CN105294936A - Bi-functionality-degree acrylic ester cross-linking agent and application thereof to 3D printing - Google Patents
Bi-functionality-degree acrylic ester cross-linking agent and application thereof to 3D printing Download PDFInfo
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- CN105294936A CN105294936A CN201510676153.2A CN201510676153A CN105294936A CN 105294936 A CN105294936 A CN 105294936A CN 201510676153 A CN201510676153 A CN 201510676153A CN 105294936 A CN105294936 A CN 105294936A
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Abstract
The invention relates to the field of high molecular materials for photocuring 3D printing fast forming equipment and aims to provide a bi-functionality-degree acrylic ester cross-linking agent and application thereof to 3D printing. According to the preparation steps, under protection of nitrogen, furfuryl alcohol, N-hydroxyalkyl maleimide and solvent react, and suction filtration, washing and vacuum drying are carried out on the reaction product to obtain a dihydroxy-terminated Diels-Alder addition product; the addition product is dissolved into the solvent, a pyridine catalyst and acid anhydride are added, the mixture reacts, methyl alcohol is added, the mixture continues to react, methylene chloride is used for dissolving the product, and organic phases are collected to obtain a final product. The initial raw materials are wide in source, the preparation process and purification are simple, and the cross-linking agent is suitable for industrial production process; the product has universality, and the prepared vinyl polymer has excellent mechanical performance and solvent resistant performance of a thermosetting material at normal temperature, and has a recovery processing characteristic of thermoplastic at high temperature; use performance of the product is met, and the application is important breakthrough of the 3D printing material equipment technology.
Description
Technical field
The present invention relates to photocuring 3D printing rapid shaping and prepare polymeric material field, particularly a kind of two functionality acrylic ester cross-linking agents, its preparation method and 3D thereof print and prepare reversible crosslink macromolecular material.
Background technology
General, according to different physicochemical properties, plastics can be divided into thermoset and thermoplasticity two type.Wherein thermosetting resin is as epoxy resin etc., chemical reaction occurs in machine-shaping process and forms three-dimensional net structure, thus impart material plurality of advantages, as shape, dimensional stabilizing, excellent physical and mechanical property, excellent solvent resistant and ageing resistance etc.On the other hand, also just because of its insoluble not molten three-dimensional net structure, goods after a procedure, can not circulate and mould processing again.Therefore traditional thermosetting resin becomes solid waste after using, and will cause serious environmental pollution and the wasting of resources.And thermoplastic plastics are as synthetic glass etc., post softening of being heated, cure hard again after cooling, this repeatedly shaping character, is conducive to its recycling.But this kind of plastics machinery intensity, resistance toheat and solvent resistant corrodibility are relatively low.For improving intensity and the thermotolerance of plastics, usually take some chemical means as peroxide crosslinking, radiation crosslinking or directly add polyfunctionality monomer etc. when being polymerized and make thermoplastics appropriately crosslinked, if polymethylmethacrylate is after ethyleneglycol dimethyacrylate is crosslinked, the intensity of aeronautical glasses can be improved.
Therefore, if introduce a kind of polyfunctional monomer containing reversible covalent bonds in resin polymerization system, this dynamic covalency Cheng Jian at low temperatures, and scission of link at a relatively high temperature.The plastics then formed after polymerization possess the various excellent properties of conventional thermosetting plastics at low temperatures, and possess the reprocessing processability of thermoplastics at a relatively high temperature.Stable six-ring Diels-Alder (DA) chemical bond generated as there is [4+2] cycloaddition reaction between maleimide ring under the condition of normal temperature or heating as the imide ring of furan nucleus and electron deficiency by the divinyl macromer of electron rich, inverse (r-DA) reaction can be there is again under higher than the condition of 100 DEG C, again form free furan nucleus and imide ring, namely DA key has thermal reversibility.This characteristic of DA key can be utilized thus, preparation is containing two functionality vinyl monomers of DA key, again by the vinyl monomer copolymerization of this two functionality monomer and simple function, namely utilize this two functionality monomer to be linking agent, thus preparation have the cross-linking plastic of thermal reversion characteristic and self-healing, self-healing properties.
On the other hand, rapid shaping technique (RapidPrototyping, RP) be Developing one of manufacturing technology the most rapidly, it is based on the principle of material discrete/accumulation, manufactures automatically, directly, quickly and accurately and have definite shape, the prototype of structure and function or goods under area of computer aided effect.Therefore RP technology easily can realize the complex object that a lot of traditional manufacturing technology is difficult to processing and fabricating, has epoch-making effect in processing technique field.Rapid shaping technique is called in the narrow sense " 3D printing ".Strictly, " 3D printing " is the branch of rapid shaping technique, can only represent part quick shaping process.
