CN106750417B - A kind of Silicon-containing Polyester 3D printing material and preparation method thereof - Google Patents
A kind of Silicon-containing Polyester 3D printing material and preparation method thereof Download PDFInfo
- Publication number
- CN106750417B CN106750417B CN201710032883.8A CN201710032883A CN106750417B CN 106750417 B CN106750417 B CN 106750417B CN 201710032883 A CN201710032883 A CN 201710032883A CN 106750417 B CN106750417 B CN 106750417B
- Authority
- CN
- China
- Prior art keywords
- parts
- acid
- silicon
- polyester
- preparation
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2499/00—Characterised by the use of natural macromolecular compounds or of derivatives thereof not provided for in groups C08J2401/00 - C08J2407/00 or C08J2489/00 - C08J2497/00
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
Landscapes
- 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)
- Developing Agents For Electrophotography (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of Silicon-containing Polyester 3D printing material and preparation method thereof, its main feature is that component raw material and proportion (molfraction) are as follows: 0-5 parts of 100 parts of oligomer, the catalyst of the terminal hydroxy group containing maleimide, 1-50 parts of 2- methoxyl group furfuryl group dimethylsilane double.Polyurethane 3D printing material produced by the present invention has excellent inoxidizability, thermal stability, high lubricating ability, low surface tension.
Description
Technical field
The present invention relates to polyester 3D printing Material Fields, and in particular to a kind of Silicon-containing Polyester 3D printing material and its preparation side
Method.
Background technique
Polyester resin occupies very important status in high molecular material, and polyester material has thermal stability good, resist cold,
The advantages that heat-resisting, moisture-proof, resistant to chemical etching, biodegradable, it can be used for 3D printing.Institute of Chemistry, Academia Sinica is in patent
201410181487.8 a kind of 3D printing aromatic polyester material and preparation method thereof is disclosed in, mainly utilizes aromatic series
Polycarbonate and aromatic polyester carry out blending and modifying and improve its shock resistance, then bring it about certain journey with electron beam irradiation
The method of the crosslinking of degree achievees the purpose that ontology enhances, but the higher cost of this kind of polyester material, and preparation method is relatively multiple
It is miscellaneous.Hangzhou First Photovoltaic Material Co., Ltd. discloses a kind of for 3 D-printing in patent 201310467296.3
Co-polyester thermoplastic's material and its preparation and application.The main raw material list following by quality proportioning of co-polyester thermoplastic's material
Body is copolymerized in the presence of a catalyst to be made: 35~48 parts of dicarboxylic acids, 30~43 parts of dihydric alcohol, and 8~15 parts of acrylate, loop coil
7~15 parts of compound；Spiro-compound expansion class monomer is added in the present invention makes the steady of copolyesters high molecular material compositions
It is qualitative to greatly improve, so that the product printed is kept good structural stability.Institute of Chemistry, Academia Sinica is in patent
201410181498.6 disclose a kind of highly viscous 3D printing polyester and polycarbonate and preparation method thereof, the invention preparation
Method specifically includes that 1) melt polycondensation obtains low viscosity resin；2) low viscosity resin melt is laid in special film reactor,
Thin film melt polycondensation is carried out, target product of the invention is obtained.The characteristics of technique is to accelerate melting contracting by thin film melt polycondensation
The removing of by-product in poly- reaction process, significantly improves the efficiency of solid-phase tack producing, finally obtain be suitable for 3D printing superelevation it is viscous
Spend polyester or polycarbonate resin.Beijing Ju Liwei Science and Technology Ltd. discloses a kind of 3D in patent 201410821411.7 and beats
Print high-strength PET copolyester material and preparation method thereof, the weight percent composition of raw material are as follows: PET70~85%, reinforcing fiber
15~30%, coupling agent 0.5~2.0%, stabilizer 0.1~2.0%, antioxidant 0.1~1.0%, lubricant 0.1~1.0%.
Pass through twin-screw extrusion, tie rod, cooling, granulation.3D printing PET copolyester material prepared by the present invention, price is low, mechanical strength
Height, melting temperature is low, shrinking percentage is small, good stability of the dimension, can replace expensive 3D printing ABS material and polylactic acid material
Material Shanghai Tianyang Holt Melt Adhesive Materials Co., Ltd. discloses one kind and is suitable for 3D and beats in patent 201510341345.8
The copolyesters and preparation method thereof of material is printed, raw material composition includes: to be made of terephthalic acid (TPA), M-phthalic acid and sebacic acid
Binary acid, and the dihydric alcohol being made of 1,4-butanediol, neopentyl glycol and hexylene glycol and catalyst, antioxidant, addition
Agent, auxiliary agent；The present invention is to prepare copolyester material by being esterified with the method for polycondensation completion copolyreaction, preparation process letter
It is single, it reduces costs, and can effectively avoid because bring consistency problem is blended.
