CN106883341A - A kind of polyacrylate resin 3D printing material of new structure and preparation method thereof - Google Patents
A kind of polyacrylate resin 3D printing material of new structure and preparation method thereof Download PDFInfo
- Publication number
- CN106883341A CN106883341A CN201710032881.9A CN201710032881A CN106883341A CN 106883341 A CN106883341 A CN 106883341A CN 201710032881 A CN201710032881 A CN 201710032881A CN 106883341 A CN106883341 A CN 106883341A
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- polyacrylate resin
- printing
- new structure
- preparation
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- 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
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
Polyacrylate resin 3D printing material the invention discloses a kind of new structure and preparation method thereof, is characterized in that component raw material and proportioning (parts by weight) are：5 20 parts of penylene BMI between 13 parts of acrylic acid, 20 40 parts of butyl acrylate, 10 40 parts of methacrylic acid chaff ester, 0.5 1.2 parts of benzoyl peroxide, 50 100 parts of solvent, 0.3 1.0 parts of hydroquinones, N, N.Contain thermal reversion chemical bond Diels Alder keys in the molecular structure of polyacrylate resin, the melt temperature of polyacrylate resin printed material produced by the present invention is low, printing is smooth, material mechanical property is good.
Description
Technical field
The present invention relates to polyacrylate resin 3D printing Material Field, and in particular to a kind of polyacrylic acid of new structure
Ester resin 3D printing material and preparation method thereof.
Background technology
3D printing be one kind based on mathematical model file, with powdery metal or plastics etc. can jointing material, lead to
Carry out the technology of constructed object after the mode for successively printing, in jewelry, footwear, industrial design, building, engineering construction, automobile, aviation
Before space flight, dentistry and medical industries, education, GIS-Geographic Information System, civil engineering, gun and other field are widely used
Scape.Melting 3D printing is commercial Application form main at present, it is adaptable to which the material of FDM techniques is mainly some thermoplasticity materials
Material, conventional at present has acrylonitrile-butadiene-styrene copolymer (ABS plastic), PLA (PLA), nylon, artificial rubber
With makrolon (PC) etc..
Acrylic resin is made up of the polymerization of acrylic acid, methacrylic acid and its derivative (such as esters, nitrile, amide-type)
One resinoid, with preferable physical and mechanical properties, chemical-resistant and excellent water resistance are widely used.Acrylic resin is again
It is divided into the mechanical property of thermoplasticity and thermosetting, thermoplastic acrylic resin handling ease, but material compared with thermoset acrylics tree
Fat is poor；The material mechanical performance of thermosetting acrylic resin is good, but poor processability, and is not easy to reclaim.At present, it is relevant poly-
The report of acrylate 3D printing material is also little, and Zhongshan Vocational Technical College is disclosed in patent 201510936726.0
Disclose a kind of polyacrylic acid ester group 3D printing material and preparation method thereof, the 3D printing material by 40-90 parts of hard monomer,
10-60 parts of soft monomer, 5-10 parts of carboxyl group-containing monomer, 1-3 parts of emulsifying agent, 0.2-1 parts of initiator are made acrylic emulsion, then will
Acrylic emulsion and inorganic compound powder mix, grind and obtain.Polyacrylate resin emulsion is adsorbed in sulfuric acid by the invention
In the inorganic compound powder such as calcium, the 3D of the high-flexibility of the high structural strength and organic polymer that have inorganic compound concurrently is obtained
Printed material.Zhongshan Vocational Technical College discloses a kind of polyacrylate resin class 3D printing in patent 201510214321.6
Material and preparation method thereof, the 3D printing material is prepared by the raw material of following weight portion using precipitation polymerization method：Acrylic acid
6-13 parts；Soft monomer 20-40 parts；Hard monomer 45-60 parts；Solvent 50-100 parts；Crosslinking agent 30-50 parts；Initiator 0.2-0.6
Part.The invention uses precipitation polymerization method, by changing synthesizing formula and synthetic technological condition containing carboxylated polypropylene acid ester resin
To adjust the carboxyl-content of resin and the molecular weight of resin and its distribution, prepare high-performance polypropylene acid ester resin class 3D and beat
Print material, the finished product printed using the 3D printing material powder of the invention has high bond strength, printing precision high, excellent
Pliability.Taicang Biqi New Material Research and Development Co., Ltd. discloses the poly- methyl for 3D printing in patent 201410425012.9
Methyl acrylate composite and preparation method thereof, its preparation methods steps are that acrylic acid is dissolved in ethyl acetate, are added even
Nitrogen bis-isobutyronitrile, room temperature is placed, and sequentially adds paranitrobenzoic acid, cyanoacetic acid isobutyl ester, is stirred at room temperature, and is subsequently adding poly-
Methacrylate particles, continue to be stirred at room temperature, and obtain the composite material of polymethyl methacrylate for 3D printing.Wherein gather
The content of methyl methacrylate is 30-60%, and cyanoacetic acid isobutyl ester content is 10-30%, and acrylic acid content is 1-10%,
Ethyl acetate content is 20-40%, and azodiisobutyronitrile content is 1-2%, and paranitrobenzoic acid content is 1-10%.The invention
The composite of preparation can carry out 3D printing, and preparation process is simple within the temperature range of 10-35 DEG C, and raw material are easy to get, raw
Low cost is produced, is easy to be extended and applied.
