CN108264725A - A kind of high compression ratio 3D high emulates the preparation method and product for model of bootstrapping - Google Patents
A kind of high compression ratio 3D high emulates the preparation method and product for model of bootstrapping Download PDFInfo
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- CN108264725A CN108264725A CN201810123427.9A CN201810123427A CN108264725A CN 108264725 A CN108264725 A CN 108264725A CN 201810123427 A CN201810123427 A CN 201810123427A CN 108264725 A CN108264725 A CN 108264725A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- B33Y10/00—Processes of additive manufacturing
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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
- 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
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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
- 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
- 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
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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
Abstract
The present invention relates to the preparation methods and product that a kind of high compression ratio 3D high emulates model of bootstrapping, and belong to technical field of polymer materials, this method mainly includes the following steps：(1) the degradable enhancing composite material of high compression is prepared by raw material of high-compressibility resin, degradable resin, fiber, compatilizer, antioxidant and lubricant；(2) it is molded using the degradable enhancing composite material of step (1) mesohigh contracting as raw material by fusion sediment 3D printing, high compression ratio 3D high then, which is made, by Milling Process emulates model of bootstrapping.What this method was prepared bootstrap, and model has the characteristics that high simulation quality, high-compressibility and environment friendly, simultaneously, the model of bootstrapping can realize the functions such as Fast Compression, expansion, can be widely used in industrial design, aerospace, commercially bootstrap, real estate sale, the fields such as academic exchange.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of high compression ratio 3D high emulates the system for model of bootstrapping
Preparation Method and product.
Background technology
With the raising of development and the social demand of modern science and technology, version develops from traditional areal model
To 3D three-dimensional models.By the displaying of this kind of 3D physical models, the thought marrow of exhibitor can be quickly and effectively embodied, meanwhile,
Also spectators can be assisted intuitively to understand its purpose.Therefore, 3D three-dimensional models are widely used to industrial design, commercially bootstrap, room
The fields such as real estate sale, academic exchange.
It is presently used for the 3D models bootstrapped and includes Inflated model, foamed polystyrene pattern, plaster cast etc..Inflated model has
There is the characteristics of high compression ratio, folding portable transport；But it compares shortcoming, therefore in phase in the appearance emulation of minutia
It is upper similar with entity like degree；Simultaneously as the reason of film gas leakage, when in use, needs continuous pump gas.Foamed polystyrene pattern and
Plaster cast has the feature of high emulation, very high with entity similarity in terms of datail description, therefore is also that we are common
Model；But they need specially to protect in transportational process, avoiding colliding with leads to the damage of model detail characteristic, therefore, lacks
Weary portable transportation.In addition, the weatherability of this three categories model is relatively good, it is impossible to by microorganism in environment, light, heat, acid,
Therefore the factors fast degradation such as alkali, can be present in the form of rubbish in nature, environment friendly is poor for a long time.
Therefore, it is badly in need of that a kind of simulated effect is good, is convenient for carrying and environment amenable model of bootstrapping.
Invention content
In view of this, one of the objects of the present invention is to provide the preparation sides that a kind of high compression ratio 3D high emulates model of bootstrapping
Method；The second purpose is that providing a kind of high compression ratio 3D high emulates model of bootstrapping.
In order to achieve the above objectives, the present invention provides following technical solution：
1st, a kind of high compression ratio 3D high emulates the preparation method for model of bootstrapping, and described method includes following steps：
(1) high pressure is prepared by raw material of high-compressibility resin, degradable resin, fiber, compatilizer, antioxidant and lubricant
Contract degradable enhancing composite material；
(2) it is molded using the degradable enhancing composite material of step (1) mesohigh contracting as raw material by fusion sediment 3D printing, so
High compression ratio 3D high is made by Milling Process afterwards and emulates model of bootstrapping.
Further, described method includes following steps：
(1) after being dried high-compressibility resin and degradable resin, with fiber, compatilizer, antioxidant and lubricant
It adds in high-speed mixer and is premixed together, obtain premix, then squeeze the premix by extruder melting extrusion
Go out melt after cooling, the degradable enhancing composite material of high compression is made；
(2) fusion sediment 3D printing is passed through as raw material using the degradable enhancing composite material of the high compression prepared in step (1)
Then molding is made high compression ratio 3D high by Milling Process and emulates model of bootstrapping.