There is polyester melt poor fluidity, printing water outlets to be not easy the disadvantages of unstable for 3D printing for polyester.Due to D-A
Key has the function of thermal reversion, thus the characteristics of being reacted using D-A D-A key is constructed in polyester molecule structure can effectively gram
Take polyester melting when viscosity it is larger result in poor fluidity, printing water outlet be not easy the disadvantages of unstable.
The research of silicon-containing polymer anti-fouling coatings becomes more and more active in recent years, and reality causes extensive pass with application potential
Note.Siliceous 3 material of polyester has excellent inoxidizability, thermal stability, high lubricating ability, high gas permeability, low glass
Change transition temperature, good biocompatibility and low surface tension.The research opinion retrieving a large amount of patent document and publishing
Text, not yet find using double 2- methoxyl group furfuryl group dimethylsilanes as crosslinking agent, the siliceous of 3D printing is constructed using D-A key
The report of polyester material.
Summary of the invention
In order to efficiently against polyester melting when viscosity it is larger result in poor fluidity, printing water outlet be not easy it is unstable etc.
Disadvantage, preparation high-performance Silicon-containing Polyester 3D printing material, the present invention provide one kind with double 2- methoxyl group furfuryl group dimethylsilanes and are
Silicon-containing Polyester 3D printing material of the key containing D-A of crosslinking agent and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
Component raw material and proportion (unless otherwise specified, being molfraction)
A kind of preparation method of Silicon-containing Polyester 3D printing material, comprising the following steps:
Weigh 0-5 parts of 100 parts of oligomer, catalyst, double 2- methoxyl group furfuryl group dimethylsilane 1- containing maleimide
Dendritic 0.1-5 parts is added after reaction, through cooling, cuts in 90-200 DEG C of reaction 1-5h for 50 parts of addition reaction kettles
Grain, drying, obtain the polyester resin.
The composition (molfraction) of the polyester oligomer containing maleimide and the preparation method comprises the following steps: organic binary carboxylic
100 parts of acid, 10-50 parts, 0-1.0 parts of polymerization inhibitor methylnaphthohydroquinone of N- (2,3- dihydroxypropyl) maleimide are added to reactor
In melt polycondensation 0.5-2 hours at 170~230 DEG C, then be added dihydric alcohol 50-90 parts, 0-1.0 parts of titanate catalyst after
Continue at 170~230 DEG C melt polycondensation 0.5-2 hours, control the molecular weight of oligomer between 2000-20000, obtains containing horse
Carry out imido polyester oligomer.Wherein molar ratio >=1 of-OH/-COOH.
The catalyst is or mixtures thereof alchlor, boron trifluoride.
The binary acid are as follows: terephthalic acid (TPA), M-phthalic acid, ethanedioic acid, malonic acid, succinic acid, glutaric acid, oneself two
One of acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid or combinations thereof.
The dihydric alcohol are as follows: ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, butanediol, pentanediol, hexylene glycol, heptan two
Alcohol, ethohexadiol, nonanediol, decanediol, isobide, isomannite, bisphenol-A.
The invention has the following advantages that
1, contain D-A key in molecular structure, crosslink material system, improve the mechanical property of product；
2, dendritic is added improves processing fluidity, makes print procedure smoothness, free from extraneous odour, and product surface is bright and clean,
Dimensionally stable is not easy to shrink；
3, polyester 3D printing material has excellent inoxidizability, thermal stability, high lubricating ability, good bio-compatible
Property and low surface tension.
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 the further explanation that the present invention carries out, it should not be understood as limiting the scope of the invention, person skilled in art can
Some nonessential modifications and adaptations are made with the content according to foregoing invention.It is molar part without the following number of specified otherwise
Number.
