CN106433178A - Glass fiber composite material for 3D printing - Google Patents
Glass fiber composite material for 3D printing Download PDFInfo
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- CN106433178A CN106433178A CN201610914382.8A CN201610914382A CN106433178A CN 106433178 A CN106433178 A CN 106433178A CN 201610914382 A CN201610914382 A CN 201610914382A CN 106433178 A CN106433178 A CN 106433178A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
Abstract
The invention discloses a glass fiber composite material for 3D printing, belonging to the technical field of the preparation of materials for the 3D printing. The glass fiber composite material comprises the following raw materials in parts by weight: 82-124 parts of glass fiber, 24-32 parts of waste plastic, 8-14 parts of octadecanamide, 4-8 parts of metacetaldehyde, 6-12 parts of polycarbonate, 5-9 parts of polypropylene resin, 7-11 parts of PBT resin, 6-10 parts of dibutyl phthalate, 9-16 parts of stearic acid, 4-7 parts of polyacrylamide, 12-20 parts of a specific synthesis agent and 8-12 parts of a flame retardant. The prepared glass fiber composite material has the characteristics of great tensile strength, bending strength and notch impact strength, high heat distortion temperature and melt index and the like; and a product printed by virtue of a 3D printing technique has high quality, impact resistance and strength and wide market prospect.
Description
Technical field
The invention belongs to 3D printing technical field of material, and in particular to a kind of 3D printing glass fibre composite wood
Material.
Background technology
Glass fibre is a kind of Inorganic Non-metallic Materials of excellent performance, and species is various, with good insulating, thermostability
By force, corrosion resistance is good, the advantages of high mechanical strength.Glass fibre is typically used as the reinforcing material in composite, and be electrically insulated material
Material and heat-insulating material, the national economy every field such as circuit substrate.Galss fiber reinforced resin based composites, are current
The ripe and widely used class composite of Technical comparing, with good formability, good insulation preformance, anticorrosive and tired
Excellent properties and the cheap costs such as strain wound.
Glass fiber compound material can be used for the material of 3D printing, and the product stiffness of printing is mainly subject to glass fibre
The impact of composite, therefore, the intensity for improving glass fiber compound material is the important means of improve product quality.
Chinese patent application document " a kind of glass fiber compound material for 3D printing and preparation method thereof "（Open
Number：CN104479282A）, a kind of glass fiber compound material for 3D printing is disclosed, including：Glass fibre 50-60 part,
Ethylene bis stearic acid amide 5-10 part, ABS plastic 10-15 part, polyformaldehyde 3-5 part, Merlon 5-10 part, 0.5 part of stearic acid,
Methylbenzene acrylamide 1-3 part, Palmic acid magnesium soap 1-3 part, antioxidant 3-5 part, 3-5 parts of coupling agent, the glass of the 3D printing
It is little that fibrous composite has tensile strength, bending strength and a notch impact strength, and heat distortion temperature and melt index are low
Problem.
Content of the invention
The present invention provides a kind of 3D printing glass fiber compound material, is combined with the glass fibre that solves existing 3D printing
It is little that material has tensile strength, bending strength and a notch impact strength, heat distortion temperature and the low problem of melt index.This
It is big that the bright 3D printing glass fiber compound material that makes has tensile strength, bending strength and a notch impact strength, thermal deformation
The features such as temperature and high melt index, the product high-quality for being printed by 3D printing technique, high-impact, high intensity, have
Wide market prospect.
