CN110003665A - A kind of 3D printing material and preparation method thereof - Google Patents
A kind of 3D printing material and preparation method thereof Download PDFInfo
- Publication number
- CN110003665A CN110003665A CN201910315878.7A CN201910315878A CN110003665A CN 110003665 A CN110003665 A CN 110003665A CN 201910315878 A CN201910315878 A CN 201910315878A CN 110003665 A CN110003665 A CN 110003665A
- Authority
- CN
- China
- Prior art keywords
- parts
- condensation polymer
- printing material
- bis
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of 3D printing materials, are made of the raw material of following parts by weight: 30-40 parts of modified fluoride-containing aminoacyl amido phenylate class condensation polymer, 25-35 parts of 1- adamantane modified formaldehyde polylactic acid, 5-10 parts of nanometer boron fibre, 0.5-1.5 parts of antioxidant, 1-3 parts of coupling agent, 0.5-1 parts of toughener, 1-3 parts of triglycidyl group ether of glycerol propoxyl group；The modified fluoride-containing aminoacyl amido phenylate class condensation polymer is to pass through N1 first, bis- (3- chlorphenyl) malonamides and 2 of N3-, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2- occur polycondensation reaction and generate condensation polymer, are then modified again with single-ended epoxy silicon oil to condensation polymer.The invention also discloses the preparation methods of the 3D printing material.3D printing material preparation cost disclosed by the invention is cheap, has enough intensity and coloring, and heat resistance, resistance to ag(e)ing, corrosion resistance are excellent, not cracky, bonds strong, long service life.
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
3D printing (3D printing) technology is also known as three-dimensional printing technology, is one kind based on digital model file, fortune
With adhesive materials such as powdery metal or plastics, carry out quick increases material manufacturing technology by layer-by-layer printing.It is not necessarily to machine
Tool processing or any mold, can generate the part of any shape, to greatly shorten directly from computer graphics data
The lead time of product improves productivity and reduces production cost.It overcomes tradition and subtracts the loss problem that material manufacture generates, and
And make more intelligent product manufacturing, precision and efficiently.Improved day by day with 3D printing technique, 3D printing technique is answered extensively
For fields such as military affairs, electronics, medicine, biology, new energy, people just is influenced as a kind of completely new manufacturing technology of fast development
Production and life.
Essential one kind material is 3D printing material in 3D printing technique, common 3D printing currently on the market
Material be mostly take plastics as basic material, and then it is each using the adhesiveness of plastics and plasticity other to be added in Base Material
The powder of kind material makes it in manufacturing process in conjunction with plastics.The generally existing price mistake of this kind of 3D printing material in the prior art
Height, intensity is inadequate, and coloring is poor, and the hardness of printing shaping entity finished product is high, flexibility is poor, causes entity finished product more crisp frangible,
And its adhesion strength is lower, firmness is bad, easy to aging, heat resistance is poor, and environmental-protecting performance is bad.These defects limit such
Further genralrlization and application of the material in material increasing field.
The Chinese invention patent that application publication number is CN103980593A discloses a kind of modification high-density polyethylene 3D and beats
Moulding material and preparation method thereof is printed, this method uses the carbon nanotube activated through pernitric acid, and adding talcum powder, calcium carbonate will
It is high-density polyethylene modified, enhance the tensile strength and impact flexibility of high density polyethylene (HDPE), expands its application field, make high density
Polythene material is more in line with the characteristics of 3D printing material.This method uses mixed at high speed machining various additives and high density
Polyethylene is mixed, then carries out extrusion granulation.Its disadvantage is in each additive and high density polyethylene (HDPE) and not sufficiently mixed and connect
Touching, what the modifying function of additive played is not enough, while the price of nanotube is more expensive, causes totle drilling cost higher.
Therefore, it is cheap to develop a kind of preparation cost, there is enough intensity and coloring, heat resistance, resistance to ag(e)ing, anti-corruption
Corrosion is excellent, not cracky, and bonding is strong, and 3D printing material with long service life has very important significance, and can have
Conducive to the further development for promoting 3D printing technique.
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, and raw material is easy to get, cheap, is suitble to large-scale production；The 3D printing material preparation cost being prepared is low
It is honest and clean, there is enough intensity and coloring, heat resistance, resistance to ag(e)ing, corrosion resistance are excellent, not cracky, and bonding is strong,
Long service life.
To achieve the above object of the invention, the technical solution adopted by the present invention is that, a kind of 3D printing material is by following weight
The raw material of part is made: 30-40 parts of modified fluoride-containing aminoacyl amido phenylate class condensation polymer, 1- adamantane modified formaldehyde polylactic acid 25-
35 5-10 parts of part, nanometer boron fibres, 0.5-1.5 parts of antioxidant, 1-3 parts of coupling agent, 0.5-1 parts of toughener, glycerol propoxyl group
1-3 parts of triglycidyl group ether；The modified fluoride-containing aminoacyl amido phenylate class condensation polymer is first by N1, bis- (the 3- chlorine of N3-
Phenyl) malonamide and 2, bis- (3- amino-4-hydroxylphenyl) the hexafluoropropane generation polycondensation reactions generation condensation polymers of 2-, then again
Condensation polymer is modified with single-ended epoxy silicon oil.