Different according to forming method, rapid shaping technique can be divided into: stereolithography apparatus (Stereolighthoraphy, SLA), shaping (DigitalLightProcessing, selects technology such as territory laser powder sintering (SLS), fused glass pellet (FDM) etc. at (DLP), layer separated growth technology (LOM) to digital light projection.The difference of these methods is mainly that material therefor is different with technique, respectively has purposes and relative merits.Wherein, SLA and DLP technique mainly uses vinyl-based photosensitive resin monomer, utilizes photocuring technology to make it shaping.
Everything is favourable, has fraud, above-mentioned said rapid shaping technique, although have incomparable advantage with conventional molding techniques compared with injection moulding, its forming principle be layering has been doomed goods and there is interface layer in microscopic dimensions.Namely, compared with traditional once shaped, the inner heterogeneity of high molecular products, surface flatness is poor, have impact on the mechanical property of goods, limits its use range.The photocuring 3D of SLA or DLP type prints no exception.In fact, 3D printing technique is just because of above feature, and current application mainly concentrates in the making of toy and model, and uses as structural articles, also far immature.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of two functionality acrylic ester cross-linking agents.
For technical solution problem, solution of the present invention is:
There is provided a kind of two functionality acrylic ester cross-linking agents, its chemical general formula is as shown in formula I;
In formula: R is methyl or H, n is the positive integer of 1 to 6.
Invention further provides the method preparing aforementioned two functionality acrylic ester cross-linking agents, comprise the following steps:
(1) both-end hydroxyl Diels-Alder affixture is prepared
Under nitrogen protection, furfuryl alcohol, N-hydroxyalkyl maleimide and solvent orange 2 A are added in container, 60 ~ 85 DEG C, lucifuge, reaction 2 ~ 48 hours under agitation condition; Suction filtration after cooling, with cold solvent orange 2 A washing leaching cake, vacuum-drying, obtains the pressed powder of both-end hydroxyl Diels-Alder affixture;
Wherein, the mol ratio of furfuryl alcohol and N-hydroxyalkyl maleimide is 1 ~ 4: 1; Described solvent orange 2 A is ethyl acetate or toluene, and its consumption is 200 ~ 300ml/0.1molN-hydroxyalkyl maleimide;
(2) acrylate cross linked dose of two functionality are prepared
Under nitrogen protection, the pressed powder of both-end hydroxyl Diels-Alder affixture is dissolved in solvent B, then adds pyridines catalyzer and acid anhydrides; React after 0.5 ~ 5 hour under 0 ~ 50 DEG C of condition, in reaction system, add methyl alcohol; Continue reaction after 0.5 hour, gained mixture is revolved and steams to remove desolventizing B; Products therefrom is dissolved, then with 0.1M aqueous hydrochloric acid washing at least 3 times with methylene dichloride; Collect organic phase after drying, vacuum rotary steam removing methylene dichloride, obtaining thick white thing, is acrylate cross linked dose of final product two functionality;
Wherein, described solvent B is methylene dichloride, trichloromethane or tetrahydrofuran (THF), and its consumption is 100 ~ 150ml/0.1mol both-end hydroxyl Diels-Alder affixture; Described pyridines catalyzer is pyridine or DMAP; Described acid anhydrides is acrylic anhydride or methacrylic anhydride; The molar ratio of both-end hydroxyl Diels-Alder affixture, pyridines catalyzer and acid anhydrides is: 1: 1.8-2: 2.5-3; The consumption of methyl alcohol is 20 ~ 30ml/0.1mol both-end hydroxyl Diels-Alder affixture.
In the present invention, described N-hydroxyalkyl maleimide is N-methylol maleimide or N-hydroxyethylmaleimide.
Present invention also offers the application of aforementioned two functionality acrylic ester cross-linking agents at the photosensitive resin composition printed for the preparation of photocuring 3D.
Invention further provides the photosensitive resin composition printed for photocuring 3D utilizing acrylate cross linked dose of aforementioned two functionality to be prepared from, comprise the component of following weight part:
Two functionality acrylate cross linked dose 20 ~ 70 parts
Monofunctional vinyl monomer 30 ~ 80 parts
Ultraviolet free radical photo-initiation 1 ~ 5 part
Wherein, acrylate cross linked dose of two functionality add up to 100 weight parts with the total amount of monofunctional vinyl monomer.
In the present invention, described monofunctional vinyl monomer is: any one or a few the mixture in vinyl cyanide, vinylbenzene, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) alkyl acrylate, (methyl) crylic acid hydroxy ester, (methyl) glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid tetrahydrofuran ester, acrylate, vinyl acetate or NVP.