Embodiment 1:
100 parts of terephthalic acid (TPA), 40 parts of N- (2,3- dihydroxypropyl) maleimide, polymerization inhibitor methylnaphthohydroquinone 0.2
Part is added in reactor at 190-200 DEG C melt polycondensation 2 hours, 65 parts of ethylene glycol, titanate catalyst 1.0 then is added
Part continues melt polycondensation 1.5 hours at 220-230 DEG C, controls the molecular weight of oligomer between 2000-3000, obtains containing horse
Carry out imido polyester oligomer.
Weigh 100 parts of the above-mentioned oligomer containing maleimide, 0.6 part of alchlor, double 2- methoxyl group furfuryl group dimethyl
10 parts of addition reaction kettles of silane are added 2 parts of dendritic in 135 DEG C of reaction 2h after reaction, through cooling, pelletizing, do
It is dry, obtain the polyester resin.
Resulting Silicon-containing Polyester 3D printing material squeezes out wire drawing through single screw extrusion machine and obtains polyester printing wire rod, through surveying
Examination, prints the mechanical property of wire rod are as follows: tensile strength 59Mpa, bending strength 87Mpa, bending modulus 3350Mpa, extension at break
Rate 18%, tested through 2648h Weatherometer (313nm) its light-protection rate be 90%.
Embodiment 2:
100 parts of terephthalic acid (TPA), 20 parts of N- (2,3- dihydroxypropyl) maleimide, polymerization inhibitor methylnaphthohydroquinone 0.4
Part is added in reactor at 220-230 DEG C melt polycondensation 1 hour, 83 parts of 1,4- butanediol, metatitanic acid ester catalysis then is added
0.8 part of agent is continued melt polycondensation 2 hours at 170-190 DEG C, is controlled the molecular weight of oligomer between 3000-5000, is obtained
Polyester oligomer containing maleimide.
Weigh 2 parts of 100 parts of oligomer, boron trifluoride containing maleimide, 5 parts of 2- methoxyl group furfuryl group dimethylsilane double
Reaction kettle is added in 130 DEG C of reaction 5h, 5 parts of dendritic are added after reaction, through cooling, pelletizing, drying, obtain
The polyester resin.
Resulting Silicon-containing Polyester 3D printing material squeezes out wire drawing through single screw extrusion machine and obtains polyester printing wire rod, through surveying
Examination, prints the mechanical property of wire rod are as follows: tensile strength 66Mpa, bending strength 85Mpa, bending modulus 2960Mpa, extension at break
Rate 21%, tested through 2648h Weatherometer (313nm) its light-protection rate be 88%.
Claims (6)
1. a kind of Silicon-containing Polyester 3D printing material, which is characterized in that following components and material rate are used, wherein described raw material part
Number is molfraction unless otherwise specified；
Component raw material and proportion:
2. a kind of preparation method of Silicon-containing Polyester 3D printing material, which comprises the following steps:
Weigh 0-5 parts of 100 parts of polyester oligomer, catalyst, double 2- methoxyl group furfuryl group dimethylsilane 1- containing maleimide
Dendritic 0.1-5 parts is added after reaction, through cooling, cuts in 90-200 DEG C of reaction 1-5h for 25 parts of addition reaction kettles
Grain, drying, obtain the polyester resin.
3. the preparation method of a kind of Silicon-containing Polyester 3D printing material according to claim 2, it is characterized in that: organic binary
100 parts of carboxylic acid, 10-50 parts, 0-1.0 parts of polymerization inhibitor methylnaphthohydroquinone of N- (2,3- dihydroxypropyl) maleimide are added to reaction
In device melt polycondensation 0.5-2 hours at 170~230 DEG C, then dihydric alcohol 50-90 parts, 0-1.0 parts of titanate catalyst of addition
Continue melt polycondensation 0.5-2 hours at 170~230 DEG C, controls the molecular weight of oligomer between 2000-20000, contained
The polyester oligomer of maleimide, wherein molar ratio >=1 of-OH/-COOH.
4. the preparation method of a kind of Silicon-containing Polyester 3D printing material according to claim 2, it is characterized in that the catalyst
For or mixtures thereof alchlor, boron trifluoride.
5. the preparation method of a kind of Silicon-containing Polyester 3D printing material according to claim 3, it is characterized in that described is organic
Dicarboxylic acids are as follows: terephthalic acid (TPA), M-phthalic acid, ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pungent
One of diacid, azelaic acid, decanedioic acid or combinations thereof.
