtration, collecting the filter cake, and drying the filter cake for 24 hours under vacuum conditions to obtain the 4, 4-diphenyliodonium hexafluorophosphate.
The raw materials for preparing the liquid crystal epoxy material provided by the invention comprise 4.9-5.5 parts by weight of photosensitizer, preferably 5 parts by weight of liquid crystal epoxy monomer; the photosensitizer is ferrocenium salt; the ferrocenium salt is preferably cumyl cyclopentadienyl iron hexafluorophosphate or phenyl cyclopentadienyl iron hexafluorophosphate.
In the present invention, the cumylcyclopentadienyliron hexafluorophosphate salt is preferably prepared by a method comprising the steps of:
adding 9.3g of ferrocene, 1.33g of aluminum powder and 26.668g of anhydrous aluminum chloride into a three-mouth reaction bottle provided with an electric stirrer, a thermometer and a reflux condenser tube, adding 50mL of isopropyl benzene, raising the temperature to 100 ℃ under stirring, carrying out condensation reflux reaction at 100 ℃ for 8 hours, pouring a reaction product into a beaker filled with deionized water under ice bath, extracting, and separating out a water phase and an organic phase; the organic phase was extracted 3 times with water and the aqueous phases were combined; then adding 300mL of potassium hexafluorophosphate saturated water solution into the water phase under stirring, and separating out a yellow brown precipitate; filtering the precipitate, collecting a filter cake, and vacuum-drying the obtained filter cake for 24h to obtain a crude product; and recrystallizing the crude product by using absolute ethyl alcohol to obtain the cumyl cyclopentadienyl iron hexafluorophosphate.
In the present invention, the phenylcyclopentadienyl iron hexafluorophosphate is preferably prepared by a method comprising the steps of:
adding 9.3g of ferrocene, 1.33g of aluminum powder and 26.67g of anhydrous aluminum trichloride into a three-neck flask provided with an electric stirrer and a condensation reflux device, adding 50mL of benzene, raising the reaction temperature to 100 ℃, and reacting for 8 hours; after the reaction is finished, dripping the obtained reaction product into deionized water under an ice bath condition, extracting for 1 time, collecting a water layer, performing suction filtration on the obtained water layer, removing unreacted aluminum powder, collecting a filtrate, dripping the filtrate into 250mL of saturated potassium hexafluorophosphate aqueous solution, precipitating a dark yellow solution, standing for 12 hours, performing suction filtration, and performing vacuum drying on the obtained filter cake for 24 hours to obtain a crude product; and recrystallizing the crude product with absolute ethyl alcohol, and drying for 24 hours in vacuum to obtain the phenylcyclopentadienyl iron hexafluorophosphate.
Based on the weight parts of the liquid crystal epoxy monomer, the liquid crystal epoxy material provided by the invention comprises 2620-2808 parts by weight of an organic solvent; the organic solvent is preferably N, N-dimethylacetamide or dimethylsulfoxide.
In the invention, the curing mode of the liquid crystal epoxy material is preferably ultraviolet curing; the wavelength of the ultraviolet light for ultraviolet light curing is preferably 365nm, and the time is preferably 10-20 minutes.
In the liquid crystal epoxy material provided by the invention, the ferrocenium salt is used as a photosensitizer, the diaryl iodonium salt is used as a photoinitiator, and the synergistic effect of the ferrocenium salt and the photoinitiator can shorten the curing time of the liquid crystal epoxy monomer; meanwhile, compared with epoxy resin E51, the liquid crystal epoxy material provided by the invention has improved toughness.
The invention also provides a preparation method of the liquid crystal type epoxy material, which comprises the following steps:
and mixing the liquid crystal epoxy monomer with a solvent, and then adding a curing agent, a photoinitiator and a photosensitizer for mixing to obtain the liquid crystal epoxy material.
The mixing method of the present invention is not particularly limited, and a mixing method known to those skilled in the art may be used.
