CN108227381A - A kind of photocuring 3D printing high-performance photosensitive resin and preparation method thereof - Google Patents
A kind of photocuring 3D printing high-performance photosensitive resin and preparation method thereof Download PDFInfo
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- CN108227381A CN108227381A CN201810001456.8A CN201810001456A CN108227381A CN 108227381 A CN108227381 A CN 108227381A CN 201810001456 A CN201810001456 A CN 201810001456A CN 108227381 A CN108227381 A CN 108227381A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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Abstract
The present invention provides a kind of photocuring 3D printing high-performance photosensitive resins, prepare raw material and include：Epoxy resin, acrylic resin, reactive diluent, cation light initiator, free radical photo-initiation, levelling agent, antifoaming agent, photosensitizer and enhanced expansion prepolymer, prepolymer is by tetraethyl orthocarbonate and the dihydroxyl compound containing vinyl forms intumescent monomer, then generated with cyclosiloxane by addition reaction by the intumescent monomer by esterification for the enhanced expansion.
Description
Technical field
The invention belongs to Functional polymer materials technology fields, and in particular to a kind of photocuring 3D printing high-performance is photosensitive
Resin and preparation method thereof.
Background technology
Photocuring 3D printing is using liquid photosensitive resin molded part, is cured by ultraviolet light, by be successively superimposed come
The efficiently new technology of production precise fine product.Compared to other 3 D-printing materials, due to the photocuring tree of small molecule structure
Fat has fabulous mobility, and the stream length ratio of moulded products can reach more than 100, be more suitable for micro-nano of the processing with labyrinth
Product facilitates realization micromation and precise treatment.Meanwhile photocuring 3 D-printing forming process is without heating and cooling, it is active dilute
It releases agent and directly participates in curing reaction, toxic solvent will not be discharged, there is outstanding advantages of energy-saving and environmental protection, production efficiency is high.Due to
Photosensitive resin can be shunk in photocured cross-linked, generated and shunk internal stress, cause part buckling deformation, make forming part
Precision is greatly affected, and patent CN 201310498194.8 discloses a kind of 3D printing photosensitive resin of fast-photocurable,
Have the characteristics that curing rate is fast, but this photosensitive resin serious volume contraction occurs when photocuring forms material and shows
As affecting the size and precision of product；On the other hand, illumination field is in non-uniform Distribution in material internal, it will leads to product
Contraction distortion and mechanical property non-homogeneous, unstable state, close coupling are presented on space-time the characteristics of, reducing its volume contraction
The physical mechanical property of formation of parts is also taken into account while property, patent CN 201510761930.3, which is disclosed, passes through intumescent
Monomer (such as spiromonomer) can reduce the method for volume photosensitive resin contraction, but the introducing of Expanding Monomer micromolecular substance reduces
The mechanical property of material.
Therefore, the 3D printing of low volume shrinking percentage, low warpage, high-precision and strong mechanical performance how is prepared with photosensitive tree
Fat becomes the technical issues of urgently to be resolved hurrily.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of photosensitive tree of photocuring 3D printing high-performance
Fat and preparation method thereof and a kind of 3D printing method, photocuring 3D printing high-performance photosensitive resin provided by the invention have
Low volume shrinking percentage, low warpage and strong mechanical performance can be used as 3D printing material.
The present invention provides a kind of photocuring 3D printing high-performance photosensitive resins, which is characterized in for preparing raw material and includes：
Epoxy resin, acrylic resin, reactive diluent, cation light initiator, free radical photo-initiation, levelling agent, antifoaming agent, light
Quick dose and enhanced expansion prepolymer, the enhanced expansion prepolymer is by tetraethyl orthocarbonate and the bishydroxy containing vinyl
It closes object and intumescent monomer is formed, then given birth to cyclosiloxane by addition reaction by the intumescent monomer by esterification
Into.
Preferably, the preparation method of the enhanced expansion prepolymer is：
A after) dihydroxyl compound containing vinyl, tetraethyl orthocarbonate and p-methyl benzenesulfonic acid are mixed, heating stirring, into
Row reaction, obtains intumescent monomer；
B) in the presence of a catalyst, the intumescent monomer being mixed with cyclosiloxane, heating stirring is reacted,
Obtain enhanced expansion prepolymer.
Preferably, the dihydroxyl compound containing vinyl is selected from trimethyolol propane monoallyl ether and 6,8- dihydroxy
One or two kinds of mixing of base -1- nonenes；
The cyclosiloxane is tetramethyl-ring tetrasiloxane, eight sulfydryl silsesquioxanes and octahydro silsesquioxane are a kind of or
Several mixing.
Preferably, the molar ratio of the cyclosiloxane and intumescent monomer is (9.4~10.6) ︰ (0.8~1.2).
Preferably, step B) in, the temperature of the reaction is at 110~130 DEG C, and the time of the reaction is 4~8h；Step
Rapid C) in, the temperature of the reaction is 60~80 DEG C, and the time of the reaction is 4~8h.
Preferably, the epoxy resin, acrylic resin, reactive diluent, enhanced expansion prepolymer, cationic photopolymerization draw
It is (40~50) ︰ (30~40) ︰ (10~20) ︰ to send out agent, free radical photo-initiation, levelling agent, antifoaming agent and photosensitizer mass ratio
(5~25) ︰ (2~10) ︰ (1~6) ︰ (0.1~1) ︰ (0.1~1) ︰ (0.1~1).
