CN110423473A - A kind of 3D printing material and preparation method thereof - Google Patents
A kind of 3D printing material and preparation method thereof Download PDFInfo
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- CN110423473A CN110423473A CN201910745848.XA CN201910745848A CN110423473A CN 110423473 A CN110423473 A CN 110423473A CN 201910745848 A CN201910745848 A CN 201910745848A CN 110423473 A CN110423473 A CN 110423473A
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- phenylselanyl
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- 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
-
- 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
Abstract
The invention discloses a kind of 3D printing materials, which is characterized in that is made of component A and B component, the quality proportioning of the component A and B component is (4-8): 1；The component A includes each raw material composition of following parts by weight: 10-20 parts of amino-terminated polyurethane, 80-120 parts of phenylselanyl adamantyl fluorine-silicon copolymer object, 1-3 parts of glass fibre, 0.03-0.06 parts of coupling agent；The B component includes each raw material composition of following parts by weight: end carboxyl super branched polyester 50-60 parts, 0.2-0.5 parts of -1,2- dihydroquinoline of ethoxy carbonic acyl radical of 2- ethyoxyl -1-.The invention also discloses the preparation methods of the 3D printing material.3D printing material disclosed by the invention has more excellent high temperature resistance and weatherability, and its bonding is strong, and intensity is good, and precision is higher, and excellent combination property, stability is good, and the materials'use service life is long.
Description
Technical field
The present invention relates to 3D printing technique fields more particularly to a kind of 3D printing material and preparation method thereof.
Background technique
In recent years, as social progress and the improvement of people's living standards, 3D printing technique are grown rapidly, it is as one
Kind completely new manufacturing technology active influence people's production and life.3D printing technique is to utilize CAD object 3D number
According to model, and a kind of increases material manufacturing technology of three-dimension object is successively constructed, is just becoming modern tip materials manufacture and molding at present
Major way, in Medical Devices, dental appliance, aviation, automobile manufacture industry, toy, Furniture manufacture, art and fashion etc.
Industrial application is extensive.
3D printing technique is that production three-dimensional is combined by threes' new technique such as CAD model, laser technology, new material in fact
Body, the method for fundamentally having overturned conventionally manufactured material, so that production efficiency and manufacture flexibility has been significantly increased, so that
The preparation and molding of material with complex part are more efficiently accurate.3D printing material is the important substance base of 3D printing technique development
Plinth, to a certain extent, the development of 3D printing material decide that can 3D printing have wider application.
Currently, there are many 3D printing material category on the market, common 3D printing consumptive material is mainly pure thermoplasticity silk material, packet
Include acrylonitrile-butadiene-styrene copolymer (ABS), polylactic acid (PLA) etc..This kind of generally existing bearing capacity of material is weak, layer
Between performance it is very poor, tensile strength is insufficient, and adhesion strength is lower, and firmness is bad, easy to aging, heat resistance is poor, and environmental-protecting performance is not
Good defect, these defects seriously limit its further application and development.In addition to this, 3D printing in the prior art
The also generally existing selling at exorbitant prices of material, intensity is inadequate, and coloring is poor, and the hardness of printing shaping entity finished product is high, flexibility is poor, leads
Cause the more crisp frangible technical problem of entity finished product.
The Chinese invention patent of Patent No. ZL201010530017.X reports a kind of for 3D printing rapid shaping
The preparation method of material, the entity finished product adhesion strength that prints of rapid prototyping material prepared using it is lower and flexibility
It is poor, cause entity crisp perishable at moral character.
Therefore, develop that a kind of intensity is good, and precision is higher, the 3D printing material of excellent combination property has very important meaning
Justice has facilitation to the development of intellectual material and manufacturing process.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of 3D printing material and preparation method thereof, the preparation
Method is simple and easy, of less demanding to equipment and reaction condition, and preparation cost is cheap, is suitble to large-scale production；It is prepared
After the molding of 3D printing material, three-dimensional net structure is formed, there is more excellent high temperature resistance and weatherability, and it bonds journey
Spend high, intensity is good, and precision is higher, and excellent combination property, stability is good, and the materials'use service life is long.