For solving above technical problem, the present invention is employed the following technical solutions：
A kind of 3D printing glass fiber compound material, in units of weight portion, including following raw material：Glass fibre 82-124
Part, waste plastic 24-32 part, stearic amide 8-14 part, metacetaldehyde 4-8 part, Merlon 6-12 part, acrylic resin 5-9
Part, PBT resin 7-11 part, dibutyl phthalate 6-10 part, stearic acid 9-16 part, polyacrylamide 4-7 part, specific synthesis
Agent 12-20 part, fire retardant 8-12 part；
The specific syntheticses in units of weight portion, including following raw material：Initiator 3-5 part, catalyst 1-3 part, regulator
8-12 part, viscosifier 3-5 part, propellant 7-11 part, coupling agent 10-14 part, compatilizer 9-14 part, plasticizer 7-13 part, toughness reinforcing
Agent 8-12 part, antioxidant 6-12 part, flocculation agent 5-9 part, terminator 2-4 part, stabilizer 3-5 part；
The initiator is two isopropylformic acid. of azo（Acrylic acid ethylene glycol）Ester；
The catalyst is platinum catalyst；
The toughener is poly- propylene diene rubber；
The antioxidant is antioxidant 1076；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer is organic tin stabilizer；
The fire retardant in units of weight portion, including following raw material：Triphenyl phosphate 23-28 part, alkyd resin 10-16 part,
Diammonium phosphate 11-14 part, aluminium hydroxide 7-12 part, antimony oxide 6-9 part, silane 5-8 part, kieselguhr 4-7 part, fatty alcohol
Polyoxyethylene ether 1-1.8 part；
The preparation method of described 3D printing glass fiber compound material, comprises the following steps：
S1：Glass fibre is infiltrated using coupling agent 560, just level fiberglass is obtained；
S2：Using duroplastss disintegrating machine, preliminary crushing is carried out to waste plastic, will followed by batch type plastic cleaning machine
The waste plastic for crushing carries out thoroughly cleaning, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are -90--110 DEG C in temperature
Lower by plastic crushing 2-3h, obtain the plastic grains of 400-600 mesh after sieving；
S4：By plastic grains, stearic amide, metacetaldehyde, poly- carbon obtained in first level fiberglass, step S1 obtained in step S1
Acid esters, acrylic resin, PBT resin, dibutyl phthalate, stearic acid, polyacrylamide, specific syntheticses, fire retardant
Mixing, is warming up to 231-246 DEG C, and stirring under rotating speed is for 200-400r/min melts 2.5-3.5h, is subsequently cooled to room temperature, system
Obtain modified glass fibre 3D printing secondary-material；
The preparation method of the specific syntheticses, comprises the following steps：
（a）Propellant, coupling agent, initiator, catalyst, compatilizer, antioxidant mixing are warming up to 123-131 DEG C, are being turned
Speed is for reacting 52-78 min, prepared material A under 200-300r/min；
（b）To in material A obtained in step a, add regulator, flocculation agent, viscosifier 158-164 DEG C to be warming up to after mixing, turning
Speed is for reacting 128-212 min, prepared material B under 200-400r/min；
（c）To in material B obtained in step b, add plasticizer, toughener, terminator, stabilizer to be cooled to 126-135 after mixing
DEG C, 52-112 min is reacted under rotating speed is for 200-300r/min, specific syntheticses are obtained；
The preparation method of the fire retardant, comprises the following steps：
（1）Diammonium phosphate, water 120-150 part are added in microwave reactor, is stirred under speed of agitator is for 200-300r/min
9-12min is mixed, prepared mixture a；
（2）Triphenyl phosphate, alkyd resin, aluminium hydroxide, antimony oxide, silicon is added in mixture a obtained in step 1
Alkane, kieselguhr, fatty alcohol-polyoxyethylene ether, are 300-500r/min in speed of agitator, and microwave power is that 200-225W, temperature is
1.2-1.7h, prepared mixture b is stirred at 84-93 DEG C；
（3）Mixture b obtained in step 2 is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤3.2%, prepared fire retardant；
S5：Put after modified glass fibre 3D printing secondary-material obtained in step S4 is crushed at temperature is -92--118 DEG C
Enter in screw extruding forming machine, be 209-218 DEG C in temperature, rotating speed is under 210-434r/min, melt extrudes pelletize, prepared 3D
Printing glass fiber compound material.
Further, the regulator is ACR.
Further, the viscosifier are propyl trimethoxy silicane.
