A kind of high-strength quick-solidifying polymer creamy material and preparation method for 3D printingTechnical field
The invention belongs to the technical fields of 3D printing material, provide a kind of high-strength quick-solidifying polymer cream for 3D printingShape material and preparation method.
Background technology
3D printing refers to go out three-dimensional processing pattern with computer software design and then be used by specific formerLiquefaction, powdered, silk solid material successively print product, and traditional to subtract material manufacture different.3D printing technique belongs toIncreasing material manufacturing without proembryo and grinding tool, just can produce shape directly according to computer graphics data by the method for increasing materialThe object of shape simplifies the fabrication schedule of product, shortens the R＆D cycle of product, improves efficiency and reduces cost.As it can be seen that 3D printingIt is a kind of new and high technology for relying on the multi-crossed disciplines such as information technology, precision machinery and material science.
3D printing material is the important substance basis of 3D printing technique development, and the development of material to a certain extent decidesCan 3D printing have wider application.At present 3D printing material mainly include engineering plastics, photosensitive resin, rubber type of material,Metal material and ceramic material etc..In addition to this, the foods such as coloured plaster material, artificial bone meal, cell biological raw material and granulated sugarProduct material is also applied in 3D printing field.
The material and forming method of its selection of the printing technology being typically different are also different, common powdered 3D printingThe grain size of material is differed for 1-100um；And in order to which powder is made to keep good mobility, generally require powder that there is high ballShape degree；Have the characteristics that oxygen and other impurity contents are low, epigranular is controllable, compactness is good, bond strength is high simultaneously.It grinds at presentThe polymer creamy material studied carefully and developed is concerned by people, which is by polymer, solvent and optional auxiliary agentIt is mixed, then paste obtained by use carries out 3D printing, wherein printing last layer again after the solvent volatilization of preceding layer.The major subjects of this kind of printed material research are the raisings of printing effect and printing precision at present.
It has been achieved in terms of 3D printing material, especially high-strength, rapid hardening 3D printing creamy material both at home and abroad at present certainEffect.Wherein Li Tao et al. has invented a kind of 3D printing material of paste rapid shaping（Chinese invention patent application number201611106435.X）, it is made of following raw material：Cementitious material, gypsum, filler, pigment, water-reducing agent, cellulose ether, morning are strongAgent, antifoaming agent, rubber powder；Compared with prior art, the invention has following advantageous effect：Reach and do not discharged printing in 3DInto the paste time, simultaneously curing molding can quickly dry after discharging by being squeezed out from 3D printing head for before existing certain storage,Creamy material is made to be unlikely to slump and can not complete to accumulate, be superimposed and form high intensity, the 3D printing effect of high adhesion force.SeparatelyOutside, Huang Zhongjia et al. has invented a kind of photocuring 3D printing material and preparation method thereof（Chinese invention patent application number201611049408.3）, preparation method includes：Diallyl phthalate and initiator are mixed, obtained after heating reactionPre-polymerization liquid；By pre-polymerization liquid, 1- hydroxy cyclohexyl phenylketones and photosensitive resin Hybrid Heating, the light is obtained after StereolithographyCure 3D printing material；Solving common photocuring printed material, viscosity can rise after storing for a long time, and material is perishable,The problem of leveraging its storge quality.
As it can be seen that there are the evaporation rates of solvent slow etc. to ask for the polymer creamy material of the prior art for 3D printingTopic causes to print green body slow curing, and intensity is insufficient and easily caves in, and so as to influence printing effect and printing precision, restricts its developmentAnd application.
Invention content
For such case, it is proposed that a kind of for the high-strength quick-solidifying polymer creamy material of 3D printing and preparation sideMethod adds in calcium carbonate crystal whisker in the precursor of Behavior of Copolymerized Gels With Sulfonic Acid Groups, is carried on whisker wherein with the generation of gel, thenDivided with polymer powder, the curing agent mixture of low-melting heat sensitive wax and MS glue, liquid tackifiers etc. in high-speed mixerMixing is dissipated, high-strength, rapid hardening paste printed material is made.Its remarkable result is to utilize gel and calcium carbonate crystal whisker containing sulfonic acid groupReact to each other, be equipped on inside gel and disperseed, enhance the interaction between whisker and polymeric matrix, uniformlyThe whisker of dispersion plays a supporting role to paste printed material, and the strong of printing green body is just improved before curing agent plays a roleDegree, avoids caving in, improves printing effect and printing precision.
