CN113321912B - High-temperature-resistant 3D printing photosensitive resin and preparation method and application thereof - Google Patents
High-temperature-resistant 3D printing photosensitive resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-temperature-resistant 3D printing photosensitive resin and a preparation method and application thereof. The high-temperature-resistant 3D printing photosensitive resin is prepared from the following components in parts by weight: 20-90 parts of acrylate resin, 5-60 parts of epoxy resin, 15-40 parts of rigid monomer, 0.1-5 parts of hybrid modified reinforcement, 3-10 parts of hyperbranched resin, 1-5 parts of free radical photoinitiator and 3-8 parts of cationic photoinitiator, wherein the hybrid modified reinforcement is a reinforcement with the surface grafted with epoxy groups and acrylate groups simultaneously. The prepared material has better mechanical property and heat resistance: the glass transition temperature of the material is 130-165 ℃; the thermal deformation temperature is up to 197-278 ℃; and can be used at 200 ℃ for at least 6 h; the viscosity of the prepared photosensitive resin is 300-800 cps; the molding shrinkage is 0.5-3.0%.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a high-temperature-resistant 3D printing photosensitive resin, and a preparation method and application thereof.
Background
The photosensitive resin has the characteristics of high curing speed, low energy consumption and the like, and has larger and larger share of the protective coating market along with the improvement of environmental protection consciousness of people. The photocuring 3D printing technology has been widely applied to the fields of aerospace, automobile manufacturing, mold manufacturing, biomedicine, cultural art and the like due to the advantages of high forming speed, high precision, low cost, environmental friendliness and the like.
The photosensitive resin is a main material for photocuring 3D printing and forming, the performance of the photosensitive resin has direct and significant influence on the forming precision, the mechanical property, the application field and the like of devices, and the photosensitive resin is also a main bottleneck for restricting the development of the photocuring 3D printing technology at present. The temperature resistance of general photocuring 3D printing resin is between 40 ~ 50 ℃, and serious deformation can take place under the high temperature, but high temperature resistant resin can not warp when receiving high temperature to influence, can solve some problems to the application ambient temperature well. Therefore, the photosensitive resin needs to be modified at high temperature, and the existing modification mainly improves the high-temperature resistance of the photocurable resin by adding fillers, such as chinese patents CN110724236A and CN106749986A, but the addition of too much inorganic nano-fillers can affect the increase of the viscosity of the resin system, and is not suitable for the 3D printing technology requiring low-viscosity resin; in the chinese patent CN106380556A, the high temperature resistant cross-linking agent is selected, and the CN106947205A is used to select a specific resin raw material, so that the problem of viscosity increase caused by adding an inorganic filler is overcome, and the high temperature resistant photosensitive resin is prepared, but the high temperature resistant duration time of the resin is still to be improved.
Therefore, it is required to provide a photocurable resin for 3D printing having high temperature resistance and long high temperature service life.
Disclosure of Invention
In order to solve the problem that the service life of the high-temperature-resistant 3D printing photosensitive resin in the prior art needs to be improved at high temperature, the invention provides the high-temperature-resistant 3D printing photosensitive resin which can be continuously used for a long time at higher temperature. The high-temperature-resistant 3D printing photosensitive resin can be continuously used for at least 6 hours at 200 ℃.
The invention also aims to provide a preparation method of the high-temperature-resistant 3D printing photosensitive resin.
The invention also aims to provide application of the high-temperature-resistant 3D printing photosensitive resin in 3D printing technology.
In order to solve the problems, the invention adopts the following technical scheme:
a high-temperature-resistant 3D printing photosensitive resin is prepared from at least the following components in parts by weight:
the hybrid modified reinforcement is a reinforcement with the surface grafted with an epoxy group and an acrylate group simultaneously.
The invention selects acrylate resin, epoxy resin, hyperbranched resin, rigid monomer, hybrid modified reinforcer, free radical type and cationic photoinitiator to form photosensitive resin, and the material obtained after curing through double photo-initiation of free radical and cation has the characteristics of low molding shrinkage, high glass transition temperature and high thermal deformation temperature. In the photocuring system, the acrylate resin can be cured by free radicals, the epoxy resin can be cured by cations, and the interpenetrating network structures which are interpenetrating network structures can be respectively formed after the free radicals and the cations are cured can improve the mechanical property (such as tensile property) and the heat resistance of the material.
