CN110204870A - A kind of resistance to PTT 3D printing wire rod and preparation method thereof for shrinking warpage - Google Patents
A kind of resistance to PTT 3D printing wire rod and preparation method thereof for shrinking warpage Download PDFInfo
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- CN110204870A CN110204870A CN201910522558.9A CN201910522558A CN110204870A CN 110204870 A CN110204870 A CN 110204870A CN 201910522558 A CN201910522558 A CN 201910522558A CN 110204870 A CN110204870 A CN 110204870A
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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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The present invention relates to a kind of resistance to PTT 3D printing wire rods and preparation method thereof for shrinking warpage.This method is made of PTT 50 ~ 65%, PBAT 15 ~ 25%, elastomer-Fanglun slurry cake compound 10 ~ 25%, expanding material 3 ~ 8%, tackifier 3-8%, transesterification promotor 0.2-2%, antioxidant 0.2-1% and paraffin oil 0.2 ~ 1% by weight percentage, and the resistance to PTT 3D printing wire rod for shrinking warpage is made by drying, material mixing, melt blending, extrusioning shaping and traction winding.The wire rod forms under the conditions of lower baseplate temp does not generate contraction warping phenomenon, while having excellent mechanical performance, good adhesive property and excellent processability, has a wide range of application, and is especially suitable for the 3D printing of engineering field.
Description
Technical field
The present invention relates to a kind of resistance to PTT 3D printing wire rods and preparation method thereof for shrinking warpage.
Background technique
Increasing material manufacturing is also known as 3D printing, is a kind of set numerical software, machinery and the multidisciplinary novel system being integrated of material
Make technology.With the characteristics of it is formed by material stacking, it is widely used in the fields such as medical treatment, education, military project.Fused glass pellet conduct
One of mainstream technology of 3D printing, since it is attracted attention with characteristics such as low in cost, low temperature moulding, safe operations by people.
PTT resin is the engineering plastics being polymerize by propylene glycol and terephthalic acid (TPA), which has superior processing
Performance, mechanical performance and chemical corrosion resistance.But PTT resin is during fused glass pellet, due to 3D printing it is open at
Type mode, lacks mold pressure maintaining styling, easily makes strand is regular to pile up to form stress concentration to produce in temperature-fall period
Raw to shrink warping phenomenon, this can seriously affect the size and precision of printed sample, and printing is then caused to fail.Prior art scenario
Lower mainly to overcome contraction warping phenomenon by improving baseplate temp (>=120 DEG C), this can improve printing cost and increase safe
Risk is unfavorable for the application and popularization of PTT material.In addition, 3D printing is material superposition manufacture, it is weaker to will form interface interaction power
Weld mark, be easy to cause sample generate cracking phenomena, to influence product appearance and purposes.Therefore, put forth effort to solve it is above-mentioned not
For foot to application of the PTT material in 3D printing is widened, meaning is self-evident.
Summary of the invention
Based on the above background and problem, the purpose of the present invention is to provide a kind of resistance to PTT 3D printing wire rods for shrinking warpage
And preparation method thereof.This method using PTT resin as raw material, by addition PBAT, elastomer-Fanglun slurry cake compound, expanding material,
Tackifier and transesterification promotor, which are modified preparation, has the resistance to PTT 3D printing wire rod for shrinking warpage.It is produced by the present invention
PTT 3D printing wire rod forms the mechanicalness for not generating contraction warping phenomenon, while having excellent under the conditions of lower baseplate temp
Energy, good adhesive property and excellent processability, have a wide range of application, and are especially suitable for the 3D printing of engineering field.
Said effect of the invention is achieved by the following technical solution: a kind of resistance to PTT 3D printing line for shrinking warpage
Material, which is characterized in that component is compound by PTT 50 ~ 65%, PBAT 15 ~ 25%, elastomer-Fanglun slurry cake by weight percentage
Object 10 ~ 25%, expanding material 3-8%, tackifier 3 ~ -8%, transesterification promotor 0.2 ~ 2%, antioxidant 0.2 ~ 1%, paraffin oil 0.2 ~ 1%
Composition.
