CN109337298A - A kind of preparation method of 3D printing material - Google Patents

A kind of preparation method of 3D printing material Download PDF

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Publication number
CN109337298A
CN109337298A CN201810996828.5A CN201810996828A CN109337298A CN 109337298 A CN109337298 A CN 109337298A CN 201810996828 A CN201810996828 A CN 201810996828A CN 109337298 A CN109337298 A CN 109337298A
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Prior art keywords
printing material
mixture
toluene
preparation
alpha
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CN201810996828.5A
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Chinese (zh)
Inventor
刘菊花
周立
史志新
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Foshan Chao Hung New Mstar Technology Ltd
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Foshan Chao Hung New Mstar Technology Ltd
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Priority to CN201810996828.5A priority Critical patent/CN109337298A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)

Abstract

The present invention relates to a kind of preparation methods of 3D printing material, belong to environmental friendly material technical field.The present invention takes α, and alpha, alpha-dimethyl oxygroup benzil ketals, bisphenol-a epoxy acrylate and tripropylene glycol diacrylate mixing obtain mixture A；Triaryl silicon oxygen ether, POLYBUTADIENE EPOXY RESIN and triethylene glycol divinyl ether mixing are taken, mixture B is obtained；Take magnetic agitation after di-nbutyltin oxide, toluene, trimethylolpropane mixing uniform, heating is cooling to device, and carbon disulfide is added dropwise, and removes toluene, reaction solution is obtained, with n-hexane washing reaction liquid；Reaction solution after washing is dissolved by heating with toluene, Expanding Monomer is obtained after vacuum drying；Mixture A, mixture B, Expanding Monomer, ethyl orthosilicate, nano-titanium dioxide and glass fibre mixing are taken, vacuumizes to obtain 3D printing material.3D printing material solidification speed prepared by the present invention is fast, solidification volume contraction is small, has good mechanical performance and heat resistance.