In the present invention, described ultraviolet free radical photo-initiation is: any one or a few the mixture in bitter almond oil camphor or derivatives thereof, benzil or derivatives thereof, methyl phenyl ketone or derivatives thereof, alpha-alcohol ketone derivative, α-amido ketone derivatives, acylphosphine oxide, sulfur-bearing light trigger, thioxanthone or derivatives thereof, anthraquinone or derivatives thereof.
In the present invention, described ultraviolet free radical photo-initiation is: benzoin ether, α, α '-dimethyl benzil ketals, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy cyclohexyl phenylketone, 2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone, 2-methyl isophthalic acid-(4-first mercaptophenyl)-2-morpholine-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2,4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide, TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 4-is to toluene sulfydryl benzophenone, benzophenone, 2,4,6-tri-methyl benzophenone, 4-methyl benzophenone, 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylin) benzophenone, 4,4 '-bis-(methyl, ethylamino) benzophenone, isopropyl thioxanthone, 2-chlorothiaxanthenone, 1-chloro-4-propoxy-thioxanthone, 2,4-diethyl thioxanthone, any one or a few mixture in 2-ethyl-anthraquinone.
Invention further provides and utilize aforementioned light-sensitive resin combination to carry out photocuring 3D printing to realize the method for stereolithography rapid shaping, be using described photosensitive resin composition as formed material, adopt stereolithography apparatus (SLA) photocuring 3D printer or digital light projection shaping (DLP) photocuring 3D printer; Optical maser wavelength used in print procedure is 365 ~ 425nm, and the shaping curing depth (resolving power) of single pass is 25 ~ 100 microns.
Present invention also offers the method for after utilizing aforementioned light-sensitive resin combination to carry out photocuring 3D printing, Stereolithography sample being carried out to aftertreatment, by the thermal treatment 0.5 ~ 2 hour at 100 ~ 130 DEG C of Stereolithography sample, then thermal treatment 2 ~ 24 hours at 60 ~ 80 DEG C.
Inventive principle describes:
Theoretical basis of the present invention is: stable six-ring Diels-Alder (DA) chemical bond that the divinyl macromer of electron rich generates as there is [4+2] cycloaddition reaction between maleimide ring under the condition of normal temperature or heating as the imide ring of furan nucleus and electron deficiency, inverse (r-DA) reaction can be there is again under higher than 100 DEG C of conditions, again form free furan nucleus and imide ring, namely DA key has thermal reversibility.The DA key that this is had thermal reversion characteristic by the present invention is in advance implanted in two functionality acrylic ester monomers, then with this two functionality acrylic ester monomer as the method copolymerization that linking agent and monofunctional vinyl monomer adopt photocuring 3D the to print cross-linked network shape plastics that to prepare with DA key be cross-linking set.Owing to have employed photocuring 3D printing shaping method, in preparation process, system keeps low temperature or room temperature, thus can not there is thermal reversion reaction in DA key, and material straight forming, avoid and take conventional processing routes can not be polymerized very well due to gel in polymerization synthesis and the shortcoming of reshaping processing.In the present invention, the vinyl polymeric materials obtained containing two functionality acrylic ester cross-linking agents of the present invention is at room temperature chemically crosslinked structure, cross-linked network is at high temperature reversible opens formation linear molecule, there is DA reaction post-crosslinking network and formed again in cooling, the system that can the realize phase co-conversion between thermosetting-thermoplastic at appropriate temperatures again.Equally, utilize the thermal reversion of DA key, self-healing, self-healing properties, by prepared plastics at high temperature (100-130 DEG C) thermal treatment for some time, again at relatively low temperature after (60-80 DEG C) aftertreatment for some time, the present invention can effectively eliminate because 3D prints the bed interface increasing the material manufacturing technology goods inside be layering caused by mode and exist, thus improve the surface flatness of goods, make the goods prepared have the even performance the same with conventional shaping method, thus meet the structure using function of goods.
Compared with prior art, the present invention has following significant technical superiority and beneficial effect:
1, two functionality acrylic ester cross-linking agents of the present invention, initial feed wide material sources, preparation process and purifying simply, are applicable to commercial process;
2, two functionality acrylic ester cross-linking agents of the present invention have versatility, can prepare crosslinking vinyl polymkeric substance with most mono-vinyl monomer copolymerization;
3, the vinyl polymer adopting two functionality acrylic ester cross-linking agents of the present invention to prepare has excellent mechanical mechanical property and the solvent resistance of thermosetting material at normal temperatures, and what at high temperature have again thermoplastics can reclaim processing characteristics again;
4, the present invention adopts photocuring 3D printing technique directly to prepare shaping, and in preparation moulding process, do not need solvent, preparation technology is simply controlled, therefore low, the non-pollution discharge of energy consumption; The goods of the complex construction that traditional processing and forming technology cannot be prepared can be prepared in batches.Technical scheme of the present invention has good economic benefit and environmental benefit, has good market application foreground.