Further improved: the elastomer in the elastomer-Fanglun slurry cake compound is total for ethylene-methyl acrylate
Polymers (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene methyl methacrylate copolymer (EMMA) it is a kind of or
It is two or more to be mixed with any mixing ratio.
Further improved: the mass ratio of the elastomer-Fanglun slurry cake compound elastomer and Fanglun slurry cake is
0.5:1~3:1。
Further improved: the expanding material is Vinyl Graft glycidyl methacrylate copolymer (PE-g-
GMA), Vinyl Graft copolymer-maleic anhydride (PE-g-MA), ethylene/n-butyl acrylate-glycidyl methacrylate
(E-BA-GMA) one or two kinds of to be mixed above with any mixing ratio.
Further improved: the tackifier are rosin resin, terpene resin, coumarone-indene resin, C5 petroleum tree
It is mixed more than rouge, C9 Petropols are one or two kinds of with any mixing ratio.
Further improved: the transesterification promotor is Mono-n-butyltin, Dibutyltin oxide, trifluoromethyl sulphur
It is mixed more than sour samarium, tributyltin chloride, butyl tin trichloride are one or two kinds of with any mixing ratio.
Further improved: the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester (antioxidant 1010), three [2.4- di-tert-butyl-phenyl] phosphite esters (irgasfos 168), β-(3,5- di-t-butyl -4- hydroxyl
Base phenyl) propionic acid octadecanol ester (antioxidant 1076) is one or two kinds of above is mixed with any mixing ratio.
It is purchased and is thought based on same invention, the present invention also proposes a kind of preparation side of resistance to PTT 3D printing wire rod for shrinking warpage
Method, which comprises the following steps:
1), the step of elastomer-Fanglun slurry cake compound preparation:
A. elastomer, Fanglun slurry cake are dried in vacuo respectively；
B. the elastomer by step A after dry, Fanglun slurry cake according to 0.5:1 ~ 3:1 mass than precise, after then weighing
Each group be placed in high-speed kneading machine be uniformly mixed, obtain mixture；
C. the mixture of step B is kneaded by continuous mixer, obtains elastomer-Fanglun slurry cake compound material, be kneaded temperature
90 ~ 120 DEG C of degree, 140 ~ 170 DEG C of extrusion temperature, screw speed is 35 ~ 55rpm;
2), PTT, PBAT are dried in vacuo respectively, by PTT 50 ~ 65%, PBAT 15 ~ 25%, transesterification promotor 0.2 ~ 2% according to
Then each group after weighing is placed in high-speed kneading machine and is uniformly mixed, obtains mixture by weight percent precise, will
Mixture makes material by double screw extruder melting extrusion, obtains blended particles A, and barrel temperature is 190 ~ 260 DEG C, screw speed
For 10 ~ 100rpm；
3), elastomer-Fanglun slurry cake compound, expanding material, tackifier and antioxidant is dried in vacuo respectively, it will be each after drying
Proportion speed weighs component as following weight percent: elastomer-Fanglun slurry cake compound 10 ~ 25%, expanding material 3 ~ 8%, thickening
Agent 3 ~ 8%, antioxidant 0.2 ~ 1% and paraffin oil 0.2 ~ 1%, then by the blended particles A of step A preparation with after the weighing of 3) step
Each group is placed in high-speed kneader and is uniformly mixed, and obtains mixture, and mixture makes material by double screw extruder melting extrusion,
Blended particles B is obtained, barrel temperature is 190 ~ 260 DEG C, and screw speed is 10 ~ 100rpm；
4) the blended particles B of step preparation, 3) is subjected to extrusioning shaping by wire rod machine and traction is wound, obtains 3D printing line
Material, barrel temperature are 190 ~ 260 DEG C, and screw speed is 30 ~ 120rpm.
The beneficial effects of the present invention are:
(1) processability is excellent.The material is not related to inorganic material addition, has good processability, and print procedure is not present
The problems such as plug, bubble and burr, prints continuity and duration is strong, and moulded products surface is moist.
(2) resistance to contraction warpage.The material adapts to the printing under lower baseplate temp and guarantees without generating contraction warping phenomenon
The dimensional stability and precision of moulded products, reduce the energy consumption of forming process, while improving the safety of printing.