Further, in step (1), by weight, the degradable enhancing composite material of high compression is by following component system
：1-99 parts of high-compressibility resins, 1-99 parts of degradable resins, 1-40 parts of fibers, 0.5-7 parts of compatilizers, 1-2 parts of antioxidant and
0-3 parts of lubricants.
Further, in step (1), the high-compressibility resin is high resilience resin, high-elongation resin, obturator-type hair
Steep one or more of resin, open cell type Foamex.
Further, in step (1), the high-compressibility resin is contains 15-35wt% acrylonitrile, 5-30wt% fourths two
Alkene, the ABS resin of 40-60wt% styrene.
Further, in step (1), the degradable resin for Biodegradable resin, light degradation resin, thermal degradation resin or
One or more of soda acid degradative resin.
Further, in step (1), the degradable resin is PLA resin.
Further, in step (1), the PLA resin is one in l-lactic acid, dextrorotation polylactic acid or racemic polylactic acid
Kind is several.
Further, in step (1), the fiber is one kind in glass fibre, carbon fiber, carbon nanotube or synthetic fibers
It is or several；The compatilizer is maleic anhydride grafted ABS, maleic anhydride is grafted ST+AN, styrene-acrylonitrile-metering system
Ternary atactic copolymer, acrylic acid and the polystyrene copolymer or oxazoline of acid glycidyl ester and polystyrene copolymer
It is one or several kinds of；The antioxidant for four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, N, N '-
In double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine or three [2,4- di-tert-butyl-phenyls] phosphite esters
One or several kinds；The lubricant is pentaerythritol stearate, ethylene bis stearic acid amide, ethylene-acrylic acid copolymer
One or several kinds in object or silicone powder.
Further, in step (1), the extruder is double screw extruder, and extrusion temperature is 200 during the melting extrusion
DEG C, extruded velocity is 300 revs/min.
2nd, the high compression ratio 3D high prepared by the method emulates model of bootstrapping.
The beneficial effects of the present invention are：The present invention provides the preparation sides that a kind of high compression ratio 3D high emulates model of bootstrapping
Method and product in this method when preparing the degradable enhancing composite material of high compression ratio, by rationally designing composition of raw materials, make system
Standby composite material not only has high-compressibility, high resilience, also with high intensity and degradability.Using the composite material as original
Material, by 3D printing technique and Milling Process, prepare bootstrap model the characteristics of：1st, model has similar shape with entity
The minutias such as shape, color, glossiness and 3D are three-dimensional；2nd, model by light-weight high-strength material, privileged sites engraved structure,
Negative poisson's ratio geometric figure realized under conditions of no external constraint power, model can according to specific different purposes amplifications, reduce or
Person's full size 3D solids self-deploy；3rd, model is designed by degradable formula, has environmental degradability.Therefore, the high compression ratio
3D high, which emulates model of bootstrapping, has the characteristics that high simulation quality, high compression/resilience and environment friendly, meanwhile, the model of bootstrapping
It can realize the functions such as Fast Compression, expansion, industrial design can be widely used in, aerospace, commercially bootstrapped, premises production and marketing
It sells, the fields such as academic exchange.
Description of the drawings
In order to make the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides drawings described below and carries out
Explanation：
Fig. 1 is that the negative poisson's ratio, the engraved structure that prepare are bootstrapped model shape appearance figure in embodiment 6；
Fig. 2 is the thermogravimetric analysis figure of fibre-reinforced ABS/PLA composite materials prepared in embodiment 1；
Fig. 3 is the Heat Treatment Analysis figure of fibre-reinforced ABS/PLA composite materials prepared in embodiment 1.
Specific embodiment
The preferred embodiment of the present invention will be described in detail below.