The invention also provides application of the liquid crystal epoxy material in the technical scheme in the fields of aerospace, intelligent robots and 4D printing. The application mode of the liquid crystal epoxy material in the fields of aerospace, intelligent robots and 4D printing is not specifically limited, and the liquid crystal epoxy material is selected according to actual conditions.
In the invention, the liquid crystal epoxy material provided by the invention has short curing time and excellent toughness, and can be widely applied to the fields of aerospace, intelligent robots and 4D printing.
The liquid crystal epoxy material, the preparation method and the application thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 18.6g (0.1mol) of biphenol into a 250mL three-neck flask, adding 62.7mL (0.8mol) of epichlorohydrin and 50mL of isopropanol, heating to 75 ℃, uniformly stirring, and dropwise adding 28.8% NaOH aqueous solution (NaOH: 8.8 g; H) by mass percent by using a constant pressure funnel2O: 21.8mL) is added in the reaction solution, after the dropwise addition is finished for 6 hours, the temperature is slowly raised to 95 ℃, the reflux reaction is carried out for 4 hours, the heating is stopped, the obtained reaction solution is washed and filtered by isopropanol, the obtained filter cake is dried for 24 hours, and then toluene is usedAnd recrystallizing and drying the obtained filter cake to obtain 17.35g of the target product liquid crystal epoxy monomer, wherein the yield is 58%.
Weighing 15.0g (0.07mol) of potassium iodate and 11g (0.14mol) of benzene, placing the potassium iodate and the benzene into a three-neck flask (250mL) with a condensation reflux device, and slowly dripping 30mL of acetic anhydride, 10mL of acetic acid and 8mL of concentrated sulfuric acid in sequence under the condition of ice bath stirring, wherein the solution has no obvious change when dripping the acetic anhydride and the acetic acid; when concentrated sulfuric acid is dripped, the color of the solution turns yellow and gradually deepens; after the dropwise addition of the concentrated sulfuric acid is finished, reacting for 24 hours at room temperature, and finding that a large amount of white precipitates appear after 2 hours of reaction; after the reaction is finished, adding 100mL of deionized water into the solution, stirring for 2h, carrying out suction filtration when a small amount of white solid is insoluble, collecting filtrate, extracting the filtrate for 3 times by using benzene, and collecting a water layer to obtain a 4, 4-diphenyl iodonium bisulfate aqueous solution; adding 19g of potassium hexafluorophosphate solid into a 4, 4-diphenyliodonium hydrogen sulfate aqueous solution for ion exchange, separating out a large amount of white precipitate along with hydrolysis of potassium hexafluorophosphate, performing suction filtration, washing the obtained filter cake with deionized water, performing suction filtration, collecting the filter cake, and performing vacuum drying for 24 hours to obtain a target product, namely 4, 4-diphenyliodonium hexafluorophosphate: 10.14 g.
Weighing 9.3g (0.05mol) of ferrocene, 1.33g (0.05mol) of aluminum powder and 26.67g (0.2mol) of anhydrous aluminum trichloride, adding the weighed materials into a three-neck flask (100mL) provided with an electric stirrer and a condensation reflux device, adding 50mL of benzene which is used as a reactant and a solvent, slowly raising the reaction temperature to 100 ℃ under stirring, and reacting for 8 hours; in the reaction process, no gas is generated above the solution in the flask, the solution is dark green, and the solution is dark red after reacting for 2 hours; after the reaction is finished, the product is dripped into deionized water under ice bath conditions for extraction for 1 time, a water layer is collected, suction filtration is carried out to remove unreacted aluminum powder, filtrate is collected, the filtrate is dripped into 250mL of saturated potassium hexafluorophosphate aqueous solution (8.35g/100g, 25 ℃), dark yellow solution is separated out, standing is carried out for 12 hours, suction filtration is carried out, and the obtained filter cake is dried for 24 hours in vacuum. And (3) recrystallizing with absolute ethyl alcohol, and drying in vacuum for 24 hours to obtain a target product, namely phenylcyclopentadienyl iron hexafluorophosphate: 2.55 g.