Preferably, the antioxidant is 2,6- three-level butyl -4- methylphenol, bis- (3,5- three-level butyl -4- hydroxy benzenes
Base) one of thioether, pentaerythritol ester, double Lauryl Alcohol esters, bi-myristoleyl and double octadecanol esters or a variety of.
Preferably, the coupling agent be monoalkoxy Pyrophosphate Type Yitanate Coupling Agent, KH570 type silane coupling agent,
One of KH792 type silane coupling agent and DL602 type silane coupling agent are a variety of.
Further, toughener is preferably ethylene-vinyl acetate copolymer, liquid propene acid esters rubber, the poly- fourth of liquid
At least one of diene rubber, thermoplastic polyurethane elastomer.
Further, the preparation method of the modified fluoride-containing aminoacyl amido phenylate class condensation polymer, includes the following steps:
I by N1, bis- (3- chlorphenyl) malonamides of N3-, 2,2- bis- (3- amino-4-hydroxylphenyl) hexafluoropropane, alkalinity
Catalyst is added in the there-necked flask for being connected to water segregator, then increases boiling point solvent and toluene, and reaction system is heated to 100-110
DEG C, it is stirred to react under nitrogen or inert gas shielding 3-5 hours, the Shui Hejia generated in reaction process is removed by water segregator
Benzene eliminates water and reaction temperature is slowly increased to 135-150 DEG C later, continues return stirring and reacts 15-20 hours, reaction terminates
Reaction system is cooled to room temperature afterwards, is precipitated in water, by the polymer of precipitation with ethanol washing 4-6 times, then vacuum is placed in and does
It dries at 85-95 DEG C of dry case to constant weight, obtains condensation polymer；
II is added to the condensation polymer, the single-ended epoxy silicon oil that are prepared by step I in dimethyl sulfoxide, at 60-80 DEG C
Under be stirred to react 6-8 hours, after settle out in water, and with isopropanol washed product 3-5 times, then be placed in vacuum oven 85-95
It dries at DEG C to constant weight.
Preferably, bis- (3- chlorphenyl) malonamides of N1 described in step I, N3-, bis- (the 3- amino-4-hydroxy benzene of 2,2-
Base) hexafluoropropane, basic catalyst, high boiling solvent, toluene mass ratio be 1:1.13:(0.5-0.8): (6-10): 4.
Preferably, the basic catalyst is selected from least one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate.
Preferably, the high boiling solvent be selected from dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide,
At least one of N-Methyl pyrrolidone.
Preferably, the inert gas is selected from one of helium, neon, argon gas.
Preferably, condensation polymer described in step II, single-ended epoxy silicon oil, dimethyl sulfoxide mass ratio be 1:0.2:(3-5).
Further, the preparation method of the 1- adamantane modified formaldehyde polylactic acid, includes the following steps: catalyst is molten
Solution is formed in n,N-Dimethylformamide, 1- adamantane formaldehyde is then added, and 20-30 points are stirred at -30~-40 DEG C
Clock, then polylactic acid is added thereto continues insulation reaction 40-60 minute, after be down to room temperature, revolving removing solvent, after use ether
Washed product 3-5 times is washed with water and washs product 3-5 times, then is placed in a vacuum drying oven at 80-90 DEG C and dries to constant weight.
Preferably, the catalyst, n,N-Dimethylformamide, 1- adamantane formaldehyde, polylactic acid mass ratio be
(0.5-1):(15-25):0.5:(3-5)。
Preferably, the catalyst is selected from one of tert-butyl potassium alcoholate, sodium hydride, boryl lithium, boronation trisodium or several
Kind.
Further, the preparation method of the 3D printing material includes the following steps: modified fluoride-containing aminoacyl amido benzene
Ethers condensation polymer, 1- adamantane modified formaldehyde polylactic acid, nanometer boron fibre, antioxidant, coupling agent, glycerol propoxyl group three shrink
It mills at -15~-5 DEG C after the mixing of glyceryl ether and prepares mixture, then mixture and toughener are added to twin-screw extrusion
Extruding pelletization in machine.
Preferably, described mill is carried out in freezing grinding mill, and the revolving speed for freezing grinding mill is 400-600rpm.
Preferably, the extruding pelletization squeezes out wire-drawing shape using double screw extruder, each area of double screw extruder
Extrusion temperature are as follows: the first 180-190 DEG C of area, 192-200 DEG C of the secondth area, 205-210 DEG C of third area, the 4th 210-220 DEG C of area,
5th 220-225 DEG C of area, die head temperature are 220-230 DEG C.
The beneficial effects of adopting the technical scheme are that
(1) 3D printing material provided by the invention, preparation method is simple, and raw material is easy to get, cheap, is suitble to scale
Metaplasia produces.
(2) 3D printing material provided by the invention, preparation cost is cheap, reasonable compatibility between various components, so that 3D is beaten
Printing material has enough intensity and coloring, and heat resistance, resistance to ag(e)ing, corrosion resistance are excellent, not cracky, bonds degree pole
Height, long service life.
(3) 3D printing material provided by the invention is modified polylactic acid by 1- adamantane formaldehyde, so that 3D is beaten
The advantages that it is small that print material not only remains polylactic acid cooling meat rate, transparent easy dyeing, and overcome the crystallization of polylactic acid
It is small to spend ester bond bond energy in smaller, strand, the factor being easily broken off cause the heat distortion temperature of polylactic acid is low, impact strength is low,
The bad defect of toughness, so that the 3D printing material comprehensive performance that the present invention is prepared is more preferably, toughness and impact strength are more preferable,
Heat distortion temperature is higher, the processing and molding being suitable in 3D printing technique.