6. the preparation method of a kind of Silicon-containing Polyester 3D printing material according to claim 3, it is characterized in that the binary
Alcohol are as follows: ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol,
Decanediol, isobide, isomannite, bisphenol-A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032883.8A CN106750417B (en) | 2017-01-18 | 2017-01-18 | A kind of Silicon-containing Polyester 3D printing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032883.8A CN106750417B (en) | 2017-01-18 | 2017-01-18 | A kind of Silicon-containing Polyester 3D printing material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106750417A CN106750417A (en) | 2017-05-31 |
| CN106750417B true CN106750417B (en) | 2019-05-17 |
Family
ID=58946140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710032883.8A Active CN106750417B (en) | 2017-01-18 | 2017-01-18 | A kind of Silicon-containing Polyester 3D printing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106750417B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980675A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing aromatic polyester material and preparation method |
| CN104559196A (en) * | 2014-12-29 | 2015-04-29 | 大连理工常熟研究院有限公司 | Colorless and transparent light-cured 3D printing material |
| CN104672402A (en) * | 2013-11-28 | 2015-06-03 | 比亚迪股份有限公司 | Conducting photosensitive resin for 3D printing and preparation method thereof |
| CN104877118A (en) * | 2015-06-18 | 2015-09-02 | 上海天洋热熔粘接材料股份有限公司 | Copolyester used as 3D printing material and preparation method of copolyester |
-
2017
- 2017-01-18 CN CN201710032883.8A patent/CN106750417B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672402A (en) * | 2013-11-28 | 2015-06-03 | 比亚迪股份有限公司 | Conducting photosensitive resin for 3D printing and preparation method thereof |
| CN103980675A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing aromatic polyester material and preparation method |
| CN104559196A (en) * | 2014-12-29 | 2015-04-29 | 大连理工常熟研究院有限公司 | Colorless and transparent light-cured 3D printing material |
| CN104877118A (en) * | 2015-06-18 | 2015-09-02 | 上海天洋热熔粘接材料股份有限公司 | Copolyester used as 3D printing material and preparation method of copolyester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106750417A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Preparation and properties of biodegradable poly (lactic acid)/poly (butylene adipate-co-terephthalate) blend with glycidyl methacrylate as reactive processing agent | |
| TWI302919B (en) | ||
| JP2017518396A (en) | Compositions and methods for composites impregnated with reactive compositions of polyamide prepolymers and diepoxide chain extenders | |
| Mashouf Roudsari et al. | A study of mechanical properties of biobased epoxy network: Effect of addition of epoxidized soybean oil and poly (furfuryl alcohol) | |
| CN103819621B (en) | A kind of preparation method of methylene-succinic acid class copolyesters of macromolecular network structure | |
| CN102174182A (en) | Unsaturated polyester resin for die pressing and preparation method thereof | |
| Mahata et al. | Poly (butylene adipate-co-terephthalate) polyester synthesis process and product development | |
| CN106883544A (en) | A kind of polyester 3D printing material with cross-linked structure and preparation method thereof | |
| CN106750417B (en) | A kind of Silicon-containing Polyester 3D printing material and preparation method thereof | |
| CN110591010B (en) | Water-resistant styrene-free artificial stone resin and preparation method thereof | |
| EP1044232A1 (en) | Reclaimed poly(ethylene terephthalate) coating | |
| CN106832308B (en) | Polyurethane modified polyester 3D printing material and preparation method thereof | |
| CN105504692A (en) | Toughened thermosetting epoxy resin composition and preparation method thereof | |
| WO2002042354A2 (en) | Polyester resins based on terephthalic acid and 2-methyl-1,3-propanediol and processes for the preparation thereof | |
| CN101063030B (en) | High molecular weight unsaturated polyester binding agent | |
| CN112961463A (en) | Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof | |
| CN103237830A (en) | Unsaturated polyester resins modified by substitution, with lactic acid, of an acid and alcohol component of the polyester | |
| US5177159A (en) | Polyhydroxy esters containing carboxyl end groups and their use | |
| JPH093181A (en) | Polyester resin and its production | |
| CN101200537B (en) | Thermoplastic composite material and preparation method thereof | |
| CN106832843A (en) | A kind of polyester 3D printing material of low melting point and preparation method thereof | |
| CN101560293A (en) | Pultrusion unsaturated polyester resin prepared from bio-alcohol and preparation method thereof | |
| JPH032261A (en) | Liquid crystal polyester resin composition | |
| CN101469062B (en) | Novel thermoplastic polyester-amides copolymer and preparation thereof | |
| CN107075230A (en) | Ester resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |