CN106893285A - 3D printing reversible temperature-sensitive discoloration PHA material and its preparation method and application - Google Patents
3D printing reversible temperature-sensitive discoloration PHA material and its preparation method and application Download PDFInfo
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- CN106893285A CN106893285A CN201710220006.3A CN201710220006A CN106893285A CN 106893285 A CN106893285 A CN 106893285A CN 201710220006 A CN201710220006 A CN 201710220006A CN 106893285 A CN106893285 A CN 106893285A
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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
-
- 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
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/06—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
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- 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 reversible temperature-sensitive discoloration PHA material for 3D printing and its preparation method and application, the material is made up of PHA plastics, color masterbatch, inorganic filler, plasticizer and dispersant；Described color masterbatch is made up of PHA plastics, dispersant and colouring agent；Described colouring agent is made up of more than one heat discoloration powder, or is formed with pigment color-matching by more than one heat discoloration powder.3D printing prepared by present invention reversible temperature-sensitive discoloration PHA material, outside the biological degradability and biocompatibility for keeping PHA good, moreover it is possible to the change of color is produced under different operating temperatures, and this change procedure is reversible.Because warm color-change powder has different discoloring temperatures interval and color changeable effect, therefore can select that there is different temperatures constant interval and color changeable effect according to the requirement of working environment.
Description
Technical field
The invention belongs to 3D printing Material Field, and in particular to a kind of reversible temperature-sensitive discoloration PHA material for 3D printing
And its preparation method and application.
Background technology
3D printing technique starts to be developed so far since the eighties in 20th century, because formed precision is high, utilization rate of raw materials is high,
Personalized strong the features such as, it is applied in the requirement such as naval vessels, Aero-Space, medical treatment field higher.Current 3D printing technique
The mode and principle of conventionally manufactured industry have been overturned, but 3D printing material shortcoming turns into the Main Bottleneck of limitation 3D printing development,
It is also key point and the difficult point place of 3D printing breakthrough and innovation.
Polyhydroxyalkanoate (PHA) is the linear polyester that a class is made up of the hydroxy fatty acid of Microbe synthesis, is one
Plant under appropriate natural environmental condition, the Biodegradable material of low molecular compound can be decomposed by the microorganisms into.PHA exists
Exist primarily as the Stored Matter of carbon source and the energy in organism, with good biocompatibility, biodegradation
Property, the hot-workability of plastics, optical activity, piezoelectricity, gas phase are every performances such as property.PHA biodegradable packaging material,
Tissue engineering material, slow-release material, electricity material and medical material aspect have broad application prospects.
As society is increasingly partial to the demand of 3D printing product variation and functionalization, therefore exploitation diversity and work(
The PHA material of energy property is determined to carry out sth important.Current Reversible Thermochromic Materials are applied in fields such as industry, medical treatment, lives, but use
Change colour PHA material also without related report in the reversible temperature-sensitive of 3D printing forming technique.
The content of the invention
Primary and foremost purpose of the invention is to provide a kind of reversible temperature-sensitive discoloration PHA material for 3D printing, this material
Outside the biological degradability and biocompatibility for keeping PHA good, moreover it is possible to the change of color is produced under different operating temperatures,
And this change procedure is reversible.
Another object of the present invention is to provide the preparation method that above-mentioned 3D printing reversible temperature-sensitive changes colour PHA material.
It is still another object of the present invention to provide application of the above-mentioned reversible temperature-sensitive discoloration PHA material in 3D printing.
The purpose of the present invention is achieved through the following technical solutions：
A kind of reversible temperature-sensitive changes colour PHA material, by following parts by weight into being grouped into：
Described inorganic filler is one or more of micron order modified montmorillonoid, nano zine oxide or nano silicon oxide；
Described micron order modified montmorillonoid is APTES (aminopropyl triethoxysilane) or the modified illiteracy of titanate takes off
Soil.
Described plasticizer is in ATBC (tributyl 2-acetylcitrate), PEG (polyethylene glycol) 200 or pentaerythrite
More than kind.
In above-mentioned formula, the use of inorganic filler not only reduces production cost, improves the tensile strength of PHA resins
And elastic modelling quantity；On the other hand, inorganic filler as nucleator, can improve the percent crystallization in massecuite and heat endurance of PHA, improve temperature-sensitive
The unstability of the system that the addition of color-change powder causes.
Described color masterbatch is by following mass percent into being grouped into：
PHA plastics：45-65%
Dispersant：10-15%
Colouring agent：20-40%.
The preferred extrusion grade of PHA plastics of the present invention, and be to be grafted to pre-process with methyl methacrylate monomer, use
In the crystallinity for improving PHA.
Dispersant of the present invention is one or more of atoleine, Tissuemat E, odium stearate or white oil.
Described colouring agent is made up of more than one heat discoloration powder, or heat discoloration powder by more than one with
Pigment color-matching is formed；Discoloring temperature and color change of the specific species and consumption of heat discoloration powder according to needed for are selected；
The color changeable effect of color masterbatch is realized by heat discoloration powder, because the color change of color-change powder is limited, can by with
Common pigments colorant match, increases the diversity of color.
When described colouring agent is formed by more than one heat discoloration powder and pigment color-matching, pigment accounts for heat discoloration silty
The 0.5-2.5% of amount；
The particle diameter of the colouring agent is preferably smaller than 10 μm, to avoid the wire rod for preparing from blocking syringe needle when 3D printing is molded.
The preparation method of above-mentioned reversible temperature-sensitive discoloration PHA material, comprises the following steps：
PHA plastics, dispersant and colouring agent are well mixed, color masterbatch is obtained；By PHA plastics, color masterbatch, inorganic fill out
Material, plasticizer and dispersant are uniformly mixed, and by mechanical-moulded, the reversible temperature-sensitive discoloration of 3D printing are obtained after cooling
PHA material；
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 obtained.
Obtained reversible temperature-sensitive discoloration PHA material of the invention can apply in 3D printing, can add as a kind of additive
It is added in plastics or is used alone, be made intelligent equipment and articles for use with temperature-sensing discoloration function, can also be used to pack in addition, prevents
The fields such as puppet, the art work, medical treatment.
The present invention has the following advantages and effect relative to prior art：
(1) 3D printing prepared by present invention reversible temperature-sensitive discoloration PHA material, in the biological degradability for keeping PHA good
Outside biocompatibility, moreover it is possible to the change of color is produced under different operating temperatures, and this change procedure is reversible.Due to temperature
Color-change powder has different discoloring temperatures interval and color changeable effect, therefore can be selected with not according to the requirement of working environment
Synthermal constant interval and color changeable effect.
(2) compared with prior art, present invention process is simple, there is provided composite can be made with heat discoloration work(
The intelligent equipment and articles for use of energy, such as intelligent appliance, film, carrier with alarm function, can also be used to pack in addition, prevent
The fields such as puppet, the art work, medical treatment.
(3) in the present invention, easy unstable, the inorganic filler for causing system heat-resisting with ageing-resistant performance of addition of color-change powder
Use not only reduce production cost, the tensile strength and elastic modelling quantity of PHA resins are improve, while inorganic filler can be made
It is nucleator, improves the percent crystallization in massecuite and heat endurance of PHA, improves the stability of system.
Specific 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 (methyl methacrylate monomer grafting pretreatment) used in the embodiment of the present invention are deep
The EM40010 of ditch between fields Yi Keman, heat discoloration powder is purchased from extensive and profound in meaning safety anti-fake Technology Co., Ltd. of Shenzhen.
Embodiment 1
A kind of 3D printing reversible temperature-sensitive changes colour PHA material, by following parts by weight into being grouped into：
Wherein color masterbatch by following parts by weight into being grouped into：
PHA plastics：65 parts
White oil：10 parts
Heat discoloration powder：25 parts；
Wherein heat discoloration powder selection discoloring temperature is 33 DEG C, and its color is changed into blue from purple when reaching 33 DEG C from room temperature
Color.
The preparation method of above-mentioned PHA material is comprised the following steps：
PHA plastics, dispersant and colouring agent are well mixed, color masterbatch is obtained；By PHA plastics, color masterbatch, inorganic fill out
Material, plasticizer and dispersant stir 5-25min under 50-200rpm, are well mixed it.Material is passed through into twin-screw extrusion
Machine, under the booster action of water-cooled, then secondary granulation reuses single screw extrusion machine into wire rod, and 3D printing is obtained with reversible
Heat discoloration PHA material；
Wire rod obtained in the present embodiment is at normal temperatures purple, 33 DEG C of time-varying au bleus is heated to, when being cooled to room temperature
Become purple again again.
Embodiment 2
A kind of 3D printing reversible temperature-sensitive changes colour PHA material, by following parts by weight into being grouped into：
Wherein color masterbatch by following parts by weight into being grouped into：
PHA plastics：58 parts
Odium stearate：12 parts
Heat discoloration powder：30 parts；
Wherein heat discoloration powder is constituted by two kinds, and one kind is discoloring temperature for 33 DEG C, when reaching 33 DEG C by room temperature color by
Blueness becomes colorless；Another discoloring temperature is 55 DEG C, and its color is changed into orange from colourless when reaching 55 DEG C from normal temperature.Two kinds of senses
The quality of warm color-change powder is impartial.
Preparation method is with embodiment 1.
Wire rod obtained in the present embodiment is colourless in 33-55 DEG C of display, and blueness is shown when being spent less than 33 DEG C, higher than 55
DEG C when show orange, and color developing effect is reversible.
Embodiment 3
A kind of 3D printing reversible temperature-sensitive changes colour PHA material, by following parts by weight into being grouped into：
Wherein color masterbatch by following parts by weight into being grouped into：
Wherein heat discoloration powder selection discoloring temperature is 15 DEG C, is red when environment temperature is less than 15 DEG C, higher than 15 DEG C
When its color by red bleach, the color of common pigments is green.