To achieve the above object of the invention, the technical solution adopted by the present invention is that, a kind of 3D printing material, by component A and B group
It is grouped as, the quality proportioning of the component A and B component is (4-8): 1；The component A includes each raw material group of following parts by weight
At: 10-20 parts of amino-terminated polyurethane, 80-120 parts of phenylselanyl adamantyl fluorine-silicon copolymer object, 1-3 parts of glass fibre, coupling
0.03-0.06 parts of agent；The B component includes each raw material composition of following parts by weight: end carboxyl super branched polyester 50-60 parts, 2-
0.2-0.5 parts of -1,2- dihydroquinoline of ethoxy carbonic acyl radical of ethyoxyl -1-.
Preferably, the preparation method of the phenylselanyl adamantyl fluorine-silicon copolymer object, includes the following steps: allyl
Phenyl selenium, the fluoro- 2- of 1,1,2,2- tetra- [(1,2,2- trifluoro vinyl) oxygroup] ethane -1- sulfuryl fluoride, (2Z) -4- oxo -4- [3-
(trifluoromethyl) -5,6- dihydro-[1,2,4] triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) butyl-
2- alkene -2- amine, 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tert-butyl two
Silyloxy -5- oxo-(6E)-methyl heptanoate, (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- biphenyl] -4-
Base) -2- acrylic acid, initiator be added in high boiling solvent, 3- is stirred to react at nitrogen or 65-75 DEG C of atmosphere of inert gases
5 hours, after settle out in water, and wash crude product 3-5 times with ethyl alcohol, then be placed at 80-90 DEG C of vacuum oven and dry to constant weight,
Obtain phenylselanyl adamantyl fluorine-silicon copolymer object.
Preferably, the allyl phenyl selenium, 1,1,2,2- tetra- fluoro- 2- [(1,2,2- trifluoro vinyl) oxygroup] ethane-
1- sulfuryl fluoride, (2Z) -4- oxo -4- [3- (trifluoromethyl) -5,6- dihydro-[1,2,4] triazol [4,3-a] pyrazine -7 (8H) -
Base] -1- (2,4,5- trifluorophenyl) but-2-ene -2- amine, 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide
Base) -5- pyrimidine]-(3R)-tert-butyl dimethylsilyloxy -5- oxo-(6E)-methyl heptanoate, (2E) -3- (4'- hydroxyl -3'- gold
Rigid alkane -1- base [1,1'- biphenyl] -4- base) -2- acrylic acid, initiator, high boiling solvent mass ratio be 1:1:1:0.7:1:
(0.04-0.06):(15-20)。
Preferably, the initiator is selected from least one of azodiisobutyronitrile, azobisisoheptonitrile.
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is at least one.
Preferably, the inert gas is selected from one of helium, neon, argon gas.
Preferably, the coupling agent is selected from Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570
At least one of.
Preferably, the end carboxyl super branched polyester is selected from HyPer C10, HyPer C20, HyPer C30 or HyPer
One or more of C40.
Further, a kind of preparation method of 3D printing material, includes the following steps:
Step S1, the preparation of component A: by amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object, glass fibers
Dimension, coupling agent are proportionally added into extruding pelletization in double screw extruder, obtain component A；
Step S2, the preparation of B component: by end carboxyl super branched polyester, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydro
Quinoline is dissolved in n,N-Dimethylformamide, is stirred 0.5-1 hours, and n,N-Dimethylformamide is evaporated off in back spin, then is placed in true
It dries in empty drying box to constant weight, obtains B component；The mass ratio of the end carboxyl super branched polyester and N,N-dimethylformamide
For 1:(4-6)；
Step S3, the preparation of composite material: will be by component A made from step S1 and by B component made from step S2
Mixing, mills, mechanical stirring 1-2 hours, obtains composite material；
Step S4, the composite material being prepared by step S3 is added in the propeller socket of printer, is utilized
Computer model is successively printed；Then, it takes out product to be solidified under the conditions of temperature is 90~110 DEG C, curing time
For 4~6h；The syringe needle internal diameter of the printer is 1~1.3mm, and print speed is 1~3mm/s.
Preferably, the technological parameter of the extruding pelletization is the extrusion temperature in each area of double screw extruder are as follows: the firstth area
185-195 DEG C, 197-203 DEG C of the secondth area, 205-210 DEG C of third area, the 4th 212-220 DEG C of area, the 5th 220-225 DEG C of area, mould
Head temperature is 225-235 DEG C.
The beneficial effects of adopting the technical scheme are that
(1) 3D printing material provided by the invention, preparation process is simple, and raw material is easy to get, and preparation cost is cheap, to equipment and
Reaction condition is of less demanding, is able to satisfy large-scale production demand, market popularization value with higher.