Further, the propellant is aerogel generating agent.
Further, the coupling agent is coupling agent 560.
Further, the compatilizer is acrylic type compatilizer.
Further, the plasticizer is citrate.
The invention has the advantages that：
（1）The present invention uses waste plastic, and source is wide, and price is low, has widened the range of choice of 3D printing material feedstock；
（2）It is strong that the 3D printing glass fiber compound material that the present invention makes has tensile strength, bending strength and notch shock
Degree is big, the features such as heat distortion temperature and high melt index, the product high-quality that printed by 3D printing technique, high-impact,
High intensity, with wide market prospect；
（3）The 3D printing that the present invention makes glass fiber compound material low cost, it is easy to industrialized production.
Specific embodiment
For ease of more fully understanding the present invention, it is illustrated by following examples, these embodiments belong to the present invention's
Protection domain, but do not limit the scope of the invention.
In an embodiment, the 3D printing glass fiber compound material, in units of weight portion, including following raw material：
Glass fibre 82-124 part, waste plastic 24-32 part, stearic amide 8-14 part, metacetaldehyde 4-8 part, Merlon 6-12 part,
Acrylic resin 5-9 part, PBT resin 7-11 part, dibutyl phthalate 6-10 part, stearic acid 9-16 part, polyacrylamide
4-7 part, specific syntheticses 12-20 part, fire retardant 8-12 part；
The specific syntheticses in units of weight portion, including following raw material：Initiator 3-5 part, catalyst 1-3 part, regulator
8-12 part, viscosifier 3-5 part, propellant 7-11 part, coupling agent 10-14 part, compatilizer 9-14 part, plasticizer 7-13 part, toughness reinforcing
Agent 8-12 part, antioxidant 6-12 part, flocculation agent 5-9 part, terminator 2-4 part, stabilizer 3-5 part；
The initiator is two isopropylformic acid. of azo（Acrylic acid ethylene glycol）Ester；
The catalyst is platinum catalyst；
The regulator is ACR；
The viscosifier are propyl trimethoxy silicane；
The propellant is aerogel generating agent；
The coupling agent is coupling agent 560；
The compatilizer is acrylic type compatilizer；
The plasticizer is citrate；
The toughener is poly- propylene diene rubber；
The antioxidant is antioxidant 1076；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer is organic tin stabilizer；
The fire retardant in units of weight portion, including following raw material：Triphenyl phosphate 23-28 part, alkyd resin 10-16 part,
Diammonium phosphate 11-14 part, aluminium hydroxide 7-12 part, antimony oxide 6-9 part, silane 5-8 part, kieselguhr 4-7 part, fatty alcohol
Polyoxyethylene ether 1-1.8 part；
The preparation method of described 3D printing glass fiber compound material, comprises the following steps：
S1：Glass fibre is infiltrated using coupling agent 560, just level fiberglass is obtained；
S2：Using duroplastss disintegrating machine, preliminary crushing is carried out to waste plastic, will followed by batch type plastic cleaning machine
The waste plastic for crushing carries out thoroughly cleaning, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are -90--110 DEG C in temperature
Lower by plastic crushing 2-3h, obtain the plastic grains of 400-600 mesh after sieving；
S4：By plastic grains, stearic amide, metacetaldehyde, poly- carbon obtained in first level fiberglass, step S1 obtained in step S1
Acid esters, acrylic resin, PBT resin, dibutyl phthalate, stearic acid, polyacrylamide, specific syntheticses, fire retardant
Mixing, is warming up to 231-246 DEG C, and stirring under rotating speed is for 200-400r/min melts 2.5-3.5h, is subsequently cooled to room temperature, system
Obtain modified glass fibre 3D printing secondary-material；
The preparation method of the specific syntheticses, comprises the following steps：
（a）Propellant, coupling agent, initiator, catalyst, compatilizer, antioxidant mixing are warming up to 123-131 DEG C, are being turned