(4) 3D printing material provided by the invention adds modified fluoride-containing aminoacyl amido phenylate class condensation polymer, is provided simultaneously with
The advantages of fluoropolymer, polyamide, polyphenyl ether material, amino on strand and drawn by the modification of single-ended epoxy silicon oil
The hydroxyl entered acts synergistically with molecular bulk, so that material cementitiousness is stronger；The glycerol propoxyl group triglycidyl group of addition
Ether further increases the comprehensive performance of material so that each bulk composition forms three-dimensional net structure.
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.
Present invention raw material as used in the following examples is commercially available.
Embodiment 1
A kind of 3D printing material, is made of the raw material of following parts by weight: modified fluoride-containing aminoacyl amido phenylate class polycondensation
30 parts of object, 5 parts of 25 part, nanometer boron fibre of 1- adamantane modified formaldehyde polylactic acid, 2,6- three-level butyl -4- methylphenol 0.5
Part, 1 part of monoalkoxy Pyrophosphate Type Yitanate Coupling Agent, 0.5 part of ethylene-vinyl acetate copolymer, glycerol propoxyl group three
1 part of glycidyl ether；The modified fluoride-containing aminoacyl amido phenylate class condensation polymer is first by N1, bis- (the 3- chlorobenzenes of N3-
Base) malonamide and 2, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2- occur polycondensation reactions and generate condensation polymers, then use again
Single-ended epoxy silicon oil is modified condensation polymer.
The preparation method of the modified fluoride-containing aminoacyl amido phenylate class condensation polymer, includes the following steps:
I by N1, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of N3- bis- (3- chlorphenyl) malonamide 1kg, 2,2-
1.13kg, sodium hydroxide 0.5kg are added in the there-necked flask for being connected to water segregator, then plus dimethyl sulfoxide 6kg and toluene 4kg, will react
System is heated to 100 DEG C, is stirred to react under nitrogen protection 3 hours, by water segregator remove in reaction process the water that generates and
Toluene eliminates water and reaction temperature is slowly increased to 135 DEG C later, continues return stirring and reacts 15 hours, after reaction will be anti-
It answers system to be cooled to room temperature, is precipitated in water, by the polymer of precipitation with ethanol washing 4 times, then be placed in 85 DEG C of vacuum oven
Lower drying obtains condensation polymer to constant weight；
The condensation polymer 1kg, the single-ended epoxy silicon oil 0.2kg that are prepared by step I are added to dimethyl sulfoxide 3kg by II
In, be stirred to react at 60 DEG C 6 hours, after settle out in water, and with isopropanol washed product 3 times, then be placed in vacuum oven
It dries at 85 DEG C to constant weight.
The preparation method of the 1- adamantane modified formaldehyde polylactic acid includes the following steps: tert-butyl potassium alcoholate 0.5kg
It is dissolved in n,N-Dimethylformamide 15kg and forms solution, 1- adamantane formaldehyde 0.5kg is then added, stirs 20 at -30 DEG C
Minute, then polylactic acid 3kg is added thereto, continues insulation reaction 40 minutes, after be down to room temperature, revolving removes solvent, after use second
It ether washed product 3 times, is washed with water and washs product 3 times, then be placed in a vacuum drying oven at 80 DEG C and dry to constant weight.
The preparation method of the 3D printing material includes the following steps: modified fluoride-containing aminoacyl amido phenylate class polycondensation
Object, 1- adamantane modified formaldehyde polylactic acid, nanometer boron fibre, 2,6- three-level butyl -4- methylphenol, monoalkoxy pyrophosphate
It mills at -15 DEG C after type titanate coupling agent, the mixing of glycerol propoxyl group triglycidyl group ether and prepares mixture, then will mixing
Material and ethylene-vinyl acetate copolymer are added to extruding pelletization in double screw extruder.
Described mill is carried out in freezing grinding mill, and the revolving speed for freezing grinding mill is 400rpm.
The extruding pelletization squeezes out wire-drawing shape, the extrusion temperature in each area of double screw extruder using double screw extruder
Are as follows: the first 180 DEG C of area, 192 DEG C of the secondth area, 205 DEG C of third area, 210 DEG C of the 4th area, 220 DEG C of the 5th area, die head temperature 220
℃。
Embodiment 2
A kind of 3D printing material, is made of the raw material of following parts by weight: modified fluoride-containing aminoacyl amido phenylate class polycondensation
33 parts of object, 6 parts of 27 part, nanometer boron fibre of 1- adamantane modified formaldehyde polylactic acid, bis- (3,5- three-level butyl -4- hydroxy phenyl) sulphur
0.7 part of ether, 1.5 parts of KH570 type silane coupling agent, 0.6 part of liquid propene acid esters rubber, glycerol propoxyl group triglycidyl group ether
1.5 part；The modified fluoride-containing aminoacyl amido phenylate class condensation polymer is first by N1, bis- (3- chlorphenyl) malonamides of N3-
Polycondensation reaction occurs with bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2- and generates condensation polymer, then again with single-ended epoxy silicon
Oil is modified condensation polymer.
