CN106832091A - A kind of thermosetting polyacrylate resin 3D printing material and preparation method thereof - Google Patents
A kind of thermosetting polyacrylate resin 3D printing material and preparation method thereof Download PDFInfo
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- CN106832091A CN106832091A CN201710032831.0A CN201710032831A CN106832091A CN 106832091 A CN106832091 A CN 106832091A CN 201710032831 A CN201710032831 A CN 201710032831A CN 106832091 A CN106832091 A CN 106832091A
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- polyacrylate resin
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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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses a kind of thermosetting polyacrylate resin 3D printing material and preparation method thereof, is characterized in that component raw material and proportioning (parts by weight) are：17 parts of functional monomer, 20 40 parts of soft monomer, 50 80 parts of hard monomer, 2 20 parts of methacrylic acid chaff ester, 0.5 1.2 parts of initiator, 50 100 parts of solvent, 0.3 1.0 parts of hydroquinones, 1 10 parts of diphenyl methane dimaleimide.Contain dynamic chemical key Diels Alder keys in the molecular structure of polyacrylate resin of the invention, effectively overcome thermosetting polyacrylate resin poor processability, be not easy the shortcoming that reclaims, the melt temperature of polyacrylate resin printed material produced by the present invention is low, printing is smooth, material mechanical property is good, easy recycling.
Description
Technical field
The present invention relates to polyacrylate resin 3D printing Material Field, and in particular to a kind of thermosetting polyacrylate tree
Fat 3D printing material and preparation method thereof.
Background technology
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
D-A keys are built in structure efficiently against thermosetting polyacrylate resin poor processability, and can be not easy lacking for recovery
Point.Substantial amounts of patent document and the research paper published are retrieved, not yet found with BMI as crosslinking agent, utilized
D-A keys build the report of the thermosetting polyacrylate resin 3D printing material of 3D printing.
The content of the invention
In order to effectively overcome thermosetting polyacrylate resin poor processability, and it is not easy the shortcoming for reclaiming, this hair
It is bright that a kind of thermosetting polyacrylate resin 3D printing material 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 parts by weight)
A kind of preparation method of thermosetting polyacrylate resin 3D printing material, comprises the following steps：
Methacrylic acid chaff ester, diphenyl methane dimaleimide, solvent is added to be reacted at 40-80 DEG C in four-necked bottle
The addition product for obtaining methacrylic acid chaff ester and diphenyl methane dimaleimide in 2-60 hours, be subsequently adding functional monomer,
Soft monomer, hard monomer, initiator, lead to nitrogen, constant temperature and are reacted 4-6 hours at 75-80 DEG C；It is eventually adding 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 thermosetting polyacrylic acid
Ester resin 3D printing material.
The functional monomer is acrylic acid, methacrylic acid, acrylic acid -2- hydroxyl ethyl esters, 2-hydroxypropyl acrylate, first
At least one of base acrylic acid -2- hydroxyl ethyl esters and Hydroxypropyl methacrylate.
The soft monomer is at least one of methyl acrylate, ethyl acrylate, butyl acrylate and Isooctyl acrylate monomer.
The hard monomer is at least one of methyl methacrylate, styrene and acrylonitrile.
The initiator is azodiisobutyronitrile, ABVN, benzoyl peroxide, lauroyl peroxide, isopropyl
Benzene hydrogen peroxide, TBHP, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate and
At least one of peroxidating trimethylacetic acid.
The solvent is at least one of ethyl acetate, hexamethylene, normal hexane, dioxane, chloroform and acetone.
Contain dynamic chemical key Di el s-Alder keys in the molecular structure of polyacrylate resin of the invention, effectively
Overcome thermosetting polyacrylate resin poor processability, and be not easy the shortcoming for reclaiming, polyacrylic acid produced by the present invention
The melt temperature of ester resin printed material is low, printing is smooth, material mechanical property is good, easy recycling.
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：
10 parts of methacrylic acid chaff ester, 5 parts of diphenyl methane dimaleimide, ethyl acetate 50 are added in four-necked bottle
Part, 50 parts of chloroform react the addition for obtaining methacrylic acid chaff ester and diphenyl methane dimaleimide for 20 hours at 40 DEG C
Thing, is subsequently adding 2 parts of acrylic acid, 1 part of acrylic acid -2- hydroxyl ethyl esters, 30 parts of butyl acrylate, 80 parts of methyl methacrylate, idol
1.0 parts of nitrogen bis-isobutyronitrile；Constant temperature reacts 6 hours at 75-77 DEG C；0.8 part of termination polymerisation of hydroquinones is subsequently adding, is down to
Room temperature, through suction filtration, washing is dried to constant weight product at 45 DEG C of vacuum drying chamber, obtains 3D printing polyacrylate resin.
Through granulating tie rod, the mechanical property for obtaining thermosetting polyacrylate resin 3D printing wire rod is：Tensile strength 55Mpa, bending
Intensity 86Mpa, bending modulus 3000Mpa, elongation at break 7%.