(2) 3D printing material provided by the invention, it is weak to overcome the generally existing bearing capacity of traditional 3D printing material, layer
Between performance it is very poor, tensile strength is insufficient, and adhesion strength is lower, and firmness is bad, easy to aging, heat resistance is poor, and environmental-protecting performance is not
Good, selling at exorbitant prices, coloring is poor, and the hardness of printing shaping entity finished product is high, and flexibility is poor, and entity finished product is more crisp frangible to be lacked
It falls into, there is more excellent high temperature resistance and weatherability, and its bonding is strong, intensity is good, and precision is higher, comprehensive performance
Excellent, stability is good, and the materials'use service life is long.
(3) 3D printing material provided by the invention, while it is total to add amino-terminated polyurethane, phenylselanyl adamantyl fluorine silicon
Between the amino and carboxyl on strand esterification condensation occurs for polymers and end carboxyl super branched polyester after printing curing molding
Reaction forms three-dimensional net structure, improves the comprehensive performance of material, widened the use scope of 3D printing material, be prepared into
The material arrived is suitble to space flight and aviation, automotive field to use；In addition joined glass fibre wherein can play humidification, into one
Step improves the comprehensive performance of material；Phenylselanyl adamantyl fluorine-silicon copolymer object is by allyl phenyl selenium, the fluoro- 2- of 1,1,2,2- tetra-
[(1,2,2- trifluoro vinyl) oxygroup] ethane -1- sulfuryl fluoride, (2Z) -4- oxo -4- [3- (trifluoromethyl) -5,6- dihydro -
[1,2,4] triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) but-2-ene -2- amine, 7- [4- (4- fluorine
Phenyl) -6- isopropyl -2- (N- methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tert-butyl dimethylsilyloxy -5- oxo -
(6E)-methyl heptanoate, (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- biphenyl] -4- base) -2- acrylic acid these lists
Body copolymerization is made, so that introducing phenyl selenium structure in material molecule chain, improves the anti-flammability and resistance to ag(e)ing of material；It introduces
Sulfuryl fluoride, pyrazine, pyrimidine, adamantane structure, synergistic effect are conducive to improve high temperature resistance, weather resistance and the machinery of material
Mechanical property；And these resin flexibilities and adhesion strength are excellent, it is ensured that 3D printing material will not delamination, the 3D made beats
Type entity finished product is printed as with good comprehensive performance.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Wherein, the raw material being related in embodiment is commercially available.
Embodiment 1
A kind of 3D printing material, is made of component A and B component, and the quality proportioning of the component A and B component is 4:1；Institute
State each raw material composition that component A includes following parts by weight: 10 parts of amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object
80 parts, 1 part of glass fibre, 0.03 part of Silane coupling agent KH550；The B component includes each raw material composition of following parts by weight:
End carboxyl super branched 50 parts of polyester HyPer C10,0.2 part of dihydroquinoline of ethoxy carbonic acyl radical -1,2- of 2- ethyoxyl -1-.
The preparation method of the phenylselanyl adamantyl fluorine-silicon copolymer object, includes the following steps: allyl phenyl selenium
The fluoro- 2- of 1kg, 1,1,2,2- tetra- [(1,2,2- trifluoro vinyl) oxygroup] ethane -1- sulfuryl fluoride 1kg, (2Z) -4- oxo -4- [3-
(trifluoromethyl) -5,6- dihydro-[1,2,4] triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) butyl-
2- alkene -2- amine 1kg, 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tertiary fourth
Base dimethylsilyloxy -5- oxo-(6E)-methyl heptanoate 0.7kg, (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- connection
Benzene] -4- base) -2- acrylic acid 1kg, azodiisobutyronitrile 0.04kg be added in dimethyl sulfoxide 15kg, at 65 DEG C of nitrogen atmosphere
Be stirred to react 3 hours, after settle out in water, and washed crude product 3 times with ethyl alcohol, then be placed at 80 DEG C of vacuum oven and dry to perseverance
Weight, obtains phenylselanyl adamantyl fluorine-silicon copolymer object.