Dissolving 400mg of liquid crystal type epoxy monomer 4, 4-biphenol diglycidyl ether in 3mLN, N-dimethylacetamide, and heating until the epoxy monomer is completely dissolved; adding 0.121mL of curing agent m-xylylenediamine, 10mg of photoinitiator 4, 4-diphenyl iodonium hexafluorophosphate and 5mg of photosensitizer phenyl cyclopentadienyl iron hexafluorophosphate, uniformly mixing, pouring into a polytetrafluoroethylene mold with the thickness of 60mm x 40mm x 30mm, and respectively irradiating the front side and the back side for 15 minutes under ultraviolet light (the wavelength is 365nm) to obtain the liquid crystal type epoxy polymer film.
Example 2
A liquid crystal type epoxy monomer was prepared according to the method of example 1;
weighing 15.0g (0.07mol) of potassium iodate and 11g (0.14mol) of benzene, placing the potassium iodate and the benzene into a three-neck flask (250mL) with a condensation reflux device, and sequentially dropwise adding 30mL of acetic anhydride, 10mL of acetic acid and 8mL of concentrated sulfuric acid under the condition of ice bath stirring, wherein the solution has no obvious change when the acetic anhydride and the acetic acid are dropwise added; when concentrated sulfuric acid is dripped, the color of the solution turns yellow and gradually deepens; after the concentrated sulfuric acid is added, reacting for 24 hours at room temperature; after 2h of reaction, a large amount of white precipitate was found to appear; adding 100mL of deionized water into the solution after the reaction is finished, stirring for 2h, carrying out suction filtration, collecting filtrate, extracting the filtrate for 3 times by using benzene, collecting a water layer to obtain a 4, 4-diphenyliodonium bisulfate aqueous solution, adding 19g of potassium hexafluorophosphate solid into the 4, 4-diphenyliodonium bisulfate aqueous solution for ion exchange, carrying out suction filtration along with hydrolysis of potassium hexafluorophosphate to obtain a filter cake, washing the filter cake by using the deionized water, carrying out suction filtration, collecting the filter cake, and carrying out vacuum drying for 24h to obtain a target product 4, 4-diphenyliodonium hexafluorophosphate: 14 g.
Weighing 9.3g (0.05mol) of ferrocene, 1.33g (0.05mol) of aluminum powder and 26.668g (0.2mol) of anhydrous aluminum chloride, adding the obtained product into a three-mouth reaction bottle provided with an electric stirrer, a thermometer and a reflux condenser tube at one time, adding 50mL (0.356mol) of cumene which is used as a reactant and a solvent, slowly raising the temperature to 100 ℃ under stirring, carrying out condensation reflux reaction at 100 ℃ for 8 hours, pouring the reaction product into a beaker filled with deionized water under an ice bath, extracting, separating out an aqueous phase and an organic phase, extracting the organic phase with water for 3 times, and combining the aqueous phases; and then adding 300mL of potassium hexafluorophosphate saturated aqueous solution into the water phase under stirring, separating out a yellow brown precipitate, filtering the precipitate, collecting a filter cake, drying in vacuum for 24h to obtain a crude product, and recrystallizing the crude product by using absolute ethyl alcohol to obtain the target product cumyl cyclopentadienyl iron hexafluorophosphate.
Dissolving 400mg of liquid crystal type epoxy monomer 4, 4-biphenol diglycidyl ether in 3mLN, N-dimethylacetamide, and heating until the epoxy monomer is completely dissolved; adding 0.121mL of curing agent m-xylylenediamine, 10mg of photoinitiator 4, 4-diphenyliodonium hexafluorophosphate and 5mg of photosensitizer cumyl cyclopentadienyl iron hexafluorophosphate, uniformly mixing, pouring into a polytetrafluoroethylene mold with the thickness of 60mm x 40mm x 30mm, and respectively irradiating the front side and the back side for 15 minutes under ultraviolet light (the wavelength is 365nm) to obtain a polymer film with uniform crosslinking.