The preparation method of the modified fluoride-containing aminoacyl amido phenylate class condensation polymer, includes the following steps:
I by N1, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of N3- bis- (3- chlorphenyl) malonamide 1kg, 2,2-
1.13kg, sodium carbonate 0.6kg are added in the there-necked flask for being connected to water segregator, then plus n,N-Dimethylformamide 7kg and toluene 4kg,
Reaction system is heated to 103 DEG C, is stirred to react 3.5 hours under helium protection, is removed by water segregator raw in reaction process
At water and toluene, eliminate and reaction temperature be slowly increased to 138 DEG C after water, continue return stirring and react 16.5 hours, reaction
After reaction system is cooled to room temperature, be precipitated in water, by the polymer of precipitation with ethanol washing 4 times, then be placed in vacuum
It dries at 87 DEG C of drying box to constant weight, obtains condensation polymer；
The condensation polymer 1kg, the single-ended epoxy silicon oil 0.2kg that are prepared by step I are added to dimethyl sulfoxide 3.5kg by II
In, be stirred to react at 65 DEG C 6.5 hours, after settle out in water, and with isopropanol washed product 3 times, then be placed in vacuum drying
It dries at 88 DEG C of case to constant weight.
The preparation method of the 1- adamantane modified formaldehyde polylactic acid, includes the following steps: for sodium hydride 0.65kg to be dissolved in
Solution is formed in n,N-Dimethylformamide 18kg, 1- adamantane formaldehyde 0.5kg is then added, and 23 points are stirred at -33 DEG C
Clock, then polylactic acid 3.5kg is added thereto, continues insulation reaction 45 minutes, after be down to room temperature, revolving removes solvent, after use second
It ether washed product 4 times, is washed with water and washs product 3 times, then be placed in a vacuum drying oven at 83 DEG C and dry to constant weight.
The preparation method of the 3D printing material includes the following steps: modified fluoride-containing aminoacyl amido phenylate class polycondensation
Object, 1- adamantane modified formaldehyde polylactic acid, nanometer boron fibre, bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers, KH570 type
Mill at -12 DEG C after silane coupling agent, the mixing of glycerol propoxyl group triglycidyl group ether and prepare mixture, then by mixture and
Liquid propene acid esters rubber is added to extruding pelletization in double screw extruder.
Described mill is carried out in freezing grinding mill, and the revolving speed for freezing grinding mill is 450rpm.
The extruding pelletization squeezes out wire-drawing shape, the extrusion temperature in each area of double screw extruder using double screw extruder
Are as follows: the first 183 DEG C of area, 195 DEG C of the secondth area, 207 DEG C of third area, 213 DEG C of the 4th area, 222 DEG C of the 5th area, die head temperature 223
℃。
Embodiment 3
A kind of 3D printing material, is made of the raw material of following parts by weight: modified fluoride-containing aminoacyl amido phenylate class polycondensation
35 parts of object, 7 parts of 28 part, nanometer boron fibre of 1- adamantane modified formaldehyde polylactic acid, 1 part of pentaerythritol ester, KH792 type silane are even
Join 2 parts of agent, 0.8 part of liquid polybutadiene rubber, 2 parts of ether of glycerol propoxyl group triglycidyl group；The modified fluoride-containing aminoacyl
Amido phenylate class condensation polymer is first by N1, bis- (3- chlorphenyl) malonamides of N3- and bis- (the 3- amino-4-hydroxy benzene of 2,2-
Base) hexafluoropropane generation polycondensation reaction generation condensation polymer, then condensation polymer is modified with single-ended epoxy silicon oil again.
The preparation method of the modified fluoride-containing aminoacyl amido phenylate class condensation polymer, includes the following steps:
I by N1, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of N3- bis- (3- chlorphenyl) malonamide 1kg, 2,2-
1.13kg, potassium hydroxide 0.7kg are added in the there-necked flask for being connected to water segregator, then plus n,N-dimethylacetamide 8kg and toluene
Reaction system is heated to 105 DEG C by 4kg, is stirred to react 4 hours under neon protection, is removed in reaction process by water segregator
The water and toluene of generation eliminate water and reaction temperature are slowly increased to 142 DEG C later, continue return stirring reaction 17.5 hours, instead
Reaction system is cooled to room temperature after answering, is precipitated in water, by the polymer of precipitation with ethanol washing 5 times, then is placed in true
It dries at 90 DEG C of empty drying box to constant weight, obtains condensation polymer；
The condensation polymer 1kg, the single-ended epoxy silicon oil 0.2kg that are prepared by step I are added to dimethyl sulfoxide 4kg by II
In, be stirred to react at 70 DEG C 7 hours, after settle out in water, and with isopropanol washed product 4 times, then be placed in vacuum oven
It dries at 89 DEG C to constant weight.
The preparation method of the 1- adamantane modified formaldehyde polylactic acid includes the following steps: boryl lithium 0.85kg is molten
Solution is formed in n,N-Dimethylformamide 21kg, 1- adamantane formaldehyde 0.5kg is then added, and 25 points are stirred at -35 DEG C
Clock, then polylactic acid 4kg is added thereto, continues insulation reaction 50 minutes, after be down to room temperature, revolving removes solvent, after use ether
It washed product 4 times, is washed with water and washs product 4 times, then be placed in a vacuum drying oven at 86 DEG C and dry to constant weight.