Preferably, the epoxy resin is glycidyl ether type epoxy resin, glycidol lipid epoxy resin, line style fat
It is one or more in fat race epoxy resin and alicyclic based epoxy resin；
The acrylic resin is isobornyl acrylate, 2-Hydroxy ethyl acrylate, methyl acrylate, acrylic acid second
It is one or more in ester, n-butyl acrylate and acrylic acid-2-ethyl caproite；
The reactive diluent is dodecyl vinyl, glycol divinyl, glycerol carbonate propenyl ether, three
Ethylene glycol divinyl ether, polyoxyethylene polyoxypropylene glycerin ether, butyl glycidyl ether 501, lauryl diglycidyl ether
It is one or more in AGE, benzyl glycidyl ether 692 and organic-silicon-modified polysiloxanes；
The cation light initiator is xanthone base phenyl salt compounded of iodine, Fluorenone base phenyl salt compounded of iodine, isopropylbenzene are luxuriant (II)
Hexafluorophosphate, dialkyl benzene formyl sulfosalt, triaryl (1- pyrenes) bismuth salt, dialkyl benzene formyl sulfosalt, dialkyl benzene formyl
Sulfosalt, bis- (5- fluorine thiophene -2- bases) iodine formates, S, S- dialkyl group-S- (diformazan oxyphenyl) sulfosalts and Phenylsulfanylphenyl
Diphenyl sulfosalt it is one or more；
The free radical photo-initiation is (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide, dibenzoyl, propylene
It is one or more that acyl-oxygen fears quinone, 1- hydroxycyclohexylphenylketones, thioxanthones, benzoin ether and acylphosphanes oxygen；
The levelling agent is epoxy levelling agent 2874, epoxy levelling agent B1484, epoxy levelling agent BYK333, polymethyl-benzene
Ethyl polyethylene-oxide copolymer, heptamethyltrisiloxane polyethylene glycol oxide propylene oxide copolymer, poly- dimethoxysiloxane stream
Flat agent it is one or more；
The antifoaming agent is antifoaming agent M5600, antifoaming agent KS-603, antifoaming agent BKY-A535, butyl stearate/hydrophobic are white
Carbon black composite anti-foaming agent and polysiloxanes/hydrophobic silicic aerogels composite anti-foaming agent are one or more；
The photosensitizer for camphorquinone, naphthalene, anthracene, pyrene, N- unsaturated double-bonds carbazole, benzophenone, dibenzoyl and 3,
5- diphenyl dithienos [3,2-b:2,3-a] anthracene, cumarin and curcumin it is one or more.
The present invention also provides a kind of preparation methods of above-mentioned photocuring 3D printing high-performance photosensitive resin, will be enhanced
Expand prepolymer and epoxy resin, acrylic resin, reactive diluent, cation light initiator, free radical photo-initiation, levelling
Rear froth in vacuum is mixed evenly with the speed of 200~300rpm in agent, antifoaming agent and photosensitizer, obtains photosensitive resin.
The present invention also provides a kind of 3D printing methods, are cured using ultraviolet light, by the high property of above-mentioned photocuring 3D printing
Energy photosensitive resin is successively superimposed by 3D printer, obtains 3D printing product, 20~60mW/ of laser power of the 3D printer
cm2, 0.03~1.00mm of sweep span, 1000~4000mm/s of sweep speed, 0.03~0.150mm of lift height, liquid bath temperature
It is 30 DEG C to spend temperature.
Compared with prior art, the present invention provides a kind of photocuring 3D printing high-performance photosensitive resin, raw material is prepared
Including：Epoxy resin, acrylic resin, reactive diluent, cation light initiator, free radical photo-initiation, levelling agent, defoaming
Agent, photosensitizer and enhanced expansion prepolymer, the enhanced expansion prepolymer are double by tetraethyl orthocarbonate and containing vinyl
Hydroxy compounds forms intumescent monomer, then pass through addition reaction by the intumescent monomer and cyclosiloxane by esterification
And it generates.The spiro-cyclic groups of enhanced expansion prepolymer are as a kind of special functional group in the present invention, the meeting under illumination effect
Cationic ring-opening polymerization is carried out, even counteracting model ylid bloom action moment can be reduced and caused from intermolecular force is transformed into
Contraction internal stress, so as to reduce cubical contraction and reduce angularity, improve the precision of product；Enhanced expansion pre-polymerization simultaneously
Object has the cyclosiloxane of octatomic ring shape structure, occupies certain space, can offset the generation of internal stress and reach reduction body
Product shrinking percentage, excellent mechanical property is provided for product, another aspect, cyclosiloxane structure be capable of providing multiple crosslinking points from
And improve crosslinking degree and crosslink density so that epoxy resin and acrylic resin form and be more closely crosslinked interpenetrating networks.It is logical
Relative amount of the enhanced expansion prepolymer of toning in resin system, makes obtained photosensitive resin have in solidification process low
Cubical contraction, low warpage and strong mechanical performance can be used as 3D printing material.
Description of the drawings
Fig. 1 is 1 synthetic route of intumescent monomer；
Fig. 2 is enhanced expansion 1 synthetic route of prepolymer；
Fig. 3 is 2 synthetic route of intumescent monomer；
Fig. 4 is enhanced expansion 2 synthetic route of prepolymer；
Fig. 5 is enhanced expansion 3 synthetic route of prepolymer；
Fig. 6 is enhanced expansion 4 synthetic route of prepolymer；
Fig. 7 is enhanced expansion 5 synthetic route of prepolymer；
Fig. 8 is enhanced expansion 6 synthetic route of prepolymer；
Fig. 9 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 1；
Figure 10 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 2；
Figure 11 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 3；
Figure 12 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 4；
Figure 13 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 5；
Figure 14 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 6.