The invention creatively discovers that if the two interpenetrating network structures form a more compact cross-linked network structure, the high temperature resistance of the material can be further improved, and the high temperature resistance time of the material can be prolonged, namely the material can be kept at the critical temperature for a longer time to deform. According to the invention, the reinforcement in the light-cured resin system is modified, and the epoxy group and the acrylate group are grafted on the surface of the reinforcement simultaneously, so that an interpenetrating network formed by the acrylate resin and the epoxy resin can be crosslinked to form a tighter crosslinked network structure.
Specifically, the cross-linked network structure takes the reinforcement as a cross-linking point, and after the reinforcement is modified, the reinforcement is connected with the resin matrix through a cross-linked bond (an epoxy group on the surface of the reinforcement is polymerized with the epoxy resin matrix, and an acrylate group on the surface of the reinforcement is polymerized with the acrylate resin matrix), so that the interaction between the reinforcement and the resin matrix is reduced, and therefore, the viscosity of the composite material is reduced, and the composite material can be used as a 3D printing material with a low viscosity requirement. Meanwhile, the cross-linked network structure can also improve the mechanical property (such as tensile property) and the heat resistance of the material and reduce the molding shrinkage rate; in addition, the rigid monomer can further enhance the mechanical property, and the hyperbranched resin can further adjust the cross-linked network structure, so that the mechanical property and the heat resistance are further improved. Through the combined action of the cross-linked network structure, the rigid monomer and the hyperbranched resin, the mechanical property, the heat distortion temperature and the service time at high temperature (such as 200 ℃) of the material are obviously improved.
Preferably, the high-temperature-resistant 3D printing photosensitive resin is prepared from at least the following components in parts by weight:
preferably, the acrylate resin is one or a combination of more of polyester acrylate, bisphenol A epoxy acrylate, bisphenol F epoxy acrylate or acrylated silicone resin.
Preferably, the epoxy resin is novolac epoxy resin, cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 3-epoxyethyl-7-oxabicyclo [4,1,0] heptane, 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, triglycidyl meta-aminophenol, N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, bis (7-oxabicyclo [4.1.0] 3-heptamethyl) adipate, poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1) or epoxidized silicone resin.
Preferably, the rigid monomer is one or a combination of more of 1-adamantane acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, dicyclopentadienyl methacrylate, tricyclodecane dimethanol diacrylate, 2,6, 6-tetrabromobisphenol A dimethacrylate, hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropionate-diacrylate, bisphenol A glycerol dimethacrylate, dipropylene glycol diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, di-trimethylpropane tetraacrylate or ditrimethylolpropane tetraacrylate.
Preferably, the hybrid modified reinforcement is obtained by a grafting reaction of a silane coupling agent containing an epoxy group, a silane coupling agent containing an acrylate group and the reinforcement.
Preferably, the reinforcement is one or a combination of several of glass fiber, quartz fiber, carbon fiber or ceramic fiber.
Preferably, the silane coupling agent containing epoxy groups is one or a combination of more of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma- (2, 3-epoxypropoxy) propyl triethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane or 2- (3, 4-epoxycyclohexyl) ethyl triethoxy silane; further preferred is 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
Preferably, the acrylate group-containing silane coupling agent is one or a combination of more of 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane or 3- (methacryloyloxy) propylmethyldimethoxysilane; more preferably 3- (methacryloyloxy) propyltrimethoxysilane.
Preferably, in the hybrid modified reinforcement, the grafting ratio of an epoxy group is 5-15%; the grafting rate of the acrylate group is 5-15%.
Preferably, the hyperbranched resin is one or a combination of more of hyperbranched polyester acrylate, hyperbranched silicon resin or hyperbranched epoxy resin. The addition of the hyperbranched resin not only can reduce the viscosity of the resin by virtue of the advantage of a spherical structure of the hyperbranched resin, but also can improve the reaction rate and the crosslinking density of a system by utilizing a large number of reaction groups at the tail end of the hyperbranched resin, thereby being beneficial to improving the thermal deformation temperature of the material.