The acrylic resin of above-mentioned patent report or and its composite be all it is thermoplastic, it is rarely seen to have thermoset acrylics
The report of resin 3D printing material.To overcome thermosetting acrylic resin poor processability, and it is not easy the shortcoming for reclaiming, base
The characteristics of having the function of thermal reversion in D-A keys, therefore reacted using D-A is in polyacrylate resin 3D printing material molecule knot
Built in structure D-A keys can efficiently against thermosetting polyacrylate resin poor processability, be not easy the shortcoming that reclaims.Inspection
The substantial amounts of patent document of rope and the research paper published, not yet find with BMI as crosslinking agent, using D-A keys
To build the report of the thermosetting polyacrylate resin 3D printing material of 3D printing.
The content of the invention
For effective thermosetting polyacrylate resin poor processability, and it is not easy the shortcoming for reclaiming, the present invention
Polyacrylate resin 3D printing material of a kind of new structure and preparation method thereof is provided.
The purpose of the present invention can be achieved through the following technical solutions：
Component raw material and proportioning (unless otherwise specified, being molfraction)
A kind of preparation method of the polyacrylate resin 3D printing material of new structure, comprises the following steps：
Penylene BMI between acrylic acid, butyl acrylate, methacrylic acid chaff ester, N, N- is added in four-necked bottle
And solvent, stirring is started, nitrogen is passed through to exclude oxygen, benzoyl peroxide is added after being reacted 10-60 hours at 40-80 DEG C,
Continue logical nitrogen；Constant temperature reacts 4-6 hours at 75-80 DEG C；It is subsequently adding hydroquinones and terminates polymerisation, be down to room temperature, produces
Through suction filtration, washing is dried to constant weight thing at 45 DEG C of vacuum drying chamber, obtains the material of 3D printing polyacrylate resin.
The solvent is at least one of ethyl acetate, hexamethylene, normal hexane, dioxane, chloroform and acetone.
Chemistry by changing the synthesizing formula and synthetic technological condition of polyacrylate resin to adjust resin of the invention
Structure, molecular weight and its distribution, prepare high performance polyacrylate resin 3D printing material, polyacrylate resin
Contain thermal reversion chemical bond Diels-Alder keys in molecular structure, polyacrylate resin printed material produced by the present invention
Melt temperature is low, printing is smooth, material mechanical property is good.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which this is pointed out that the present embodiment is served only for again
To further illustrating that the present invention is carried out, it is impossible to be interpreted as limiting the scope of the invention, person skilled in art can
Some nonessential modifications and adaptations are made with according to the content of foregoing invention.Molar part is without the following number of specified otherwise
Number.
Embodiment one：
Penylene between 3 parts of acrylic acid, 40 parts of butyl acrylate, 10 parts of methacrylic acid chaff ester, N, N- is added in four-necked bottle
5 parts of BMI, 40 parts of ethyl acetate, 50 parts of chloroform, start stirring, are passed through nitrogen to exclude oxygen, in 40 DEG C of reactions
1.0 parts of benzoyl peroxide is added after 50 hours；Constant temperature reacts 6 hours at 75-77 DEG C；It is subsequently adding 0.6 part of end of hydroquinones
Only polymerisation, is down to room temperature, and through suction filtration, washing is dried to constant weight product at 45 DEG C of vacuum drying chamber, obtains 3D printing use
Polyacrylate resin.Through granulating tie rod, the mechanical property of the polyacrylate resin 3D printing wire rod with new structure is obtained
Can be：Tensile strength 60Mpa, bending strength 90Mpa, bending modulus 2900Mpa, elongation at break 10%.