The preparation method of the 3D printing material includes the following steps: modified fluoride-containing aminoacyl amido phenylate class polycondensation
Object, 1- adamantane modified formaldehyde polylactic acid, nanometer boron fibre, pentaerythritol ester, KH792 type silane coupling agent, glycerol propoxyl group
It mills at -10 DEG C after the mixing of triglycidyl group ether and prepares mixture, then mixture and liquid polybutadiene rubber are added
The extruding pelletization into double screw extruder.
Described mill is carried out in freezing grinding mill, and the revolving speed for freezing grinding mill is 500rpm.
The extruding pelletization squeezes out wire-drawing shape, the extrusion temperature in each area of double screw extruder using double screw extruder
Are as follows: the first 186 DEG C of area, 197 DEG C of the secondth area, 208 DEG C of third area, 216 DEG C of the 4th area, 223 DEG C of the 5th area, die head temperature 226
℃。
Embodiment 4
A kind of 3D printing material, is made of the raw material of following parts by weight: modified fluoride-containing aminoacyl amido phenylate class polycondensation
38 parts of object, 1.4 parts of antioxidant, 2.5 parts of coupling agent, increases 9 parts of 33 part, nanometer boron fibre of 1- adamantane modified formaldehyde polylactic acid
Tough dose 0.9 part, 2.5 parts of ether of glycerol propoxyl group triglycidyl group；The modified fluoride-containing aminoacyl amido phenylate class condensation polymer is
Polycondensation occurs by N1, bis- (3- chlorphenyl) malonamides of N3- and bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2- first
Reaction generates condensation polymer, is then modified again with single-ended epoxy silicon oil to condensation polymer.
The antioxidant be 2,6- three-level butyl -4- methylphenol, bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers,
Pentaerythritol ester, double Lauryl Alcohol esters, bi-myristoleyl, double octadecanol ester 1:1:1:2:3:5 in mass ratio are mixed.
The coupling agent is monoalkoxy Pyrophosphate Type Yitanate Coupling Agent, KH570 type silane coupling agent, KH792 type
Silane coupling agent, DL602 type silane coupling agent 1:3:2:5 in mass ratio are mixed.
Toughener is ethylene-vinyl acetate copolymer, liquid propene acid esters rubber, liquid polybutadiene rubber, thermoplastic
Property polyurethane elastomer 1:1:3:2 in mass ratio is mixed.
The preparation method of the modified fluoride-containing aminoacyl amido phenylate class condensation polymer, includes the following steps:
I by N1, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of N3- bis- (3- chlorphenyl) malonamide 1kg, 2,2-
1.13kg, basic catalyst 0.75kg are added in the there-necked flask for being connected to water segregator, then increase boiling point solvent 9kg and toluene 4kg,
Reaction system is heated to 109 DEG C, is stirred to react under protection of argon gas 4.5 hours, is removed by water segregator raw in reaction process
At water and toluene, eliminate and reaction temperature be slowly increased to 145 DEG C after water, continue return stirring and react 19 hours, reaction knot
Reaction system is cooled to room temperature after beam, is precipitated in water, by the polymer of precipitation with ethanol washing 6 times, then vacuum is placed in and does
It dries at 93 DEG C of dry case to constant weight, obtains condensation polymer；The basic catalyst is sodium hydroxide, sodium carbonate, potassium hydroxide, carbonic acid
Potassium 1:3:2:2 in mass ratio is mixed；The high boiling solvent is dimethyl sulfoxide, N,N-dimethylformamide, N, N- diformazan
Yl acetamide, N-Methyl pyrrolidone 1:2:3:2 in mass ratio are mixed；
The condensation polymer 1kg, the single-ended epoxy silicon oil 0.2kg that are prepared by step I are added to dimethyl sulfoxide 4.5kg by II
In, be stirred to react at 75 DEG C 7.5 hours, after settle out in water, and with isopropanol washed product 5 times, then be placed in vacuum drying
It dries at 93 DEG C of case to constant weight.
The preparation method of the 1- adamantane modified formaldehyde polylactic acid, includes the following steps: for catalyst 0.9kg to be dissolved in
Solution is formed in n,N-Dimethylformamide 24kg, 1- adamantane formaldehyde 0.5kg is then added, and 28 points are stirred at -38 DEG C
Clock, then polylactic acid 4.5kg is added thereto, continues insulation reaction 55 minutes, after be down to room temperature, revolving removes solvent, after use second
It ether washed product 5 times, is washed with water and washs product 5 times, then be placed in a vacuum drying oven at 88 DEG C and dry to constant weight；The catalyst
It is that tert-butyl potassium alcoholate, sodium hydride, boryl lithium, boronation trisodium 2:3:3:1 in mass ratio are mixed.
The preparation method of the 3D printing material includes the following steps: modified fluoride-containing aminoacyl amido phenylate class polycondensation
Object, 1- adamantane modified formaldehyde polylactic acid, nanometer boron fibre, antioxidant, coupling agent, glycerol propoxyl group triglycidyl group ether
It mills at -8 DEG C after mixing and prepares mixture, then mixture and toughener are added to extruding pelletization in double screw extruder.
Described mill is carried out in freezing grinding mill, and the revolving speed for freezing grinding mill is 580rpm.