Preferably, the free radical type photoinitiator is one or a combination of a plurality of benzoin dimethyl ether, 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Preferably, the cationic photoinitiator is one or a combination of more of diphenyl iodonium hexafluorophosphate, triphenyl sulfur tetrafluoroborate, triphenyl sulfur hexafluorophosphate or triphenyl sulfur hexafluoroantimonate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
and dispersing the hybrid modified reinforcement in acrylate resin under a dark condition, adding epoxy resin, a rigid monomer, hyperbranched resin, a free radical photoinitiator and a cationic photoinitiator, and uniformly mixing to obtain the high-temperature-resistant 3D printing photosensitive resin.
The application of the high-temperature-resistant 3D printing photosensitive resin in the 3D printing technology is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the hybrid modification is carried out on the reinforcement, the hybrid modified reinforcement is taken as a cross-linking point, and the interpenetrating network structure of the acrylate resin and the interpenetrating network of the epoxy resin are cross-linked to form a new cross-linked network structure with higher thermal stability, so that the material has higher glass transition temperature; meanwhile, the interaction between the reinforcement and the resin matrix is reduced, the viscosity of the resin system is reduced, and the resin system can be used in a 3D printing technology; the cross-linked network structure, the hyperbranched resin and the rigid monomer have synergistic effect, so that the thermal deformation temperature of the material and the service time at high temperature (such as 200 ℃) are further improved.
The high-temperature-resistant 3D printing photosensitive resin provided by the invention has better mechanical property and heat resistance: the glass transition temperature of the material is 130-165 ℃; the thermal deformation temperature is up to 197-278 ℃; and can be used at 200 ℃ for at least 6 h; the viscosity of the prepared light-cured resin is 300-800 cps; the molding shrinkage is 0.5-3.0%.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
40 parts of aromatic polyester acrylate, 20 parts of novolac epoxy resin, 20 parts of adamantane acrylate, 3 parts of hyperbranched polyester acrylate, 1.5 parts of hybrid modified glass fiber, 1.5 parts of benzoin dimethyl ether and 4 parts of triphenyl sulfur tetrafluoroborate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified glass fiber
5g of reinforcement glass fiber, 10g of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane and 10g of 3- (methacryloxy) propyl trimethoxy silane are uniformly mixed and react for 6 hours at 60 ℃ to obtain hybrid modified glass fiber;
in the hybrid modified glass fiber, the grafting rate of the epoxy group is 8%, and the grafting rate of the acrylate group is 10%. The grafting yield of this example refers to the ratio of the mass of the epoxy group-containing silane coupling agent (specifically, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane) or the acrylate group-containing silane coupling agent (specifically, 3- (methacryloyloxy) propyltrimethoxysilane) grafted onto the reinforcement to the mass of the reinforcement, and so on for the remaining examples.
S2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 1.5 parts of hybrid modified glass fiber in 40 parts of aromatic polyester acrylate, and then shearing and dispersing 20 parts of novolac epoxy resin, 20 parts of adamantane acrylate, 3 parts of hyperbranched polyester acrylate, 1.5 parts of benzoin dimethyl ether and 4 parts of triphenyl sulfur tetrafluoroborate at a high speed for 0.5h to obtain the high-temperature resistant photosensitive resin.
Example 2
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
40 parts of bisphenol A epoxy acrylate, 10 parts of cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 10 parts of 4- (2, 3-epoxypropoxy) -N, N-di (2, 3-epoxypropyl) aniline, 20 parts of dicyclopentyl acrylate, 5 parts of hyperbranched silicon resin, 5 parts of hybrid modified carbon fiber, 1.5 parts of 1-hydroxycyclohexyl phenyl ketone and 4 parts of diphenyl iodine hexafluorophosphate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified carbon fiber
5g of reinforcement carbon fiber, 10g of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane and 10g of 3- (methacryloyloxy) propyl trimethoxy silane are uniformly mixed and react for 6 hours at 60 ℃ to obtain hybrid modified carbon fiber;
in the hybrid modified carbon fiber, the grafting rate of an epoxy group is 6 percent, and the grafting rate of an acrylate group is 8 percent;
s2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 5 parts of hybrid modified carbon fiber in 40 parts of bisphenol A epoxy acrylate, then dispersing 10 parts of cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 10 parts of 4- (2, 3-epoxypropoxy) -N, N-di (2, 3-epoxypropyl) aniline, 20 parts of dicyclopentyl acrylate, 5 parts of hyperbranched silicon resin, 1.5 parts of 1-hydroxycyclohexyl phenyl ketone and 4 parts of diphenyl iodine hexafluorophosphate for high-speed shearing and dispersing for 0.5h to obtain the high-temperature resistant photosensitive resin.