Example 3
A liquid crystal type epoxy monomer was prepared according to the method of example 1;
weighing 15.0g (0.07mol) of potassium iodate and 12.88g (0.14mol) of toluene, placing the potassium iodate and the toluene into a reaction bottle, under the condition of ice bath stirring, slowly and dropwise adding 30mL of acetic anhydride, 10mL of glacial acetic acid and 8mL of concentrated sulfuric acid in sequence, wherein the solution turns to yellow brown, heating to room temperature, continuing stirring for reaction for 24 hours, dropwise adding 50mL of deionized water into the reaction liquid, extracting the solution for 2-3 times by using benzene, separating out a water layer, combining and washing the benzene layer for 1 time, and then combining the water layers to obtain a p-tolyl iodonium bisulfate aqueous solution; weighing 26g (0.14mol) of potassium hexafluorophosphate solid, adding the potassium hexafluorophosphate solid into p-tolyliodonium bisulfate aqueous solution, carrying out ion exchange, adding deionized water properly under stirring, slowly separating out 4, 4-dimethyldiphenyliodonium hexafluorophosphate along with the dissolution of potassium hexafluorophosphate, collecting precipitate, washing with deionized water, filtering, and drying a filter cake at 40 ℃ for 48 hours in vacuum to obtain a target product, namely 4, 4-dimethyldiphenyliodonium hexafluorophosphate;
weighing 9.3g (0.05mol) of ferrocene, 1.33g (0.05mol) of aluminum powder and 26.67g (0.2mol) of anhydrous aluminum trichloride, adding the weighed materials into a three-neck flask (100mL) provided with an electric stirrer and a condensation reflux device, adding 50mL of benzene which is used as a reactant and a solvent, slowly raising the reaction temperature to 100 ℃ under stirring, and reacting for 8 hours; in the reaction process, no gas is generated above the solution in the flask, the solution is dark green, and the solution is dark red after reacting for two hours; after the reaction is finished, dripping the product into deionized water under an ice bath condition, extracting for 1 time, collecting a water layer, performing suction filtration, removing unreacted aluminum powder, collecting a filtrate, dripping the filtrate into 250mL of saturated potassium hexafluorophosphate aqueous solution (8.35g/100g, 25 ℃), precipitating a dark yellow solution, standing for 12 hours, performing suction filtration, and performing vacuum drying on the obtained filter cake for 24 hours; and (3) recrystallizing with absolute ethyl alcohol, and drying in vacuum for 24 hours to obtain a target product, namely phenylcyclopentadienyl iron hexafluorophosphate: 2.55 g;
dissolving 400mg of liquid crystal type epoxy monomer 4, 4-biphenol diglycidyl ether in 3mLN, N-dimethylacetamide, and heating until the epoxy monomer is completely dissolved; adding 0.121mL of curing agent m-xylylenediamine, 10mg of photoinitiator 4, 4-dimethyl diphenyl iodonium hexafluorophosphate and 5mg of phenyl cyclopentadienyl iron hexafluorophosphate, uniformly mixing, pouring into a 60mm by 40mm by 30mm polytetrafluoroethylene mold, and respectively irradiating the front side and the back side for 15 minutes under ultraviolet light (the wavelength is 365nm) to obtain the liquid crystal type epoxy polymer film with uniform crosslinking.
Example 4
A liquid crystal type epoxy monomer was prepared according to the method of example 1;
weighing 15.0g (0.07mol) of potassium iodate and 11g (0.14mol) of benzene, placing the potassium iodate and the benzene into a three-neck flask (250mL) with a condensation reflux device, and slowly dripping 30mL of acetic anhydride, 10mL of acetic acid and 8mL of concentrated sulfuric acid in sequence under the condition of ice bath stirring, wherein the solution has no obvious change when dripping the acetic anhydride and the acetic acid; when concentrated sulfuric acid is dripped, the color of the solution turns yellow and gradually deepens; after the dropwise addition of the concentrated sulfuric acid is finished, reacting for 24 hours at room temperature, and finding that a large amount of white precipitates appear after 2 hours of reaction; after the reaction is finished, adding 100mL of deionized water into the solution, stirring for 2h, carrying out suction filtration when a small amount of white solid is insoluble, collecting filtrate, extracting the filtrate for 3 times by using benzene, and collecting a water layer to obtain a 4, 4-diphenyl iodonium bisulfate aqueous solution; adding 19g of potassium hexafluorophosphate solid into a 4, 4-diphenyliodonium hydrogen sulfate aqueous solution for ion exchange, separating out a large amount of white precipitate along with hydrolysis of potassium hexafluorophosphate, performing suction filtration, washing the obtained filter cake with deionized water, performing suction filtration, collecting the filter cake, and performing vacuum drying for 24 hours to obtain a target product, namely 4, 4-diphenyliodonium hexafluorophosphate: 10.14 g.
