CN106947204A - 3D printing reversible sensitization discoloration PHA composites and its preparation method and purposes - Google Patents
3D printing reversible sensitization discoloration PHA composites and its preparation method and purposes Download PDFInfo
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- CN106947204A CN106947204A CN201710234518.5A CN201710234518A CN106947204A CN 106947204 A CN106947204 A CN 106947204A CN 201710234518 A CN201710234518 A CN 201710234518A CN 106947204 A CN106947204 A CN 106947204A
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- pha
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- sensitization discoloration
- reversible
- color
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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
- C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- 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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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 invention discloses a kind of for reversible sensitization discoloration PHA composites of 3D printing and its preparation method and application, the material is made by PHA resins, color masterbatch, inorganic filler, plasticizer, light diffusing agent, ultra-violet absorber and antioxidant, described color masterbatch is made up of PHA resins, dispersant and colouring agent, colouring agent is made up of more than one ability of reverse photochromism powder, or is formed by more than one ability of reverse photochromism powder with pigment color-matching.3D printing prepared by the present invention is being kept outside the good biological degradabilities of PHA and biocompatibility with reversible sensitization discoloration PHA material, moreover it is possible to produce color change under different uitraviolet intensity irradiations, and this change procedure is reversible.In actual applications, the photochromic powder with different color changeable effects can be selected according to environmental demand.
Description
Technical field
The invention belongs to 3D printing Material Field, and in particular to a kind of reversible sensitization discoloration PHA for 3D printing is combined
Material and its preparation method and application.
Background technology
It is all multi-party that 3D printing combines digital modeling techniques, Electromechanical Control technology, information technology, material science and chemistry etc.
The technological know-how in face, is a kind of comprehensive application technology.3D printing technique mainly using discrete-superposition forming principle, that is, is layered
Manufacture, is successively superimposed, has broken away from traditional " removal " processing method.Because formed precision is high, utilization rate of raw materials is high, personalized strong
The features such as, 3D printing technique has been successfully applied to every field.3D printing technique includes a variety of forming methods, wherein melting heap
Product shaping (FDM) safeguards simple due to not using laser to do the energy, low cost, and silk material cleans, changes easy, and post processing is simple
The advantages of, quickly grow, it is adaptable to thermoplastic.
Polyhydroxyalkanoate (PHA) is a class intracellular polyester of bacterium intracellular synthesis, is a kind of natural biological high score
Sub- material.Due to PHA mechanical property and some thermoplastics such as polyethylene, PP type seemingly, but can it is degradable enter
Enter the ecological circulation of nature, not only with the physicochemical characteristic similar to synthetic plastic but also with the biology not available for synthetic plastic
Degradability, bio-compatibility, optical activity, piezoelectricity, gas phase are every many excellent in performance such as property.
It is extensive that the diversity of PHA structures makes it have in terms of degradable package material, utensil class material, electronic product
Application, with reference to photochromic material in the application in the fields such as packaging, decoration, storage, exploitation diversity and functional PHA are answered
Condensation material can expand the species of 3D printing material, meet need of the people to 3D printing product in terms of variation with functionalization
Ask.
The content of the invention
In order to fill up the blank of prior art, primary and foremost purpose of the invention is to provide a kind of PHA of reversible sensitization discoloration
Composite, the material can produce the change of color under ultraviolet irradiation, and this change procedure is reversible.
Another object of the present invention is to provide the preparation method of above-mentioned reversible sensitization discoloration PHA composites.
It is still another object of the present invention to provide application of the above-mentioned reversible sensitization discoloration PHA composites in 3D printing.