(3) anti-stress cracking.For the weld mark that 3D printing technique layer upon layer is formed, which effectively enhances printing
Interfacial adhesion in the process, prevents cracking phenomena.
(4) better mechanical property.The material not only has a good processability, while also having preferable intensity and tough
Property, the application suitable for engineering field.
(5) PBAT resin is as a kind of novel bio-based materials, by tetramethylene adipate and terephthalic acid (TPA) fourth two
Alcohol polyisocyanate polyaddition obtains, which not only has excellent processing performance and good impact flexibility, with molecular configurational and PTT phase
It is similar, ester exchange reaction can occur therewith.Work is exchanged by what addition transesterification promotor promoted PTT and PBAT molecule interchain
With, can be effectively reduced the crystallizing power of PTT, thus make the more non crystalline structures of System forming and reduce stress concentrate.Herein
On the basis of, suitable elastomer-Fanglun slurry cake compound is added, further decreases the buckling deformation of system, to effectively solve
The contraction warpage issues that PTT occurs during 3D printing.
Detailed description of the invention
Fig. 1 be modified PTT 3D printing wire rod printed sample (under) with unmodified PTT 3D printing wire rod printed sample
(on) effect contrast figure.
Specific embodiment
Son is described in further details the present invention combined with specific embodiments below, but this should not be interpreted as of the invention
Range is only limitted to following embodiment.
Embodiment 1
A kind of resistance to PTT 3D printing wire rod for shrinking warpage, which is characterized in that component is by weight percentage are as follows: PTT 52%,
PBAT 18%, EEA- Fanglun slurry cake compound 18%, E-BA-GMA 5%, rosin resin 4.5%, trifluoromethane sulfonic acid samarium 1%, 1076
Antioxidant 0.3%, paraffin oil 1.2%.
Preparation method, comprising the following steps:
A. EEA, Fanglun slurry cake are dried in vacuo respectively；
B. the EEA by step A after dry, Fanglun slurry cake are according to mass ratio 2.2:1 precise, then by each component after weighing
It is placed in high-speed kneading machine and is uniformly mixed, obtain mixture；
C. the mixture of step B is kneaded by continuous mixer, obtains EEA- Fanglun slurry cake compound material, melting temperature 95
DEG C, 150 DEG C of extrusion temperature, screw speed 36rpm.
D. PTT, PBAT are dried in vacuo respectively, PTT, PBAT, trifluoromethane sulfonic acid samarium is accurate according to weight percent
It weighs, then each group after weighing is placed in high-speed kneading machine and is uniformly mixed, obtains mixture, mixture is passed through into double spiral shells
Material is made in bar extruder melting extrusion, obtains blended particles A, 190,220,240,255,252,250 DEG C of barrel temperature, screw rod turns
Speed is 60rpm.
E. EEA- Fanglun slurry cake compound, E-BA-GMA, rosin resin and antioxidant 1076 are dried in vacuo respectively, it is dry
Various resins and paraffin oil afterwards are weighed according to weight percent proportion speed, the blended particles A and E for then preparing D step
Each group after step weighing is placed in high-speed kneader and is uniformly mixed, and obtains mixture, mixture passes through double screw extruder
Material is made in melting extrusion, obtains blended particles B, 190,222,240,256,254,250 DEG C of barrel temperature, screw speed is
50rpm；
F. the blended particles B prepared by E step carries out extrusioning shaping and traction winding by wire rod machine, obtains 3D printing wire rod,
Barrel temperature is 192,223,245,256,255,253 DEG C, screw speed 40rpm；
G. wire rod obtained in F-step is subjected to 3D printing molding, measures 3D printing spline linear dimension limit deviation levels
(GB/T1804-92), tensile strength (GB/T1040.2-2006) and impact strength (GB/T1043.1-2008), while observing sample
Item is shown in Table 1 with the presence or absence of cracking situation, test result.
Embodiment 2
A kind of resistance to PTT 3D printing wire rod for shrinking warpage, which is characterized in that component is by weight percentage are as follows: PTT 62%,
PBAT 18%, EMA- Fanglun slurry cake compound 10%, PE-g-GMA 3%, coumarone-indene resin 4%, tributyltin chloride 1.4%,
1010 antioxidant 0.6%, paraffin oil 1%.