5, the present invention utilizes the thermal reversion of DA key, self-healing, self-healing properties, effectively eliminate because 3D prints the bed interface increasing the material manufacturing technology goods inside be layering caused by mode and exist, not only increase the surface flatness of goods, and make the goods prepared have the homogeneous and integrity identical with conventional shaping method, thus be significantly different from existing similar 3D printed material, meet the use properties of goods, making 3D printing technique really move towards structured material from toy, model manufacturing, is the important breakthrough of 3D printed material technology of preparing.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of the Diels-Alder affixture of N-methylol maleimide and furfuryl alcohol.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of two functionality methacrylate cross-linker prepared by the Diels-Alder affixture of N-methylol maleimide and furfuryl alcohol.
Embodiment
Be below the specific embodiment of the present invention, described embodiment is to further describe the present invention, does not therefore limit the present invention in described embodiment invention.
The synthesis of embodiment 1 two functionality methacrylate cross-linker
1) dihydroxyl Diels-Alder affixture is prepared:
Under nitrogen protection; successively by 12.7g (0.1mol) N-methylol maleimide (CAS:5063-96-7); 19.6g furfuryl alcohol (0.2mol) (CAS:98-00-0); 200ml ethyl acetate joins in 500ml there-necked flask; under magnetic stirring, under reflux temperature (about 77 DEG C), lucifuge reacts 24 hours.After reaction terminates, cooling, suction filtration, collects filter cake, and wash three times with cold ethyl acetate, collect filter cake, 30 DEG C of vacuum-dryings, to constant weight, obtain the target product of white solid powder, yield 83%, characterize with nucleus magnetic hydrogen spectrum and confirm product structure, its nucleus magnetic hydrogen spectrum figure is shown in accompanying drawing 1.
2) two functionality methacrylate cross-linker are prepared
Under nitrogen protection; the dihydroxyl Diels-Alder affixture successively 22.5g (0.1mol) above-mentioned steps (1) obtained; 21.96g (0.18mol) DMAP (DMAP); 100ml tetrahydrofuran (THF) joins in 250ml there-necked flask; after magnetic agitation is dissolved; add 40.04g (0.26mol) methacrylic anhydride more wherein; stirring reaction 2.5 hours at 25 DEG C; add 20ml anhydrous methanol wherein, system continues stirring reaction 30 minutes.After reaction terminates, gained solution decompression is revolved and steams except after desolventizing, with methylene dichloride 250ml dissolution residual substance, after washing 3 times with 0.1M aqueous hydrochloric acid (100ml), collect organic phase, after anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, vacuum rotary steam removing methylene dichloride, obtains product, for thick white thing, productive rate 89%.Characterize with nucleus magnetic hydrogen spectrum and confirm product structure, its nucleus magnetic hydrogen spectrum figure is shown in accompanying drawing 2.
The synthesis of acrylate cross linked dose of embodiment 2 two functionality
1) dihydroxyl Diels-Alder affixture is prepared:
Under nitrogen protection; successively by 14.1g (0.1mol) N-hydroxyethylmaleimide (CAS:1585-90-6); 24.5g furfuryl alcohol (0.4mol) (CAS:98-00-0); 250ml ethyl acetate joins in 500ml there-necked flask; under magnetic stirring, at 60 DEG C, lucifuge reacts 48 hours.After reaction terminates, cooling, suction filtration, collects filter cake, and washs three times with cold ethyl acetate, and collect filter cake, 30 DEG C of vacuum-dryings, to constant weight, obtain the target product of white solid powder, yield 81%.Characterize with nucleus magnetic hydrogen spectrum and confirm product structure, its nucleus magnetic hydrogen spectrum figure omits.