Specific embodiment
The present invention provides a kind of photocuring 3D printing high-performance photosensitive resins, prepare raw material and include：Epoxy resin, third
Olefin(e) acid resin, reactive diluent, cation light initiator, free radical photo-initiation, levelling agent, antifoaming agent, photosensitizer and enhancing
Type expands prepolymer, and prepolymer is by tetraethyl orthocarbonate and the dihydroxyl compound containing vinyl passes through ester for the enhanced expansion
Change reaction and form intumescent monomer, then generated with cyclosiloxane by addition reaction by the intumescent monomer.
In the present invention, the preparation method of the enhanced expansion prepolymer is：
A after) dihydroxyl compound containing vinyl, tetraethyl orthocarbonate and p-methyl benzenesulfonic acid are mixed, heating stirring, into
Row reaction, obtains intumescent monomer；
B) in the presence of a catalyst, the intumescent monomer being mixed with cyclosiloxane, heating stirring is reacted,
Obtain enhanced expansion prepolymer.
The present invention first mixes the dihydroxyl compound of vinyl, tetraethyl orthocarbonate and p-methyl benzenesulfonic acid, is mixed
Close object；
Then, by the mixture in the case where temperature is 110~130 DEG C, preferably 115~125 DEG C, mechanic whirl-nett reaction 4
~8h, preferably 5~7 hours, to get to intumescent monomer after being then evaporated under reduced pressure at 100~150 DEG C.
Then, in the presence of a catalyst, the intumescent monomer with cyclosiloxane is mixed, is 60~80 DEG C in temperature
Under, it preferably 65~75 DEG C, preferably 4~8h of mechanic whirl-nett reaction, 5~7 hours, by 120~160 DEG C of vacuum distillations, obtains
To enhanced expansion prepolymer.The molar ratio of the cyclosiloxane and intumescent monomer for (9.4~10.6) ︰ (0.8~1.2),
Preferably (10.0~10.2)：(0.9~1.1).
Wherein, the dihydroxyl compound containing vinyl is selected from trimethyolol propane monoallyl ether and 6,8- dihydroxy
One or two kinds of mixing of base -1- nonenes；
The cyclosiloxane is tetramethyl-ring tetrasiloxane, eight sulfydryl silsesquioxanes and octahydro silsesquioxane are a kind of or
Several mixing.
In the present invention, it is above-mentioned prepare it is enhanced expansion prepolymer during, it is described stirring all be mechanical agitation.
Enhanced expansion prepolymer of the present invention is passed through by tetraethyl orthocarbonate with the dihydroxyl compound containing vinyl
Esterification forms intumescent monomer, and specific synthetic route is referring to Fig. 1 and Fig. 3, then by the intumescent monomer and cyclosiloxane
It is generated by addition reaction, specific synthetic route is referring to Fig. 2 and Fig. 4~8.
In the present invention, the epoxy resin is glycidyl ether type epoxy resin, glycidol lipid epoxy resin, line
It is one or more in type aliphatic epoxy resin and alicyclic based epoxy resin；
The acrylic resin is isobornyl acrylate, 2-Hydroxy ethyl acrylate, methyl acrylate, acrylic acid second
It is one or more in ester, n-butyl acrylate and acrylic acid-2-ethyl caproite；
The reactive diluent is dodecyl vinyl, glycol divinyl, glycerol carbonate propenyl ether, three
Ethylene glycol divinyl ether, polyoxyethylene polyoxypropylene glycerin ether, butyl glycidyl ether 501, lauryl diglycidyl ether
It is one or more in AGE, benzyl glycidyl ether 692 and organic-silicon-modified polysiloxanes；
The cation light initiator is xanthone base phenyl salt compounded of iodine, Fluorenone base phenyl salt compounded of iodine, isopropylbenzene are luxuriant (II)
Hexafluorophosphate, dialkyl benzene formyl sulfosalt, triaryl (1- pyrenes) bismuth salt, dialkyl benzene formyl sulfosalt, dialkyl benzene formyl
Sulfosalt, bis- (5- fluorine thiophene -2- bases) iodine formates, S, S- dialkyl group-S- (diformazan oxyphenyl) sulfosalts and Phenylsulfanylphenyl
Diphenyl sulfosalt it is one or more；
The free radical photo-initiation is (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide, dibenzoyl, propylene
It is one or more that acyl-oxygen fears quinone, 1- hydroxycyclohexylphenylketones, thioxanthones, benzoin ether and acylphosphanes oxygen；
The levelling agent is epoxy levelling agent 2874, epoxy levelling agent B1484, epoxy levelling agent BYK333, polymethyl-benzene
Ethyl polyethylene-oxide copolymer, heptamethyltrisiloxane polyethylene glycol oxide propylene oxide copolymer, poly- dimethoxysiloxane stream
Flat agent it is one or more；
The antifoaming agent is antifoaming agent M5600, antifoaming agent KS-603, antifoaming agent BKY-A535, butyl stearate/hydrophobic are white
Carbon black composite anti-foaming agent and polysiloxanes/hydrophobic silicic aerogels composite anti-foaming agent are one or more；
The photosensitizer for camphorquinone, naphthalene, anthracene, pyrene, N- unsaturated double-bonds carbazole, benzophenone, dibenzoyl and 3,
5- diphenyl dithienos [3,2-b:2,3-a] anthracene, cumarin and curcumin it is one or more.
The epoxy resin, acrylic resin, reactive diluent, it is enhanced expansion prepolymer, cation light initiator, from
It is (40~50) ︰ (30~40) ︰ (10~20) ︰ (5~25) ︰ by base photoinitiator, levelling agent, antifoaming agent and photosensitizer mass ratio
(2~10) ︰ (1~6) ︰ (0.1~1) ︰ (0.1~1) ︰ (0.1~1), preferably (42~48) ︰ (32~38) ︰ (12~18) ︰ (8
~15) ︰ (4~8) ︰ (2~5) ︰ (0.4~0.8) ︰ (0.4~0.8)：(0.4~0.8), more preferably (44~46) ︰ (34~
36) ︰ (14~16) ︰ (10~12) ︰ (5~7) ︰ (3~4) ︰ (0.5~0.7) ︰ (0.5~0.7) ︰ (0.5~0.7).