A kind of preparation method of 3D printing material, includes the following steps:
Step S1, the preparation of component A: by amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object, glass fibers
Dimension, Silane coupling agent KH550 are proportionally added into extruding pelletization in double screw extruder, obtain component A；
Step S2, the preparation of B component: by end carboxyl super branched polyester, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydro
Quinoline is dissolved in n,N-Dimethylformamide, is stirred 0.5 hour, n,N-Dimethylformamide is evaporated off in back spin, then is placed in vacuum
It dries in drying box to constant weight, obtains B component；The mass ratio of the end carboxyl super branched polyester and N,N-dimethylformamide is
1:4；
Step S3, the preparation of composite material: will be by component A made from step S1 and by B component made from step S2
Mixing, mills, mechanical stirring 1-2 hours, obtains composite material；
Step S4, the composite material being prepared by step S3 is added in the propeller socket of printer, is utilized
Computer model is successively printed；Then, it takes out product to be solidified under the conditions of temperature is 90 DEG C, curing time 4h；
The syringe needle internal diameter of the printer is 1mm, print speed 1mm/s.
The technological parameter of the extruding pelletization is the extrusion temperature in each area of double screw extruder are as follows: the first 185 DEG C of area,
Second 197 DEG C of area, 205 DEG C of third area, 212 DEG C of the 4th area, 220 DEG C of the 5th area, die head temperature are 225 DEG C.
Embodiment 2
A kind of 3D printing material, is made of component A and B component, and the quality proportioning of the component A and B component is 5:1；Institute
State each raw material composition that component A includes following parts by weight: 13 parts of amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object
90 parts, 1.5 parts of glass fibre, 0.04 part of silane coupling agent KH560；The B component includes each raw material group of following parts by weight
At: end carboxyl super branched 53 parts of polyester HyPer C20,0.3 part of dihydroquinoline of ethoxy carbonic acyl radical -1,2- of 2- ethyoxyl -1-.
The preparation method of the phenylselanyl adamantyl fluorine-silicon copolymer object, includes the following steps: allyl phenyl selenium
The fluoro- 2- of 1kg, 1,1,2,2- tetra- [(1,2,2- trifluoro vinyl) oxygroup] ethane -1- sulfuryl fluoride 1kg, (2Z) -4- oxo -4- [3-
(trifluoromethyl) -5,6- dihydro-[1,2,4] triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) butyl-
2- alkene -2- amine 1kg, 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tertiary fourth
Base dimethylsilyloxy -5- oxo-(6E)-methyl heptanoate 0.7kg, (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- connection
Benzene] -4- base) -2- acrylic acid 1kg, azobisisoheptonitrile 0.045kg be added in n,N-Dimethylformamide 16.5kg, in helium
Atmosphere is enclosed to be stirred to react 3.5 hours at 67 DEG C, after settle out in water, and washed crude product 4 times with ethyl alcohol, then be placed in vacuum oven
It dries at 83 DEG C to constant weight, obtains phenylselanyl adamantyl fluorine-silicon copolymer object.
A kind of preparation method of 3D printing material, includes the following steps:
Step S1, the preparation of component A: by amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object, glass fibers
Dimension, silane coupling agent KH560 are proportionally added into extruding pelletization in double screw extruder, obtain component A；
Step S2, the preparation of B component: by end carboxyl super branched polyester, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydro
Quinoline is dissolved in n,N-Dimethylformamide, is stirred 0.65 hour, n,N-Dimethylformamide is evaporated off in back spin, then is placed in vacuum
It dries in drying box to constant weight, obtains B component；The mass ratio of the end carboxyl super branched polyester and N,N-dimethylformamide is
1:4.5；
Step S3, the preparation of composite material: will be by component A made from step S1 and by B component made from step S2
Mixing, mills, mechanical stirring 1.2 hours, obtains composite material；
Step S4, the composite material being prepared by step S3 is added in the propeller socket of printer, is utilized
Computer model is successively printed；Then, it takes out product to be solidified under the conditions of temperature is 95 DEG C, curing time is
4.5h；The syringe needle internal diameter of the printer is 1.1mm, print speed 1.5mm/s.
The technological parameter of the extruding pelletization is the extrusion temperature in each area of double screw extruder are as follows: the first 188 DEG C of area,
Second 199 DEG C of area, 206 DEG C of third area, 214 DEG C of the 4th area, 221 DEG C of the 5th area, die head temperature are 227 DEG C.