Weighing 9.3g (0.05mol) of ferrocene, 1.33g (0.05mol) of aluminum powder and 26.67g (0.2mol) of anhydrous aluminum trichloride, adding the weighed materials into a three-neck flask (100mL) provided with an electric stirrer and a condensation reflux device, adding 50mL of benzene which is used as a reactant and a solvent, slowly raising the reaction temperature to 100 ℃ under stirring, and reacting for 8 hours; in the reaction process, no gas is generated above the solution in the flask, the solution is dark green, and the solution is dark red after reacting for 2 hours; after the reaction is finished, the product is dripped into deionized water under ice bath conditions for extraction for 1 time, a water layer is collected, suction filtration is carried out to remove unreacted aluminum powder, filtrate is collected, the filtrate is dripped into 250mL of saturated potassium hexafluorophosphate aqueous solution (8.35g/100g, 25 ℃), dark yellow solution is separated out, standing is carried out for 12 hours, suction filtration is carried out, and the obtained filter cake is dried for 24 hours in vacuum. And (3) recrystallizing with absolute ethyl alcohol, and drying in vacuum for 24 hours to obtain a target product, namely phenylcyclopentadienyl iron hexafluorophosphate: 2.55 g.
Dissolving 400mg of liquid crystal type epoxy monomer 4, 4-biphenol diglycidyl ether in 3mLN, N-dimethylacetamide, and heating until the epoxy monomer is completely dissolved; adding 0.089mL of curing agent m-xylylenediamine, 10mg of photoinitiator 4, 4-diphenyl iodonium hexafluorophosphate and 5mg of photosensitizer phenyl cyclopentadienyl iron hexafluorophosphate, uniformly mixing, pouring into a polytetrafluoroethylene mold with the thickness of 60mm x 40mm x 30mm, and respectively irradiating the front side and the back side for 15 minutes under ultraviolet light (the wavelength is 365nm) to obtain the liquid crystal type epoxy polymer film.
Tensile strength: 28.7 +/-5.8 MPa
Elongation at break: 7.1 +/-1.3 percent
Modulus of elasticity: 1590.0 +/-455.0 MPa
Example 5
A liquid crystal type epoxy monomer was prepared according to the method of example 1;
weighing 15.0g (0.07mol) of potassium iodate and 11g (0.14mol) of benzene, placing the potassium iodate and the benzene into a three-neck flask (250mL) with a condensation reflux device, and slowly dripping 30mL of acetic anhydride, 10mL of acetic acid and 8mL of concentrated sulfuric acid in sequence under the condition of ice bath stirring, wherein the solution has no obvious change when dripping the acetic anhydride and the acetic acid; when concentrated sulfuric acid is dripped, the color of the solution turns yellow and gradually deepens; after the dropwise addition of the concentrated sulfuric acid is finished, reacting for 24 hours at room temperature, and finding that a large amount of white precipitates appear after 2 hours of reaction; after the reaction is finished, adding 100mL of deionized water into the solution, stirring for 2h, carrying out suction filtration when a small amount of white solid is insoluble, collecting filtrate, extracting the filtrate for 3 times by using benzene, and collecting a water layer to obtain a 4, 4-diphenyl iodonium bisulfate aqueous solution; adding 19g of potassium hexafluorophosphate solid into a 4, 4-diphenyliodonium hydrogen sulfate aqueous solution for ion exchange, separating out a large amount of white precipitate along with hydrolysis of potassium hexafluorophosphate, performing suction filtration, washing the obtained filter cake with deionized water, performing suction filtration, collecting the filter cake, and performing vacuum drying for 24 hours to obtain a target product, namely 4, 4-diphenyliodonium hexafluorophosphate: 10.14 g.