The present invention also provides a kind of preparation method of above-mentioned photocuring 3D printing high-performance photosensitive resin, feature exists
In,
By enhanced expansion prepolymer and epoxy resin, acrylic resin, reactive diluent, cation light initiator, from
Rear froth in vacuum is mixed evenly with the speed of 200~300rpm by base photoinitiator, levelling agent, antifoaming agent and photosensitizer,
Obtain photosensitive resin.Wherein, the stirring is mechanical agitation, and the froth in vacuum is that mixed raw material is placed in hollow baking oven
In, it carries out excluding bubble processing.
The present invention also provides a kind of 3D printing methods, are cured using ultraviolet light, by the high property of above-mentioned photocuring 3D printing
Energy photosensitive resin is successively superimposed by 3D printer, obtains 3D printing product, 20~60mW/ of laser power of the 3D printer
cm2, preferably 30~40mW/cm2；0.03~1.00mm of sweep span, preferably 0.4~0.6mm；Sweep speed 1000~
4000mm/s, preferably 2000~3000mm/s；0.03~0.150mm of lift height, preferably 0.05~0.100mm；Liquid bath
Temperature is 30 DEG C.
The spiro-cyclic groups of enhanced expansion prepolymer are as a kind of special functional group in the present invention, the meeting under illumination effect
Cationic ring-opening polymerization is carried out, even counteracting model ylid bloom action moment can be reduced and caused from intermolecular force is transformed into
Contraction internal stress, so as to reduce cubical contraction and reduce angularity, improve the precision of product；Enhanced expansion pre-polymerization simultaneously
Object has the cyclosiloxane of octatomic ring shape structure, occupies certain space, can offset the generation of internal stress and reach reduction body
Product shrinking percentage, excellent mechanical property is provided for product, another aspect, cyclosiloxane structure be capable of providing multiple crosslinking points from
And improve crosslinking degree and crosslink density so that epoxy resin and acrylic resin form and be more closely crosslinked interpenetrating networks.It is logical
Relative amount of the enhanced expansion prepolymer of toning in resin system, makes obtained photosensitive resin have in solidification process low
Cubical contraction, low warpage and strong mechanical performance can be used as 3D printing material.
For a further understanding of the present invention, with reference to embodiment to photocuring 3D printing high-performance provided by the invention
Photosensitive resin and preparation method thereof and 3D printing method illustrate, and protection scope of the present invention is not limited by following embodiment
System.
Embodiment 1
88.9g trimethyolol propane monoallyl ethers are positioned in three-necked flask, mechanical agitation is equal with 150rpm stirrings
It is even, 115 DEG C of water removals are warming up to, are then mixed by 49.5g tetraethyl orthocarbonates and to the dropwise addition of 6.23g p-methyl benzenesulfonic acid mixture is above-mentioned
It closes in liquid, in the case where temperature is 122 DEG C, mechanic whirl-nett reaction 6h after being then evaporated under reduced pressure by 68 DEG C, obtains intumescent monomer.
56.2g intumescent monomers are positioned in three-necked flask, 50 DEG C is warming up to and mechanical agitation is equal with 175rpm stirrings
It is even, then 13.9g tetramethyl-ring tetrasiloxanes and 0.39g platinum catalyst mixtures are added drop-wise in above-mentioned solution, are in temperature
At 75 DEG C, mechanic whirl-nett reaction 7h by 70 DEG C of vacuum distillations, obtains enhanced expansion prepolymer.
Referring to Fig. 9, Fig. 9 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 1, in infrared spectrum,
2168cm-1And 1646cm-1Infrared signature absorption peak remitted its fury after the reaction at two illustrates that si-h bond and carbon-carbon double bond occur
Reaction；1201cm-1And 1068cm-1Still occur infrared signature absorption peak at two after the reaction, illustrate spiro-cyclic groups after reacting
It is remained with Si-O-Si keys.It follows that synthetic product has expected molecular structure.
By the enhanced expansion prepolymers of 20g, 50g glycidol lipids epoxy resin, 30g methyl acrylates, the contracting of 14g benzyls
Water glycerin ether 692,6g triethylene glycol divinyl ethers, 6.4g S, S- dialkyl group-S- (diformazan oxyphenyl) sulfosalt, 3.6g are free
Base photoinitiator thioxanthones, 0.32g epoxy levelling agent BYK333,0.21g antifoaming agent KS-603 and 0.19g camphorquinone are placed
It in reaction kettle, is uniformly mixed, is positioned in vacuum drying oven with 250rpm mechanical agitations, excluded bubble processing, obtain uniform
Photosensitive resin.It infuses resin into the sample bin of 3D printer, setting laser power 45mW/cm2, sweep span 0.05mm sweeps
Speed 2600mm/s, lift height 0.05mm are retouched, temperature control is 30 DEG C, carries out 3D printing rapid shaping curing.
Embodiment 2
By 123.1g6,8- dihydroxy -1- nonenes are positioned in three-necked flask, and mechanical agitation is stirred evenly with 180rpm, are risen
Above-mentioned mixed liquor then is added dropwise by 61.9g tetraethyl orthocarbonates and to 9.81g p-methyl benzenesulfonic acid mixture to 120 DEG C of water removals in temperature
In, in the case where temperature is 118 DEG C, mechanic whirl-nett reaction 5h then by 79 DEG C of vacuum distillations, obtains intumescent monomer.
