CN105440199B - A kind of polyacrylic acid ester group 3D printing material and preparation method thereof - Google Patents
A kind of polyacrylic acid ester group 3D printing material and preparation method thereof Download PDFInfo
- Publication number
- CN105440199B CN105440199B CN201510936726.0A CN201510936726A CN105440199B CN 105440199 B CN105440199 B CN 105440199B CN 201510936726 A CN201510936726 A CN 201510936726A CN 105440199 B CN105440199 B CN 105440199B
- Authority
- CN
- China
- Prior art keywords
- printing material
- parts
- monomer
- inorganic compound
- acrylic emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Abstract
The invention discloses a kind of polyacrylic acid ester group 3D printing material and preparation method thereof, acrylic emulsion is made by 40 ~ 90 parts of hard monomers, 10 ~ 60 parts of soft monomers, 5 ~ 10 parts of carboxyl group-containing monomers, 1 ~ 3 part of emulsifying agent, 0.2 ~ 1 part of initiator in the 3D printing material, then mixes acrylic emulsion and inorganic compound powder, grinds and obtains.Polyacrylate resin emulsion is adsorbed in the inorganic compound powder such as calcium sulfate by the present invention, so that the 3D printing material of the high-flexibility of the high structural strength for having inorganic compound concurrently and organic polymer is made；The entity finished product come out using the 3D printing file printing of the present invention not only has relatively more excellent mechanical strength and mechanical property, and with preferable pliability, application prospect is extremely wide；Using water as reaction medium and solution is bonded respectively in the production of 3D printing material and print procedure, Diamond Search discharge, not only environmental protection, and safe operation meets the demand of current low-carbon environment-friendly.
Description
Technical field
The present invention relates to a kind of 3D printing material and preparation method thereof, specifically a kind of polyacrylic acid ester group 3D printing material
And preparation method thereof.
Background technology
3D printing technique based on mathematical model file, with powdery metal or plastics etc. can jointing material, pass through
The mode that successively prints manufactures entity.Revolutionary manufacturing technology of the 3D printing technique as the new century across the epoch, gradually
Increasingly it is widely applied in fields such as automobile, Aero-Space, education, civil engineering, biologic medicals.
But, current 3D printing technique is also faced with many problems.Wherein, the shortage of 3D printing material is restriction 3D printing
One of maximum bottleneck of technology development.Be currently mainly used be using gypsum, photosensitive resin, plastics as matrix 3D printing material
Material, there is the defects such as printing precision is poor, entity product intensity is not enough, print speed is slow, manufacturing cost is high in them, it is difficult to full
Sufficient modern industry application.
Such as, Chinese invention patent CN 201310420778.3 discloses a kind of 3D printing material based on edible wax,
Mechanical strength by its entity finished product for printing preparation is very poor, is completely unsuitable for being applied to industrial use.Chinese invention patent
CN 201410458299.5 discloses a kind of inorganic powder class 3D printing material, although the entity finished product prepared by its printing
Mechanical strength is preferable, but pliability extreme difference, and print speed is slow, and therefore, it is difficult to obtain practical application.Chinese invention patent
CN 201310091047.9 discloses a kind of by photopolymerization curing polyurethane acrylate prepolymer class 3D printing material,
Although the pliability for the entity finished product being produced from it is excellent, mechanical strength is poor, and the manufacturing process of associated resin and
Print control technique is considerably complicated, and manufacturing cost is high, moreover needs to use many volatilizable industrial chemicals for having certain toxicity,
Therefore the material is almost difficult to popularization and used.
Therefore, developing can print with excellent mechanical strength and mechanical property, and preferably flexible entity
The 3D printing material of finished product, is the key technology difficulty of current urgent need to resolve.
The content of the invention
It is an object of the invention to overcome the existing defect of above-mentioned technology to print there is provided one kind to produce have concurrently it is excellent
The 3D printing material of mechanical strength and flexible entity finished product.
It is a further object of the present invention to provide the preparation method of the 3D printing material.
To reach one of above-mentioned purpose, the present invention uses following technical scheme：
A kind of polyacrylic acid ester group 3D printing material, according to parts by weight, the polyacrylic acid ester group 3D printing material by
40 ~ 90 parts of hard monomers, 10 ~ 60 parts of soft monomers, 5 ~ 10 parts of carboxyl group-containing monomers, 1 ~ 3 part of emulsifying agent, 0.2 ~ 1 part of initiator are made third
Olefin(e) acid emulsion, then acrylic emulsion and inorganic compound powder are mixed, ground and obtain.