The extruding pelletization squeezes out wire-drawing shape, the extrusion temperature in each area of double screw extruder using double screw extruder
Are as follows: the first 188 DEG C of area, 199 DEG C of the secondth area, 209 DEG C of third area, 218 DEG C of the 4th area, 224 DEG C of the 5th area, die head temperature 228
℃。
Embodiment 5
A kind of 3D printing material, is made of the raw material of following parts by weight: modified fluoride-containing aminoacyl amido phenylate class polycondensation
40 parts of object, 10 parts of 35 part, nanometer boron fibre of 1- adamantane modified formaldehyde polylactic acid, 1.5 parts of double octadecanol esters, DL602 type silicon
3 parts of alkane coupling agent, 1 part of thermoplastic polyurethane elastomer, 3 parts of ether of glycerol propoxyl group triglycidyl group；The modified fluoride-containing ammonia
Base amide groups phenylate class condensation polymer is first by N1, bis- (3- chlorphenyl) malonamides of N3- and the bis- (3- amino -4- hydroxyls of 2,2-
Base phenyl) hexafluoropropane occurs polycondensation reaction and generates condensation polymer, then with single-ended epoxy silicon oil condensation polymer is modified again and
At.
The preparation method of the modified fluoride-containing aminoacyl amido phenylate class condensation polymer, includes the following steps:
I by N1, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of N3- bis- (3- chlorphenyl) malonamide 1kg, 2,2-
1.13kg, potassium carbonate 0.8kg are added in the there-necked flask for being connected to water segregator, then plus N-Methyl pyrrolidone 10kg and toluene 4kg, will
Reaction system is heated to 110 DEG C, is stirred to react under nitrogen protection 5 hours, passes through what is generated in water segregator removing reaction process
Water and toluene eliminate water and reaction temperature are slowly increased to 150 DEG C later, continue return stirring reaction 20 hours, after reaction
Reaction system is cooled to room temperature, is precipitated in water, by the polymer of precipitation with ethanol washing 6 times, then is placed in vacuum oven
It dries at 95 DEG C to constant weight, obtains condensation polymer；
The condensation polymer 1kg, the single-ended epoxy silicon oil 0.2kg that are prepared by step I are added to dimethyl sulfoxide 5kg by II
In, be stirred to react at 80 DEG C 8 hours, after settle out in water, and with isopropanol washed product 5 times, then be placed in vacuum oven
It dries at 95 DEG C to constant weight.
The preparation method of the 1- adamantane modified formaldehyde polylactic acid includes the following steps: for boronation trisodium 1kg to be dissolved in
Solution is formed in n,N-Dimethylformamide 25kg, 1- adamantane formaldehyde 0.5kg is then added, and 30 points are stirred at -40 DEG C
Clock, then polylactic acid 5kg is added thereto, continues insulation reaction 60 minutes, after be down to room temperature, revolving removes solvent, after use ether
It washed product 5 times, is washed with water and washs product 5 times, then be placed in a vacuum drying oven at 90 DEG C and dry to constant weight.
The preparation method of the 3D printing material includes the following steps: modified fluoride-containing aminoacyl amido phenylate class polycondensation
Object, 1- adamantane modified formaldehyde polylactic acid, nanometer boron fibre, double octadecanol esters, DL602 type silane coupling agent, the third oxygen of glycerol
It mills at -5 DEG C after the mixing of base triglycidyl group ether and prepares mixture, then mixture and thermoplastic polyurethane elastomer are added
Enter into double screw extruder extruding pelletization.
Described mill is carried out in freezing grinding mill, and the revolving speed for freezing grinding mill is 600rpm.
The extruding pelletization squeezes out wire-drawing shape, the extrusion temperature in each area of double screw extruder using double screw extruder
Are as follows: the first 190 DEG C of area, 200 DEG C of the secondth area, 210 DEG C of third area, 220 DEG C of the 4th area, 225 DEG C of the 5th area, die head temperature 230
℃。
Comparative example 1
This example provides a kind of 3D printing material, substantially the same manner as Example 1 according to the formula and preparation method of embodiment 1,
The difference is that substituting modified fluoride-containing aminoacyl amido phenylate class condensation polymer with fluorine-containing aminoacyl amido phenylate class condensation polymer.
Comparative example 2
This example provides a kind of 3D printing material, substantially the same manner as Example 1 according to the formula and preparation method of embodiment 1,
The difference is that substituting adamantane modified formaldehyde polylactic acid with polylactic acid.
Comparative example 3
A kind of 3D printing material is made according to the preparation method of 201811051687.6 embodiment 1 of Chinese invention patent.
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 size steady
It is qualitative.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of 3D printing material, which is characterized in that be made of the raw material of following parts by weight: modified fluoride-containing aminoacyl amido benzene
30-40 parts of ethers condensation polymer, 25-35 parts of 1- adamantane modified formaldehyde polylactic acid, 5-10 parts of nanometer boron fibre, antioxidant 0.5-
1.5 parts, 1-3 parts of coupling agent, 0.5-1 parts of toughener, 1-3 parts of triglycidyl group ether of glycerol propoxyl group；The modified fluoride-containing ammonia
Base amide groups phenylate class condensation polymer is first by N1, bis- (3- chlorphenyl) malonamides of N3- and the bis- (3- amino -4- hydroxyls of 2,2-
Base phenyl) hexafluoropropane occurs polycondensation reaction and generates condensation polymer, then with single-ended epoxy silicon oil condensation polymer is modified again and
At.