Preparation method, comprising the following steps:
A. EMA, Fanglun slurry cake are dried in vacuo respectively；
B. the EMA by step A after dry, Fanglun slurry cake are according to mass ratio 0.5:1 precise, then by each component after weighing
It is placed in high-speed kneading machine and is uniformly mixed, obtain mixture；
C. the mixture of step B is kneaded by continuous mixer, obtains EMA- Fanglun slurry cake compound material, melting temperature
102 DEG C, 155 DEG C of extrusion temperature, screw speed 32rpm.
D. PTT, PBAT are dried in vacuo respectively, PTT, PBAT, tributyltin chloride is accurately claimed according to weight percent
Then each group after weighing is placed in high-speed kneading machine and is uniformly mixed, obtains mixture, mixture is passed through twin-screw by amount
Material is made in extruder melting extrusion, obtains blended particles A, and 190,225,245,256,253,250 DEG C of barrel temperature, screw speed
For 42rpm.
E. EMA- Fanglun slurry cake compound, PE-g-GMA, coumarone-indene resin and antioxidant 1010 are distinguished vacuum to do
Dry, various resins and paraffin oil after drying are weighed according to weight percent proportion speed, the blending for then preparing D step
Grain A is placed in high-speed kneader with each group after the weighing of E step and is uniformly mixed, and obtains mixture, mixture passes through twin-screw
Material is made in extruder melting extrusion, obtains blended particles B, and 192,223,245,254,255,252 DEG C of barrel temperature, screw speed
For 55rpm；
F. the blended particles B prepared by E step carries out extrusioning shaping and traction winding by wire rod machine, obtains 3D printing wire rod,
Barrel temperature is 190,225,243,253,255,250 DEG C, screw speed 40rpm；
G. wire rod obtained in F-step is subjected to 3D printing molding, measures 3D printing spline linear dimension limit deviation levels
(GB/T1804-92), tensile strength (GB/T1040.2-2006) and impact strength (GB/T1043.1-2008), while observing sample
Item is shown in Table 1 with the presence or absence of cracking situation, test result.
Embodiment 3
A kind of resistance to PTT 3D printing wire rod for shrinking warpage, which is characterized in that component is by weight percentage are as follows: PTT 50%,
PBAT 18%, EMMA- Fanglun slurry cake compound 20%, E-BA-GMA 7%, terpene resin 3%, Mono-n-butyltin 1%, 168 antioxygens
Agent 0.3%, paraffin oil 0.7%.
Preparation method, comprising the following steps:
A. EMMA, Fanglun slurry cake are dried in vacuo respectively；
B. the EMMA by step A after dry, Fanglun slurry cake are according to mass ratio 0.6:1 precise, then by each group after weighing
It is placed in high-speed kneading machine and is uniformly mixed, obtain mixture；
C. the mixture of step B is kneaded by continuous mixer, obtains EMMA- Fanglun slurry cake compound material, melting temperature
92 DEG C, 152 DEG C of extrusion temperature, screw speed 35rpm.
D. PTT, PBAT are dried in vacuo respectively, PTT, PBAT, Mono-n-butyltin is accurately claimed according to weight percent
Then each group after weighing is placed in high-speed kneading machine and is uniformly mixed, obtains mixture, mixture is passed through twin-screw by amount
Material is made in extruder melting extrusion, obtains blended particles A, and 190,222,245,255,256,254 DEG C of barrel temperature, screw speed
For 48rpm.
E. EMMA- Fanglun slurry cake compound, E-BA-GMA, terpene resin and irgasfos 168 are dried in vacuo respectively, it is dry
Various resins and paraffin oil afterwards are weighed according to weight percent proportion speed, the blended particles A and E for then preparing D step
Each group after step weighing is placed in high-speed kneader and is uniformly mixed, and obtains mixture, mixture passes through double screw extruder
Material is made in melting extrusion, obtains blended particles B, 193,220,242,252,255,250 DEG C of barrel temperature, screw speed is
55rpm；
F. the blended particles B prepared by E step carries out extrusioning shaping and traction winding by wire rod machine, obtains 3D printing wire rod,
Barrel temperature is 195,223,245,252,255,250 DEG C, screw speed 38rpm；
G. wire rod obtained in F-step is subjected to 3D printing molding, measures 3D printing spline linear dimension limit deviation levels
(GB/T1804-92), tensile strength (GB/T1040.2-2006) and impact strength (GB/T1043.1-2008), while observing sample
Item is shown in Table 1 with the presence or absence of cracking situation, test result.