Weighing 9.3g (0.05mol) of ferrocene, 1.33g (0.05mol) of aluminum powder and 26.67g (0.2mol) of anhydrous aluminum trichloride, adding the weighed materials into a three-neck flask (100mL) provided with an electric stirrer and a condensation reflux device, adding 50mL of benzene which is used as a reactant and a solvent, slowly raising the reaction temperature to 100 ℃ under stirring, and reacting for 8 hours; in the reaction process, no gas is generated above the solution in the flask, the solution is dark green, and the solution is dark red after reacting for 2 hours; after the reaction is finished, the product is dripped into deionized water under ice bath conditions for extraction for 1 time, a water layer is collected, suction filtration is carried out to remove unreacted aluminum powder, filtrate is collected, the filtrate is dripped into 250mL of saturated potassium hexafluorophosphate aqueous solution (8.35g/100g, 25 ℃), dark yellow solution is separated out, standing is carried out for 12 hours, suction filtration is carried out, and the obtained filter cake is dried for 24 hours in vacuum. And (3) recrystallizing with absolute ethyl alcohol, and drying in vacuum for 24 hours to obtain a target product, namely phenylcyclopentadienyl iron hexafluorophosphate: 2.55 g.
Dissolving 400mg of liquid crystal type epoxy monomer 4, 4-biphenol diglycidyl ether in 3mLN, N-dimethylacetamide, and heating until the epoxy monomer is completely dissolved; adding 0.089mL of curing agent m-xylylenediamine, 10mg of photoinitiator 4, 4-diphenyl iodonium hexafluorophosphate and 5mg of photosensitizer phenyl cyclopentadienyl iron hexafluorophosphate, uniformly mixing, pouring into a polytetrafluoroethylene mold with the thickness of 60mm x 40mm x 30mm, and respectively irradiating the front side and the back side for 15 minutes under ultraviolet light (the wavelength is 365nm) to obtain the liquid crystal type epoxy polymer film.
Tensile strength: 33.7 +/-4.1 MPa
Elongation at break: 70.4 +/-12.7 percent
Modulus of elasticity: 1264.4 +/-518.1 MPa
Comparative example 1
Weighing 18.6g (0.1mol) of biphenol into a 250mL three-neck flask, adding 62.7mL (0.8mol) of epichlorohydrin and 50mL of isopropanol, heating to 75 ℃, uniformly stirring, and dropwise adding 28.8% NaOH aqueous solution (NaOH: 8.8 g; H) by mass percent by using a constant pressure funnel2O: 21.8mL) is added in the reaction kettle, after the dropwise adding is finished for 6h, the temperature is slowly raised to 95 ℃, the reflux reaction is carried out for 4h, the heating is stopped, isopropanol is used for washing and filtering, and the drying is carried out for 24 h; and then toluene is used for recrystallization, and the target product, namely the liquid crystal epoxy monomer 17.35g is obtained after drying, wherein the yield is 58%.
Weighing 15.0g (0.07mol) of potassium iodate and 11g (0.14mol) of benzene, placing the potassium iodate and the benzene into a three-neck flask (250mL) with a condensation reflux device, and sequentially dropwise adding 30mL of acetic anhydride, 10mL of acetic acid and 8mL of concentrated sulfuric acid under the condition of ice bath stirring, wherein the solution has no obvious change when the acetic anhydride and the acetic acid are dropwise added; when concentrated sulfuric acid is dripped, the color of the solution turns yellow and gradually deepens; after the dropwise addition of the concentrated sulfuric acid is finished, reacting for 24 hours at room temperature; after 2h of reaction, a large amount of white precipitate was found to appear; adding 100mL of deionized water into the solution after the reaction is finished, stirring for two hours, wherein a small amount of white solid is insoluble, performing suction filtration, collecting filtrate, extracting the filtrate for 3 times by using benzene, collecting a water layer to obtain a 4, 4-diphenyliodonium bisulfate aqueous solution, adding 19g of potassium hexafluorophosphate solid into the aqueous solution for ion exchange, performing suction filtration along with hydrolysis of potassium hexafluorophosphate to separate out a large amount of white precipitate, washing the obtained filter cake by using the deionized water, performing suction filtration, collecting the filter cake, and performing vacuum drying for 24 hours to obtain a target product, namely 4, 4-diphenyliodonium hexafluorophosphate: 10.14 g.