The purpose of the present invention is achieved through the following technical solutions：
A kind of reversible sensitization discoloration PHA composites, are made up of the composition of following parts by weight：
Described inorganic filler is one or more of barium sulfate, calcium carbonate, silica or titanium dioxide, and particle diameter is less than
5μm；
Described plasticizer is ATBC (tributyl 2-acetylcitrate), PEG (polyethylene glycol) 200 or triethyl citrate
One or more of (TEC)；
The preferred organosilicon light diffusing agent of described light diffusing agent or acrylic acid light diffusing agent, average grain diameter are less than 5 μm；
Described ultra-violet absorber is 2-hydroxy-4-n-octoxybenzophenone (UV-531), 2- hydroxyl -4- methoxyl groups
One in benzophenone (UV-9) or 2'- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chlorobenzotriazoles (UV-326)
More than kind；
Described antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester (antioxidant
1010), β-positive octadecanol ester (antioxidant 1076) of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid or thio-2 acid are bimonthly
One or more of osmanthus ester (anti-oxidant DLTP).
In above-mentioned formula, the compatibility of inorganic filler and resin is good, while dispersiveness and good fluidity, are not only increased
The mobility of composite processing, improves the mechanical property of composite；The specific surface area of another aspect filler is big, and light passes through
Anaclasis is acted on particle surface many times, reaches the purpose of light diffusion.
Described color masterbatch is made up of the composition of following mass percent：
PHA resins：70-85%
Dispersant：10-15%
Colouring agent：5-15%；
The preferred extrusion grade of PHA resins of the present invention, and pretreatment is grafted with methyl methacrylate monomer, to change
Kind PHA crystallinity；
Described dispersant is one or more of Tissuemat E, stearic acid sodium, atoleine or white oil；
Described colouring agent is made up of more than one ability of reverse photochromism powder, or by the reversible photic of more than one
Color-change powder is formed with pigment color-matching；The specific species and consumption of ability of reverse photochromism powder are selected according to required color change
Select；The color changeable effect of color masterbatch is realized by ability of reverse photochromism powder, because the color change of color-change powder is limited, can be with
By with common pigments colorant match, increase color diversity；
When described colouring agent is formed by more than one ability of reverse photochromism powder and pigment color-matching, pigment accounts for reversible photic
The 0.5-2.5% of color-change powder quality；
The particle diameter of the colouring agent is preferably smaller than 10 μm, to avoid the wire rod prepared from blocking syringe needle when 3D printing is molded.
The preparation method of the PHA composites of above-mentioned ability of reverse photochromism, comprises the following steps：
PHA resins, dispersant and colouring agent are well mixed, color masterbatch is obtained；By PHA resins, color masterbatch, inorganic fill out
Material, plasticizer, light diffusing agent, ultra-violet absorber and antioxidant are uniformly mixed, by mechanical-moulded, and being obtained after cooling can
The PHA composites of nagative photochromism；
The rotating speed of the stirring is 50-200rpm, and mixing time is 5-25min；
Described mechanical-moulded preferred extrusion molding, forming machine is single screw rod or double screw extruder, and the type of cooling is water
It is cold；
It is further preferred that mechanical-moulded step is：Double screw extruder non-slurry pelletizing is first used, it is equal to improve pellet
Even property, using secondary or multiple granulation process, after pellet is dried, reuses wire rod needed for single screw extrusion machine is made.
Reversible sensitization discoloration PHA composites produced by the present invention can be applied in 3D printing, can be used as a kind of additive
It is added in plastics, intelligent equipment and articles for use with sensitization discoloration function is made, packaging, false proof, art is can be additionally used in addition
The fields such as product, toy and mark.
The present invention has the following advantages and effect relative to prior art：
(1) 3D printing prepared by the present invention is keeping the good biological degradabilities of PHA with reversible sensitization discoloration PHA material
Outside biocompatibility, moreover it is possible to produce color change under different uitraviolet intensity irradiations, and this change procedure is reversible.
In practical application, the photochromic powder with different color changeable effects can be selected according to environmental demand.
(2) in the present invention, the addition of photochromic powder easily causes the generation of light fatigue, causes system unstable.It is ultraviolet
The synergy of light absorbers and antioxidant, can not only increase the anti-light endurance of composite, moreover it is possible to slow down PHA and aoxidized
The progress of journey, suppresses PHA thermal degradation, improves the heat resistance of material, to adding unstable caused by a small amount of color-change powder act on
To coordination function.
Embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
The extrusion grade PHA plastics used in the embodiment of the present invention are purchased from Shenzhen Yi Keman EM40010, photochromic powder
Purchased from extensive and profound in meaning safety anti-fake Technology Co., Ltd. of Shenzhen.
Embodiment 1
A kind of reversible sensitization discoloration PHA composites of 3D printing, are made up of the composition of following parts by weight：
Wherein color masterbatch is made up of the composition of following parts by weight：
PHA resins：85 parts
Tissuemat E：10 parts
Photochromic powder：5 parts；
Wherein photochromic powder is changed into aubergine under ultraviolet irradiation from colourless.
The preparation method of above-mentioned PHA composites comprises the following steps：
PHA resins, dispersant and colouring agent are well mixed, color masterbatch is obtained；By PHA resins, color masterbatch, inorganic fill out
Material, plasticizer, light diffusing agent, ultra-violet absorber and antioxidant stir 5-25min under 50-200rpm, are well mixed it.
By material by double screw extruder, under the booster action of water-cooled, then secondary granulation reuses single screw extrusion machine into line
Material, is made 3D printing with reversible sensitization discoloration PHA composites.
Wire rod made from the present embodiment, in colourless, irradiate time-varying aubergine in ultraviolet, then moves to shady spot in shady spot
When become again again it is colourless.
Embodiment 2
A kind of reversible sensitization discoloration PHA composites of 3D printing, are made up of the composition of following parts by weight：
Wherein color masterbatch is made up of the composition of following parts by weight：
PHA resins：80 parts
Stearic acid sodium：12 parts
Photochromic powder：8 parts；
Wherein photochromic powder is changed into blueness under ultraviolet irradiation from colourless.
The preparation method be the same as Example 1 of PHA composites.
Wire rod made from the present embodiment, in colourless, irradiates time-varying blueness, when then moving to shady spot in shady spot in ultraviolet
Become again again colourless.
Embodiment 3
A kind of reversible sensitization discoloration PHA composites of 3D printing, are made up of the composition of following parts by weight：
Wherein color masterbatch is made up of the composition of following parts by weight：
PHA resins：70 parts
Atoleine：15 parts
Photochromic powder：15 parts；
Wherein photochromic powder is changed into yellow under ultraviolet irradiation from colourless.
The preparation method be the same as Example 1 of PHA composites.
Wire rod made from the present embodiment, in colourless, irradiates time-varying yellow, when then moving to shady spot in shady spot in ultraviolet
Become again again colourless.
Embodiment 4
A kind of reversible sensitization discoloration PHA composites of 3D printing, are made up of the composition of following parts by weight：
Wherein color masterbatch is made up of the composition of following parts by weight：
Wherein photochromic powder is changed into yellow under ultraviolet irradiation from colourless, and common pigments are blueness.
The preparation method be the same as Example 1 of PHA composites.
Wire rod made from the present embodiment, in green, irradiates time-varying yellow, when then moving to shady spot in shady spot in ultraviolet
Become green again again.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of reversible sensitization discoloration PHA composites, it is characterised in that be made up of the composition of following parts by weight：
Described color masterbatch is made up of the composition of following mass percent：
PHA resins：70-85%
Dispersant：10-15%
Colouring agent：5-15%；
Described colouring agent is made up of more than one ability of reverse photochromism powder, or by more than one ability of reverse photochromism
Powder is formed with pigment color-matching.
2. reversible sensitization discoloration PHA composites according to claim 1, it is characterised in that：Described colouring agent is by one
When the ability of reverse photochromism powder and pigment color-matching for planting the above are formed, pigment accounts for the 0.5-2.5% of ability of reverse photochromism silty amount.
3. reversible sensitization discoloration PHA composites according to claim 1, it is characterised in that：Described PHA resins are crowded
Go out level, and pretreatment is grafted with methyl methacrylate monomer.
4. reversible sensitization discoloration PHA composites according to claim 1, it is characterised in that：Described inorganic filler is
One or more of barium sulfate, calcium carbonate, silica or titanium dioxide, particle diameter are less than 5 μm.