Embodiment two：
1.6 parts of acrylic acid, 20 parts of butyl acrylate, 15 parts of methacrylic acid chaff ester, N, N- isophthalic are added in four-necked bottle
Support 8 parts of BMI, 100 parts of ethyl acetate, start stirring, be passed through nitrogen to exclude oxygen, reacted 40 hours at 60 DEG C
0.5 part of benzoyl peroxide is added afterwards；Constant temperature reacts 4 hours at 78-80 DEG C；It is subsequently adding 0.4 part of hydroquinones and terminates polymerization
Reaction, is down to room temperature, and through suction filtration, washing is dried to constant weight product at 45 DEG C of vacuum drying chamber, obtains 3D printing polypropylene
Acid ester resin.Through granulating tie rod, the mechanical property for obtaining the polyacrylate resin 3D printing wire rod with new structure is：Draw
Stretch intensity 65Mpa, bending strength 85Mpa, bending modulus 3250Mpa, elongation at break 8%.
Claims (3)
1. the polyacrylate resin 3D printing material of a kind of new structure, it is characterised in that use following components and raw material ratio
Example, wherein the raw material number is unless otherwise specified, is molfraction；
2. the preparation method of the polyacrylate resin 3D printing material of a kind of new structure, it is characterised in that including following step
Suddenly：
Acrylic acid, butyl acrylate, methacrylic acid chaff ester, N are added in four-necked bottle, penylene BMI and molten between N-
Agent, starts stirring, is passed through nitrogen to exclude oxygen, and benzoyl peroxide is added after being reacted 10-60 hours at 40-80 DEG C, continues
Logical nitrogen；Constant temperature reacts 4-6 hours at 75-80 DEG C；It is subsequently adding hydroquinones and terminates polymerisation, is down to room temperature, product warp
Suction filtration, washing, in being dried to constant weight at 45 DEG C of vacuum drying chamber, obtains the material of 3D printing polyacrylate resin.
3. the preparation method of the polyacrylate resin 3D printing material of a kind of new structure according to claim 2, its
It is characterized in that the solvent is at least one of ethyl acetate, hexamethylene, normal hexane, dioxane, chloroform and acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032881.9A CN106883341A (en) | 2017-01-18 | 2017-01-18 | A kind of polyacrylate resin 3D printing material of new structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032881.9A CN106883341A (en) | 2017-01-18 | 2017-01-18 | A kind of polyacrylate resin 3D printing material of new structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106883341A true CN106883341A (en) | 2017-06-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710032881.9A Pending CN106883341A (en) | 2017-01-18 | 2017-01-18 | A kind of polyacrylate resin 3D printing material of new structure and preparation method thereof |
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| CN (1) | CN106883341A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877058A (en) * | 2015-04-29 | 2015-09-02 | 中山职业技术学院 | Polyacrylate resin 3D printing material and preparation method thereof |
| CN105294936A (en) * | 2015-10-19 | 2016-02-03 | 杭州龙勤新材料科技有限公司 | Bi-functionality-degree acrylic ester cross-linking agent and application thereof to 3D printing |
| CN105916916A (en) * | 2013-11-19 | 2016-08-31 | 赢创德固赛有限公司 | Mouldings based on diene-functionalized (meth)acrylates and (hetero-)diels-alder dienophiles, with reversible crosslinking |
-
2017
- 2017-01-18 CN CN201710032881.9A patent/CN106883341A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105916916A (en) * | 2013-11-19 | 2016-08-31 | 赢创德固赛有限公司 | Mouldings based on diene-functionalized (meth)acrylates and (hetero-)diels-alder dienophiles, with reversible crosslinking |
| CN104877058A (en) * | 2015-04-29 | 2015-09-02 | 中山职业技术学院 | Polyacrylate resin 3D printing material and preparation method thereof |
| CN105294936A (en) * | 2015-10-19 | 2016-02-03 | 杭州龙勤新材料科技有限公司 | Bi-functionality-degree acrylic ester cross-linking agent and application thereof to 3D printing |
Non-Patent Citations (1)
| Title |
|---|
| AMALIN A. KAVITHA ET AL.: "Atom-Transfer Radical Copolymerization of Furfuryl Methacrylate (FMA) and Methyl Methacrylate (MMA): A Thermally-Amendable Copolymer", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
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| PB01 | Publication | ||
| PB01 | Publication | ||
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170623 |