Embodiment 3
A kind of 3D printing material, is made of component A and B component, and the quality proportioning of the component A and B component is 6:1；Institute
State each raw material composition that component A includes following parts by weight: 15 parts of amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object
100 parts, 2 parts of glass fibre, 0.045 part of silane coupling agent KH570；The B component includes each raw material group of following parts by weight
At: end carboxyl super branched 55 parts of polyester HyPer C30,0.35 part of dihydroquinoline of ethoxy carbonic acyl radical -1,2- of 2- ethyoxyl -1-.
The preparation method of the phenylselanyl adamantyl fluorine-silicon copolymer object, includes the following steps: allyl phenyl selenium
The fluoro- 2- of 1kg, 1,1,2,2- tetra- [(1,2,2- trifluoro vinyl) oxygroup] ethane -1- sulfuryl fluoride 1kg, (2Z) -4- oxo -4- [3-
(trifluoromethyl) -5,6- dihydro-[1,2,4] triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) butyl-
2- alkene -2- amine 1kg, 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tertiary fourth
Base dimethylsilyloxy -5- oxo-(6E)-methyl heptanoate 0.7kg, (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- connection
Benzene] -4- base) -2- acrylic acid 1kg, azodiisobutyronitrile 0.05kg be added in N-Methyl pyrrolidone 18kg, in neon atmosphere
Be stirred to react at 69 DEG C 4 hours, after settle out in water, and washed crude product 4 times with ethyl alcohol, then be placed at 85 DEG C of vacuum oven and do
It is dry to constant weight, obtain phenylselanyl adamantyl fluorine-silicon copolymer object.
A kind of preparation method of 3D printing material, includes the following steps:
Step S1, the preparation of component A: by amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object, glass fibers
Dimension, coupling agent are proportionally added into extruding pelletization in double screw extruder, obtain component A；
Step S2, the preparation of B component: by end carboxyl super branched polyester, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydro
Quinoline is dissolved in n,N-Dimethylformamide, is stirred 0.8 hour, n,N-Dimethylformamide is evaporated off in back spin, then is placed in vacuum
It dries in drying box to constant weight, obtains B component；The mass ratio of the end carboxyl super branched polyester and N,N-dimethylformamide is
1:5；
Step S3, the preparation of composite material: will be by component A made from step S1 and by B component made from step S2
Mixing, mills, mechanical stirring 1.5 hours, obtains composite material；
Step S4, the composite material being prepared by step S3 is added in the propeller socket of printer, is utilized
Computer model is successively printed；Then, it takes out product to be solidified under the conditions of temperature is 100 DEG C, curing time 5h；
The syringe needle internal diameter of the printer is 1.2mm, print speed 2mm/s.
The technological parameter of the extruding pelletization is the extrusion temperature in each area of double screw extruder are as follows: the first 190 DEG C of area,
Second 200 DEG C of area, 208 DEG C of third area, 217 DEG C of the 4th area, 223 DEG C of the 5th area, die head temperature are 230 DEG C.
Embodiment 4
A kind of 3D printing material, is made of component A and B component, and the quality proportioning of the component A and B component is 7:1；Institute
State each raw material composition that component A includes following parts by weight: 10-20 parts of amino-terminated polyurethane, phenylselanyl adamantyl fluorine silicon are total
110 parts of polymers, 2.5 parts of glass fibre, 0.055 part of coupling agent；The B component includes each raw material composition of following parts by weight: end
58 parts of carboxyl super branched polyester, 0.45 part of dihydroquinoline of ethoxy carbonic acyl radical -1,2- of 2- ethyoxyl -1-.The coupling agent is silane
Coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570 1:3:5 in mass ratio are mixed；The carboxyl end group is super
Branched polyester is that HyPer C10, HyPer C20, HyPer C30, HyPer C40 1:1:3:2 in mass ratio are mixed；
The preparation method of the phenylselanyl adamantyl fluorine-silicon copolymer object, includes the following steps: allyl phenyl selenium
The fluoro- 2- of 1kg, 1,1,2,2- tetra- [(1,2,2- trifluoro vinyl) oxygroup] ethane -1- sulfuryl fluoride 1kg, (2Z) -4- oxo -4- [3-
(trifluoromethyl) -5,6- dihydro-[1,2,4] triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) butyl-
2- alkene -2- amine 1kg, 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tertiary fourth
Base dimethylsilyloxy -5- oxo-(6E)-methyl heptanoate 1kg, (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- connection
Benzene] -4- base) -2- acrylic acid 0.7kg, initiator 1kg be added in high boiling solvent 0.055kg, stir at 73 DEG C of argon atmosphere
Mix reaction 4.5 hours, after settle out in water, and washed crude product 5 times with ethyl alcohol, then be placed at 88 DEG C of vacuum oven and dry to perseverance
Weight, obtains phenylselanyl adamantyl fluorine-silicon copolymer object；The initiator is azodiisobutyronitrile, azobisisoheptonitrile by quality
It is mixed than 3:5；The high boiling solvent is dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone by quality
It is mixed than 1:3:5.