Description

A kind of preparation method of 3D printing material
Technical field
The present invention relates to a kind of preparation methods of 3D printing material, belong to environmental friendly material technical field.
Background technique
With economic globalization, modernization market competition will be more and more fierce, and the speed of production of product necessarily will affect To the competitiveness of product in the market.Current rapid shaping technique is very wide in developed country's application surface, and is similar to three-dimensional The new techniques such as rapid shaping printing technique also gradually development comes, the technology can in speed of production, production efficiency, be produced into This, molding type, operation and operating technology, material category and the design of some complicated shapes etc. have great advantage, have Vast potential for future development, for over ten years, SL technology equipment application, software development and in terms of achieve it is very big Progress.
Introduction To Stereolithography (optical soliton interaction system, SLA) be it is most widely used, be used for rapid shaping technique Development prospect it is best, technology is most mature.Its product has high precision and good surface quality, has higher Raw material availability be the most important feature of SLA technology, it can manufacture complex contour, special shape hollow parts and phase When accurate jewelry and the art work etc..As the application field of SL technology constantly expands, the market of SL fast shaping material is wanted Ask also raising rapidly.Photosensitive resin is the key technology of SL technical application development, and research and development occupies for SL technology Vital status.
Currently, the photosensitive resin researched and developed is that solidified forming part hardness is low, heat resistance is bad, mechanical the problem of being primarily present Performance is poor, so the domestic majority of material used is dependent on import, but imported material is expensive, and production cost is caused constantly to increase Add, this, which becomes, restricts the key factor that 3D printing rapid shaping obtains major progress and application.In response to the above problems, mainly have two Kind solution: first is that the component of adjusting resin system and the formula of each ingredient reach requirement, second is that adding into resin system Add a kind of filler to improve its various aspects of performance.Particulate material and high-performance aramid fiber material are because with excellent physico It learns performance and causes the great attention of researcher, there is very wide application prospect and development potentiality.Especially has very high-tensile strength The graphene oxide and diatomite and aramid fiber of performance may be used as reinforcing filler and insert in photosensitive resin matrix to mention Rise the mechanical property of photosensitive resin raw material.
Currently, domestic 3D printing photosensitive resin material is since drip molding hardness is low, heat resistance is bad, bad mechanical property etc. Reason hinders the development speed of SL technology.The advantages of optical soliton interaction material is that curing rate is fast, stock utilization is high, to ring Border pollution is small and forming period is very short etc., but still there are many shortcomings, need further to be studied, and such as saturating sensitivity is poor, shape Poor at surface quality, hardness is low, and toughness is low, and heat resistance is bad, and the solidification of these defects, which makes to be formed, partially cannot function as functional component Directly using solidification, it is substantially reduced its application range.Scientific research personnel attempts by improving the various substances in material composition The various performances to improve it are formulated, but this often brings another performance with a kind of reduction of performance and improves.Therefore, same Intensity, heat resistance and the toughness of Shi Tigao material, traditional way are difficult to realize.
Summary of the invention
The technical problems to be solved by the invention: it is low for the 3D printing resin material mechanical performance that developed now, The problem of poor heat resistance, proposes a kind of preparation method of 3D printing material.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) α is taken, alpha, alpha-dimethyl oxygroup benzil ketals, bisphenol-a epoxy acrylate and tripropylene glycol diacrylate stirring are equal It is even, obtain mixture A；
(2) it takes triaryl silicon oxygen ether, POLYBUTADIENE EPOXY RESIN and triethylene glycol divinyl ether to stir evenly, obtains mixture B；
(3) it takes magnetic agitation after di-nbutyltin oxide, toluene, trimethylolpropane mixing uniform, is warming up to 120 DEG C of reactions 12h；
(4) stop heating, after device is cooled to 30 DEG C, carbon disulfide is added dropwise, then be warming up to 100 DEG C and be stirred at reflux reaction 12h；
(5) vacuum distillation processing removes toluene, reaction solution is obtained, with the multiple washing reaction liquid of n-hexane；
(6) reaction solution after washing is dissolved by heating with toluene, obtains Expanding Monomer after 2 ~ 4h of vacuum drying；
(7) mixture A, mixture B, Expanding Monomer, ethyl orthosilicate, nano-titanium dioxide and glass fibre is taken to be uniformly mixed, It vacuumizes removing bubble and obtains 3D printing material.
Step (1) described α, two propylene of alpha, alpha-dimethyl oxygroup benzil ketals, bisphenol-a epoxy acrylate and tripropylene glycol The mass ratio of acid esters is 1:25:3.
The mass ratio of step (2) the triaryl silicon oxygen ether, POLYBUTADIENE EPOXY RESIN and triethylene glycol divinyl ether For 1:20:3.
Step (3) di-nbutyltin oxide, toluene, trimethylolpropane mass ratio be 25:150:14.
Step (4) the carbon disulfide drop rate is 4g/min.
Step (5) number with n-hexane washing reaction liquid is 5 ~ 8 times.
Step (6) the mixture A, mixture B, Expanding Monomer, ethyl orthosilicate, nano-titanium dioxide and glass fibre Mass ratio be 50:20:10:10:3:5.
The present invention is compared with other methods, and advantageous effects are:
(1) radical UV curing has the advantages that curing rate is fast, low-cost, but resin viscosity is high, and solidification volume contraction is big；Sun Ion photocuring have many advantages, such as to solidify volume contraction is small, resin viscosity is low, can after solidify, but curing rate is slow, one-step solidification Degree is low, to water vapor sensitive, and the present invention uses the method that radically curing and cationic curing are used in combination, and two kinds are solidified Mode has complementary advantages, and makes up respective disadvantage, improves the comprehensive performance of material；
(2) since radical UV curing is different from the solidification rate of two kinds of curing modes of cation photocuring, so being added to swollen Swollen monomer makes up the problem of leading to volume contraction since photocuring is asynchronous；Ethyl orthosilicate can be in the process of photocuring In be gradually oxidized to nano silica, enhance the heat resistance of material；Nano-titanium dioxide good dispersion and have good Scattering and reflection UV resistance, can make up for it the opaqueness of nano silica, while further enhancing the machine of material Tool performance；Glass fibre, nano silica, nano-titanium dioxide form reticular structure in material internal, improve material Mechanical performance；
