CN108440744A - A kind of preparation of high tenacity PET derivatives and its application process in 3D printing field - Google Patents
A kind of preparation of high tenacity PET derivatives and its application process in 3D printing field Download PDFInfo
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- CN108440744A CN108440744A CN201810198944.2A CN201810198944A CN108440744A CN 108440744 A CN108440744 A CN 108440744A CN 201810198944 A CN201810198944 A CN 201810198944A CN 108440744 A CN108440744 A CN 108440744A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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 of high tenacity PET derivatives and its application processes in 3D printing field, the preparation process of preparation process and printing wire rod including PET derivatives, the preparation process of PET derivatives includes esterification technique step and polycondensating process step, and the esterification technique includes the following steps：Diacid, glycol, catalyst, heat stabilizer and antioxidant are added in esterifier, in 120~250 DEG C, pressure to carry out esterification under the conditions of 20Kpa 100Kpa, react 0.5 3h.After esterification, esterifier is then warming up to 200~270 DEG C and carries out depressurization condensation reaction, reacts and terminates after 1 3h, discharging obtains formula PET derivatives.The PET derivative good toughness, it is longer than general PET cooling times, it can be used for preparing the PET wire rods of 3D printing.
Description
Technical field
The present invention relates to 3D printing field application field, the preparation of especially a kind of high tenacity PET derivatives and its 3D are beaten
The application process in print field.
Background technology
Representative art one of of the fusion sediment 3D printing technique as the third time industrial revolution, is that one kind passing through three-dimensional
CAD model data analysis and the technology that target object is formed by way of material successively fusion sediment.It can not only shorten
The production cycle of product, simplify the production routine of target product, and complex-shaped, unique structure solid can be printed.
It is a kind of very most common 3D printing technique that fusion sediment, which prints (FDM), it makes thermoplasticity material by the way of hot meltblown head
It after material fusing, is squeezed and gone out by nozzle, and be deposited on designated position postcooling molding.
The material of FDM is usually thermoplastic material, such as ABS, PLA, wax, nylon, PCL, is fed with coiled material.Material is spraying
It is melted by heating in head, nozzle is moved along part section profile and filling track, while the material of fusing being squeezed out, and material is rapid
Solidification, and with the condensation of materials of surrounding.Material for FDM type 3D printings must be thermoplasticity such as PLA, ABS, PCL etc. multiple
Condensation material.Since glass transition temperature (Tg) and fusing point (Tm) can influence complexity, the target print of material molten extrusion
The thermal stability of component and its shrinkage of cooling and shaping, therefore, printing consumables should have relatively low fusing point and suitable
Glass transition temperature.In addition, suitable crystalline rate, viscosity and enough mechanical properties (intensity, rigidity, toughness etc.) are
It can self-sustained, deposition forms the necessary condition of three-dimension object layer by layer.Currently, common printing consumables be mainly ABS and
PLA.But the price of ABS is higher than 400,000 yuan/ton, and taste is bigger, and the price of polylactic acid is higher than 500,000 yuan/ton, which prevent
The development of 3D printing technique.
For polyethylene terephthalate (PET) as one of five large-engineering plastics, price is low, and with good resistance to
Hot, electrical insulating property, chemical resistance, lubricity and excellent mechanical property, existing oneself is widely used in auto parts machinery and electronics
Appliance field.So in terms of being concentrated mainly on physical modification to the performance of PET and application study at present.Pure PET is outstanding due to it
Beam notch impact strength and non-notch impact strength are all smaller, and fracture is easily deformed under certain loading condition, is not inconsistent
Close 3D printing requirement.To solve the above-mentioned problems, it is prepared for modified PET herein by direct esterification and decompression condensation methods, be used for
The toughness of PET is improved, 3D printing field is used for.
Invention content
The purpose of the present invention is to solve defects of the existing technology, provide a kind of system of high tenacity PET derivatives
Standby and its 3D printing field application process.