A kind of preparation method of 3D printing material, includes the following steps:
Step S1, the preparation of component A: by amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object, glass fibers
Dimension, coupling agent are proportionally added into extruding pelletization in double screw extruder, obtain component A；
Step S2, the preparation of B component: by end carboxyl super branched polyester, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydro
Quinoline is dissolved in n,N-Dimethylformamide, is stirred 0.9 hour, n,N-Dimethylformamide is evaporated off in back spin, then is placed in vacuum
It dries in drying box to constant weight, obtains B component；The mass ratio of the end carboxyl super branched polyester and N,N-dimethylformamide is
1:5.5；
Step S3, the preparation of composite material: will be by component A made from step S1 and by B component made from step S2
Mixing, mills, mechanical stirring 1.9 hours, obtains composite material；
Step S4, the composite material being prepared by step S3 is added in the propeller socket of printer, is utilized
Computer model is successively printed；Then, it takes out product to be solidified under the conditions of temperature is 106 DEG C, curing time is
5.5h；The syringe needle internal diameter of the printer is 1.3mm, print speed 2.5mm/s.
The technological parameter of the extruding pelletization is the extrusion temperature in each area of double screw extruder are as follows: the first 194 DEG C of area,
Second 201 DEG C of area, 209 DEG C of third area, 219 DEG C of the 4th area, 224 DEG C of the 5th area, die head temperature are 233 DEG C.
Embodiment 5
A kind of 3D printing material, is made of component A and B component, and the quality proportioning of the component A and B component is 8:1；Institute
State each raw material composition that component A includes following parts by weight: 20 parts of amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object
120 parts, 3 parts of glass fibre, 0.06 part of silane coupling agent KH560；The B component includes each raw material composition of following parts by weight:
End carboxyl super branched 60 parts of polyester HyPer C40,0.5 part of dihydroquinoline of ethoxy carbonic acyl radical -1,2- of 2- ethyoxyl -1-.
The preparation method of the phenylselanyl adamantyl fluorine-silicon copolymer object, includes the following steps: allyl phenyl selenium
The fluoro- 2- of 1kg, 1,1,2,2- tetra- [(1,2,2- trifluoro vinyl) oxygroup] ethane -1- sulfuryl fluoride 1kg, (2Z) -4- oxo -4- [3-
(trifluoromethyl) -5,6- dihydro-[1,2,4] triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) butyl-
2- alkene -2- amine 1kg, 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tertiary fourth
Base dimethylsilyloxy -5- oxo-(6E)-methyl heptanoate 0.7kg, (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- connection
Benzene] -4- base) -2- acrylic acid 1kg, azodiisobutyronitrile 0.06kg be added in n,N-Dimethylformamide 20kg, in nitrogen atmosphere
Enclose and be stirred to react at 75 DEG C 5 hours, after settle out in water, and washed crude product 5 times with ethyl alcohol, then be placed at 90 DEG C of vacuum oven
Drying obtains phenylselanyl adamantyl fluorine-silicon copolymer object to constant weight.
A kind of preparation method of 3D printing material, includes the following steps:
Step S1, the preparation of component A: by amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object, glass fibers
Dimension, coupling agent are proportionally added into extruding pelletization in double screw extruder, obtain component A；
Step S2, the preparation of B component: by end carboxyl super branched polyester, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydro
Quinoline is dissolved in n,N-Dimethylformamide, is stirred 1 hour, and n,N-Dimethylformamide is evaporated off in back spin, then is placed in vacuum and is done
It dries in dry case to constant weight, obtains B component；The mass ratio of the end carboxyl super branched polyester and N,N-dimethylformamide is 1:
6；
Step S3, the preparation of composite material: will be by component A made from step S1 and by B component made from step S2
Mixing, mills, mechanical stirring 2 hours, obtains composite material；
Step S4, the composite material being prepared by step S3 is added in the propeller socket of printer, is utilized
Computer model is successively printed；Then, it takes out product to be solidified under the conditions of temperature is 110 DEG C, curing time 6h；
The syringe needle internal diameter of the printer is 1.3mm, print speed 3mm/s.