Speed is for reacting 52-78 min, prepared material A under 200-300r/min；
（b）To in material A obtained in step a, add regulator, flocculation agent, viscosifier 158-164 DEG C to be warming up to after mixing, turning
Speed is for reacting 128-212 min, prepared material B under 200-400r/min；
（c）To in material B obtained in step b, add plasticizer, toughener, terminator, stabilizer to be cooled to 126-135 after mixing
DEG C, 52-112 min is reacted under rotating speed is for 200-300r/min, specific syntheticses are obtained；
The preparation method of the fire retardant, comprises the following steps：
（1）Diammonium phosphate, water 120-150 part are added in microwave reactor, is stirred under speed of agitator is for 200-300r/min
9-12min is mixed, prepared mixture a；
（2）Triphenyl phosphate, alkyd resin, aluminium hydroxide, antimony oxide, silicon is added in mixture a obtained in step 1
Alkane, kieselguhr, fatty alcohol-polyoxyethylene ether, are 300-500r/min in speed of agitator, and microwave power is that 200-225W, temperature is
1.2-1.7h, prepared mixture b is stirred at 84-93 DEG C；
（3）Mixture b obtained in step 2 is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤3.2%, prepared fire retardant；
S5：Put after modified glass fibre 3D printing secondary-material obtained in step S4 is crushed at temperature is -92--118 DEG C
Enter in screw extruding forming machine, be 209-218 DEG C in temperature, rotating speed is under 210-434r/min, melt extrudes pelletize, prepared 3D
Printing glass fiber compound material.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of 3D printing glass fiber compound material, in units of weight portion, including following raw material：103 parts of glass fibre, useless
Abandon 28 parts of plastics, 12 parts of stearic amide, 6 parts of metacetaldehyde, 9 parts of Merlon, 7 parts of acrylic resin, 9 parts of PBT resin, adjacent benzene
8 parts of dibutyl carboxylic acid, 12 parts of stearic acid, 6 parts of polyacrylamide, 16 parts of specific syntheticses, 10 parts of fire retardant；
The specific syntheticses in units of weight portion, including following raw material：4 parts of initiator, 2 parts of catalyst, regulator 10
Part, 4 parts of viscosifier, 9 parts of propellant, 12 parts of coupling agent, 13 parts of compatilizer, 10 parts of plasticizer, 11 parts of toughener, antioxidant 9
Part, 7 parts of flocculation agent, 3 parts of terminator, 4 parts of stabilizer；
The initiator is two isopropylformic acid. of azo（Acrylic acid ethylene glycol）Ester；
The catalyst is platinum catalyst；
The regulator is ACR；
The viscosifier are propyl trimethoxy silicane；
The propellant is aerogel generating agent；
The coupling agent is coupling agent 560；
The compatilizer is acrylic type compatilizer；
The plasticizer is citrate；
The toughener is poly- propylene diene rubber；
The antioxidant is antioxidant 1076；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer is organic tin stabilizer；
The fire retardant in units of weight portion, including following raw material：25 parts of triphenyl phosphate, 13 parts of alkyd resin, phosphoric acid hydrogen
13 parts of diammonium, 10 parts of aluminium hydroxide, 8 parts of antimony oxide, 7 parts of silane, 6 parts of kieselguhr, 1.5 parts of fatty alcohol-polyoxyethylene ether；
The preparation method of described 3D printing glass fiber compound material, comprises the following steps：
S1：Glass fibre is infiltrated using coupling agent 560, just level fiberglass is obtained；
S2：Using duroplastss disintegrating machine, preliminary crushing is carried out to waste plastic, will followed by batch type plastic cleaning machine
The waste plastic for crushing carries out thoroughly cleaning, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, will at temperature is -100 DEG C
Plastic crushing 2.5h, obtains the plastic grains of 500 mesh after sieving；
S4：By plastic grains, stearic amide, metacetaldehyde, poly- carbon obtained in first level fiberglass, step S1 obtained in step S1