73.6g intumescent monomers are positioned in three-necked flask, 50 DEG C is warming up to and mechanical agitation is equal with 163rpm stirrings
It is even, then 22.6g tetramethyl-ring tetrasiloxanes and 0.55g platinum catalyst mixtures are added drop-wise in above-mentioned solution, are in temperature
At 80 DEG C, mechanic whirl-nett reaction 6h by 80 DEG C of vacuum distillations, obtains enhanced expansion prepolymer.
Referring to Figure 10, Figure 10 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 2, in infrared spectrum
In, 2216cm-1And 1640cm-1Infrared signature absorption peak remitted its fury after the reaction at two illustrates si-h bond and carbon-carbon double bond hair
Raw reaction；1208cm-1And 1082cm-1Still occur infrared signature absorption peak at two after the reaction, illustrate loop coil base after reacting
Group and Si-O-Si keys remain.It follows that synthetic product has expected molecular structure.
By the enhanced expansion prepolymers of 20g, 45g glycidol lipids epoxy resin, 35g methyl acrylates, 12g dialkyl group
Glycidol ether AGE, 8g glycerol carbonate propenyl ether, 6.2g Irgacure842,3.8g free radical photo-initiations (2,4,6-
Trimethylbenzoyl) diphenyl phosphine oxide, 0.35g epoxies levelling agent 2874,0.19g antifoaming agent M5600 and 0.15g styraxes
Class photosensitizer is positioned in reaction kettle, is uniformly mixed, is positioned in vacuum drying oven with 250rpm mechanical agitations, is excluded at bubble
Reason, obtains uniform photosensitive resin.It infuses resin into the sample bin of 3D printer, setting laser power 55mW/cm2, scanning
Spacing 0.10mm, sweep speed 4000mm/s, lift height 0.09mm, temperature control are 30 DEG C, carry out 3D printing rapid shaping
Curing.
Embodiment 3
102.8g trimethyolol propane monoallyl ethers are positioned in three-necked flask, mechanical agitation is equal with 175rpm stirrings
It is even, 118 DEG C of water removals are warming up to, are then mixed by 53.7g tetraethyl orthocarbonates and to the dropwise addition of 8.25g p-methyl benzenesulfonic acid mixture is above-mentioned
It closes in liquid, in the case where temperature is 116 DEG C, mechanic whirl-nett reaction 7h then by 80 DEG C of vacuum distillations, obtains intumescent monomer.
68.2g intumescent monomers are positioned in three-necked flask, 50 DEG C is warming up to and mechanical agitation is equal with 170rpm stirrings
It is even, then the poly- caged silsesquioxane of 18.5g octahydros and 0.45g platinum catalyst mixtures are added drop-wise in above-mentioned solution, in temperature
It spends at 75 DEG C, mechanic whirl-nett reaction 7h by 75 DEG C of vacuum distillations, obtains enhanced expansion prepolymer.
Referring to Figure 11, Figure 11 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 3, in infrared spectrum
In, 2196cm-1And 1636cm-1Infrared signature absorption peak remitted its fury after the reaction at two illustrates si-h bond and carbon-carbon double bond hair
Raw reaction；1287cm-1And 1101cm-1Still occur infrared signature absorption peak at two after the reaction, illustrate loop coil base after reacting
Group and Si-O-Si keys remain.It follows that synthetic product has expected molecular structure.
By the enhanced expansion prepolymers of 20g, 40g linear aliphatic epoxy resins, 40g ethyl acrylates, 10g dodecyls
Vinyl ethers, 10g butyl glycidyl ethers 501,6.0g dialkyl benzene formyls sulfosalt, 4.0g free radical photo-initiation biphenyl first
Acyl, 0.25g epoxy levelling agent B1484,0.15g antifoaming agent BKY-A535 and 0.17g benzophenone photosensitizers are positioned over reaction kettle
In, it is uniformly mixed, is positioned in vacuum drying oven with 225rpm mechanical agitations, excluded bubble processing, obtain uniform photosensitive resin.
It infuses resin into the sample bin of 3D printer, setting laser power 40mW/cm2, sweep span 0.02mm, sweep speed
2500mm/s, lift height 0.03mm, temperature control are 30 DEG C, carry out 3D printing rapid shaping curing.
Embodiment 4
By 82.45g 6,8- dihydroxy -1- nonenes are positioned in three-necked flask, and mechanical agitation is stirred evenly with 175rpm,
120 DEG C of water removals are warming up to, above-mentioned mixing then is added dropwise by 40.78g tetraethyl orthocarbonates and to 6.4g p-methyl benzenesulfonic acid mixture
In liquid, in the case where temperature is 130 DEG C, mechanic whirl-nett reaction 6h then by 75 DEG C of vacuum distillations, obtains intumescent monomer.
80.9g intumescents monomer and 360mL toluene are positioned in three-necked flask, be warming up to 50 DEG C and mechanical agitation with
190rpm is stirred evenly, and is then added drop-wise to the poly- caged silsesquioxane of 51.5g octahydros and 0.67g platinum catalyst mixtures above-mentioned
In solution, in the case where temperature is 78 DEG C, mechanic whirl-nett reaction 6.5h by 78 DEG C of vacuum distillations, obtains enhanced expansion prepolymer.
Referring to Figure 12, Figure 12 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 4, in infrared spectrum
In, 2217cm-1And 1659cm-1Infrared signature absorption peak remitted its fury after the reaction at two illustrates si-h bond and carbon-carbon double bond hair
Raw reaction；1269cm-1And 1037cm-1Still occur infrared signature absorption peak at two after the reaction, illustrate loop coil base after reacting
Group and Si-O-Si keys remain.It follows that synthetic product has expected molecular structure.