Example 3
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
50 parts of bisphenol F type epoxy acrylate, 20 parts of N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, 25 parts of dicyclopentenyl acrylate, 10 parts of hyperbranched epoxy resin, 1.5 parts of hybrid modified quartz fiber, 1 part of benzoin dimethyl ether, 1 part of 1-hydroxycyclohexyl phenyl ketone and 4 parts of diphenyl iodide hexafluorophosphate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified quartz fiber
5g of reinforcement quartz fiber, 15g of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane and 10g of 3- (methacryloyloxy) propyl trimethoxy silane are uniformly mixed and react for 10 hours at 70 ℃ to obtain hybrid modified quartz fiber;
in the hybrid modified quartz fiber, the grafting rate of an epoxy group is 8 percent, and the grafting rate of an acrylate group is 12 percent;
s2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 1.5 parts of hybrid modified quartz fiber in 50 parts of bisphenol F type epoxy acrylate, and then shearing and dispersing at high speed for 0.5h N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane 20 parts, dicyclopentenyl acrylate 25 parts, hyperbranched epoxy resin 10 parts, benzoin dimethyl ether 1 part, 1-hydroxycyclohexyl phenyl ketone 1 part and diphenyl iodide hexafluorophosphate 4 parts to obtain the high temperature resistant photosensitive resin.
Example 4
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
40 parts of acrylic acid-containing silicon resin, 20 parts of triglycidyl meta-aminophenol, 10 parts of 3-epoxy ethyl-7-oxabicyclo [4,1,0] heptane, 10 parts of tricyclodecane dimethanol diacrylate, 20 parts of methacrylic acid dicyclopentadiene ester, 5 parts of hyperbranched polyester acrylate, 3 parts of hybrid modified ceramic fiber, 2 parts of 1-hydroxycyclohexyl phenyl ketone and 4 parts of triphenyl sulfur hexafluoroantimonate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified ceramic fiber
5g of reinforcement ceramic fiber, 15g of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane and 15g of 3- (methacryloyloxy) propyl trimethoxy silane are uniformly mixed and react for 10 hours at 70 ℃ to obtain hybrid modified ceramic fiber;
in the hybrid modified ceramic fiber, the grafting rate of an epoxy group is 10 percent, and the grafting rate of an acrylate group is 15 percent;
s2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 3 parts of hybrid modified ceramic fiber in 40 parts of acrylated silicone resin, then dispersing 20 parts of triglycidyl meta-aminophenol, 10 parts of 3-epoxy ethyl-7-oxabicyclo [4,1,0] heptane, 10 parts of tricyclodecane dimethanol diacrylate, 20 parts of methacrylic acid dicyclopentadiene ester, 5 parts of hyperbranched polyester acrylate, 2 parts of 1-hydroxycyclohexyl phenyl ketone and 4 parts of triphenyl sulfur hexafluoroantimonate for high-speed shearing and dispersing for 0.5h to obtain the high-temperature resistant photosensitive resin.
Example 5
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
60 parts of aromatic polyester polyol polyester acrylate, 15 parts of 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 15 parts of triglycidyl meta-aminophenol, 5 parts of tricyclodecane dimethanol diacrylate (DCPDA), 20 parts of 2,2,6, 6-tetrabromobisphenol A dimethacrylate, 10 parts of hyperbranched silicon resin, 2 parts of hybrid modified glass fiber, 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 4 parts of triphenyl sulfur hexafluoroantimonate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified glass fiber
5g of reinforcement glass fiber, 20g of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane and 15g of 3- (methacryloxy) propyl trimethoxy silane are uniformly mixed and then react for 12 hours at 70 ℃ to obtain hybrid modified glass fiber;
in the hybrid modified glass fiber, the grafting rate of an epoxy group is 10 percent, and the grafting rate of an acrylate group is 14 percent;
s2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 2 parts of hybrid modified glass fiber in 60 parts of aromatic polyester polyol type polyester acrylate, then dispersing 15 parts of 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 15 parts of triglycidyl-m-aminophenol, 5 parts of tricyclodecane dimethanol diacrylate (DCPDA), 20 parts of 2,2,6, 6-tetrabromobisphenol A dimethacrylate, 10 parts of hyperbranched silicon resin, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 4 parts of triphenyl sulfur hexafluoroantimonate for high-speed shearing and dispersing for 0.5h to obtain the high-temperature resistant photosensitive resin.