Further, the hard monomer is at least one of styrene, methyl acrylate and methyl methacrylate.
Further, the soft monomer is at least one in ethyl acrylate, butyl acrylate and butyl methacrylate
Kind.
Further, the carboxyl group-containing monomer is acrylic acid and/or methacrylic acid.
Further, the emulsifying agent be lauryl sodium sulfate, dodecyl sodium sulfate, neopelex,
At least one of APES, sapn, tween and AEO.
Further, the initiator is at least one of ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate.
Further, the inorganic compound powder is dead plaster and/or two calcium sulfate of hydration.
Further, the mass ratio of acrylic emulsion and the inorganic compound powder is 1：20~200.
The preparation method of foregoing polyacrylic acid ester group 3D printing material, comprises the following steps：
S1, using semi-continuous emulsion polymerizing technique, through copolyreaction acrylic acid synthesizing emulsion；
S2, prepared acrylic emulsion and inorganic compound powder be well mixed, and be fully ground not low to particle diameter
In 2000 mesh, that is, 3D printing material is made.
Further, the step S1 is specially：Hard monomer, soft monomer and carboxyl group-containing monomer are well mixed first,
Then 1/5~1/3 mix monomer and emulsifying agent are added in reactor and be sufficiently stirred for, then reactor is warming up to 70~
85 DEG C and start that initiator solution and remaining mix monomer is added dropwise respectively, control time for adding for 1~3h；Insulation reaction afterwards
3~6h, is finally cooled to room temperature and extracts remaining unreacted monomer completely, that is, acrylic emulsion is made.
Hard monomer main function is to provide the hardness of entity finished product, intensity（Such as compression strength, tensile strength）, water resistance
Etc. performance.But, hard monomer consumption is excessive, the bonding force of acrylic emulsion and inorganic compound powder can be reduced, so as to reduce
The adhesion strength of entity finished product.
Soft monomer main function is to provide the flexibility and its bonding force to inorganic compound powder of entity finished product.But
It is that soft monomer consumption is excessive, can cause the surfaces of tacky of entity finished product, easily stains and set-off.
The main function of carboxylic monomer is to provide a number of-COOH for acrylic resin macromolecular chain, and it not only may be used
To improve the bonding force of acrylic emulsion and inorganic compound powder, it is often more important that so that printed material is met in print procedure
Water breakthrough（I.e. as bonding solution）When can be swelled slightly so that it is wrapped around one another formation entity finished product.But, carboxyl group-containing monomer is used
Amount is excessive, when can make it that printed material meets water in print procedure, the degree of swelling aggravation of acrylic resin, directly results in and beats
Print precision and resolution ratio are deteriorated rapidly.
In emulsifying agent, anionic emulsifier and nonionic emulsifier compounding use effect are preferable, both mass ratioes
The preferred range of example is 1 ~ 3：1.Emulsifier is very few, and emulsion polymerization is difficult to control to, in addition produce implode, layering or even
The phenomenons such as gel；Emulsifier is excessive, and the water absorption rate for causing entity finished product is higher, is long placed in air and easily absorbs moisture and understand
The adverse consequences such as deform, expand, turning to be yellow.
The effect of initiator is to provide free radical, guides polymerization；Its consumption can neither be too low, can not be too high.
Dead plaster and two calcium sulfate of hydration not only pore structure and surface can with absorbing propenoic acid emulsion, and it
Due to that can be reacted with water so that acrylic resin is firmly adsorbed on their surfaces.The major function of inorganic compound
It is to provide sufficiently high mechanical strength and mechanical property for entity finished product, but its consumption will excessively cause the soft of entity finished product
Toughness is not enough.
The invention has the advantages that：
1st, polyacrylate resin emulsion is adsorbed in the inorganic compound powder such as calcium sulfate by the present invention, so as to be made simultaneous
Has the 3D printing material of the high structural strength of inorganic compound and the high-flexibility of organic polymer；Using the 3D printing of the present invention
The entity finished product that file printing comes out not only has relatively more excellent mechanical strength and mechanical property, and with preferably flexible
Property, the shortcoming of current 3D printing material is efficiently solved, therefore application prospect is extremely wide.
2nd, respectively so that water is as reaction medium and bonds solution, Diamond Search in the production of 3D printing material and print procedure
Discharge, not only environmental protection, and safe operation, meet the demand of current low-carbon environment-friendly.
3rd, manufacturing process of the invention is simple, low production cost.