To achieve the above object, specific technical solution of the present invention is as follows：
A kind of preparation method of high-strength quick-solidifying polymer creamy material for 3D printing prepares the preceding body of Behavior of Copolymerized Gels With Sulfonic Acid GroupsBody adds in calcium carbonate crystal whisker during gel-forming, obtained plural gel and polymer powder, low-melting heat sensitive wax and MSThe curing agent mixture of glue, liquid tackifiers mixing, are made the high-strength quick-solidifying polymer creamy material for 3D printing, preparationIt is as follows：
（1）Ethylene glycol is dissolved in water, adds in 2- acrylamide-2-methylpro panesulfonic acids and methacrylic acid -2- hydroxy propyl esters, is led toEnter 10 ~ 15min of nitrogen, then add in initiator, be heated to 68 ~ 72 DEG C, 5 ~ 18min of copolymer-1 obtains Behavior of Copolymerized Gels With Sulfonic Acid GroupsPrecursor；Wherein：25 ~ 32 parts by weight of 2- acrylamide-2-methylpro panesulfonic acids, methacrylic acid -2- hydroxy propyl esters 18.5 ~ 24Parts by weight, 0.5 ~ 1 parts by weight of initiator, 15 ~ 20 parts by weight of ethylene glycol, 23 ~ 41 parts by weight of water；
（2）In step（1）Crosslinking agent and calcium carbonate crystal whisker are added in the precursor of Behavior of Copolymerized Gels With Sulfonic Acid Groups obtained, is cooled to 55~ 60 DEG C, continue polyase 13 ~ 5min, be carried on whisker wherein with the generation of gel, the sulfonic group of obtained calcium carbonate whiskerGel copolymer；Wherein：63 ~ 71 parts by weight of precursor of Behavior of Copolymerized Gels With Sulfonic Acid Groups, 1 ~ 2 parts by weight of crosslinking agent, calcium carbonate crystal whisker 28 ~35 parts by weight；
（3）By step（2）The Behavior of Copolymerized Gels With Sulfonic Acid Groups of calcium carbonate whisker obtained and polymer powder, low-melting heat sensitive wax withThe curing agent mixture of MS glue, liquid tackifiers carry out 20 ~ 30min of dispersion mixing in high-speed mixer, are made and are beaten for 3DThe high-strength quick-solidifying polymer creamy material of print；Wherein：30 ~ 40 parts by weight of Behavior of Copolymerized Gels With Sulfonic Acid Groups of calcium carbonate whisker, polymerization15 ~ 18 parts by weight of curing agent mixture of 40 ~ 54 parts by weight of object powder, low-melting heat sensitive wax and MS glue, 1 ~ 2 weight of liquid tackifiersMeasure part.
Preferably, step（1）The initiator is methyl ethyl ketone peroxide, cyclohexanone peroxide, isopropyl benzene hydroperoxide, uncleAt least one of butylhydroperoxide.
Preferably, step（2）The crosslinking agent is N,N-DMAA, diethylenetriamines, triethylene fourAt least one of amine.
Preferably, step（2）A diameter of 0.5 ~ 1.2 μm of the calcium carbonate crystal whisker, length are 20 ~ 40 μm, moistureNo more than 0.2%.
Preferably, step（3）The polymer powder is polyethylene powders, polypropylene powder, polycarbonate powder, polyamidesAt least one of amine powder.
Preferably, step（3）The low-melting heat sensitive wax is the paraffin or polyethylene wax that fusing point is 40 ~ 60 DEG C.
Preferably, step（3）The curing agent of the MS glue is ethylenediamine, hexamethylene diamine, aminoethyl ethanolamine, six Asia of trimethylAt least one of methanediamine.
Preferably, step（3）In the curing agent mixture of the low-melting heat sensitive wax and MS glue, low-melting heat sensitive wax and MSThe mass ratio of the curing agent of glue is 10:1~15:1.
Preferably, step（3）The liquid tackifiers are lauric acid diethyl amide, lauric acid amide of ethanol, bayAt least one of base sulfate.
The present invention also provides the high-strength quick-solidifying polymer pastes for 3D printing that a kind of above-mentioned preparation method is preparedMaterial.
This method prepares the precursor of Behavior of Copolymerized Gels With Sulfonic Acid Groups, and calcium carbonate crystal whisker is added in during gel-forming, obtainsPlural gel and polymer powder, the curing agent mixture of low-melting heat sensitive wax and MS glue, liquid tackifiers mix, be made and useIn the high-strength quick-solidifying polymer creamy material of 3D printing.Compared with conventional method, the polymer creamy material of preparation of the inventionDuring for 3D printing, solvent evaporation rate is fast, prints green body curing rate, intensity is high, can effectively avoid and caves in, is obviously improvedPrinting effect and printing precision, and it is highly practical, and printing effect is good, can be widely used for 3D printing field.
By the hardening time of polymer creamy material prepared by the present invention with general polymer creamy material and impact strengthIt is compared, as shown in table 1, it is seen then that polymer creamy material curing rate prepared by the present invention is fast, and impact strength is high.
Table 1：
The present invention provides a kind of high-strength quick-solidifying polymer creamy material and preparation method for 3D printing, with prior art phaseThan, protrude the characteristics of and excellent effect be：
1. polymer creamy material prepared by the present invention, highly practical, printing effect is good, can be widely used for 3D printing field.
2. the polymer creamy material of the preparation of the present invention, solvent evaporation rate is fast, and printing green body curing rate is fast.
3. reacting to each other using the gel containing sulfonic acid group and calcium carbonate crystal whisker, enhances whisker in the preparation of the present inventionInteraction between polymeric matrix, homodisperse whisker play a supporting role to paste printed material, print green bodyIntensity is high, can effectively avoid and caves in, has been obviously improved printing effect and printing precision.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present inventionRange be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skillThe various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
18kg ethylene glycol is dissolved in 32.2kg water, adds in 29kg2- acrylamide-2-methylpro panesulfonic acids and 20kg metering systemsAcid -2- hydroxy propyl esters, are passed through nitrogen 13min, then add in 0.8kg methyl ethyl ketone peroxides, are heated to 70 DEG C, copolymer-1 6min is obtainedTo the precursor of Behavior of Copolymerized Gels With Sulfonic Acid Groups；1kg N, N- dimethyl propylenes are added in the precursor of 68 kg Behavior of Copolymerized Gels With Sulfonic Acid GroupsAcrylamide and 31 kg calcium carbonate crystal whiskers, are cooled to 58 DEG C, continue to polymerize 4min, and the sulfonic group copolymerization of calcium carbonate whisker is madeGel；By Behavior of Copolymerized Gels With Sulfonic Acid Groups and 49 kg polyethylene powders, the 15 kg paraffin or and ethylenediamine of 35 kg calcium carbonate whiskersMixture, 1 kg lauric acid diethyl amides carry out dispersion mixing 25min in high-speed mixer, wherein paraffin and ethylenediamineMass ratio is 12:1, the high-strength quick-solidifying polymer creamy material for 3D printing is made.
Test method：
Polymer creamy material produced by the present invention for 3D printing is tested, measures hardening time, 3 experiments are repeated,Average value is calculated, characterizes printing effect；
It fights each other hand-pressing body respectively using Charpy impact machine tester and printout is tested, measure impact value, characterizationThe shock resistance of resulting materials.
The data obtained is as shown in table 2.
Embodiment 2
15kg ethylene glycol is dissolved in 41kg water, adds in 25kg2- acrylamide-2-methylpro panesulfonic acids and 18.5kg metering systemsAcid -2- hydroxy propyl esters, are passed through nitrogen 10min, then add in 0.5kg cyclohexanone peroxides, are heated to 68 DEG C, copolymer-1 8min is obtainedTo the precursor of Behavior of Copolymerized Gels With Sulfonic Acid Groups；1 kg diethylenetriamines is added in the precursor of 63 kg Behavior of Copolymerized Gels With Sulfonic Acid GroupsWith 35 kg calcium carbonate crystal whiskers, 55 DEG C are cooled to, continues to polymerize 5min, the Behavior of Copolymerized Gels With Sulfonic Acid Groups of calcium carbonate whisker is made；It willThe Behavior of Copolymerized Gels With Sulfonic Acid Groups of 30 kg calcium carbonate whiskers is mixed with 54 kg polypropylene powders, 15 kg polyethylene waxes with hexamethylene diamineObject, 1kg lauric acid amide of ethanol carry out dispersion mixing 20min in high-speed mixer, wherein polyethylene wax and hexamethylene diamineMass ratio is 10:1, the high-strength quick-solidifying polymer creamy material for 3D printing is made.
Test method is consistent with embodiment 1, and the data obtained is as shown in table 2.
Embodiment 3
20kg ethylene glycol is dissolved in 23kg water, adds in 32kg2- acrylamido -2- methyl-prop sulphur 24kg methacrylic acid -2- hydroxylsBase propyl ester is passed through nitrogen 15min, then adds in 1kg isopropyl benzene hydroperoxides, is heated to 72 DEG C, copolymer-1 5min obtains sulfonic groupThe precursor of gel copolymer；2 kg triens and 28 kg carbon are added in the precursor of 71 kg Behavior of Copolymerized Gels With Sulfonic Acid GroupsSour calcium pyroborate is cooled to 60 DEG C, continues polyase 13 min, and the Behavior of Copolymerized Gels With Sulfonic Acid Groups of calcium carbonate whisker is made；40 kg are carbon containingThe Behavior of Copolymerized Gels With Sulfonic Acid Groups of sour calcium pyroborate and 40kg polycarbonate powders, 18 kg paraffin and aminoethyl ethanolamine mixture, 2 kgLauryl sulfate carries out dispersion mixing 30min in high-speed mixer, and the mass ratio of wherein paraffin and aminoethyl ethanolamine is15:1, the high-strength quick-solidifying polymer creamy material for 3D printing is made.
Test method is consistent with embodiment 1, and the data obtained is as shown in table 2.
Embodiment 4
16kg ethylene glycol is dissolved in 36.4kg water, adds in 27kg2- acrylamide-2-methylpro panesulfonic acids and 20kg metering systemsAcid -2- hydroxy propyl esters, are passed through nitrogen 12min, then add in 0.6kg tert-butyl hydroperoxide, are heated to 69 DEG C, copolymer-1 7minObtain the precursor of Behavior of Copolymerized Gels With Sulfonic Acid Groups；1 kg N, N- dimethyl is added in the precursor of 65kg Behavior of Copolymerized Gels With Sulfonic Acid GroupsAcrylamide and 34 kg calcium carbonate crystal whiskers, are cooled to 58 DEG C, continue to polymerize 5min, the sulfonic group that calcium carbonate whisker is made is total toCoagel；By the Behavior of Copolymerized Gels With Sulfonic Acid Groups of 32 kg calcium carbonate whiskers and 52kg polyamide powders, 16 kg polyethylene waxes and threeMethyl hexamethylene diamine mixture, 1 kg lauric acid diethyl amides carry out dispersion mixing 23min in high-speed mixer,The mass ratio of middle polyethylene wax and trimethylhexamethylenediamine is 12:1, the high-strength quick-solidifying polymer cream for 3D printing is madeShape material.
Test method is consistent with embodiment 1, and the data obtained is as shown in table 2.
Embodiment 5
18kg ethylene glycol is dissolved in 29kg water, add in 30kg2- acrylamide-2-methylpro panesulfonic acids and 22kg methacrylic acids-2- hydroxy propyl esters are passed through nitrogen 14min, then add in 1kg methyl ethyl ketone peroxides, are heated to 71 DEG C, copolymer-1 6min obtains sulfonic acidThe precursor of base gel copolymer；2 kg N,N-DMAAs are added in the precursor of 70kg Behavior of Copolymerized Gels With Sulfonic Acid GroupsWith 28 kg calcium carbonate crystal whiskers, 58 DEG C are cooled to, continues polyase 13 min, the Behavior of Copolymerized Gels With Sulfonic Acid Groups of calcium carbonate whisker is made；It willThe Behavior of Copolymerized Gels With Sulfonic Acid Groups of 37 kg calcium carbonate whiskers and 464kg polyethylene powders, 17 kg paraffin and ethylenediamine mixture, 2Kg lauric acid diethyl amides carry out the quality of 20 ~ 308min of dispersion mixing, wherein paraffin and ethylenediamine in high-speed mixerThan being 14:1, the high-strength quick-solidifying polymer creamy material for 3D printing is made.
Test method is consistent with embodiment 1, and the data obtained is as shown in table 2.
Embodiment 6
18kg ethylene glycol is dissolved in 31kg water, add in 28kg2- acrylamide-2-methylpro panesulfonic acids and 22kg methacrylic acids-2- hydroxy propyl esters are passed through nitrogen 14min, then add in 1kg tert-butyl hydroperoxide, are heated to 68 ~ 72 DEG C, and copolymer-1 5 ~18min obtains the precursor of Behavior of Copolymerized Gels With Sulfonic Acid Groups；2 kg Sanyas are added in the precursor of 68 kg Behavior of Copolymerized Gels With Sulfonic Acid GroupsTetramine and 30 kg calcium carbonate crystal whiskers, are cooled to 57 DEG C, continue to polymerize 4min, the sulfonic group that calcium carbonate whisker is made is total toCoagel；By the Behavior of Copolymerized Gels With Sulfonic Acid Groups of 36kg calcium carbonate whiskers and 45 kg polypropylene powders, 17kg polyethylene waxes and front threeBase hexamethylene diamine mixture, 2 kg lauryl sulfates carry out dispersion mixing 26min in high-speed mixer, wherein poly- secondThe mass ratio of alkene wax and trimethylhexamethylenediamine is 13:1, the high-strength quick-solidifying polymer paste material for 3D printing is madeMaterial.
Test method is consistent with embodiment 1, and the data obtained is as shown in table 2.
Comparative example 1
30 kg calcium carbonate crystal whiskers are configured to slurry, with six methylene of 45 kg polypropylene powders, 17kg polyethylene waxes and trimethylBase diamine mixture, 2 kg lauryl sulfates carry out dispersion mixing 26min, wherein polyethylene wax and three in high-speed mixerThe mass ratio of methyl hexamethylene diamine is 13:1, the high-strength quick-solidifying polymer creamy material for 3D printing is made.
Test method is consistent with embodiment 1, and the data obtained is as shown in table 2.
Table 2：