2. a kind of 3D printing material according to claim 1, which is characterized in that the antioxidant is 2,6- three-level butyl-
4- methylphenol, bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers, pentaerythritol ester, double Lauryl Alcohol esters, double ten four carbon alcohols
One of ester and double octadecanol esters are a variety of；The coupling agent be monoalkoxy Pyrophosphate Type Yitanate Coupling Agent,
One of KH570 type silane coupling agent, KH792 type silane coupling agent and DL602 type silane coupling agent are a variety of；The toughening
Agent is ethylene-vinyl acetate copolymer, liquid propene acid esters rubber, liquid polybutadiene rubber, thermoplastic polyurethane elastic
At least one of body.
3. a kind of 3D printing material according to claim 1, which is characterized in that the modified fluoride-containing aminoacyl amido phenylate
The preparation method of class condensation polymer, includes the following steps:
I by N1, bis- (3- chlorphenyl) malonamides of N3-, 2,2- bis- (3- amino-4-hydroxylphenyl) hexafluoropropane, base catalysis
Agent is added in the there-necked flask for being connected to water segregator, then increases boiling point solvent and toluene, and reaction system is heated to 100-110 DEG C,
It is stirred to react under nitrogen or inert gas shielding 3-5 hours, the water and toluene that generate in reaction process is removed by water segregator, removed
Reaction temperature is slowly increased to 135-150 DEG C after water to the greatest extent, continues return stirring and reacts 15-20 hours, it after reaction will be anti-
It answers system to be cooled to room temperature, is precipitated in water, by the polymer of precipitation with ethanol washing 4-6 times, then be placed in vacuum oven 85-
It dries at 95 DEG C to constant weight, obtains condensation polymer；
II is added to the condensation polymer, the single-ended epoxy silicon oil that are prepared by step I in dimethyl sulfoxide, stirs at 60-80 DEG C
Mix reaction 6-8 hours, after settle out in water, and with isopropanol washed product 3-5 times, then be placed at 85-95 DEG C of vacuum oven
It dries to constant weight.
4. a kind of 3D printing material according to claim 3, which is characterized in that bis- (the 3- chlorobenzenes of N1 described in step I, N3-
Base) malonamide, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-, the matter of basic catalyst, high boiling solvent, toluene
Amount is than being 1:1.13:(0.5-0.8): (6-10): 4；The basic catalyst is selected from sodium hydroxide, sodium carbonate, potassium hydroxide, carbon
At least one of sour potassium；The high boiling solvent is selected from dimethyl sulfoxide, N,N-dimethylformamide, N, N- dimethylacetamide
At least one of amine, N-Methyl pyrrolidone；The inert gas is selected from one of helium, neon, argon gas.
5. a kind of 3D printing material according to claim 3, which is characterized in that condensation polymer described in step II, single-ended ring
Oxygen silicone oil, dimethyl sulfoxide mass ratio be 1:0.2:(3-5).
6. a kind of 3D printing material according to claim 1, which is characterized in that the 1- adamantane modified formaldehyde polylactic acid
Preparation method, include the following steps: for catalyst to be dissolved in n,N-Dimethylformamide and form solution, 1- Buddha's warrior attendant is then added
Alkane formaldehyde stirs 20-30 minutes at -30~-40 DEG C, then polylactic acid is added thereto, continues insulation reaction 40-60 minutes,
After be down to room temperature, revolving removes solvent, rear to use ether washed product 3-5 times, is washed with water and washs product 3-5 times, then is placed in vacuum
It is dried at 80-90 DEG C to constant weight in drying box.
7. a kind of 3D printing material according to claim 6, which is characterized in that the catalyst, N, N- dimethyl formyl
Amine, 1- adamantane formaldehyde, polylactic acid mass ratio be (0.5-1): (15-25): 0.5:(3-5)；The catalyst is selected from tertiary fourth
One or more of base potassium alcoholate, sodium hydride, boryl lithium, boronation trisodium.
8. a kind of 3D printing material according to claim 1-7, which is characterized in that the system of the 3D printing material
Preparation Method, include the following steps: by modified fluoride-containing aminoacyl amido phenylate class condensation polymer, 1- adamantane modified formaldehyde polylactic acid,
Nanometer boron fibre, antioxidant, coupling agent, glycerol propoxyl group triglycidyl group ether mixing after at -15~-5 DEG C the system of milling
Standby mixture, then mixture and toughener are added to extruding pelletization in double screw extruder.
9. a kind of 3D printing material according to claim 8, which is characterized in that it is described mill be freezing grinding mill in into
Capable, the revolving speed for freezing grinding mill is 400-600rpm.