By the enhanced expansion prepolymers of 22g, the alicyclic based epoxy resins of 47g, 33g acrylic acid-2-ethyl caproites, 12.5g
Bis- (5- fluorine thiophene -2- bases) the iodine formates of dodecyl vinyl, 7.5g glycerol carbonates propenyl ether, 5.4g, 4.6g
The poly- dimethoxysiloxane levelling agent of free radical photo-initiation acylphosphanes, 0.37g and 0.23g dibenzoyl photosensitizers are positioned over
It in reaction kettle, is uniformly mixed, is positioned in vacuum drying oven with 250rpm mechanical agitations, excluded bubble processing, obtain uniform light
Quick resin.It infuses resin into the sample bin of 3D printer, setting laser power 80mW/cm2, sweep span 0.12mm, scanning
Speed 2700mm/s, lift height 0.04mm, temperature control are 30 DEG C, carry out 3D printing rapid shaping curing.
Embodiment 5
By 65.32g 6,8- dihydroxy -1- nonenes are positioned in three-necked flask, and mechanical agitation is stirred evenly with 165rpm,
110 DEG C of water removals are warming up to, above-mentioned mixing then is added dropwise by 30.54g tetraethyl orthocarbonates and to 5.3g p-methyl benzenesulfonic acid mixture
In liquid, in the case where temperature is 120 DEG C, mechanic whirl-nett reaction 7h then by 65 DEG C of vacuum distillations, obtains intumescent monomer.
72.3g intumescents monomer and 330mL toluene are positioned in three-necked flask, be warming up to 50 DEG C and mechanical agitation with
180rpm is stirred evenly, and is then added drop-wise to the poly- caged silsesquioxane of 66.7g sulfydryls and 0.88g basic catalyst mixtures
It states in solution, in the case where temperature is 30 DEG C, mechanic whirl-nett reaction 6h by 75 DEG C of vacuum distillations, obtains enhanced expansion prepolymer.
Referring to Figure 13, Figure 13 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 5, in infrared spectrum
In, 2543cm-1And 1667cm-1Infrared signature absorption peak remitted its fury after the reaction at two illustrates that sulfydryl and carbon-carbon double bond occur
Reaction；1268cm-1And 1042cm-1Still occur infrared signature absorption peak at two after the reaction, illustrate spiro-cyclic groups after reacting
It is remained with Si-O-Si keys.It follows that synthetic product has expected molecular structure.
By 21g it is enhanced expansion prepolymer, 42g glycidyl ether type epoxies resin, 38g 2-Hydroxy ethyl acrylates,
13.5g glycol divinyls, 6.5g polyoxyethylene polyoxypropylenes glycerin ether, 5.9gIrgacure261,3.2g free radical light draw
Send out agent 1- hydroxycyclohexylphenylketones, 0.31g butyl stearates/hydrophobic silicic aerogels composite anti-foaming agent, seven methyl of 0.29g, three silica
Alkane polyethylene glycol oxide propylene oxide copolymer and 0.17g per-compound photosensitizers are positioned in reaction kettle, with 250rpm machineries
It is uniformly mixed, is positioned in vacuum drying oven, exclude bubble processing, obtain uniform photosensitive resin.3D is infused resin into beat
In the sample bin of print machine, laser power 60mW/cm is set2, sweep span 0.09mm, sweep speed 3400mm/s, lift height
0.07mm, temperature control are 30 DEG C, carry out 3D printing rapid shaping curing.
Embodiment 6
71.02g trimethyolol propane monoallyl ethers are positioned in three-necked flask, mechanical agitation is equal with 172rpm stirrings
It is even, 120 DEG C of water removals are warming up to, are then mixed by 37.22g tetraethyl orthocarbonates and to the dropwise addition of 6.7g p-methyl benzenesulfonic acid mixture is above-mentioned
It closes in liquid, in the case where temperature is 117 DEG C, mechanic whirl-nett reaction 7h then by 76 DEG C of vacuum distillations, obtains intumescent monomer.
66.8g intumescents monomer and 340mL toluene are positioned in three-necked flask, be warming up to 50 DEG C and mechanical agitation with
175rpm is stirred evenly, and is then added drop-wise to the poly- caged silsesquioxane of 31.4g sulfydryls and 0.49g basic catalyst mixtures
It states in solution, in the case where temperature is 35 DEG C, mechanic whirl-nett reaction 5h by 78 DEG C of vacuum distillations, obtains enhanced expansion prepolymer.
Referring to Figure 14, Figure 14 is the infrared spectrogram of enhanced expansion prepolymer prepared by embodiment 6, in infrared spectrum
In, 2588cm-1And 1653cm-1Infrared signature absorption peak remitted its fury after the reaction at two illustrates that sulfydryl and carbon-carbon double bond occur
Reaction；1259cm-1And 1062cm-1Still occur infrared signature absorption peak at two after the reaction, illustrate spiro-cyclic groups after reacting
It is remained with Si-O-Si keys.It follows that synthetic product has expected molecular structure.
By the enhanced expansion prepolymers of 25g, 40g linear aliphatic epoxy resins, 35g ethyl acrylates, 11.8g triethylene glycols
Divinyl ether, 7.2g butyl glycidyl ethers 501,6.2g dialkyl benzene formyls sulfosalt, 1.8g free radical photo-initiations benzene are even
Relation by marriage ether, 1.4g free radical photo-initiations benzoin ether, 0.23gM5600 antifoaming agent, 0.34g epoxy levelling agents BYK333 and 0.15g
N- unsaturated double-bond carbazole photosensitizers are positioned in reaction kettle, are uniformly mixed with 234rpm mechanical agitations, are positioned over vacuum drying oven
In, bubble processing is excluded, obtains uniform photosensitive resin.It infuses resin into the sample bin of 3D printer, laser power is set
65mW/cm2, sweep span 0.08mm, sweep speed 3500mm/s, lift height 0.05mm, temperature control is 30 DEG C, carries out 3D
Print rapid shaping curing.