Preparation method is with embodiment 1.
Wire rod obtained in the present embodiment is in yellow when less than 15 DEG C, and temperature becomes green, is cooled to when being higher than 15 DEG C
Yellow is become again again at 15 DEG C or less.
Embodiment 4
A kind of 3D printing reversible temperature-sensitive changes colour PHA material, by following parts by weight into being grouped into：
Wherein color masterbatch by following parts by weight into being grouped into：
PHA plastics：45 parts
Tissuemat E：15 parts
Heat discoloration powder：40 parts；
Wherein heat discoloration powder selection discoloring temperature is 45 DEG C, and when ambient temperature is higher than 45 DEG C, its color is by purple
It is changed into red.
Preparation method is with embodiment 1.
Wire rod obtained in the present embodiment is in purple when less than 45 DEG C, and temperature becomes red, is cooled to when being higher than 45 DEG C
Purple is become again again at 45 DEG C or less.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of reversible temperature-sensitive discoloration PHA material, it is characterised in that：It is into being grouped into by following parts by weight：
Described color masterbatch is by following mass percent into being grouped into：
PHA plastics：45-65%
Dispersant：10-15%
Colouring agent：20-40%；
Described colouring agent is made up of more than one heat discoloration powder, or by more than one heat discoloration powder and pigment
Colorant match is formed.
2. reversible temperature-sensitive according to claim 1 discoloration PHA material, it is characterised in that：Described colouring agent by one kind with
On heat discoloration powder and pigment color-matching when forming, pigment accounts for the 0.5-2.5% of heat discoloration silty amount.
3. reversible temperature-sensitive according to claim 1 discoloration PHA material, it is characterised in that：Described PHA plastics are extrusions
Level, and be to be grafted to pre-process with methyl methacrylate monomer.
4. reversible temperature-sensitive according to claim 1 discoloration PHA material, it is characterised in that：Described inorganic filler is micron
One or more of level modified montmorillonoid, nano zine oxide or nano silicon oxide.
5. reversible temperature-sensitive according to claim 4 discoloration PHA material, it is characterised in that：Described micron order is modified to cover de-
Soil is APTES or the modified montmorillonite of titanate.
6. reversible temperature-sensitive according to claim 1 discoloration PHA material, it is characterised in that：Described plasticizer be ATBC,
One or more of PEG200 or pentaerythrite.
7. reversible temperature-sensitive according to claim 1 discoloration PHA material, it is characterised in that：Described dispersant is liquid stone
One or more of wax, Tissuemat E, odium stearate or white oil.
8. described in any one of claim 1-7 reversible temperature-sensitive change colour PHA material preparation method, it is characterised in that including following step
Suddenly：
PHA plastics, dispersant and colouring agent are well mixed, color masterbatch is obtained；By PHA plastics, color masterbatch, inorganic filler, increasing
Modeling agent and dispersant are uniformly mixed, and by mechanical-moulded, the reversible temperature-sensitive discoloration PHA materials of 3D printing are obtained after cooling
Material.
9. according to claim 8 reversible temperature-sensitive change colour PHA material preparation method, it is characterised in that：Mechanical-moulded step
Suddenly it is：Double screw extruder non-slurry pelletizing is first used, to improve pellet uniformity, secondary or multiple granulation process, pellet is used
After drying, wire rod needed for single screw extrusion machine is obtained is reused.
10. application of the reversible temperature-sensitive discoloration PHA material described in any one of claim 1-7 in 3D printing.
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Cited By (4)
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| CN107353665A (en) * | 2017-07-10 | 2017-11-17 | 晋江瑞碧科技有限公司 | Reversible thermochromic 3D printing elastic wire composition and preparation method thereof |
| CN107550627A (en) * | 2017-09-30 | 2018-01-09 | 上海创始实业（集团）有限公司 | Cold/hot dressing product with temperature warning function |
| CN107652620A (en) * | 2017-09-30 | 2018-02-02 | 浙江三赢新材料有限公司 | Packaging material with heat discoloration ability and preparation method thereof |
| CN113831704A (en) * | 2021-08-10 | 2021-12-24 | 珠海市三绿实业有限公司 | Biodegradable PHA composite material for 3D printer consumable and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353665A (en) * | 2017-07-10 | 2017-11-17 | 晋江瑞碧科技有限公司 | Reversible thermochromic 3D printing elastic wire composition and preparation method thereof |
| CN107550627A (en) * | 2017-09-30 | 2018-01-09 | 上海创始实业（集团）有限公司 | Cold/hot dressing product with temperature warning function |
| CN107652620A (en) * | 2017-09-30 | 2018-02-02 | 浙江三赢新材料有限公司 | Packaging material with heat discoloration ability and preparation method thereof |
| CN113831704A (en) * | 2021-08-10 | 2021-12-24 | 珠海市三绿实业有限公司 | Biodegradable PHA composite material for 3D printer consumable and preparation method thereof |
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Application publication date: 20170627 |