10. a kind of 3D printing material according to claim 8, which is characterized in that the extruding pelletization is squeezed using twin-screw
Machine squeezes out wire-drawing shape, the extrusion temperature in each area of double screw extruder are as follows: the first 180-190 DEG C of area, the second area 192-200 out
DEG C, 205-210 DEG C of third area, the 4th 210-220 DEG C of area, the 5th 220-225 DEG C of area, die head temperature be 220-230 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910315878.7A CN110003665A (en) | 2019-04-19 | 2019-04-19 | A kind of 3D printing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910315878.7A CN110003665A (en) | 2019-04-19 | 2019-04-19 | A kind of 3D printing material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110003665A true CN110003665A (en) | 2019-07-12 |
Family
ID=67172986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910315878.7A Withdrawn CN110003665A (en) | 2019-04-19 | 2019-04-19 | A kind of 3D printing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110003665A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698855A (en) * | 2019-10-08 | 2020-01-17 | 浙江乾欣科技有限公司 | 3D printing material and preparation method thereof |
| CN114180906A (en) * | 2021-11-22 | 2022-03-15 | 蒋雨炎 | Environment-friendly pervious concrete and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440613A (en) * | 2015-11-05 | 2016-03-30 | 张晓军 | PLA 3D printing material and product thereof |
| CN106700456A (en) * | 2015-11-16 | 2017-05-24 | 黑龙江鑫达企业集团有限公司 | Enhanced PLA material for 3D printing |
| CN107266872A (en) * | 2017-06-01 | 2017-10-20 | 北京聚丽威科技有限公司 | A kind of 3D printing high-strength PET copolyester material and preparation method thereof |
| KR20180127694A (en) * | 2017-05-22 | 2018-11-30 | 재단법인 한국탄소융합기술원 | Manufacturing Method for Polymer composite with carbon fiber for 3D printers |
-
2019
- 2019-04-19 CN CN201910315878.7A patent/CN110003665A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440613A (en) * | 2015-11-05 | 2016-03-30 | 张晓军 | PLA 3D printing material and product thereof |
| CN106700456A (en) * | 2015-11-16 | 2017-05-24 | 黑龙江鑫达企业集团有限公司 | Enhanced PLA material for 3D printing |
| KR20180127694A (en) * | 2017-05-22 | 2018-11-30 | 재단법인 한국탄소융합기술원 | Manufacturing Method for Polymer composite with carbon fiber for 3D printers |
| CN107266872A (en) * | 2017-06-01 | 2017-10-20 | 北京聚丽威科技有限公司 | A kind of 3D printing high-strength PET copolyester material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 何敬文: "《药物合成》", 30 September 2013, 中国轻工业出版社 * |
| 苏企洵: "《有机化学反应历程》", 31 December 1965, 高等教育出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698855A (en) * | 2019-10-08 | 2020-01-17 | 浙江乾欣科技有限公司 | 3D printing material and preparation method thereof |
| CN114180906A (en) * | 2021-11-22 | 2022-03-15 | 蒋雨炎 | Environment-friendly pervious concrete and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102040808B (en) | Glass fiber enhanced PET/PBT (Polyethylene Terephthalate)/(Polybutylene Terephthalate) alloy with high glossiness and low warping degree and preparation method thereof | |
| CN110003665A (en) | A kind of 3D printing material and preparation method thereof | |
| CN108276747B (en) | Degradable ribbon material and preparation method thereof | |
| CN103382297B (en) | Fine REINFORCED PET/polyester alloy of a kind of low warpage carbon and preparation method thereof | |
| CN101538401A (en) | High temperature resistance binary fiber/polylactic acid based composite material and preparation method thereof | |
| CN102070884B (en) | Fire resistant glass fiber reinforced polyethylene terephthalate/polybutylece terephthalate alloy and preparation method thereof | |
| CN109720055B (en) | Polyvinyl alcohol/polylactic acid composite film and preparation method thereof | |
| CN109486142B (en) | Polylactic acid-polycaprolactone composite material for 3D printing and preparation method thereof | |
| CN104629280A (en) | High-strength high-toughness polyactic acid composite material suitable for 3D printing molding and preparation method of composite material | |
| CN1995124A (en) | High tenacious polypropylene material for manufacturing central conditioner air-discharge hose and its preparation method | |
| CN113321869A (en) | Scratch-resistant easy-spraying polypropylene composite material and preparation method and application thereof | |
| CN114773810B (en) | High-performance polylactic acid-based 3D printing wire rod and preparation method thereof | |
| CN117362946B (en) | Nanocellulose modified polyester composite material and preparation method thereof | |
| CN109504089A (en) | A kind of low cost polysulfones alloy | |
| CN113429762A (en) | Starch/polylactic acid/PBAT nano composite material and preparation method thereof | |
| CN115260751B (en) | Preparation method of extrusion-grade super-tough nylon | |
| CN111363351A (en) | Polyamide 66 composition and preparation method thereof | |
| CN106700040A (en) | Method for preparing polylactic acid through twin screw reactive extrusion method and ring open polymerization method | |
| CN113831732A (en) | Low-water-absorption high-toughness high-temperature nylon composite material and preparation method thereof | |
| CN111499801B (en) | Reactive flame retardant and vinyl SMC resin containing same | |
| CN109825065B (en) | Preparation process of sensor shell | |
| CN106674740A (en) | Polypropylene (PP) composite material specially used for packaging bags, and preparation method of PP composite material | |
| CN112552631A (en) | Degradable pearl cotton and low-temperature degradation treatment process thereof | |
| CN110804309A (en) | 3D printing polymer powder material and preparation method thereof | |
| CN110936584B (en) | Processing method of polyvinyl alcohol hollow container |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190712 |
|
| WW01 | Invention patent application withdrawn after publication |