Embodiment 7
By 58.62g 6,8- dihydroxy -1- nonenes are positioned in three-necked flask, and mechanical agitation is stirred evenly with 160rpm,
116 DEG C of water removals are warming up to, above-mentioned mixing then is added dropwise by 27.97g tetraethyl orthocarbonates and to 4.0g p-methyl benzenesulfonic acid mixture
In liquid, in the case where temperature is 125 DEG C, mechanic whirl-nett reaction 6h then by 77 DEG C of vacuum distillations, obtains intumescent monomer.
61.1g intumescents monomer and 325mL toluene are positioned in three-necked flask, be warming up to 50 DEG C and mechanical agitation with
171rpm is stirred evenly, and is then added drop-wise to the poly- caged silsesquioxane of 34.4g sulfydryls and 0.61g basic catalyst mixtures
It states in solution, in the case where temperature is 32 DEG C, mechanic whirl-nett reaction 6h by 70 DEG C of vacuum distillations, obtains enhanced expansion prepolymer.
By the enhanced expansion prepolymers of 19g, the alicyclic based epoxy resins of 44g, 37g isobornyl acrylates, 11.7g glycerine
Luxuriant (II) hexafluorophosphate of carbonic ester propenyl ether, 7.0g glycerol carbonates propenyl ether, 4.8g isopropylbenzenes, 4.1g free radical light
Initiator acryloyl-oxy fears quinone, the poly- dimethoxysiloxane stream of 0.53g antifoaming agent M5600,0.11g antifoaming agent KS-603,0.33g
Flat agent and 0.16g pyrene photosensitizers are positioned in reaction kettle, are uniformly mixed, are positioned in vacuum drying oven with 243rpm mechanical agitations,
Bubble processing is excluded, obtains uniform photosensitive resin.It infuses resin into the sample bin of 3D printer, laser power is set
64mW/cm2, sweep span 0.13mm, sweep speed 3700mm/s, lift height 0.13mm, temperature control is 28 DEG C, carries out 3D
Print rapid shaping curing.
Comparative example 1
88.9g trimethyolol propane monoallyl ethers are positioned in three-necked flask, mechanical agitation is equal with 150rpm stirrings
It is even, 115 DEG C of water removals are warming up to, are then mixed by 49.5g tetraethyl orthocarbonates and to the dropwise addition of 6.23g p-methyl benzenesulfonic acid mixture is above-mentioned
It closes in liquid, in the case where temperature is 122 DEG C, mechanic whirl-nett reaction 6h then by 68 DEG C of vacuum distillations, obtains intumescent monomer.
By 20g intumescents monomer, 50g glycidol lipids epoxy resin, 30g methyl acrylates, 14g benzyl glycidols
Ether 692,6g triethylene glycol divinyl ethers, 6.4g S, S- dialkyl group-S- (diformazan oxyphenyl) sulfosalt, 3.6g free radical light draw
Hair agent thioxanthones, 0.32g epoxy levelling agent BYK333,0.21g antifoaming agent KS-603 and 0.19g camphorquinones are positioned over reaction
It in kettle, is uniformly mixed, is positioned in vacuum drying oven with 250rpm mechanical agitations, excluded bubble processing, obtain uniform photosensitive tree
Fat is infused resin into the sample bin of 3D printer, setting laser power 45mW/cm2, sweep span 0.05mm, sweep speed
2600mm/s, lift height 0.05mm, temperature control are 30 DEG C, carry out 3D printing rapid shaping curing.
Comparative example 2
By 50g glycidol lipids epoxy resin, 30g methyl acrylates, 14g benzyl glycidyl ethers 692,6g triethylene glycols
Divinyl ether, 6.4g S, S- dialkyl group-S- (diformazan oxyphenyl) sulfosalt, 3.6g free radical photo-initiations thioxanthones,
0.32g epoxy levelling agent BYK333,0.21g antifoaming agent KS-603 and 0.19g camphorquinones are positioned in reaction kettle, with 250rpm machines
Tool is uniformly mixed, and is positioned in vacuum drying oven, is excluded bubble processing, is obtained uniform photosensitive resin.Infuse resin into 3D
In the sample bin of printer, laser power 45mW/cm is set2, sweep span 0.05mm, sweep speed 2600mm/s, layering thickness
0.05mm is spent, temperature control is 30 DEG C, carries out 3D printing rapid shaping curing.
The embodiment of the present invention 1~7 and comparative example 1~2 is fast curing-formed into mark by 3D printer progress 3D printing
Quasi- batten：Extension test is carried out in universal testing machine (SANS), rate of extension 50mm/min obtains the tensile strength of material；
Radial-boom impact tester (XJU) carries out impact strength test, impact energy 11J；With densitometer (AUY120) into line density
Test measures solidified resin cubical contraction；Material warp degree is measured using laser displacement sensor.
1 photosensitive resin cubical contraction situation of table
The Some Mechanical Properties of the embodiment of the present invention 1~7 and the 3D printing photosensitive resin of the preparation of comparative example 1~2, volume are received
Contracting measures and the test data of angularity is listed in table 1.The result shows that Examples 1 to 7 is compared with comparative example 1~2, embodiment 1
3D printing resin batten prepared by~7 has low volume shrinking percentage, low warpage, high tensile and high impact,
By changing the relative amount of enhanced expansion prepolymer, the performances such as the formed precision of composite material and mechanical property can be carried out
Regulation and control.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of photocuring 3D printing high-performance photosensitive resin, which is characterized in that prepare raw material and include：Epoxy resin, propylene
Acid resin, reactive diluent, cation light initiator, free radical photo-initiation, levelling agent, antifoaming agent, photosensitizer and enhanced
Prepolymer is expanded, prepolymer is by tetraethyl orthocarbonate and the dihydroxyl compound containing vinyl passes through esterification for the enhanced expansion
Reaction forms intumescent monomer, then generated with cyclosiloxane by addition reaction by the intumescent monomer.