Acid esters, acrylic resin, PBT resin, dibutyl phthalate, stearic acid, polyacrylamide, specific syntheticses, fire retardant
Mixing, is warming up to 242 DEG C, and stirring under rotating speed is for 300r/min melts 3h, is subsequently cooled to room temperature, and modified glass fibers are obtained
Dimension 3D printing secondary-material；
The preparation method of the specific syntheticses, comprises the following steps：
（a）Propellant, coupling agent, initiator, catalyst, compatilizer, antioxidant mixing are warming up to 126 DEG C, in rotating speed are
65 min, prepared material A is reacted under 250r/min；
（b）To in material A obtained in step a, add regulator, flocculation agent, viscosifier 162 DEG C to be warming up to after mixing, in rotating speed be
180 min, prepared material B are reacted under 300r/min；
（c）To in material B obtained in step b, add plasticizer, toughener, terminator, stabilizer to be cooled to 130 DEG C after mixing,
85min is reacted under rotating speed is for 250r/min, specific syntheticses are obtained；
The preparation method of the fire retardant, comprises the following steps：
（1）Diammonium phosphate, 135 parts of water are added in microwave reactor, under speed of agitator is for 250r/min, 10min is stirred,
Prepared mixture a；
（2）Triphenyl phosphate, alkyd resin, aluminium hydroxide, antimony oxide, silicon is added in mixture a obtained in step 1
Alkane, kieselguhr, fatty alcohol-polyoxyethylene ether, are 400r/min in speed of agitator, and microwave power is to stir at 215W, temperature is 89 DEG C
1.5h is mixed, prepared mixture b；
（3）Mixture b obtained in step 2 is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 4000r/min
It is 3.2%, prepared fire retardant to dry to water content；
S5：Spiral shell is put into after modified glass fibre 3D printing secondary-material obtained in step S4 is crushed at temperature is -100 DEG C
In bar single lead screw ex truding briquetting machine, it is 213 DEG C in temperature, rotating speed is under 320r/min, melt extrudes pelletize, prepared 3D printing glass fibers
Dimension composite.
Embodiment 2
A kind of 3D printing glass fiber compound material, in units of weight portion, including following raw material：82 parts of glass fibre, useless
Abandon 24 parts of plastics, 8 parts of stearic amide, 4 parts of metacetaldehyde, 6 parts of Merlon, 5 parts of acrylic resin, 7 parts of PBT resin, adjacent benzene
6 parts of dibutyl carboxylic acid, 9 parts of stearic acid, 4 parts of polyacrylamide, 12 parts of specific syntheticses, 8 parts of fire retardant；
The specific syntheticses in units of weight portion, including following raw material：3 parts of initiator, 1 part of catalyst, 8 parts of regulator,
3 parts of viscosifier, 7 parts of propellant, 10 parts of coupling agent, 9 parts of compatilizer, 7 parts of plasticizer, 8 parts of toughener, 6 parts of antioxidant, coacervation
5 parts of agent, 2 parts of terminator, 3 parts of stabilizer；
The initiator is two isopropylformic acid. of azo（Acrylic acid ethylene glycol）Ester；
The catalyst is platinum catalyst；
The regulator is ACR；
The viscosifier are propyl trimethoxy silicane；
The propellant is aerogel generating agent；
The coupling agent is coupling agent 560；
The compatilizer is acrylic type compatilizer；
The plasticizer is citrate；
The toughener is poly- propylene diene rubber；
The antioxidant is antioxidant 1076；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer is organic tin stabilizer；
The fire retardant in units of weight portion, including following raw material：23 parts of triphenyl phosphate, 10 parts of alkyd resin, phosphoric acid hydrogen
11 parts of diammonium, 7 parts of aluminium hydroxide, 6 parts of antimony oxide, 5 parts of silane, 4 parts of kieselguhr, 1 part of fatty alcohol-polyoxyethylene ether；
The preparation method of described 3D printing glass fiber compound material, comprises the following steps：
S1：Glass fibre is infiltrated using coupling agent 560, just level fiberglass is obtained；