The technological parameter of the extruding pelletization is the extrusion temperature in each area of double screw extruder are as follows: the first 195 DEG C of area,
Second 203 DEG C of area, 210 DEG C of third area, 220 DEG C of the 4th area, 225 DEG C of the 5th area, die head temperature are 235 DEG C.
Comparative example 1
A kind of 3D printing material, formula and preparation method are substantially the same manner as Example 1, the difference is that phenylselanyl Buddha's warrior attendant
It does not include allyl phenyl selenium in the comonomer of alkyl fluoride siliceous copolymer.
Comparative example 2
A kind of 3D printing material, formula and preparation method are substantially the same manner as Example 1, the difference is that phenylselanyl Buddha's warrior attendant
It does not include the fluoro- 2- of 1,1,2,2- tetra- [(1,2,2- trifluoro vinyl) oxygroup] ethane-in the comonomer of alkyl fluoride siliceous copolymer
1- sulfuryl fluoride.
Comparative example 3
A kind of 3D printing material, formula and preparation method are substantially the same manner as Example 1, the difference is that phenylselanyl Buddha's warrior attendant
It does not include [dihydro-[1,2,4] 3- (trifluoromethyl) -5,6- (2Z) -4- oxo -4- in the comonomer of alkyl fluoride siliceous copolymer
Triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) but-2-ene -2- amine.
Comparative example 4
A kind of 3D printing material, formula and preparation method are substantially the same manner as Example 1, the difference is that phenylselanyl Buddha's warrior attendant
It does not include 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide in the comonomer of alkyl fluoride siliceous copolymer
Base) -5- pyrimidine]-(3R)-tert-butyl dimethylsilyloxy -5- oxo-(6E)-methyl heptanoate.
Comparative example 5
A kind of 3D printing material, formula and preparation method are substantially the same manner as Example 1, the difference is that phenylselanyl Buddha's warrior attendant
It does not include (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- biphenyl] -4- in the comonomer of alkyl fluoride siliceous copolymer
Base) -2- acrylic acid.
Comparative example 6
A kind of 3D printing material, according to the formula and preparation method system of Chinese invention patent CN106832091A embodiment 1
It is standby to form.
The 3D printing material described in embodiment 1-5 and comparative example 1-3 is tested for the property, and test result and test method are shown in
Table 1.
Table 1
As seen from Table 1,3D printing material disclosed by the embodiments of the present invention has preferable mechanical mechanics property and anti-flammability,
This is the result of each structure synergistic effect.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (8)
1. a kind of 3D printing material, which is characterized in that be made of component A and B component, the quality proportioning of the component A and B component
For (4-8): 1；The component A includes each raw material composition of following parts by weight: 10-20 parts of amino-terminated polyurethane, phenylselanyl gold
Rigid 80-120 parts of alkyl fluoride siliceous copolymer, 1-3 parts of glass fibre, 0.03-0.06 parts of coupling agent；The B component includes following weight
Measure each raw material composition of part: end carboxyl super branched polyester 50-60 parts, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline
0.2-0.5 parts.
2. a kind of 3D printing material according to claim 1, which is characterized in that the phenylselanyl adamantyl fluorine silicon is total
The preparation method of polymers includes the following steps: allyl phenyl selenium, 1,1,2,2- tetra- fluoro- 2- [(1,2,2- trifluoro vinyl)
Oxygroup] ethane -1- sulfuryl fluoride, (2Z) -4- oxo -4- [3- (trifluoromethyl) -5,6- dihydro-[1,2,4] triazol [4,3-a]
Pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) but-2-ene -2- amine, 7- [4- (4- fluorophenyl) -6- isopropyl -2- (N-
Methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tert-butyl dimethylsilyloxy -5- oxo-(6E)-methyl heptanoate, (2E) -3-
(4'- hydroxyl -3'- adamantane -1- base [1,1'- biphenyl] -4- base) -2- acrylic acid, initiator are added in high boiling solvent, In
Be stirred to react 3-5 hours at nitrogen or 65-75 DEG C of atmosphere of inert gases, after settle out in water, and wash crude product 3-5 with ethyl alcohol
It is secondary, then be placed at 80-90 DEG C of vacuum oven and dry to constant weight, obtain phenylselanyl adamantyl fluorine-silicon copolymer object.