Embodiment 1
Prepare fibre-reinforced ABS/PLA composite materials
By 80 parts containing 15wt% acrylonitrile, 30wt% butadiene, the ABS resin of 55wt% styrene and 20 parts it is left-handed poly-
Lactic acid is after drying process, with 20 parts of glass fibres, 2 parts of maleic anhydride grafted ABSs, 1.5 part three [2,4- di-tert-butyl-phenyl]
Phosphite ester and 2 parts of pentaerythritol stearates add in high-speed mixer premixed together, premix are obtained, then by institute
Premix is stated by double screw extruder melting extrusion, extrusion temperature is 200 DEG C, and extruded velocity is 300 revs/min, is squeezed out molten
After body is cooled down by sink, fibre-reinforced ABS/PLA composite materials silk material is made；
Embodiment 2
Prepare fibre-reinforced ABS/PLA composite materials
By 60 parts containing 20wt% acrylonitrile, 20wt% butadiene, the ABS resin of 60wt% styrene and 40 parts of dextrorotation gather
Lactic acid is after drying process, with 10 parts of carbon fibers, 4 parts of maleic anhydride grafting ST+AN, 2 part of four [β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] pentaerythritol ester and 1 part of ethylene-acrylic acid copolymer add in high-speed mixer premixed together, obtain
Premix, then by the premix by double screw extruder melting extrusion, extrusion temperature is 200 DEG C, extruded velocity 300
Rev/min, after melt extrusion is cooled down by sink, fibre-reinforced ABS/PLA composite materials silk material is made；
Embodiment 3
Prepare fibre-reinforced ABS/PLA composite materials
By 40 parts containing 25wt% acrylonitrile, 25wt% butadiene, the ABS resin of 50wt% styrene and 60 parts it is left-handed poly-
Lactic acid is after drying process, with 20 parts of carbon nanotubes, 2 parts of acrylic acid and polystyrene copolymer, 1.5 part of three [2,4- bis- tertiary fourth
Base phenyl] phosphite ester and 2 parts of ethylene bis stearic acid amides add in high-speed mixer premixed together, premix is obtained,
Then by the premix by double screw extruder melting extrusion, extrusion temperature is 200 DEG C, and extruded velocity is 300 revs/min
After melt extrusion is cooled down by sink, fibre-reinforced ABS/PLA composite materials silk material is made in clock；
Embodiment 4
Prepare fibre-reinforced ABS/PLA composite materials
By 20 parts containing 30wt% acrylonitrile, 30wt% butadiene, the ABS resin of 40wt% styrene and 80 parts of racemizations gather
Lactic acid after drying process, with 40 parts of glass fibres, 7 parts of styrene-acrylonitrile-glycidyl methacrylate ternary without
It is hard to advise copolymer, 1 part of N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and 3 parts of pentaerythrites
Resin acid ester is added in high-speed mixer together to be premixed, and obtains premix, the premix then is passed through twin-screw extrusion
Machine melting extrusion, extrusion temperature are 200 DEG C, and extruded velocity is 300 revs/min, and after melt extrusion is cooled down by sink, fibre is made
Tie up the ABS/PLA composite material silk materials of enhancing；
Embodiment 5
Prepare fibre-reinforced ABS/PLA composite materials
By 60 parts containing 35wt% acrylonitrile, 5wt% butadiene, the ABS resin of 60wt% styrene and 40 parts of dextrorotation gather
Lactic acid is after drying process, with 20 parts of carbon nanotubes, 2 parts of oxazolines and polystyrene copolymer, 1.5 part of three [2,4- bis- tertiary fourth
Base phenyl] phosphite ester and 2 parts of pentaerythritol stearates add in high-speed mixer premixed together, premix is obtained,
Then by the premix by double screw extruder melting extrusion, extrusion temperature is 200 DEG C, and extruded velocity is 300 revs/min
After melt extrusion is cooled down by sink, fibre-reinforced ABS/PLA composite materials silk material is made in clock；
Embodiment 6
Prepare negative poisson's ratio, engraved structure is bootstrapped model
It is beaten using the fibre-reinforced ABS/PLA composite materials silk material prepared in embodiment 1 as raw material by fusion sediment 3D
Type is printed as, wherein, process conditions are set as during 3D printing：Into silk amount 2mm/s, 70 DEG C of baseplate temp, 220 DEG C of nozzle temperature；So
Negative poisson's ratio is made by Milling Process afterwards, engraved structure is bootstrapped model, this bootstraps model as shown in a figures in Fig. 1, has hollow out
Structure, in cylinder, R=0.25m, h=2m, volume 0.785m3, color is black, and glossiness is adjustable；After compressing it such as
In Fig. 1 shown in b figures；Then expansion is discharged, as shown in c figures in Fig. 1；It will discharge and be unfolded after model compression 96h again, such as scheme
In 1 shown in d figures.