Embodiment 4
A kind of resistance to PTT 3D printing wire rod for shrinking warpage, which is characterized in that component is by weight percentage are as follows: PTT 53%,
PBAT 17%, EMA- Fanglun slurry cake compound 18%, PE-g-MA 4%, C5 Petropols 5%, Dibutyltin oxide 1.2%, 1076
Antioxidant 0.8%, paraffin oil 1%.
Preparation method, comprising the following steps:
A. EMA, Fanglun slurry cake are dried in vacuo respectively；
B. the EMA by step A after dry, Fanglun slurry cake are according to mass ratio 1.2:1 precise, then by each component after weighing
It is placed in high-speed kneading machine and is uniformly mixed, obtain mixture；
C. the mixture of step B is kneaded by continuous mixer, obtains EMA- Fanglun slurry cake compound material, melting temperature 92
DEG C, 150 DEG C of extrusion temperature, screw speed 36rpm.
D. PTT, PBAT are dried in vacuo respectively, PTT, PBAT, Dibutyltin oxide is accurately claimed according to weight percent
Then each group after weighing is placed in high-speed kneading machine and is uniformly mixed, obtains mixture, mixture is passed through twin-screw by amount
Material is made in extruder melting extrusion, obtains blended particles A, and 190,223,245,255,255,250 DEG C of barrel temperature, screw speed
For 46rpm.
E. EMA- Fanglun slurry cake compound, PE-g-MA, C5 Petropols and antioxidant 1076 are dried in vacuo respectively, are done
Various resins and paraffin oil after dry are weighed according to weight percent proportion speed, the blended particles A for then preparing D step with
Each group after the weighing of E step is placed in high-speed kneader and is uniformly mixed, and obtains mixture, mixture passes through double screw extruder
Material is made in melting extrusion, obtains blended particles B, 192,222,244,255,258,250 DEG C of barrel temperature, screw speed is
53rpm；
F. the blended particles prepared by E step carry out extrusioning shaping and traction winding by wire rod machine, obtain 3D printing wire rod, expect
Cylinder temperature is 193,225,245,255,254,252 DEG C, screw speed 48rpm；
G. wire rod obtained in F-step is subjected to 3D printing molding, measures 3D printing spline linear dimension limit deviation levels
(GB/T1804-92), tensile strength (GB/T1040.2-2006) and impact strength (GB/T1043.1-2008), while observing sample
Item is shown in Table 1 with the presence or absence of cracking situation, test result.
Embodiment 5
A kind of resistance to PTT 3D printing wire rod for shrinking warpage, which is characterized in that component is by weight percentage are as follows: PTT 60%,
PBAT 16%, EMMA- Fanglun slurry cake compound 14%, PE-g-GMA 3.5%, C9 Petropols 5%, butyl tin trichloride 0.6%,
168 antioxidant 0.4%, paraffin oil 0.5%.
Preparation method, comprising the following steps:
A. EMMA, Fanglun slurry cake are dried in vacuo respectively；
B. the EMMA by step A after dry, Fanglun slurry cake are according to mass ratio 0.8:1 precise, then by each group after weighing
It is placed in high-speed kneading machine and is uniformly mixed, obtain mixture；
C. the mixture of step B is kneaded by continuous mixer, obtains EMMA- Fanglun slurry cake compound material, melting temperature
100 DEG C, 160 DEG C of extrusion temperature, screw speed 50rpm.
D. PTT, PBAT are dried in vacuo respectively, PTT, PBAT, butyl tin trichloride is accurately claimed according to weight percent
Then each group after weighing is placed in high-speed kneading machine and is uniformly mixed, obtains mixture, mixture is passed through twin-screw by amount
Material is made in extruder melting extrusion, obtains blended particles A, and 192,225,245,255,255,253 DEG C of barrel temperature, screw speed
For 43rpm.