2) acrylate cross linked dose of two functionality are prepared
Under nitrogen protection; the dihydroxyl Diels-Alder affixture successively 23.9g (0.1mol) above-mentioned steps (1) obtained; 15.8g (0.2mol) pyridine; 120ml methylene dichloride joins in 250ml there-necked flask; after magnetic agitation is dissolved, then add 37.8g (0.3mol) acrylic anhydride wherein, stirring reaction 2 hours at 30 DEG C; add 25ml anhydrous methanol wherein, system continues stirring reaction 30 minutes.After reaction terminates, gained solution decompression is revolved and steams except after desolventizing, with methylene dichloride 250ml dissolution residual substance, after washing 3 times with 0.1M aqueous hydrochloric acid (100ml), collect organic phase, after anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, vacuum rotary steam removing methylene dichloride, obtains product, for thick white thing, productive rate 87%.Characterize with nucleus magnetic hydrogen spectrum and confirm product structure, its nucleus magnetic hydrogen spectrum figure omits.
The synthesis of acrylate cross linked dose of embodiment 3 two functionality
1) dihydroxyl Diels-Alder affixture is prepared:
Under nitrogen protection; successively by 12.7g (0.1mol) N-methylol maleimide (CAS:5063-96-7); 9.8g furfuryl alcohol (0.1mol) (CAS:98-00-0); 300ml ethyl acetate joins in 500ml there-necked flask; under magnetic stirring, under reflux temperature (about 77 DEG C), lucifuge reacts 48 hours.After reaction terminates, cooling, suction filtration, collects filter cake, and wash three times with cold ethyl acetate, collect filter cake, 30 DEG C of vacuum-dryings, to constant weight, obtain the target product of white solid powder, yield 83%, characterize with nucleus magnetic hydrogen spectrum and confirm product structure, its nucleus magnetic hydrogen spectrum figure omits.
2) acrylate cross linked dose of two functionality are prepared
Under nitrogen protection; the dihydroxyl Diels-Alder affixture successively 22.5g (0.1mol) above-mentioned steps (1) obtained; 23.18g (0.19mol) DMAP (DMAP); 150ml trichloromethane joins in 250ml there-necked flask; after magnetic agitation is dissolved; add 35.28g (0.28mol) acrylic anhydride more wherein; stirring reaction 30 minutes at 50 DEG C; add 30ml anhydrous methanol wherein, system continues stirring reaction 30 minutes.After reaction terminates, gained solution decompression is revolved and steams except after desolventizing, with methylene dichloride 250ml dissolution residual substance, after washing 3 times with 0.1M aqueous hydrochloric acid (100ml), collect organic phase, after anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, vacuum rotary steam removing methylene dichloride, obtains product, for thick white thing, productive rate 89%.Characterize with nucleus magnetic hydrogen spectrum and confirm product structure, its nucleus magnetic hydrogen spectrum figure omits.
The synthesis of embodiment 4 two functionality methacrylate cross-linker
1) dihydroxyl Diels-Alder affixture is prepared:
Under nitrogen protection; successively by 14.1g (0.1mol) N-hydroxyethylmaleimide (CAS:1585-90-6); 24.5g furfuryl alcohol (0.25mol) (CAS:98-00-0); 250ml toluene joins in 500ml there-necked flask; under magnetic stirring, at 85 DEG C, lucifuge reacts 2 hours.After reaction terminates, cooling, suction filtration, collects filter cake, and washs three times with cold toluene, and collect filter cake, 30 DEG C of vacuum-dryings, to constant weight, obtain the target product of white solid powder, yield 81%.Characterize with nucleus magnetic hydrogen spectrum and confirm product structure, its nucleus magnetic hydrogen spectrum figure omits.
2) two functionality methacrylate cross-linker are prepared
Under nitrogen protection; the dihydroxyl Diels-Alder affixture successively 23.9g (0.1mol) above-mentioned steps (1) obtained; 15.8g (0.2mol) pyridine; 120ml tetrahydrofuran (THF) joins in 250ml there-necked flask; after magnetic agitation is dissolved, then add 38.5g (0.25mol) methacrylic anhydride wherein, stirring reaction 5 hours at 0 DEG C; add 28ml anhydrous methanol wherein, system continues stirring reaction 30 minutes.After reaction terminates, gained solution decompression is revolved and steams except after desolventizing, with methylene dichloride 250ml dissolution residual substance, after washing 3 times with 0.1M aqueous hydrochloric acid (100ml), collect organic phase, after anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, vacuum rotary steam removing methylene dichloride, obtains product, for thick white thing, productive rate 87%.Characterize with nucleus magnetic hydrogen spectrum and confirm product structure, its nucleus magnetic hydrogen spectrum figure omits.