5. reversible sensitization discoloration PHA composites according to claim 1, it is characterised in that：Described plasticizer is second
One or more of acyl ATBC, polyethylene glycol 200 or triethyl citrate.
6. reversible sensitization discoloration PHA composites according to claim 1, it is characterised in that：Described light diffusing agent is
Organosilicon light diffusing agent or acrylic acid light diffusing agent, average grain diameter are less than 5 μm.
7. reversible sensitization discoloration PHA composites according to claim 1, it is characterised in that：
Described ultra-violet absorber be 2-hydroxy-4-n-octoxybenzophenone, ESCALOL 567 or
One or more of 2'- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chlorobenzotriazoles；
Described antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, β-(the tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyls) one or more of the positive octadecanol ester of propionic acid or the double lauryls (anti-oxidant DLTP) of thio-2 acid.
8. reversible sensitization discoloration PHA composites according to claim 1, it is characterised in that：Described dispersant is poly-
One or more of ethylene waxes, stearic acid sodium, atoleine or white oil.
9. the preparation method of the ability of reverse photochromism PHA composites described in claim any one of 1-8, it is characterised in that including
Following steps：
PHA resins, dispersant and colouring agent are well mixed, color masterbatch is obtained；By PHA resins, color masterbatch, inorganic filler, increasing
Modeling agent, light diffusing agent, ultra-violet absorber and antioxidant are uniformly mixed, by mechanical-moulded, and being obtained after cooling can backlight
The PHA composites of mutagens color.
10. application of the ability of reverse photochromism PHA composites in 3D printing described in claim any one of 1-8.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710234518.5A CN106947204A (en) | 2017-04-11 | 2017-04-11 | 3D printing reversible sensitization discoloration PHA composites and its preparation method and purposes |
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| CN201710234518.5A CN106947204A (en) | 2017-04-11 | 2017-04-11 | 3D printing reversible sensitization discoloration PHA composites and its preparation method and purposes |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003718A (en) * | 2019-01-08 | 2019-07-12 | 蔡昕运 | The method of photic changeable colour toner and ink, the photic changeable colour vessel surface of production |
| CN110294932A (en) * | 2019-03-29 | 2019-10-01 | 绍兴文理学院元培学院 | A kind of flexible compound pressure sensitive for 3D printing |
| CN110527262A (en) * | 2019-09-16 | 2019-12-03 | 苏州宝丽迪材料科技股份有限公司 | Photochromic polyester fiber master batch and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462201A (en) * | 2015-12-23 | 2016-04-06 | 江苏道勤新材料科技有限公司 | Polyhydroxybutyrate-based degradable 3D (Three Dimensional) printing supplies |
| CN105482241A (en) * | 2016-02-16 | 2016-04-13 | 湖北工程学院 | Reversible thermochromic insulating sheath material and preparation method thereof |
| CN105524399A (en) * | 2015-12-29 | 2016-04-27 | 银禧工程塑料（东莞）有限公司 | A 3D printing polymer material and a preparing method thereof |
-
2017
- 2017-04-11 CN CN201710234518.5A patent/CN106947204A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462201A (en) * | 2015-12-23 | 2016-04-06 | 江苏道勤新材料科技有限公司 | Polyhydroxybutyrate-based degradable 3D (Three Dimensional) printing supplies |
| CN105524399A (en) * | 2015-12-29 | 2016-04-27 | 银禧工程塑料（东莞）有限公司 | A 3D printing polymer material and a preparing method thereof |
| CN105482241A (en) * | 2016-02-16 | 2016-04-13 | 湖北工程学院 | Reversible thermochromic insulating sheath material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003718A (en) * | 2019-01-08 | 2019-07-12 | 蔡昕运 | The method of photic changeable colour toner and ink, the photic changeable colour vessel surface of production |
| CN110294932A (en) * | 2019-03-29 | 2019-10-01 | 绍兴文理学院元培学院 | A kind of flexible compound pressure sensitive for 3D printing |
| CN110527262A (en) * | 2019-09-16 | 2019-12-03 | 苏州宝丽迪材料科技股份有限公司 | Photochromic polyester fiber master batch and preparation method thereof |
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