E. EMMA- Fanglun slurry cake compound, PE-g-GMA, C9 Petropols and irgasfos 168 are dried in vacuo respectively, are done
Various resins and paraffin oil after dry are weighed according to weight percent proportion speed, the blended particles A for then preparing D step with
Each group after the weighing of E step is placed in high-speed kneader and is uniformly mixed, and obtains mixture, mixture passes through double screw extruder
Material is made in melting extrusion, obtains blended particles B, 192,224,246,254,255,252 DEG C of barrel temperature, screw speed is
50rpm。
F. the blended particles B prepared by E step carries out extrusioning shaping and traction winding by wire rod machine, obtains 3D printing line
Material, 192,225,246,254,256,252 DEG C of barrel temperature, screw speed 32rpm；
G. wire rod obtained in F-step is subjected to 3D printing molding, measures 3D printing spline linear dimension limit deviation levels
(GB/T1804-92), tensile strength (GB/T1040.2-2006) and impact strength (GB/T1043.1-2008), while observing sample
Item is shown in Table 1 with the presence or absence of cracking situation, test result.
Comparative example 1
PTT resin vacuum is dry, by melting extrusion, sizing traction preparation 3D printing wire rod, by wire rod carry out 3D printing at
Type measures 3D printing spline linear dimension limit deviation levels (GB/T1804-92), tensile strength (GB/T1040.2-2006)
With impact strength (GB/T1043.1-2008), while batten is observed with the presence or absence of cracking situation, test result is shown in Table 1.
1 material properties test result of table
Claims (8)
1. a kind of resistance to PTT 3D printing wire rod for shrinking warpage, which is characterized in that component by weight percentage by PTT 50 ~
65%, PBAT 15 ~ 25%, elastomer-Fanglun slurry cake compound 10 ~ 25%, expanding material 3-8%, tackifier 3 ~ -8%, transesterification promote
Agent 0.2 ~ 2%, antioxidant 0.2 ~ 1%, paraffin oil 0.2 ~ 1% form.
2. the resistance to PTT 3D printing wire rod for shrinking warpage according to claim 1, it is characterised in that: the elastomer-
Elastomer in Fanglun slurry cake compound is ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer
(EEA), ethylene methyl methacrylate copolymer (EMMA) is one or two kinds of is mixed above with any mixing ratio.
3. the resistance to PTT 3D printing wire rod for shrinking warpage according to claim 1, it is characterised in that: the elastomer-
The mass ratio of Fanglun slurry cake compound elastomer and Fanglun slurry cake is 0.5:1 ~ 3:1.
4. the resistance to PTT 3D printing wire rod for shrinking warpage according to claim 1, it is characterised in that: the expanding material is
Vinyl Graft glycidyl methacrylate copolymer (PE-g-GMA), Vinyl Graft copolymer-maleic anhydride (PE-g-MA),
Ethylene/n-butyl acrylate-glycidyl methacrylate (E-BA-GMA) is one or two kinds of above with any mixing ratio
It mixes.
5. the resistance to PTT 3D printing wire rod for shrinking warpage according to claim 1, it is characterised in that: the tackifier are
Rosin resin, terpene resin, coumarone-indene resin, C5 Petropols, C9 Petropols are one or two kinds of above with arbitrarily mixed
Composition and division in a proportion mixes.
6. the resistance to PTT 3D printing wire rod for shrinking warpage according to claim 1, it is characterised in that: the transesterification promotees
It is Mono-n-butyltin, Dibutyltin oxide, trifluoromethane sulfonic acid samarium, tributyltin chloride, butyl tin trichloride one kind into agent
Or it two or more is mixed with any mixing ratio.
7. the resistance to PTT 3D printing wire rod for shrinking warpage according to claim 1, it is characterised in that: the antioxidant is
Four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010), three [2.4- di-tert-butyls
Base] phosphite ester (irgasfos 168), β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (antioxidant 1076)
It is mixed more than one or two kinds of with any mixing ratio.