Embodiment two：
6 parts of methacrylic acid chaff ester, 3 parts of diphenyl methane dimaleimide, 100 parts of ethyl acetate are added in four-necked bottle
Reaction obtains the addition product of methacrylic acid chaff ester and diphenyl methane dimaleimide for 10 hours at 50 DEG C, is subsequently adding first
1 part of base acrylic acid, 1 part of acrylic acid -2- hydroxyl ethyl esters, 20 parts of Isooctyl acrylate monomer, 50 parts of methyl methacrylate, styrene 10
Part, 0.5 part of azodiisobutyronitrile；Constant temperature reacts 4 hours at 78-80 DEG C；It is subsequently adding 0.3 part of hydroquinones and terminates polymerization instead
Should, it is down to room temperature, through suction filtration, washing is dried to constant weight product at 45 DEG C of vacuum drying chamber, obtains 3D printing polyacrylic acid
Ester resin.Through granulating tie rod, the mechanical property for obtaining thermosetting polyacrylate resin 3D printing wire rod is：Tensile strength
60Mpa, bending strength 90Mpa, bending modulus 3500Mpa, elongation at break 5%.
Claims (7)
1. a kind of thermosetting polyacrylate resin 3D printing material, it is characterised in that use following components and material rate, its
Described in raw material number unless otherwise specified, be parts by weight；
2. a kind of preparation method of thermosetting polyacrylate resin 3D printing material, it is characterised in that comprise the following steps：
Methacrylic acid chaff ester, diphenyl methane dimaleimide, solvent is added to react 2-60 at 40-80 DEG C in four-necked bottle
Hour obtains the addition product of methacrylic acid chaff ester and diphenyl methane dimaleimide, is subsequently adding functional monomer, soft list
Body, hard monomer, initiator, continue logical nitrogen；Constant temperature reacts 4-6 hours at 75-80 DEG C；It is subsequently adding 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 polyacrylic acid
The material of ester resin.
3. the preparation method of the polyacrylate resin 3D printing material of a kind of cross-linked structure according to claim 2, its
It is characterized in that the functional monomer is acrylic acid, methacrylic acid, acrylic acid -2- hydroxyl ethyl esters, 2-hydroxypropyl acrylate, methyl
At least one of acrylic acid -2- hydroxyl ethyl esters and Hydroxypropyl methacrylate.
4. the preparation method of the polyacrylate resin 3D printing material of a kind of cross-linked structure according to claim 2, its
It is characterized in that the soft monomer is at least one of methyl acrylate, ethyl acrylate, butyl acrylate and Isooctyl acrylate monomer.
5. the preparation method of the polyacrylate resin 3D printing material of a kind of cross-linked structure according to claim 2, its
It is characterized in that the hard monomer is at least one of methyl methacrylate, styrene and acrylonitrile.
6. the preparation method of the polyacrylate resin 3D printing material of a kind of cross-linked structure according to claim 2, its
It is characterized in that the initiator is azodiisobutyronitrile, ABVN, benzoyl peroxide, lauroyl peroxide, isopropylbenzene
Hydrogen peroxide, TBHP, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate and mistake
Aoxidize at least one of trimethylacetic acid.
7. the preparation method of the polyacrylate resin 3D printing material of a kind of cross-linked 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 |
|---|---|---|---|
| CN201710032831.0A CN106832091A (en) | 2017-01-18 | 2017-01-18 | A kind of thermosetting polyacrylate resin 3D printing material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032831.0A CN106832091A (en) | 2017-01-18 | 2017-01-18 | A kind of thermosetting polyacrylate resin 3D printing material and preparation method thereof |
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| CN106832091A true CN106832091A (en) | 2017-06-13 |
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| CN201710032831.0A Pending CN106832091A (en) | 2017-01-18 | 2017-01-18 | A kind of thermosetting polyacrylate resin 3D printing material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676306A (en) * | 2018-06-13 | 2018-10-19 | 东莞宜安科技股份有限公司 | A kind of 3D printing material |
| CN112707855A (en) * | 2020-12-24 | 2021-04-27 | 福州大学 | Bismaleimide resin containing methacrylic acid structure and preparation method thereof |
| US20210395420A1 (en) * | 2018-10-01 | 2021-12-23 | Cubicure Gmbh | Resin composition |
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 CN201710032831.0A patent/CN106832091A/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》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676306A (en) * | 2018-06-13 | 2018-10-19 | 东莞宜安科技股份有限公司 | A kind of 3D printing material |
| US20210395420A1 (en) * | 2018-10-01 | 2021-12-23 | Cubicure Gmbh | Resin composition |
| CN112707855A (en) * | 2020-12-24 | 2021-04-27 | 福州大学 | Bismaleimide resin containing methacrylic acid structure and preparation method thereof |
| CN112707855B (en) * | 2020-12-24 | 2022-02-22 | 福州大学 | Bismaleimide resin containing methacrylic acid structure and preparation method thereof |
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Application publication date: 20170613 |
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