Example 6
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
30 parts of bisphenol A epoxy acrylate, 30 parts of bisphenol F epoxy acrylate, 30 parts of bis (7-oxabicyclo [4.1.0] 3-heptamethyl) adipate, 10 parts of adamantane acrylate, 10 parts of dicyclopentyl acrylate, 10 parts of hyperbranched epoxy resin, 3 parts of hybrid modified glass fiber, 2 parts of 1-hydroxycyclohexyl phenyl ketone and 4 parts of triphenyl sulfur hexafluorophosphate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified glass fiber
5g of reinforcement glass fiber, 20g of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane and 15g of 3- (methacryloxy) propyl triethoxy silane are uniformly mixed and then react for 12 hours at 60 ℃ to obtain hybrid modified glass fiber;
in the hybrid modified glass fiber, the grafting rate of an epoxy group is 9 percent, and the grafting rate of an acrylate group is 11 percent;
s2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 3 parts of hybrid modified glass fiber in 30 parts of bisphenol A type epoxy acrylate and 30 parts of bisphenol F type epoxy acrylate, then dispersing 10 parts of adamantane acrylate, 10 parts of dicyclopentyl acrylate, 10 parts of hyperbranched epoxy resin, 2 parts of 1-hydroxycyclohexyl phenyl ketone and 4 parts of triphenyl sulfur hexafluorophosphate at high speed for 0.5h to obtain the high temperature resistant photosensitive resin.
Example 7
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
60 parts of aromatic polyester acrylate, 20 parts of poly [ (2-ethylene oxide) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1), 10 parts of N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, 10 parts of dicyclopentenyl acrylate, 10 parts of 2,2,6, 6-tetrabromobisphenol A dimethacrylate, 7 parts of hyperbranched polyester acrylate, 1 part of hybrid modified ceramic fiber, 1 part of hybrid modified quartz fiber, 2.5 parts of benzoin dimethyl ether and 5 parts of triphenyl sulfur hexafluorophosphate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified ceramic fiber
5g of reinforcement ceramic fiber, 20g of 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane and 15g of 3- (methacryloyloxy) propylmethyldimethoxysilane are uniformly mixed and react for 12h at 65 ℃ to obtain hybrid modified ceramic fiber;
in the hybrid modified ceramic fiber, the grafting rate of an epoxy group is 8 percent, and the grafting rate of an acrylate group is 12 percent;
s2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 1 part of hybrid modified ceramic fiber and 1 part of hybrid modified quartz fiber in 60 parts of aromatic polyester acrylate, then dispersing 20 parts of poly [ (2-ethylene oxide) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1), 10 parts of N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, 10 parts of dicyclopentenyl acrylate, 10 parts of 2,2,6, 6-tetrabromobisphenol A dimethacrylate, 7 parts of hyperbranched polyester acrylate, 2.5 parts of benzoin dimethacrylate and 5 parts of triphenyl sulfur hexafluorophosphate for high-speed shearing dispersion for 0.5h to obtain the high-temperature resistant photosensitive resin.