Dissolving 400mg of liquid crystal type epoxy monomer 4, 4-biphenol diglycidyl ether in 2.8mLN, N-dimethylacetamide, and heating until the epoxy monomer is completely dissolved; adding 0.121mL of curing agent m-xylylenediamine and 10mg of photoinitiator 4, 4-diphenyl iodonium hexafluorophosphate, uniformly mixing, pouring into a 60mm 40mm 30mm polytetrafluoroethylene die, respectively irradiating the front side and the back side for 15min under ultraviolet light (the wavelength is 365nm), finding that the solution is not completely cured, and then continuously irradiating for 5min to completely cure, thereby obtaining the liquid crystal epoxy polymer film with uniform crosslinking.
Comparative example 2
Weighing 15.0g (0.07mol) of potassium iodate and 11g (0.14mol) of benzene, placing the potassium iodate and the benzene into a three-neck flask (250mL) with a condensation reflux device, and sequentially dropwise adding 30mL of acetic anhydride, 10mL of acetic acid and 8mL of concentrated sulfuric acid under the condition of ice bath stirring, wherein the solution has no obvious change when the acetic anhydride and the acetic acid are dropwise added; when concentrated sulfuric acid is dripped, the color of the solution turns yellow and gradually deepens; after the dropwise addition of the concentrated sulfuric acid is finished, reacting for 24 hours at room temperature; after 2h of reaction, a large amount of white precipitate was found to appear; and after the reaction is finished, adding 100mL of deionized water into the solution, stirring for 2h, carrying out suction filtration, collecting filtrate, extracting the filtrate for 3 times by using benzene, collecting a water layer to obtain a 4, 4-diphenyliodonium bisulfate aqueous solution, adding 19g of potassium hexafluorophosphate solid into the solution for ion exchange, carrying out suction filtration along with hydrolysis of potassium hexafluorophosphate to separate out a large amount of white precipitate, washing the obtained filter cake by using the deionized water, carrying out suction filtration, collecting the filter cake, and carrying out vacuum drying for 24h to obtain the target product, namely 4, 4-diphenyliodonium hexafluorophosphate.
Weighing 9.3g (0.05mol) of ferrocene, 1.33g (0.05mol) of aluminum powder and 26.67g (0.2mol) of anhydrous aluminum trichloride, adding the weighed materials into a three-neck flask (100mL) provided with an electric stirrer and a condensation reflux device, adding 50mL of benzene which is used as a reactant and a solvent, slowly raising the reaction temperature to 100 ℃ under stirring, and reacting for 8 hours; in the reaction process, no gas is generated above the solution in the flask, the solution is dark green, and the solution is dark red after reacting for two hours; after the reaction is finished, dripping the product into deionized water under an ice bath condition, extracting for 1 time, collecting a water layer, performing suction filtration, removing unreacted aluminum powder, collecting a filtrate, dripping the filtrate into 250mL of saturated potassium hexafluorophosphate aqueous solution (8.35g/100g, 25 ℃), precipitating a dark yellow solution, standing for 12h, performing suction filtration, and performing vacuum drying on the obtained filter cake for 24 h; and (3) recrystallizing with absolute ethyl alcohol, and drying in vacuum for 24 hours to obtain the target product phenylcyclopentadienyl iron hexafluorophosphate.