8. the preparation method of any resistance to PTT 3D printing wire rod for shrinking warpage, feature exist in a kind of the claims 1-7
In, comprising the following steps:
1), the step of elastomer-Fanglun slurry cake compound preparation:
A. elastomer, Fanglun slurry cake are dried in vacuo respectively；
B. the elastomer by step A after dry, Fanglun slurry cake according to 0.5:1 ~ 3:1 mass than precise, after then weighing
Each group be placed in high-speed kneading machine be uniformly mixed, obtain mixture；
C. the mixture of step B is kneaded by continuous mixer, obtains elastomer-Fanglun slurry cake compound material, be kneaded temperature
90 ~ 120 DEG C of degree, 140 ~ 170 DEG C of extrusion temperature, screw speed is 35 ~ 55rpm;
2), PTT, PBAT are dried in vacuo respectively, by PTT 50 ~ 65%, PBAT 15 ~ 25%, transesterification promotor 0.2 ~ 2% according to
Then each group after weighing is placed in high-speed kneading machine and is uniformly mixed, obtains mixture by weight percent precise, will
Mixture makes material by double screw extruder melting extrusion, obtains blended particles A, and barrel temperature is 190 ~ 260 DEG C, screw speed
For 10 ~ 100rpm；
3), elastomer-Fanglun slurry cake compound, expanding material, tackifier and antioxidant is dried in vacuo respectively, it will be each after drying
Proportion speed weighs component as following weight percent: elastomer-Fanglun slurry cake compound 10 ~ 25%, expanding material 3 ~ 8%, thickening
Agent 3 ~ 8%, antioxidant 0.2 ~ 1% and paraffin oil 0.2 ~ 1%, then by the blended particles A of step A preparation with after the weighing of 3) step
Each group is placed in high-speed kneader and is uniformly mixed, and obtains mixture, and mixture makes material by double screw extruder melting extrusion,
Blended particles B is obtained, barrel temperature is 190 ~ 260 DEG C, and screw speed is 10 ~ 100rpm；
4) the blended particles B of step preparation, 3) is subjected to extrusioning shaping by wire rod machine and traction is wound, obtains 3D printing line
Material, barrel temperature are 190 ~ 260 DEG C, and screw speed is 30 ~ 120rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910522558.9A CN110204870B (en) | 2019-06-17 | 2019-06-17 | PTT 3D printing wire rod resistant to shrinkage and warping and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910522558.9A CN110204870B (en) | 2019-06-17 | 2019-06-17 | PTT 3D printing wire rod resistant to shrinkage and warping and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN110204870A true CN110204870A (en) | 2019-09-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112759879A (en) * | 2020-12-30 | 2021-05-07 | 广东顺德顺炎新材料股份有限公司 | Low-warpage ASA composite material for 3D printing and preparation method thereof |
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| CN1569931A (en) * | 2004-04-26 | 2005-01-26 | 东莞市正昱塑胶五金有限公司 | Fiber reinforced thermolplastic plastic preparation method |
| WO2008133262A1 (en) * | 2007-04-24 | 2008-11-06 | Toyo Boseki Kabushiki Kaisha | Polyester elastomer composition, and method for production thereof |
| CN107603121A (en) * | 2017-09-20 | 2018-01-19 | 福建师范大学 | A kind of ABS3D printing wire rods of resistance to warpage crack resistence and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1569931A (en) * | 2004-04-26 | 2005-01-26 | 东莞市正昱塑胶五金有限公司 | Fiber reinforced thermolplastic plastic preparation method |
| WO2008133262A1 (en) * | 2007-04-24 | 2008-11-06 | Toyo Boseki Kabushiki Kaisha | Polyester elastomer composition, and method for production thereof |
| CN107603121A (en) * | 2017-09-20 | 2018-01-19 | 福建师范大学 | A kind of ABS3D printing wire rods of resistance to warpage crack resistence and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759879A (en) * | 2020-12-30 | 2021-05-07 | 广东顺德顺炎新材料股份有限公司 | Low-warpage ASA composite material for 3D printing and preparation method thereof |
| CN112759879B (en) * | 2020-12-30 | 2022-04-08 | 广东顺德顺炎新材料股份有限公司 | Low-warpage ASA composite material for 3D printing and preparation method thereof |
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