Embodiment 5
By two sense methacrylate cross-linker prepared by 45g embodiment 1, after 55g vinyl cyanide mixes in beaker, add 5g benzoin dimethylether (being called for short 651) light trigger wherein, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine (producer: Zhuhai Xi Tong Electronic Science and Technology Co., Ltd.) and prints Stereolithography, optical maser wavelength 370nm, the shaping curing depth (resolving power) of single pass is 100 microns, prepare thermal reversion crosslinked polymer material.Prepared article have obvious microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 60 minutes in 110 DEG C, then process 12 hours at 75 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 6
By acrylate cross linked dose of two functionality prepared by 60g embodiment 2, after 40g vinylbenzene mixes in beaker, add 2g2-hydroxy-methyl phenyl-propane-1-ketone (being called for short 1173) wherein, 2g2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone (being called for short 907) light trigger, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 370nm, the shaping curing depth (resolving power) of single pass is 25 microns, prepare thermal reversion crosslinked polymer material.Prepared article have microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 2 hours in 100 DEG C, then process 24 hours at 60 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 7
By two sense methacrylate cross-linker prepared by 20g embodiment 3, 40g methyl methacrylate, after 40gN-vinyl pyrrolidone mixes in beaker, add 2g1-hydroxy-cyclohexyl phenyl ketone (being called for short 184) light trigger wherein, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on DLP type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 425nm, the shaping curing depth (resolving power) of single pass is 100 microns, prepare thermal reversion crosslinked polymer material.Prepared article have obvious microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 30 minutes in 130 DEG C, then process 12 hours at 75 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 8
By two sense methacrylate cross-linker prepared by 70g embodiment 4, after 30g hydroxyethyl methylacrylate mixes in beaker, add 2g1-hydroxy-cyclohexyl phenyl ketone (being called for short 184) wherein, 1g2, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide (being called for short 1110) light trigger, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 370nm, the shaping curing depth (resolving power) of single pass is 50 microns, prepare thermal reversion crosslinked polymer material.Prepared article have microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 1 hour in 110 DEG C, then process 2 hours at 80 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 9
By acrylate cross linked dose of two functionality prepared by 60g embodiment 2, 20g vinylbenzene, after 20g isobornyl acrylate mixes in beaker, add 1g2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone (being called for short 369) light trigger wherein, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 365nm, the shaping curing depth (resolving power) of single pass is 75 microns, prepare thermal reversion crosslinked polymer material.Prepared article still have microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 1 hour in 120 DEG C, then process 24 hours at 70 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 10
By two sense methacrylate cross-linker prepared by 50g embodiment 1, 30g methyl acrylate, after 20g acrylate mixes in beaker, add 1.5g benzophenone (being called for short 1220) wherein, 1.5g2-EAQ light trigger, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on DLP type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 425nm, the shaping curing depth (resolving power) of single pass is 50 microns, prepare thermal reversion crosslinked polymer material.Prepared article have obvious microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 30 minutes in 120 DEG C, then process 12 hours at 75 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 11
By two sense methacrylate cross-linker prepared by 40g embodiment 3, 30g glycidyl methacrylate, after 30g vinylformic acid tetrahydrofuran ester mixes in beaker, add 1g α wherein, α '-dimethyl benzil ketals, 2g two (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide light trigger, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on DLP type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 425nm, the shaping curing depth (resolving power) of single pass is 75 microns, prepare thermal reversion crosslinked polymer material.Prepared article have obvious microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 60 minutes in 110 DEG C, then process 12 hours at 70 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 12
By two sense methacrylate cross-linker prepared by 30g embodiment 4, 20g ethyl propenoate, after 50g vinylbenzene mixes in beaker, add 1g2-hydroxy-2-methyl-1-wherein to hydroxyethyl ether phenyl-acetone, 1g isopropyl thioxanthone, 1g4, 4 '-bis-(dimethylamino) diphenyl ketone photo initiator, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 370nm, the shaping curing depth (resolving power) of single pass is 50 microns, prepare thermal reversion crosslinked polymer material.Prepared article still have microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 2 hours in 110 DEG C, then process 24 hours at 70 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 13