2. photosensitive resin according to claim 1, which is characterized in that the preparation method of the enhanced expansion prepolymer
For：
A after) mixing the dihydroxyl compound containing vinyl, tetraethyl orthocarbonate and p-methyl benzenesulfonic acid, heating stirring carries out anti-
Should, obtain intumescent monomer；
B) in the presence of a catalyst, the intumescent monomer is mixed with cyclosiloxane, heating stirring is reacted, and is obtained
Enhanced expansion prepolymer.
3. photosensitive resin according to claim 2, which is characterized in that the dihydroxyl compound containing vinyl is selected from three
One or two kinds of mixing of hydroxymethyl-propane mono allyl ether and 6,8- dihydroxy -1- nonenes；
The cyclosiloxane is tetramethyl-ring tetrasiloxane, eight sulfydryl silsesquioxanes and octahydro silsesquioxane are one or more of
Mixing.
4. photosensitive resin according to claim 2, which is characterized in that the molar ratio of the cyclosiloxane and intumescent monomer
For (9.4~10.6) ︰ (0.8~1.2).
5. photosensitive resin according to claim 2, which is characterized in that step A) in, the temperature of the reaction for 110~
At 130 DEG C, the time of the reaction is 4~8h；Step B) in, the temperature of the reaction is 60~80 DEG C, the reaction when
Between be 4~8h.
6. photosensitive resin according to claim 1, which is characterized in that the epoxy resin, acrylic resin, activity dilution
Agent, enhanced expansion prepolymer, cation light initiator, free radical photo-initiation, levelling agent, antifoaming agent and photosensitizer mass ratio
For (40~50) ︰ (30~40) ︰ (10~20) ︰ (5~25) ︰ (2~10) ︰ (1~6) ︰ (0.1~1) ︰ (0.1~1) ︰ (0.1~
1)。
7. photosensitive resin according to claim 1, which is characterized in that the epoxy resin is glycidyl ether type epoxy tree
It is one or more in fat, glycidol lipid epoxy resin, linear aliphatic epoxy resins and alicyclic based epoxy resin；
The acrylic resin is isobornyl acrylate, 2-Hydroxy ethyl acrylate, methyl acrylate, ethyl acrylate, third
It is one or more in olefin(e) acid N-butyl and acrylic acid-2-ethyl caproite；
The reactive diluent is dodecyl vinyl, glycol divinyl, glycerol carbonate propenyl ether, triethylene glycol
Divinyl ether, polyoxyethylene polyoxypropylene glycerin ether, butyl glycidyl ether 501, lauryl diglycidyl ether AGE, benzyl
It is one or more in base glycidol ether 692 and organic-silicon-modified polysiloxanes；
The cation light initiator is xanthone base phenyl salt compounded of iodine, luxuriant (II) hexafluoro of Fluorenone base phenyl salt compounded of iodine, isopropylbenzene
Phosphate, dialkyl benzene formyl sulfosalt, triaryl (1- pyrenes) bismuth salt, dialkyl benzene formyl sulfosalt, dialkyl benzene formyl sulfosalt,
Bis- (5- fluorine thiophene -2- bases) iodine formates, S, S- dialkyl group-S- (diformazan oxyphenyl) sulfosalts and Phenylsulfanylphenyl diphenyl
Sulfosalt it is one or more；
The free radical photo-initiation is (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide, dibenzoyl, acryloyl-oxy
It is one or more to fear quinone, 1- hydroxycyclohexylphenylketones, thioxanthones, benzoin ether and acylphosphanes oxygen；
The levelling agent is epoxy levelling agent 2874, epoxy levelling agent B1484, epoxy levelling agent BYK333, polymethyl-benzene base gather
Ethylene oxide copolymer, heptamethyltrisiloxane polyethylene glycol oxide propylene oxide copolymer, poly- dimethoxysiloxane levelling agent
It is one or more；
The antifoaming agent is antifoaming agent M5600, antifoaming agent KS-603, antifoaming agent BKY-A535, butyl stearate/hydrophobic silicic aerogels
Composite anti-foaming agent and polysiloxanes/hydrophobic silicic aerogels composite anti-foaming agent are one or more；
The photosensitizer is camphorquinone, naphthalene, anthracene, pyrene, N- unsaturated double-bonds carbazole, benzophenone, dibenzoyl and 3,5- bis-
Phenyl dithieno [3,2-b:2,3-a] anthracene, cumarin and curcumin it is one or more.
8. a kind of preparation method of photocuring 3D printing high-performance photosensitive resin as described in claim 1~7 any one,
It is characterized in that,
By enhanced expansion prepolymer and epoxy resin, acrylic resin, reactive diluent, cation light initiator, free radical
Rear froth in vacuum is mixed evenly with the speed of 200~300rpm in photoinitiator, levelling agent, antifoaming agent and photosensitizer, obtains
Photosensitive resin.
A kind of 9. 3D printing method, which is characterized in that cured using ultraviolet light, by the light described in claim 1~7 any one
Curing 3D printing is successively superimposed with high-performance photosensitive resin by 3D printer, obtains 3D printing product, the 3D printer
20~60mW/cm of laser power2, 0.03~1.00mm of sweep span, 1000~4000mm/s of sweep speed, lift height 0.03
~0.150mm, bath temperature temperature are 30 DEG C.
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Application publication date: 20180629 |