S2：Using duroplastss disintegrating machine, preliminary crushing is carried out to waste plastic, will followed by batch type plastic cleaning machine
The waste plastic for crushing carries out thoroughly cleaning, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, will modeling at temperature is -90 DEG C
The broken 3h of feed powder, obtains the plastic grains of 400 mesh after sieving；
S4：By plastic grains, stearic amide, metacetaldehyde, poly- carbon obtained in first level fiberglass, step S1 obtained in step S1
Acid esters, acrylic resin, PBT resin, dibutyl phthalate, stearic acid, polyacrylamide, specific syntheticses, fire retardant
Mixing, is warming up to 231 DEG C, and stirring under rotating speed is for 200r/min melts 3.5h, is subsequently cooled to room temperature, and modified glass is obtained
Fiber 3D printing secondary-material；
The preparation method of the specific syntheticses, comprises the following steps：
（a）Propellant, coupling agent, initiator, catalyst, compatilizer, antioxidant mixing are warming up to 123 DEG C, in rotating speed are
78 min, prepared material A is reacted under 200r/min；
（b）To in material A obtained in step a, add regulator, flocculation agent, viscosifier 158 DEG C to be warming up to after mixing, in rotating speed be
212 min, prepared material B are reacted under 200r/min；
（c）To in material B obtained in step b, add plasticizer, toughener, terminator, stabilizer to be cooled to 126 DEG C after mixing,
112 min are reacted under rotating speed is for 200r/min, specific syntheticses are obtained；
The preparation method of the fire retardant, comprises the following steps：
（1）Diammonium phosphate, 120 parts of water are added in microwave reactor, under speed of agitator is for 200r/min, 12min is stirred,
Prepared mixture a；
（2）Triphenyl phosphate, alkyd resin, aluminium hydroxide, antimony oxide, silicon is added in mixture a obtained in step 1
Alkane, kieselguhr, fatty alcohol-polyoxyethylene ether, are 300r/min in speed of agitator, and microwave power is to stir at 200W, temperature is 84 DEG C
1.7h is mixed, prepared mixture b；
（3）Mixture b obtained in step 2 is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 3000r/min
It is 2.8%, prepared fire retardant to dry to water content；
S5：Spiral shell is put into after modified glass fibre 3D printing secondary-material obtained in step S4 is crushed at temperature is -92 DEG C
In bar single lead screw ex truding briquetting machine, it is 209 DEG C in temperature, rotating speed is under 210r/min, melt extrudes pelletize, prepared 3D printing glass fibers
Dimension composite.
Embodiment 3
A kind of 3D printing glass fiber compound material, in units of weight portion, including following raw material：124 parts of glass fibre, useless
Abandon 32 parts of plastics, 14 parts of stearic amide, 8 parts of metacetaldehyde, 12 parts of Merlon, 9 parts of acrylic resin, 11 parts of PBT resin, neighbour
10 parts of phthalic acid dibutyl ester, 16 parts of stearic acid, 7 parts of polyacrylamide, 20 parts of specific syntheticses, 12 parts of fire retardant；
The specific syntheticses in units of weight portion, including following raw material：5 parts of initiator, 3 parts of catalyst, 12 parts of regulator,
5 parts of viscosifier, 11 parts of propellant, 14 parts of coupling agent, 14 parts of compatilizer, 13 parts of plasticizer, 12 parts of toughener, antioxidant 12
Part, 9 parts of flocculation agent, 4 parts of terminator, 5 parts of stabilizer；
The initiator is two isopropylformic acid. of azo（Acrylic acid ethylene glycol）Ester；
The catalyst is platinum catalyst；
The regulator is ACR；
The viscosifier are propyl trimethoxy silicane；
The propellant is aerogel generating agent；
The coupling agent is coupling agent 560；
The compatilizer is acrylic type compatilizer；
The plasticizer is citrate；
The toughener is poly- propylene diene rubber；
The antioxidant is antioxidant 1076；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer is organic tin stabilizer；