Embodiment
With reference to specific embodiment, the present invention is described further：
The fraction of following examples refers both to parts by weight.
Embodiment 1
A kind of polyacrylic acid ester group 3D printing material, is prepared from according to following steps：
1st, 40 parts of methyl methacrylates, 10 parts of butyl acrylates and 5 parts of acrylic acid are well mixed first, then will
1/5 mix monomer and 1 part of lauryl sodium sulfate are added in reactor and are sufficiently stirred for, then reactor is warming up into 70 DEG C
And start that 0.2 part of sodium peroxydisulfate solution and remaining mix monomer is added dropwise respectively, it is 1h to control time for adding；Insulation reaction afterwards
3h, is finally cooled to room temperature and extracts remaining unreacted monomer completely, that is, acrylic emulsion is made；
2nd, by prepared acrylic emulsion and dead plaster according to 1：200 mass ratio is well mixed, and is fully ground
It is milled to particle diameter and is not less than 2000 mesh, that is, 3D printing material 1# is made.
Embodiment 2
A kind of polyacrylic acid ester group 3D printing material, is prepared from according to following steps：
1st, first by 40 parts of methyl methacrylates, 50 parts of styrene, 10 parts of butyl acrylates, 50 parts of methacrylic acid fourths
Ester and 5 parts of acrylic acid, 5 parts of methacrylic acids are well mixed, then by 1/3 mix monomer and composite emulsifier（2 part 12
Sodium alkyl sulfate and 1 part of APES OP-10 are compounded）It is added in reactor and is sufficiently stirred for, then by reactor
It is warming up to 85 DEG C and starts that initiator is added dropwise respectively（0.2 part of sodium peroxydisulfate, 0.8 part of ammonium persulfate）Solution and remaining mixing list
Body, it is 3h to control time for adding；Insulation reaction 6h, is finally cooled to room temperature and extracts remaining unreacted monomer completely, i.e., afterwards
Acrylic emulsion is made；
2nd, by prepared acrylic emulsion and two calcium sulfate of hydration according to 1：20 mass ratio is well mixed, and fully
It is ground to particle diameter and is not less than 2000 mesh, that is, 3D printing material 2# is made.
Embodiment 3
A kind of polyacrylic acid ester group 3D printing material, is prepared from according to following steps：
1st, first by 30 parts of methyl methacrylates, 20 parts of styrene, 20 parts of methyl acrylates, 30 parts of butyl acrylates,
10 parts of butyl methacrylates, 10 parts of ethyl acrylates and 4 parts of acrylic acid, 3 parts of methacrylic acids are well mixed, then by 1/
4 mix monomer and composite emulsifier（1.5 parts of lauryl sodium sulfate are compounded with 0.5 part of APES OP-10）
It is added in reactor and is sufficiently stirred for, then reactor is warming up to 80 DEG C and starts that initiator is added dropwise respectively（0.1 part of persulfuric acid
Sodium, 0.1 part of ammonium persulfate, 0.1 part of potassium peroxydisulfate）Solution and remaining mix monomer, it is 2h to control time for adding；It is incubated afterwards
4h is reacted, room temperature is finally cooled to and extracts remaining unreacted monomer completely, that is, acrylic emulsion is made；
2nd, by prepared acrylic emulsion and inorganic compound powder（Dead plaster, two calcium sulfate of hydration）According to
1：100 mass ratio is well mixed, and is fully ground to particle diameter and is not less than 2000 mesh, that is, 3D printing material 3# is made.
Embodiment 4
A kind of polyacrylic acid ester group 3D printing material, is prepared from according to following steps：
1st, first by 30 parts of styrene, 30 parts of methyl acrylates, 30 parts of butyl methacrylates and 7 parts of methacrylic acids
It is well mixed, then by 1/4 mix monomer and composite emulsifier（1 part of dodecyl sodium sulfate and 1 part of aliphatic alcohol polyethenoxy
Ether AEO-7 is compounded）It is added in reactor and is sufficiently stirred for, then reactor is warming up to 75 DEG C and starts to be added dropwise 0.5 part respectively
Ammonium persulfate solution and remaining mix monomer, it is 2h to control time for adding；Insulation reaction 5h, is finally cooled to room temperature simultaneously afterwards
Remaining unreacted monomer is extracted completely, that is, acrylic emulsion is made；
2nd, by prepared acrylic emulsion and inorganic compound powder（Dead plaster, two calcium sulfate of hydration）According to
1：50 mass ratio is well mixed, and is fully ground to particle diameter and is not less than 2000 mesh, that is, 3D printing material 4# is made.