3. a kind of 3D printing material according to claim 2, which is characterized in that the allyl phenyl selenium, 1,1,2,2-
Four fluoro- 2- [(1,2,2- trifluoro vinyl) oxygroup] ethane -1- sulfuryl fluorides, (2Z) -4- oxo -4- [3- (trifluoromethyl) -5,6-
Dihydro-[1,2,4] triazol [4,3-a] pyrazine -7 (8H)-yl] -1- (2,4,5- trifluorophenyl) but-2-ene -2- amine, 7- [4-
(4- fluorophenyl) -6- isopropyl -2- (N- methylmethanesulfonamide base) -5- pyrimidine]-(3R)-tert-butyl dimethylsilyloxy -5- oxygen
Generation-(6E)-methyl heptanoate, draws (2E) -3- (4'- hydroxyl -3'- adamantane -1- base [1,1'- biphenyl] -4- base) -2- acrylic acid
Send out agent, the mass ratio of high boiling solvent is 1:1:1:0.7:1:(0.04-0.06): (15-20).
4. a kind of 3D printing material according to claim 2, which is characterized in that the initiator is selected from two isobutyl of azo
At least one of nitrile, azobisisoheptonitrile.
5. a kind of 3D printing material according to claim 2, which is characterized in that it is sub- that the high boiling solvent is selected from diformazan
At least one of sulfone, N,N-dimethylformamide, N-Methyl pyrrolidone；The inert gas is selected from helium, neon, argon gas
One of.
6. a kind of 3D printing material according to claim 1, which is characterized in that the coupling agent is selected from silane coupling agent
At least one of KH550, silane coupling agent KH560, silane coupling agent KH570；The end carboxyl super branched polyester is selected from
One or more of HyPer C10, HyPer C20, HyPer C30 or HyPer C40.
7. a kind of 3D printing material according to claim 1-6, which is characterized in that the system of the 3D printing material
Preparation Method includes the following steps:
Step S1, the preparation of component A: by amino-terminated polyurethane, phenylselanyl adamantyl fluorine-silicon copolymer object, glass fibre, idol
Connection agent is proportionally added into extruding pelletization in double screw extruder, obtains component A；
Step S2, the preparation of B component: by end carboxyl super branched polyester, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline
It is dissolved in n,N-Dimethylformamide, stirs 0.5-1 hours, n,N-Dimethylformamide is evaporated off in back spin, then is placed in vacuum and does
It dries in dry case to constant weight, obtains B component；The mass ratio of the end carboxyl super branched polyester and N,N-dimethylformamide is 1:
(4-6)；
Step S3, the preparation of composite material: will mix by component A made from step S1 and by B component made from step S2,
It mills, mechanical stirring 1-2 hours, obtains composite material；
Step S4, the composite material being prepared by step S3 is added in the propeller socket of printer, utilizes calculating
Machine model is successively printed；Then, take out product temperature be 90~110 DEG C under the conditions of solidified, curing time be 4~
6h；The syringe needle internal diameter of the printer is 1~1.3mm, and print speed is 1~3mm/s.
8. a kind of 3D printing material according to claim 7, which is characterized in that the technological parameter of the extruding pelletization is,
The extrusion temperature in each area of double screw extruder are as follows: the first 185-195 DEG C of area, 197-203 DEG C of the secondth area, third area 205-210
DEG C, the 4th 212-220 DEG C of area, the 5th 220-225 DEG C of area, die head temperature be 225-235 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110804309A (en) * | 2019-11-18 | 2020-02-18 | 安徽弘泰精密机械科技有限公司 | 3D printing polymer powder material and preparation method thereof |
| CN116574412A (en) * | 2023-04-04 | 2023-08-11 | 浙江浦江永进工贸有限公司 | Preparation method of flame-retardant UV (ultraviolet) inkjet ink |
-
2019
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804309A (en) * | 2019-11-18 | 2020-02-18 | 安徽弘泰精密机械科技有限公司 | 3D printing polymer powder material and preparation method thereof |
| CN116574412A (en) * | 2023-04-04 | 2023-08-11 | 浙江浦江永进工贸有限公司 | Preparation method of flame-retardant UV (ultraviolet) inkjet ink |
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