By two sense methacrylate cross-linker prepared by 50g embodiment 3, 20g vinyl cyanide, 15g methyl methacrylate, after 15g vinyl acetate mixes in beaker, add 0.5g2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone wherein, 0.5g2, 4, 6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide photoinitiator, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 370nm, the shaping curing depth (resolving power) of single pass is 100 microns, prepare thermal reversion crosslinked polymer material.Prepared article still have microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 2 hours in 110 DEG C, then process 24 hours at 65 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 14
By acrylate cross linked dose of two functionality prepared by 45g embodiment 2, 15g glycidyl acrylate, 20g methyl methacrylate, after 20g vinylbenzene mixes in beaker, add 1g2-hydroxy-2-methyl-1-phenyl-acetone wherein, 1g4-is to toluene sulfydryl benzophenone, 1g isopropyl thioxanthone light trigger, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 370nm, the shaping curing depth (resolving power) of single pass is 25 microns, prepare thermal reversion crosslinked polymer material.Prepared article still have microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 1 hour in 130 DEG C, then process 4 hours at 80 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 15
By acrylate cross linked dose of two functionality prepared by 50g embodiment 1, 20g vinylbenzene, 15g methyl methacrylate, after 15gN-vinyl pyrrolidone mixes in beaker, add 1g2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone wherein, 1g2, 4, 6-tri-methyl benzophenone, 1g1-chloro-4-propoxy-thioxanthone photo initiator, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on DLP type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 425nm, the shaping curing depth (resolving power) of single pass is 25 microns, prepare thermal reversion crosslinked polymer material.Prepared article have obvious microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 60 minutes in 120 DEG C, then process 12 hours at 75 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Embodiment 16
By acrylate cross linked dose of two functionality prepared by 70g embodiment 4, 15g methyl acrylate, after 15g glycidyl methacrylate mixes in beaker, add 1g α wherein, α-diethoxy acetophenone, 1g4, 4 '-bis-(diethylin) benzophenone, 1g2, 4-diethyl thioxanthone light trigger, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on DLP type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 425nm, the shaping curing depth (resolving power) of single pass is 50 microns, prepare thermal reversion crosslinked polymer material.Prepared article have obvious microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 2 hours in 100 DEG C, then process 24 hours at 70 DEG C, the micro interface naked eyes between article layer are invisible, and article surface is smooth, and chill mark disappears.
Comparative example 1
1.5g1-hydroxy cyclohexyl phenylketone is added at 100g methyl methacrylate; 1g2; 4; 6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide photoinitiator; lucifuge continues to stir until after mixing; prepare the photosensitive resin composition printed for photocuring 3D; it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine and prints Stereolithography; optical maser wavelength 370nm; the shaping curing depth (resolving power) of single pass is 100 microns, prepares macromolecular material.Prepared article have microcosmic interface layer to exist, and article surface is coarse wrinkle.By the material for preparing in chloroform after soaking at room temperature 24, material dissolves is clear solution; The article prepared are processed 2 hours in 100 DEG C, then process 24 hours at 60 DEG C, the micro interface between article layer is without considerable change, and material is slightly out of shape.
Comparative example 2
By 50g1, 4-butylene glycol diacrylate, after 50g methyl methacrylate mixes in beaker, add 2g2-hydroxy-2-methyl-1-phenyl-acetone wherein, 1g two (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide light trigger, lucifuge continues to stir until after mixing, prepare the photosensitive resin composition printed for photocuring 3D, it is carried out 3D according to the contoured article of setting on SLA type photocuring laser fast shaping machine and prints Stereolithography, optical maser wavelength 370nm, the shaping curing depth (resolving power) of single pass is 25 microns, prepare thermal reversion crosslinked polymer material.Prepared article have microcosmic interface layer to exist, and article surface is coarse ripple.By the material for preparing in chloroform after soaking at room temperature 24, material is only swelling not to be dissolved; The article prepared are processed 2 hours in 130 DEG C, then process 24 hours at 75 DEG C, the micro interface between article layer is without considerable change.
Above embodiment, only for technical conceive of the present invention and feature are described, its object is to allow the those skilled in the art being familiar with technique can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to spirit of the present invention or modification, all should be encompassed within protection scope of the present invention.
So, well the present invention can be realized.
Claims (10)
1. two functionality acrylic ester cross-linking agents, is characterized in that, its chemical general formula is as shown in formula I;
In formula: R is methyl or H, n is the positive integer of 1 to 6.