To achieve the goals above, the technical solution adopted by the present invention is：
A kind of preparation of high tenacity PET derivatives and its application process in 3D printing field, include the preparation of PET derivatives
Step and the preparation process for printing wire rod, the preparation processes of PET derivatives include esterification technique step and polycondensating process step,
The esterification technique includes the following steps：Diacid, glycol, catalyst, heat stabilizer and antioxidant are added to esterifier
In, in 120~250 DEG C, pressure to carry out esterification under the conditions of 20Kpa-100Kpa, react 0.5-3h.
A kind of preparation of above-mentioned high tenacity PET derivatives and its application process in 3D printing field, esterification terminate
Afterwards, esterifier is then warming up to 200~270 DEG C and carries out depressurization condensation reaction, reacted and terminate after 1-3h, discharging obtains
Formula PET derivatives.
A kind of preparation of above-mentioned high tenacity PET derivatives and its application process in 3D printing field, the catalyst are
The concentrated sulfuric acid or concentrated hydrochloric acid, heat stabilizer are triethyl phosphate, and antioxidant is peroxide-decomposing type antioxidant.
A kind of preparation of above-mentioned high tenacity PET derivatives and its application process in 3D printing field, the printing wire rod
Preparation process include：By PET derivatives, ASA, toughener, compatilizer, ultraviolet absorber, lubricant, the antioxygen of the preparation
Agent and filler are uniformly mixed, and obtain mixed material；
Mixed material is added in double screw extruder, after dragger pelletizing, obtains PET/ASA alloy granules
Son；
PET/ASA alloy particles are added in the single screw extrusion machine of 3D wire rod production lines, single screw extrusion machine die orifice
The PET/ASA wire rods of extrusion obtain extrusion of wire through supercooling；
Extrusion of wire is rolled into bundle using coil winder, obtains PET/ASA 3D printing wire rods.
Beneficial effects of the present invention are：The PET derivative good toughness, it is longer than general PET cooling times, it can be used for preparing 3D
The PET wire rods of printing.Current material ABS and PLA source material costs are more expensive at present, and PET provided by the invention derives raw material
Abundance and at low cost, and directly prepared by chemical modification, reduce later stage modified process.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific implementation mode
As shown in Figure 1, a kind of preparation of high tenacity PET derivatives and its application process in 3D printing field, including PET spread out
The preparation process of biology and the preparation process for printing wire rod, the preparation process of PET derivatives includes esterification technique step and contracting
Polymerizing technology step, the esterification technique include the following steps：Diacid, glycol, catalyst, heat stabilizer and antioxidant are added to
In esterifier, in 120~250 DEG C, pressure to carry out esterification under the conditions of 20Kpa-100Kpa, 0.5-3h is reacted.
After esterification, esterifier is then warming up to 200~270 DEG C and carries out depressurization condensation reaction, 1-
Reaction terminates after 3h, and discharging obtains formula PET derivatives.
Wherein, the catalyst is the concentrated sulfuric acid or concentrated hydrochloric acid, heat stabilizer are triethyl phosphate, and antioxidant is peroxidating
Object breakdown type antioxidant.
It is described printing wire rod preparation process include：By PET derivatives, ASA, toughener, compatilizer, the purple of the preparation
Outer absorbent, lubricant, antioxidant and filler are uniformly mixed, and obtain mixed material；
Mixed material is added in double screw extruder, after dragger pelletizing, obtains PET/ASA alloy granules
Son；
PET/ASA alloy particles are added in the single screw extrusion machine of 3D wire rod production lines, single screw extrusion machine die orifice
The PET/ASA wire rods of extrusion obtain extrusion of wire through supercooling；
Extrusion of wire is rolled into bundle using coil winder, obtains PET/ASA 3D printing wire rods.
The PET derivative good toughness, it is longer than general PET cooling times, it can be used for preparing the PET wire rods of 3D printing.Mesh
Preceding current material ABS and PLA source material costs are more expensive, and PET derivatives raw material sources provided by the invention are abundant and at low cost, and
It is directly prepared by chemical modification, reduces later stage modified process.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection domain by appended claims and its
Equivalent defines.