Embodiment 5
By above-mentioned produced 3D printing material 1#~4#, import powder bonding class 3D printing material Ni s-AP12（The U.S.
3D systems companies produce）And BM-5（Stratasy companies of the U.S. produce）By 3D printer prepare 10mm × 10mm ×
10mm entity finished product, then dependence test is carried out, as a result as shown in table 1.
The test result of the 3D printing entity finished product of table 1
| Test index | 1# | 2# | 3# | 4# | Nios-AP12 | BM-5 |
| Bending strength（MPa） | 1.1 | 1.2 | 1.0 | 1.1 | 1.1 | 0.9 |
| Compression strength（MPa） | 8.3 | 8.2 | 7.6 | 8.0 | 7.9 | 8.4 |
| Elongation percentage（%） | 54 | 50 | 56 | 54 | 47 | 48 |
3D printing experiment condition：The type 3D printers of Z 310（Z Corporation companies of the U.S.）, piezoelectricity batch (-type) printing
Shower nozzle totally 128 holes（Diameter is about 0.05mm）, thickness is set to 0.175mm, saturation degree and is set to 0.7.（Glued used in 1#~4#
Knot solution is deionized water, and Nis-AP12 and BM-5 carries supporting bonding solution using genuine）.
As shown in Table 1, the physical components that 3D printing material of the invention is come out by 3D printing have higher bending strong
Degree and compression strength and elongation percentage, show its good toughness, and mechanical property is strong, and correlated performance has reached external similar commodity.
In addition, the 3D printing material fabrication process of the present invention is simple, it is with low cost, and water need to be only used as solution is bonded, it is green
Environmental protection.Therefore, technology of the invention is applied and industrialization prospect is very wide.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (8)
1. a kind of 3D printing material, it is characterised in that according to parts by weight, by 40~90 parts of hard monomers, 10~60 parts of soft monomers,
Acrylic emulsion is made in 5~10 parts of carboxyl group-containing monomers, 1~3 part of emulsifying agent, 0.2~1 part of initiator, then by acrylic emulsion
Obtain the 3D printing material with the mixing of inorganic compound powder, grinding, the inorganic compound powder be dead plaster and/
Or two calcium sulfate of hydration, the mass ratio of the acrylic emulsion and the inorganic compound powder is 1：20~200.
2. 3D printing material according to claim 1, it is characterised in that the hard monomer is styrene, methyl acrylate
At least one of with methyl methacrylate.
3. 3D printing material according to claim 1, it is characterised in that the soft monomer is ethyl acrylate, acrylic acid
At least one of butyl ester and butyl methacrylate.
4. 3D printing material according to claim 1, it is characterised in that the carboxyl group-containing monomer is acrylic acid and/or first
Base acrylic acid.
5. 3D printing material according to claim 1, it is characterised in that the emulsifying agent is lauryl sodium sulfate, ten
In dialkyl sulfonates, neopelex, APES, sapn, tween and AEO
At least one.
6. 3D printing material according to claim 1, it is characterised in that the initiator is ammonium persulfate, potassium peroxydisulfate
At least one of with sodium peroxydisulfate.
7. the preparation method of the 3D printing material described in claim any one of 1-6, it is characterised in that comprise the following steps：
S1, using semi-continuous emulsion polymerizing technique, through copolyreaction acrylic acid synthesizing emulsion；
S2, prepared acrylic emulsion and inorganic compound powder be well mixed, and be fully ground to particle diameter and be not less than
2000 mesh, that is, be made 3D printing material.
8. preparation method according to claim 7, it is characterised in that the step S1 is specially：First by hard monomer, soft
Monomer and carboxyl group-containing monomer are well mixed, and then 1/5~1/3 mix monomer and emulsifying agent are added in reactor and filled
Divide stirring, then reactor is warming up to 70~85 DEG C and starts to be added dropwise initiator solution and remaining mix monomer, control respectively
Time for adding is 1~3h；3~6h of insulation reaction, is finally cooled to room temperature and extracts remaining unreacted monomer completely, that is, make afterwards
Obtain acrylic emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510936726.0A CN105440199B (en) | 2015-12-15 | 2015-12-15 | A kind of polyacrylic acid ester group 3D printing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510936726.0A CN105440199B (en) | 2015-12-15 | 2015-12-15 | A kind of polyacrylic acid ester group 3D printing material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105440199A CN105440199A (en) | 2016-03-30 |
| CN105440199B true CN105440199B (en) | 2017-08-22 |
Family
ID=55550876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510936726.0A Expired - Fee Related CN105440199B (en) | 2015-12-15 | 2015-12-15 | A kind of polyacrylic acid ester group 3D printing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105440199B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3231588A1 (en) | 2016-04-12 | 2017-10-18 | Evonik Röhm GmbH | Spray-dried soft phase emulsion polymer for the filling of the spandrel in polymer bead layers in binder jetting method |
| EP3235867A1 (en) * | 2016-04-20 | 2017-10-25 | Evonik Röhm GmbH | Polymer beads from hard phase with domains of a soft phase |
| KR102340960B1 (en) | 2016-09-28 | 2021-12-17 | 에보닉 오퍼레이션스 게엠베하 | Use and Preparation of Porous Bead Polymers in 3D Printing Using Binder Jetting Methods |
| CN106674433A (en) * | 2016-11-25 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3d printing powder and preparation method thereof |
| CN106749854A (en) * | 2016-12-16 | 2017-05-31 | 北方华锦化学工业集团有限公司 | A kind of preparation method of new 3D printing polyacrylic resin |
| CN107446078A (en) * | 2017-08-01 | 2017-12-08 | 安徽原动力生产力促进中心有限公司 | A kind of 3D gypsum printing technology |
| ES2732766B2 (en) * | 2018-05-24 | 2021-01-20 | Consejo Superior Investigacion | Procedure for obtaining a part by modeling by deposition of molten wire |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7332537B2 (en) * | 1996-09-04 | 2008-02-19 | Z Corporation | Three dimensional printing material system and method |
| DE10026955A1 (en) * | 2000-05-30 | 2001-12-13 | Daimler Chrysler Ag | Material system for use in 3D printing |
| CN103980397B (en) * | 2014-04-30 | 2016-02-24 | 中国科学院化学研究所 | A kind of 3D printings composition and preparing and using method and goods |
| CN104877058B (en) * | 2015-04-29 | 2019-03-26 | 中山职业技术学院 | A kind of polyacrylate resins 3D printing material and preparation method thereof |
-
2015
- 2015-12-15 CN CN201510936726.0A patent/CN105440199B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105440199A (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105440199B (en) | A kind of polyacrylic acid ester group 3D printing material and preparation method thereof | |
| CN105531340B (en) | Acrylate emulsion adhesive and preparation method thereof | |
| CN106380144B (en) | A kind of semi-interpenetrating network polymer cement-based flexible tapestry brick and preparation method thereof | |
| CN104497773B (en) | Preparation method of water-based fluorine-acrylic acid-containing self-stratifying emulsion for protection of concrete surface | |
| CN102850973A (en) | Low-water-absorptivity acrylate structural adhesive and preparation method thereof | |
| KR20100075889A (en) | Liquid resin composition and cured product using the liquid resin composition | |
| CN103694861B (en) | Dual modified, dual cure epoxy acrylate coating | |
| CN100572484C (en) | A kind of aqueous adhesive for shoes and production method thereof | |
| CN110437089A (en) | A kind of UV monomer and preparation method and application | |
| KR102228695B1 (en) | Waterproof coating agent manufacturing method and construction method using thereof | |
| CN103275260B (en) | Preparation method of acrylic plastic-plastic composite latex | |
| CN110218275A (en) | A kind of acrylic emulsion that anti-inner corner trim cracks and the aqueous damping coating comprising the lotion | |
| CN102746797A (en) | Ultraviolet-curable adhesive, as well as preparation method and application thereof | |
| CN108586677A (en) | A kind of light-cured resin and preparation method thereof with degradability | |
| CN101463235B (en) | High elongation rate acrylic ester adhesive | |
| CN101358049A (en) | Elastic emulsion for curing building putty and preparation method thereof | |
| CN105295703A (en) | Modified polyurethane waterproof material and preparation method thereof | |
| CN104211852A (en) | Preparation method of acrylate emulsion for waterborne printing ink | |
| CN102504089A (en) | Preparation method of water-resistant acrylic ester core-shell emulsion | |
| KR101349848B1 (en) | Method of producing high performance water-soluble acrylic adhesive compositon | |
| KR101230863B1 (en) | The manufacture method of the recycled additive added the polymer complex used cold recycled asphalt mixture | |
| CN103275653A (en) | Acrylic plastic-plastic composite latex | |
| JPS6221375B2 (en) | ||
| CN112917904A (en) | 3D printing method for artificial stone | |
| CN105419657A (en) | Timber adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170822 Termination date: 20211215 |