Example 8
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
50 parts of aromatic polyester acrylate, 10 parts of epoxidized silicone resin, 20 parts of 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 5 parts of N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, 15 parts of dicyclopentadienyl methacrylate, 5 parts of ditrimethylolpropane tetraacrylate, 10 parts of hyperbranched epoxy resin, 10 parts of hybrid modified glass fiber, 2.5 parts of benzoin dimethylene ether and 5 parts of diphenyl iodine hexafluorophosphate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified glass fiber
5g of reinforcement glass fiber, 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 15g of 3- (methacryloyloxy) propyl triethoxy silane are uniformly mixed and react for 10 hours at 70 ℃ to obtain hybrid modified glass fiber;
in the hybrid modified glass fiber, the grafting rate of an epoxy group is 5 percent, and the grafting rate of an acrylate group is 10 percent;
s2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 10 parts of hybrid modified glass fiber in 50 parts of aromatic polyester acrylate, then dispersing 10 parts of silicon epoxide resin, 20 parts of 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 5 parts of N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, 15 parts of dicyclopentadienyl methacrylate, 5 parts of ditrimethylolpropane tetraacrylate, 10 parts of hyperbranched epoxy resin, 2.5 parts of benzoin dimethyl ether and 5 parts of diphenyl iodine hexafluorophosphate, and carrying out high-speed shearing dispersion for 0.5h to obtain the high-temperature resistant photosensitive resin.
Example 9
The invention provides a high-temperature-resistant 3D printing photosensitive resin which is prepared from the following components in parts by weight:
70 parts of bisphenol A epoxy acrylate, 25 parts of bis (7-oxabicyclo [4.1.0] 3-heptamethyl) adipate, 30 parts of tris (2-hydroxyethyl) isocyanuric acid triacrylate, 8 parts of hyperbranched polyester acrylate, 2 parts of hybrid modified glass fiber, 2.5 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 5 parts of triphenyl thiophosphoric hexafluorophosphate.
The preparation method of the high-temperature-resistant 3D printing photosensitive resin comprises the following steps:
s1, preparation of hybrid modified glass fiber
5g of reinforcement glass fiber, 15g of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane and 15g of 3- (methacryloxy) propyl triethoxy silane are uniformly mixed and react for 8 hours at 65 ℃ to obtain hybrid modified glass fiber;
in the hybrid modified glass fiber, the grafting rate of an epoxy group is 6 percent, and the grafting rate of an acrylate group is 10 percent;
s2, preparation of high-temperature-resistant 3D printing photosensitive resin
Under the condition of keeping out of the sun, firstly dispersing 2 parts of hybrid modified glass fiber in 70 parts of bisphenol A epoxy acrylate, then dispersing 25 parts of bis (7-oxabicyclo [4.1.0] 3-heptamethyl) adipate, 30 parts of tris (2-hydroxyethyl) isocyanuric acid triacrylate, 8 parts of hyperbranched polyester acrylate, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 5 parts of triphenyl sulfur hexafluorophosphate, and performing high-speed shearing dispersion for 0.5h to obtain the high-temperature resistant photosensitive resin.
Comparative example 1
This comparative example provides a photosensitive resin, which is different from example 1 in that a cationic photoinitiator triphenylsulfonium tetrafluoroborate was not added.
Comparative example 2
This comparative example provides a photosensitive resin, which is different from example 1 in that benzoin dimethyl ether, which is a radical type photoinitiator, is not added.
Comparative example 3
This comparative example provides a photosensitive resin, which is different from example 1 in that the hybrid modified glass fiber was replaced with an unmodified glass fiber.
Comparative example 4
This comparative example provides a photosensitive resin, which is different from example 1 in that the glass fiber is modified with acrylate-based silane only.
Comparative example 5
This comparative example provides a photosensitive resin, which is different from example 1 in that the glass fiber is modified with only epoxy-based silane.
Performance testing
1. Test method
(1) Tensile strength
The photosensitive resins prepared in the examples and the comparative examples are poured into a mold to be cured to obtain a standard dumbbell-mounted tensile sample, a universal tester is adopted to perform tensile test on the sample to obtain the tensile strength of the sample, the tensile rate is 50mm/min, the test is performed for five times in parallel, and the average value is taken.
(2) Glass transition temperature (Tg)
The glass transition temperature of the materials obtained after the photosensitive resins prepared in the examples and the comparative examples are cured is measured by DSC in a nitrogen atmosphere, the test range is 40-300 ℃, the temperature rise rate is 10 ℃/min, the materials are tested for five times in parallel, and the average value is taken.
(3) Heat Distortion Temperature (HDT)
The materials obtained after curing the photosensitive resins prepared in examples and comparative examples were measured for heat distortion temperature using a heat distortion vicat temperature tester with a measurement load of 1.8MPa, and were tested in parallel five times, and the average value was taken.