Commercial epoxy resin (E51) (400 mg) was dissolved in 3mLN, N-dimethylacetamide and heated to complete dissolution; adding 0.092mL of curing agent m-xylylenediamine, 10mg of photoinitiator 4, 4-diphenyl iodonium hexafluorophosphate and 5mg of photosensitizer phenyl cyclopentadienyl iron hexafluorophosphate, uniformly mixing, pouring into a polytetrafluoroethylene mold with the thickness of 60mm x 40mm x 30mm, and irradiating the front side and the back side of the polytetrafluoroethylene mold for 15 minutes respectively under ultraviolet light (the wavelength is 365nm) to obtain a polymer film with uniform crosslinking.
FIG. 1 is an infrared spectrum of the polymer films obtained in examples 1 to 3 and comparative example 1 and the liquid crystal type epoxy monomer powder obtained in example 1, and it can be seen from FIG. 1 that: the characteristic peak of epoxy 910.87 in examples 1 to 3 and comparative example 1 has completely disappeared, indicating that epoxy in the liquid crystal type epoxy monomer has completely reacted by photo-curing, and there is no change in the pattern by comparing the examples and comparative examples, indicating that the addition of the photosensitizer not only accelerates the curing rate of epoxy-amine but also does not affect the structure thereof.
An electronic universal testing machine is adopted, and the stretching speed is 5 mm/min; the shape of the sample is in a dumbbell shape prepared by a national standard method; the stress-strain curves of the polymer films obtained in examples 1 to 3 and comparative example 2 were measured, and the results are shown in FIG. 2.
The tensile strength, elongation at break and elastic modulus of the polymer films obtained in examples 1 to 3 and comparative example 2 are shown in Table 1.
TABLE 1 tensile Strength, elongation at Break, and elastic modulus of Polymer films obtained in examples 1 to 3 and comparative example 2
As can be seen from fig. 2 and table 1: compared with commercial epoxy resin, the liquid crystal epoxy monomer polymer film has improved toughness, but the tensile strength is reduced, and the elastic modulus is not obviously changed.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The liquid crystal type epoxy material is characterized by being prepared from the following raw materials in parts by mass: 400 parts of liquid crystal epoxy monomer, 91.8-157.9 parts of curing agent, 9.5-11.2 parts of photoinitiator, 4.9-5.5 parts of photosensitizer and 2620-2808 parts of organic solvent; the curing agent is m-xylylenediamine; the photoinitiator is diaryl iodonium salt; the photosensitizer is ferrocenium salt.
2. The liquid crystal epoxy material of claim 1, which is prepared from the following raw materials in parts by mass: 400 parts of liquid crystal epoxy monomer, 124.9 parts of curing agent, 10 parts of photoinitiator, 5 parts of photosensitizer and 2620-2808 parts of organic solvent.
3. The liquid crystal-type epoxy material according to claim 1 or 2, wherein the diaryliodonium salt is 4, 4-dimethyldiphenyliodonium hexafluorophosphate or 4, 4-diphenyliodonium hexafluorophosphate.
4. The liquid crystalline epoxy material according to claim 1 or 2, wherein the ferrocenium salt is cumyl cyclopentadienyl iron hexafluorophosphate or phenyl cyclopentadienyl iron hexafluorophosphate.
5. The liquid crystal-type epoxy material according to claim 1 or 2, wherein the organic solvent is N, N-dimethylacetamide or dimethylsulfoxide.
6. The liquid crystal epoxy material according to claim 1 or 2, wherein the curing means of the liquid crystal epoxy material is ultraviolet curing.
7. The liquid crystal epoxy material according to claim 6, wherein the wavelength of the UV-curable UV light is 365nm, and the time is 10-20 minutes.
8. A method for preparing a liquid crystal type epoxy material according to any one of claims 1 to 7, comprising the steps of:
and mixing the liquid crystal epoxy monomer with a solvent, and then adding a curing agent, a photoinitiator and a photosensitizer for mixing to obtain the liquid crystal epoxy material.
9. The use of the liquid crystal type epoxy material according to any one of claims 1 to 7 in the fields of aerospace, intelligent robots and 4D printing.
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