2. prepare a method for two functionality acrylic ester cross-linking agents described in claim 1, it is characterized in that, comprise the following steps:
(1) both-end hydroxyl Diels-Alder affixture is prepared
Under nitrogen protection, furfuryl alcohol, N-hydroxyalkyl maleimide and solvent orange 2 A are added in container, 60 ~ 85 DEG C, lucifuge, reaction 2 ~ 48 hours under agitation condition; Suction filtration after cooling, with cold solvent orange 2 A washing leaching cake, vacuum-drying, obtains the pressed powder of both-end hydroxyl Diels-Alder affixture;
Wherein, the mol ratio of furfuryl alcohol and N-hydroxyalkyl maleimide is 1 ~ 4: 1; Described solvent orange 2 A is ethyl acetate or toluene, and its consumption is 200 ~ 300ml/0.1molN-hydroxyalkyl maleimide;
(2) acrylate cross linked dose of two functionality are prepared
Under nitrogen protection, the pressed powder of both-end hydroxyl Diels-Alder affixture is dissolved in solvent B, then adds pyridines catalyzer and acid anhydrides; React after 0.5 ~ 5 hour under 0 ~ 50 DEG C of condition, in reaction system, add methyl alcohol; Continue reaction after 0.5 hour, by gained mixture vacuum rotary steam to remove desolventizing; Products therefrom is dissolved, then with 0.1M aqueous hydrochloric acid washing at least 3 times with methylene dichloride; Collect organic phase after drying, vacuum rotary steam removing methylene dichloride, obtaining thick white thing, is acrylate cross linked dose of final product two functionality;
Wherein, described solvent B is methylene dichloride, trichloromethane or tetrahydrofuran (THF), and its consumption is 100 ~ 150ml/0.1mol both-end hydroxyl Diels-Alder affixture; Described pyridines catalyzer is pyridine or DMAP; Described acid anhydrides is acrylic anhydride or methacrylic anhydride; The molar ratio of both-end hydroxyl Diels-Alder affixture, pyridines catalyzer and acid anhydrides is: 1: 1.8 ~ 2: 2.5 ~ 3; The consumption of methyl alcohol is 20 ~ 30ml/0.1mol both-end hydroxyl Diels-Alder affixture.
3. method according to claim 2, is characterized in that, described N-hydroxyalkyl maleimide is N-methylol maleimide or N-hydroxyethylmaleimide.
4. two functionality acrylic ester cross-linking agents described in claim 1 are in the application of the photosensitive resin composition printed for the preparation of photocuring 3D.
5. the photosensitive resin composition printed for photocuring 3D utilizing acrylate cross linked dose of two functionality described in claim 1 to be prepared from, is characterized in that, comprise the component of following weight part:
Two functionality acrylate cross linked dose 20 ~ 70 parts
Monofunctional vinyl monomer 30 ~ 80 parts
Ultraviolet free radical photo-initiation 1 ~ 5 part
Wherein, acrylate cross linked dose of two functionality add up to 100 weight parts with the total amount of monofunctional vinyl monomer.
6. photosensitive resin composition according to claim 5, it is characterized in that, described monofunctional vinyl monomer is: any one or a few the mixture in vinyl cyanide, vinylbenzene, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) alkyl acrylate, (methyl) crylic acid hydroxy ester, (methyl) glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid tetrahydrofuran ester, acrylate, vinyl acetate or NVP.
7. photosensitive resin composition according to claim 5; it is characterized in that, described ultraviolet free radical photo-initiation is: any one or a few the mixture in bitter almond oil camphor or derivatives thereof, benzil or derivatives thereof, methyl phenyl ketone or derivatives thereof, alpha-alcohol ketone derivative, α-amido ketone derivatives, acylphosphine oxide, sulfur-bearing light trigger, thioxanthone or derivatives thereof, anthraquinone or derivatives thereof.
8. photosensitive resin composition according to claim 7, is characterized in that, described ultraviolet free radical photo-initiation is: benzoin ether, α, α '-dimethyl benzil ketals, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy cyclohexyl phenylketone, 2-hydroxy-2-methyl-1-is to hydroxyethyl ether phenyl-acetone, 2-methyl isophthalic acid-(4-first mercaptophenyl)-2-morpholine-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2,4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide, TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 4-is to toluene sulfydryl benzophenone, benzophenone, 2,4,6-tri-methyl benzophenone, 4-methyl benzophenone, 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylin) benzophenone, 4,4 '-bis-(methyl, ethylamino) benzophenone, isopropyl thioxanthone, 2-chlorothiaxanthenone, 1-chloro-4-propoxy-thioxanthone, 2,4-diethyl thioxanthone, any one or a few mixture in 2-ethyl-anthraquinone.
9. utilize photosensitive resin composition described in claim 5 to carry out photocuring 3D printing to realize the method for stereolithography rapid shaping, it is characterized in that, be using described photosensitive resin composition as formed material, adopt stereolithography apparatus photocuring 3D printer or digital light projection shaping photocuring 3D printer; Optical maser wavelength used in print procedure is 365 ~ 425nm, and the shaping curing depth of single pass is 25 ~ 100 microns.
10. after utilizing photosensitive resin composition described in claim 5 to carry out photocuring 3D printing, Stereolithography sample is carried out to the method for aftertreatment, it is characterized in that, by the thermal treatment 0.5 ~ 2 hour at 100 ~ 130 DEG C of Stereolithography sample, then thermal treatment 2 ~ 24 hours at 60 ~ 80 DEG C.
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