(4) Molding shrinkage ratio
The densities of the photosensitive resins prepared in examples and comparative examples before and after curing were measured, and then the molding shrinkage was calculated according to the formula: molding shrinkage factor ═ pRear end-ρFront side)/ρRear endX 100%, measured in parallel five times, and averaged.
(5) Viscosity of light-curing resin
The viscosity values of the photosensitive resins prepared in examples and comparative examples were measured under the conditions of 25 deg.C (working temperature of 3D printer) according to GB/T10247-.
2. Test results
TABLE 1 Performance test results of photosensitive resins obtained in examples and comparative examples
From the test results, it can be seen that the material obtained by curing the high-temperature-resistant 3D printing photosensitive resin provided in embodiments 1 to 9 of the present invention has high glass transition temperature and thermal deformation temperature, and also has excellent tensile strength and long temperature-resistant service life. Wherein, the material obtained by curing the high-temperature-resistant 3D printing photosensitive resin has better tensile strength, molding shrinkage and high-temperature resistance: the glass transition temperature is 130-165 ℃; the thermal deformation temperature is up to 197-278 ℃; and can be used at 200 ℃ for at least 6 h; the viscosity of the prepared light-cured resin is 300-800 cps; the molding shrinkage is 0.5-3.0%.
Comparative example 1 only selects a free radical type photoinitiator, two interpenetrating networks of different types are not formed in the system, the prepared photocuring resin has low tensile strength, glass transition temperature, thermal deformation temperature and molding shrinkage, and the service time at 200 ℃ is short; comparative example 2 only selects cationic photoinitiator, the cationic photoinitiator has low polymerization speed, and cannot be formed by 3D printing technology; comparative example 3 because the reinforcement glass fiber is not modified, a cross-linked network structure is not formed, the prepared photocurable resin has low tensile strength, glass transition temperature, thermal deformation temperature and molding shrinkage, and meanwhile, the interaction force between the glass fiber and the resin matrix is large, the viscosity is high compared with that of example 1, the flowability is poor, and the photocurable resin is difficult to be applied to the 3D printing technology; comparative examples 4 and 5, in which the reinforcing glass fiber was subjected to single-function modification, could not crosslink interpenetrating networks of two different types of resin matrices into a more stable crosslinked structure, and thus, the tensile strength, glass transition temperature, thermal deformation temperature, and molding shrinkage of the obtained photocurable resin were short in service time at 200 ℃.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The high-temperature-resistant 3D printing photosensitive resin is characterized by being prepared from at least the following components in parts by weight:
20-90 parts of acrylate resin;
5-60 parts of epoxy resin;
15-40 parts of rigid monomer;
0.1-5 parts of hybrid modified reinforcement;
3-10 parts of hyperbranched resin;
1-5 parts of a free radical type photoinitiator;
3-8 parts of cationic photoinitiator;
wherein the hybrid modified reinforcement is a reinforcement with the surface grafted with an epoxy group and an acrylate group simultaneously;
the hybrid modified reinforcement is obtained by a grafting reaction of a silane coupling agent containing an epoxy group, a silane coupling agent containing an acrylate group and a reinforcement;
the reinforcement is one or a combination of more of glass fiber, quartz fiber, carbon fiber or ceramic fiber;
in the hybrid modified reinforcement, the grafting rate of an epoxy group is 5-15%; the grafting rate of the acrylate group is 5-15%.
2. The high temperature resistant 3D printing photosensitive resin as claimed in claim 1, wherein the acrylate resin is one or more of polyester acrylate, bisphenol A type epoxy acrylate, bisphenol F type epoxy acrylate or acrylated silicone resin.
3. The high temperature 3D printing photosensitive resin of claim 1, wherein the epoxy resin is novolac epoxy resin, cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 3-epoxyethyl-7-oxabicyclo [4,1,0] heptane, 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, triglycidyl-m-aminophenol, N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, bis (7-oxabicyclo [4.1.0] 3-heptamethyl) adipate, poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1) or epoxidized silicone resin.