Claims (4)
1. a kind of preparation of high tenacity PET derivatives and its application process in 3D printing field include the preparation step of PET derivatives
Rapid and printing wire rod preparation process, which is characterized in that the preparation process of PET derivatives includes esterification technique step and polycondensation
Processing step, the esterification technique include the following steps：Diacid, glycol, catalyst, heat stabilizer and antioxidant are added to ester
Change in reactor, in 120~250 DEG C, pressure to carry out esterification under the conditions of 20Kpa-100Kpa, reacts 0.5-3h.
2. a kind of preparation of high tenacity PET derivatives according to claim 1 and its application process in 3D printing field,
It is characterized in that, after esterification, esterifier is then warming up to 200~270 DEG C and carries out depressurization condensation reaction, 1-
Reaction terminates after 3h, and discharging obtains formula PET derivatives.
3. a kind of preparation of high tenacity PET derivatives according to claim 1 and its application process in 3D printing field,
It is characterized in that, the catalyst is the concentrated sulfuric acid or concentrated hydrochloric acid, heat stabilizer are triethyl phosphate, and antioxidant is peroxide point
Solution type antioxidant.
4. a kind of preparation of high tenacity PET derivatives according to claim 1 and its application process in 3D printing field,
It is characterized in that, the preparation process of the printing wire rod includes：By the PET derivatives of the preparation, ASA, toughener, compatilizer,
Ultraviolet absorber, lubricant, antioxidant and filler are uniformly mixed, and obtain mixed material；
Mixed material is added in double screw extruder, after dragger pelletizing, obtains PET/ASA alloy particles；
PET/ASA alloy particles are added in the single screw extrusion machine of 3D wire rod production lines, single screw extrusion machine die orifice squeezes out
PET/ASA wire rods through supercooling, obtain extrusion of wire；
Extrusion of wire is rolled into bundle using coil winder, obtains PET/ASA 3D printing wire rods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810198944.2A CN108440744A (en) | 2018-03-12 | 2018-03-12 | A kind of preparation of high tenacity PET derivatives and its application process in 3D printing field |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810198944.2A CN108440744A (en) | 2018-03-12 | 2018-03-12 | A kind of preparation of high tenacity PET derivatives and its application process in 3D printing field |
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| Publication Number | Publication Date |
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| CN108440744A true CN108440744A (en) | 2018-08-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810198944.2A Pending CN108440744A (en) | 2018-03-12 | 2018-03-12 | A kind of preparation of high tenacity PET derivatives and its application process in 3D printing field |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440596A (en) * | 2015-11-29 | 2016-03-30 | 福建师范大学 | Highly weather-proof PBT (polybutylene terephthalate)/ASA (acrylonitrile styrene acrylate) wire for 3D printing and preparation method of PBT/ASA wire |
| CN106065067A (en) * | 2016-06-01 | 2016-11-02 | 昆山天洋热熔胶有限公司 | A kind of copolyesters being adapted as 3D printed material and preparation method thereof |
| CN106866948A (en) * | 2015-12-11 | 2017-06-20 | 清华大学 | A kind of copolyesters of amorphous state and preparation method thereof |
| CN107286331A (en) * | 2017-08-03 | 2017-10-24 | 北京化工大学 | A kind of 3D printing polyester material and preparation method thereof |
-
2018
- 2018-03-12 CN CN201810198944.2A patent/CN108440744A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440596A (en) * | 2015-11-29 | 2016-03-30 | 福建师范大学 | Highly weather-proof PBT (polybutylene terephthalate)/ASA (acrylonitrile styrene acrylate) wire for 3D printing and preparation method of PBT/ASA wire |
| CN106866948A (en) * | 2015-12-11 | 2017-06-20 | 清华大学 | A kind of copolyesters of amorphous state and preparation method thereof |
| CN106065067A (en) * | 2016-06-01 | 2016-11-02 | 昆山天洋热熔胶有限公司 | A kind of copolyesters being adapted as 3D printed material and preparation method thereof |
| CN107286331A (en) * | 2017-08-03 | 2017-10-24 | 北京化工大学 | A kind of 3D printing polyester material and preparation method thereof |
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Application publication date: 20180824 |