(3) the 3D printing material solidification speed prepared by the present invention is fast, solidification volume contraction is small, has good mechanically performance And heat resistance.
Specific embodiment
Take 2 ~ 4g α, alpha, alpha-dimethyl oxygroup benzil ketals, 50 ~ 100g bisphenol-a epoxy acrylate and 6 ~ 12g 3 the third two Alcohol diacrylate stirs evenly, and obtains mixture A；Take 1 ~ 2g triaryl silicon oxygen ether, 20 ~ 40g POLYBUTADIENE EPOXY RESIN It is stirred evenly with 3 ~ 6g triethylene glycol divinyl ether, obtains mixture B；Take 25 ~ 50g di-nbutyltin oxide, 150 ~ 300g first Magnetic agitation is uniform after benzene, the mixing of 14 ~ 28g trimethylolpropane, is warming up to 120 DEG C of reaction 12h；Stop heating, it is cold to device But to after 30 DEG C, the carbon disulfide of 8 ~ 16g is added dropwise with the rate of 4g/min, then is warming up to 100 DEG C and is stirred at reflux reaction 12h；Subtract Pressure distillation processing removes toluene, reaction solution is obtained, with 100g n-hexane washing reaction liquid 5 ~ 8 times；Reaction solution after washing is used 35g toluene dissolves by heating, and obtains Expanding Monomer after vacuum drying；Take 50 ~ 100g mixture A, 20 ~ 40g mixture B, 10 ~ 20g Expanding Monomer, 10 ~ 20g ethyl orthosilicate, 3 ~ 6g nano-titanium dioxide and 5 ~ 10g glass fibre are uniformly mixed, and are vacuumized and are removed Bubble is gone to obtain 3D printing material.
Example 1
2g α is taken, alpha, alpha-dimethyl oxygroup benzil ketals, 50g bisphenol-a epoxy acrylate and 6g tripropylene glycol diacrylate stir It mixes uniformly, obtains mixture A；Take 1g triaryl silicon oxygen ether, 20g POLYBUTADIENE EPOXY RESIN and 3g triethylene glycol divinyl ether It stirs evenly, obtains mixture B；Magnetic force after 25g di-nbutyltin oxide, 150g toluene, the mixing of 14g trimethylolpropane is taken to stir It mixes uniformly, is warming up to 120 DEG C of reaction 12h；Stop heating, after device is cooled to 30 DEG C, is added dropwise 8g's with the rate of 4g/min Carbon disulfide, then be warming up to 100 DEG C and be stirred at reflux reaction 12h；Vacuum distillation processing removes toluene, obtains reaction solution, uses 100g N-hexane washing reaction liquid 5 times；Reaction solution after washing 35g toluene is dissolved by heating, it is single that expansion is obtained after vacuum drying Body；Take 50g mixture A, 20g mixture B, 10g Expanding Monomer, 10g ethyl orthosilicate, 3g nano-titanium dioxide and 5g glass fibers Dimension is uniformly mixed, and is vacuumized removing bubble and is obtained 3D printing material.
Example 2
3g α is taken, alpha, alpha-dimethyl oxygroup benzil ketals, 75g bisphenol-a epoxy acrylate and 9g tripropylene glycol diacrylate stir It mixes uniformly, obtains mixture A；Take 1.5g triaryl silicon oxygen ether, 30g POLYBUTADIENE EPOXY RESIN and 4g Triethylene glycol divinyl base Ether stirs evenly, and obtains mixture B；Magnetic force after taking 37g di-nbutyltin oxide, 225g toluene, 21g trimethylolpropane to mix It stirs evenly, is warming up to 120 DEG C of reaction 12h；Stop heating, after device is cooled to 30 DEG C, 12g is added dropwise with the rate of 4g/min Carbon disulfide, then be warming up to 100 DEG C be stirred at reflux reaction 12h；Vacuum distillation processing removes toluene, obtains reaction solution, uses 100g n-hexane washing reaction liquid 6 times；Reaction solution after washing 35g toluene is dissolved by heating, is obtained after vacuum drying swollen Swollen monomer；Take 75g mixture A, 30g mixture B, 15g Expanding Monomer, 15g ethyl orthosilicate, 5g nano-titanium dioxide and 8g glass Glass fiber is uniformly mixed, and is vacuumized removing bubble and is obtained 3D printing material.
Example 3
Take 4g α, alpha, alpha-dimethyl oxygroup benzil ketals, 100g bisphenol-a epoxy acrylate and 12g tripropylene glycol diacrylate It stirs evenly, obtains mixture A；Take 2g triaryl silicon oxygen ether, 40g POLYBUTADIENE EPOXY RESIN and 6g Triethylene glycol divinyl base Ether stirs evenly, and obtains mixture B；Magnetic force after taking 50g di-nbutyltin oxide, 300g toluene, 28g trimethylolpropane to mix It stirs evenly, is warming up to 120 DEG C of reaction 12h；Stop heating, after device is cooled to 30 DEG C, 16g is added dropwise with the rate of 4g/min Carbon disulfide, then be warming up to 100 DEG C be stirred at reflux reaction 12h；Vacuum distillation processing removes toluene, obtains reaction solution, uses 100g n-hexane washing reaction liquid 8 times；Reaction solution after washing 35g toluene is dissolved by heating, is obtained after vacuum drying swollen Swollen monomer；Take 100g mixture A, 40g mixture B, 20g Expanding Monomer, 20g ethyl orthosilicate, 6g nano-titanium dioxide and 10g Glass fibre is uniformly mixed, and is vacuumized removing bubble and is obtained 3D printing material.
The 3D printing material that 3D printing material prepared by the present invention and Jiangsu company produce is detected, it is specific to detect As a result such as following table table 1:
Detection method:
(1) test of curing degree
It is M that composite material mixed solution, which is placed in weight,0Glass dish in, thickness about 4mm, claim gross mass M1, place it in ultraviolet Solidify under lamp, take out before the deadline, and dry uncured mixed liquor with filter paper, writes down solidfied material mass M2, with the second Table records curing time.Then:
Curing degree=M2/(M1-M0) × 100%
(2) heat stability testing
Thermogravimetry is the current common method of research material hot property, it is to be obtained in controlled heat environment using thermobalance Example weight is with temperature or a kind of technology of time change.Accurate test process be by sample to be tested in 80 DEG C of drying boxes Then dry 12h weighs 10mg sample to remove moisture removal, be put under the Elevated Temperature Conditions carried out under temperature control program in alumina container Mass change test.Test condition is nitrogen atmosphere protection, and airflow rate 20mL/min, temperature test range is 30- 800 DEG C, heating rate is 10 DEG C/min.
(3) bending property is tested
Bending strength: testing according to GB/T2567-2008, and shearing scantling is that 80mm × 10mm × 4mm uses three-point bending Test device.
(4) tensile property is tested
Tensile strength δ t, refers under defined experimental temperature, humidity, sample during stretching, institute's energy along draw direction The maximum stress being subjected to；Elongation at break is after sample is pulled off, and the length of elongated portion and sample are former in sample drawing process Carry out the ratio of length.Tensile strength 1 calculates as the following formula, and elongation at break 2 calculates as the following formula.
δ t=P/bd(formula 1)
δ t=(L-L0/L0) × 100%(formula 2)
Table 13D printed material performance characterization
3D printing material prepared by the present invention as shown in Table 1, high mechanical strength, curing degree are high, heat resistance improves, mechanical performance It is good.

Claims (7)

1. a kind of preparation method of 3D printing material, which is characterized in that specific production step are as follows:
(1) α is taken, alpha, alpha-dimethyl oxygroup benzil ketals, bisphenol-a epoxy acrylate and tripropylene glycol diacrylate stirring are equal It is even, obtain mixture A；
(2) it takes triaryl silicon oxygen ether, POLYBUTADIENE EPOXY RESIN and triethylene glycol divinyl ether to stir evenly, obtains mixture B；
(3) it takes magnetic agitation after di-nbutyltin oxide, toluene, trimethylolpropane mixing uniform, is warming up to 120 DEG C of reactions 12h；
(4) stop heating, after device is cooled to 30 DEG C, carbon disulfide is added dropwise, then be warming up to 100 DEG C and be stirred at reflux reaction 12h；
(5) vacuum distillation processing removes toluene, reaction solution is obtained, with the multiple washing reaction liquid of n-hexane；
(6) reaction solution after washing is dissolved by heating with toluene, obtains Expanding Monomer after 2 ~ 4h of vacuum drying；
(7) mixture A, mixture B, Expanding Monomer, ethyl orthosilicate, nano-titanium dioxide and glass fibre is taken to be uniformly mixed, It vacuumizes removing bubble and obtains 3D printing material.
2. a kind of preparation method of 3D printing material as described in claim 1, which is characterized in that step (1) described α, α-two The mass ratio of methoxyl group benzil ketals, bisphenol-a epoxy acrylate and tripropylene glycol diacrylate is 1:25:3.
3. a kind of preparation method of 3D printing material as described in claim 1, which is characterized in that step (2) described triaryl The mass ratio of silicon oxygen ether, POLYBUTADIENE EPOXY RESIN and triethylene glycol divinyl ether is 1:20:3.
4. a kind of preparation method of 3D printing material as described in claim 1, which is characterized in that the positive fourth of step (3) described two Base tin oxide, toluene, trimethylolpropane mass ratio be 25:150:14.
5. a kind of preparation method of 3D printing material as described in claim 1, which is characterized in that step (4) described curing Carbon drop rate is 4g/min.
6. a kind of preparation method of 3D printing material as described in claim 1, which is characterized in that step (5) described use just oneself The number of alkane washing reaction liquid is 5 ~ 8 times.
7. a kind of preparation method of 3D printing material as described in claim 1, which is characterized in that step (6) described mixture A, the mass ratio of mixture B, Expanding Monomer, ethyl orthosilicate, nano-titanium dioxide and glass fibre is 50:20:10:10:3: 5。
CN201810996828.5A 2018-08-29 2018-08-29 A kind of preparation method of 3D printing material Pending CN109337298A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104570603A (en) * 2013-10-22 2015-04-29 青岛中科新材料有限公司 Preparation method and application of photosensitive resin for ultrasonic curing 3D printing
CN105943406A (en) * 2016-05-19 2016-09-21 深圳长朗三维科技有限公司 3D printing composite material for mouth rehabilitation and preparation and using method of 3D printing composite material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104570603A (en) * 2013-10-22 2015-04-29 青岛中科新材料有限公司 Preparation method and application of photosensitive resin for ultrasonic curing 3D printing
CN105943406A (en) * 2016-05-19 2016-09-21 深圳长朗三维科技有限公司 3D printing composite material for mouth rehabilitation and preparation and using method of 3D printing composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张露等: "两种膨胀单体的合成及其对牙科修复树脂的改性", 《化工进展》 *

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Application publication date: 20190215