Thermogravimetric analysis is carried out to the fibre-reinforced ABS/PLA composite materials silk material prepared in embodiment 1, as a result sees Fig. 2,
As shown in Figure 2, it is 210 DEG C which, which decomposes initial temperature, is all carbonized at 450 DEG C, and final surplus is original vol
6.7wt%.Heat Treatment Analysis is carried out to the material, the results are shown in Figure 3, from the figure 3, it may be seen that the material is handled for 24 hours at 250 DEG C
Afterwards, degradation rate is 75 ± 1%, and after handling 96h at 210 DEG C, degradation rate is 68 ± 2%, illustrates that the material has high temperature
The performance of degradation, wherein degradation rate the mass loss ratio front and rear for material heating.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
- The preparation method of model 1. a kind of high compression ratio 3D high emulation is bootstrapped, which is characterized in that described method includes following steps：(1) preparing high compression as raw material using high-compressibility resin, degradable resin, fiber, compatilizer, antioxidant and lubricant can Degradation enhancing composite material；(2) it is molded using the degradable enhancing composite material of step (1) mesohigh contracting as raw material by fusion sediment 3D printing, Ran Houtong It crosses Milling Process high compression ratio 3D high emulation is made and bootstrap model.
- The preparation method of model 2. a kind of high compression ratio 3D high emulation according to claim 1 is bootstrapped, which is characterized in that institute The method of stating includes the following steps：(1) after being dried high-compressibility resin and degradable resin, together with fiber, compatilizer, antioxidant and lubricant It adds in high-speed mixer and is premixed, obtain premix, then squeeze out the premix molten by extruder melting extrusion After cooling, the degradable enhancing composite material of high compression is made in body；(2) it is molded using the degradable enhancing composite material of the high compression prepared in step (1) as raw material by fusion sediment 3D printing, Then high compression ratio 3D high is made by Milling Process and emulates model of bootstrapping.
- The preparation method of model 3. a kind of high compression ratio 3D high emulation according to claim 1 or 2 is bootstrapped, feature exist In in step (1), by weight, the degradable enhancing composite material of high compression is made by following component：1-99 parts of high pressures Contracting resin, 1-99 parts of degradable resins, 1-40 parts of fibers, 0.5-7 parts of compatilizers, 1-2 parts of antioxidant and 0-3 parts of lubricants.
- The preparation method of model 4. a kind of high compression ratio 3D high emulation according to claim 1 or 2 is bootstrapped, feature exist In in step (1), the high-compressibility resin is high resilience resin, high-elongation resin, obturator-type Foamex, trepanning One or more of type Foamex.
- The preparation method of model 5. a kind of high compression ratio 3D high emulation according to claim 4 is bootstrapped, which is characterized in that step Suddenly in (1), the high-compressibility resin is contains 15-35wt% acrylonitrile, 5-30wt% butadiene, 40-60wt% styrene ABS resin.
- The preparation method of model 6. a kind of high compression ratio 3D high emulation according to claim 1 or 2 is bootstrapped, feature exist In in step (1), the degradable resin is Biodegradable resin, light degradation resin, thermal degradation resin or soda acid degradative resin One or more of.
- The preparation method of model 7. a kind of high compression ratio 3D high emulation according to claim 6 is bootstrapped, which is characterized in that step Suddenly in (1), the degradable resin is PLA resin.
- The preparation method of model 8. a kind of high compression ratio 3D high emulation according to claim 1 or 2 is bootstrapped, feature exist In in step (1), the fiber is the one or several kinds in glass fibre, carbon fiber, carbon nanotube or synthetic fibers；Institute It states compatilizer and is grafted ST+AN, styrene-acrylonitrile-methyl propenoic acid glycidyl for maleic anhydride grafted ABS, maleic anhydride Ternary atactic copolymer, acrylic acid and the polystyrene copolymer or oxazoline of ester and polystyrene copolymer it is a kind of or several Kind；The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, N, N '-bis--(3- (3,5- Di-tert-butyl-hydroxy phenyl) propiono) it is a kind of or several in hexamethylene diamine or three [2,4- di-tert-butyl-phenyls] phosphite esters Kind；The lubricant is in pentaerythritol stearate, ethylene bis stearic acid amide, ethylene-acrylic acid copolymer or silicone powder One or several kinds.
- The preparation method of model 9. a kind of high compression ratio 3D high emulation according to claim 2 is bootstrapped, which is characterized in that step Suddenly in (1), the extruder is double screw extruder, and extrusion temperature is 200 DEG C during the melting extrusion, extruded velocity 300 Rev/min.
- The model 10. the high compression ratio 3D high emulation prepared by claim 1-9 any one of them method is bootstrapped.
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Application publication date: 20180710 |