4. The high temperature resistant 3D printing photosensitive resin of claim 1, wherein the rigid monomer is one or a combination of more of 1-adamantane acrylate, dicyclopentyl acrylate, dicyclopentenyl dienyl methacrylate, tricyclodecane dimethanol diacrylate, 2,6, 6-tetrabromobisphenol a dimethacrylate, hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropionate-diacrylate, bisphenol a glycerol dimethacrylate, dipropylene glycol diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, di-trimethylpropane tetraacrylate, or ditrimethylolpropane tetraacrylate.
5. The high temperature-resistant 3D printing photosensitive resin according to claim 1, wherein the silane coupling agent containing epoxy groups is one or a combination of more of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane or 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane; the silane coupling agent containing acrylic ester is one or a combination of 3- (methacryloxy) propyl trimethoxy silane, 3- (methacryloxy) propyl triethoxy silane or 3- (methacryloxy) propyl methyl dimethoxy silane.
6. The high-temperature-resistant 3D printing photosensitive resin according to claim 1, wherein the hyperbranched resin is one or a combination of hyperbranched polyester acrylate, hyperbranched silicon resin or hyperbranched epoxy resin.
7. The high temperature resistant 3D printing photosensitive resin as claimed in claim 1, wherein the cationic photoinitiator is one or a combination of diphenyl iodonium hexafluorophosphate, triphenyl sulfur tetrafluoroborate, triphenyl sulfur hexafluorophosphate or triphenyl sulfur hexafluoroantimonate; the free radical type photoinitiator is one or a combination of a plurality of benzoin dimethyl ether, 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
8. The preparation method of the high-temperature-resistant 3D printing photosensitive resin as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
and dispersing the hybrid modified reinforcement in acrylate resin under a dark condition, adding epoxy resin, a rigid monomer, hyperbranched resin, a free radical photoinitiator and a cationic photoinitiator, and uniformly mixing to obtain the high-temperature-resistant 3D printing photosensitive resin.
9. Use of the high temperature resistant 3D printing photosensitive resin of any one of claims 1 to 7 in 3D printing technology.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01259066A (en) * | 1988-04-08 | 1989-10-16 | Hitachi Ltd | Thermosetting resin composition |
| JPH09268205A (en) * | 1996-03-29 | 1997-10-14 | Asahi Denka Kogyo Kk | Resin composition for optically three-dimensional shaping and optically three-dimensional shaping |
| CN104293116A (en) * | 2014-09-22 | 2015-01-21 | 南京航空航天大学 | Photo-curable three-dimensional printing material as well as preparation method and application thereof |
| CN111333791A (en) * | 2020-03-24 | 2020-06-26 | 苏州敏斯郗科技有限公司 | Preparation method of organic silicon epoxy resin and acrylate hybrid photosensitive resin |
| CN112500823A (en) * | 2020-12-06 | 2021-03-16 | 苏州凡络新材料科技有限公司 | High-weather-resistance UV thermosetting adhesive and preparation method thereof |
| CN112662354A (en) * | 2020-12-09 | 2021-04-16 | 深圳先进技术研究院 | Silicon dioxide filler, preparation method thereof and epoxy resin composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8334025B2 (en) * | 2005-10-27 | 2012-12-18 | 3D Systems, Inc. | Antimony-free photocurable resin composition and three dimensional article |
-
2021
- 2021-06-08 CN CN202110640428.2A patent/CN113321912B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01259066A (en) * | 1988-04-08 | 1989-10-16 | Hitachi Ltd | Thermosetting resin composition |
| JPH09268205A (en) * | 1996-03-29 | 1997-10-14 | Asahi Denka Kogyo Kk | Resin composition for optically three-dimensional shaping and optically three-dimensional shaping |
| CN104293116A (en) * | 2014-09-22 | 2015-01-21 | 南京航空航天大学 | Photo-curable three-dimensional printing material as well as preparation method and application thereof |
| CN111333791A (en) * | 2020-03-24 | 2020-06-26 | 苏州敏斯郗科技有限公司 | Preparation method of organic silicon epoxy resin and acrylate hybrid photosensitive resin |
| CN112500823A (en) * | 2020-12-06 | 2021-03-16 | 苏州凡络新材料科技有限公司 | High-weather-resistance UV thermosetting adhesive and preparation method thereof |
| CN112662354A (en) * | 2020-12-09 | 2021-04-16 | 深圳先进技术研究院 | Silicon dioxide filler, preparation method thereof and epoxy resin composite material |
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