The fire retardant in units of weight portion, including following raw material：28 parts of triphenyl phosphate, 16 parts of alkyd resin, phosphoric acid hydrogen
14 parts of diammonium, 12 parts of aluminium hydroxide, 9 parts of antimony oxide, 8 parts of silane, 7 parts of kieselguhr, 1.8 parts of fatty alcohol-polyoxyethylene ether；
The preparation method of described 3D printing glass fiber compound material, comprises the following steps：
S1：Glass fibre is infiltrated using coupling agent 560, just level fiberglass is obtained；
S2：Using duroplastss disintegrating machine, preliminary crushing is carried out to waste plastic, will followed by batch type plastic cleaning machine
The waste plastic for crushing carries out thoroughly cleaning, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, will at temperature is -110 DEG C
Plastic crushing 2h, obtains the plastic grains of 600 mesh after sieving；
S4：By plastic grains, stearic amide, metacetaldehyde, poly- carbon obtained in first level fiberglass, step S1 obtained in step S1
Acid esters, acrylic resin, PBT resin, dibutyl phthalate, stearic acid, polyacrylamide, specific syntheticses, fire retardant
Mixing, is warming up to 246 DEG C, and stirring under rotating speed is for 400r/min melts 2.5h, is subsequently cooled to room temperature, and modified glass is obtained
Fiber 3D printing secondary-material；
The preparation method of the specific syntheticses, comprises the following steps：
（a）Propellant, coupling agent, initiator, catalyst, compatilizer, antioxidant mixing are warming up to 131 DEG C, in rotating speed are
52 min, prepared material A is reacted under 300r/min；
（b）To in material A obtained in step a, add regulator, flocculation agent, viscosifier 164 DEG C to be warming up to after mixing, in rotating speed be
128 min, prepared material B are reacted under 400r/min；
（c）To in material B obtained in step b, add plasticizer, toughener, terminator, stabilizer to be cooled to 135 DEG C after mixing,
52 min are reacted under rotating speed is for 300r/min, specific syntheticses are obtained；
The preparation method of the fire retardant, comprises the following steps：
（1）Diammonium phosphate, 150 parts of water are added in microwave reactor, and 9min, system is stirred under speed of agitator is for 300r/min
Obtain mixture a；
（2）Triphenyl phosphate, alkyd resin, aluminium hydroxide, antimony oxide, silicon is added in mixture a obtained in step 1
Alkane, kieselguhr, fatty alcohol-polyoxyethylene ether, are 500r/min in speed of agitator, and microwave power is to stir at 225W, temperature is 93 DEG C
1.2h is mixed, prepared mixture b；
（3）Mixture b obtained in step 2 is cooled to after room temperature, precipitate is filtered, be centrifuged under rotating speed is for 5000r/min
It is 2.5%, prepared fire retardant to dry to water content；
S5：Spiral shell is put into after modified glass fibre 3D printing secondary-material obtained in step S4 is crushed at temperature is -118 DEG C
In bar single lead screw ex truding briquetting machine, it is 218 DEG C in temperature, rotating speed is under 434r/min, melt extrudes pelletize, prepared 3D printing glass fibers
Dimension composite.
3D printing in embodiment 1-3 is detected with glass fiber compound material performance, as a result as shown in the table.
Above content it cannot be assumed that the present invention is embodied as being confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of without departing from present inventive concept, some simple deduction or replace can also be made, all answered
When being considered as belonging to the scope of patent protection that the present invention is determined by the claims that is submitted to.
Claims (7)
1. a kind of 3D printing glass fiber compound material, it is characterised in that in units of weight portion, including following raw material：Glass
Glass fiber 82-124 part, waste plastic 24-32 part, stearic amide 8-14 part, metacetaldehyde 4-8 part, Merlon 6-12 part, poly-
Allyl resin 5-9 part, PBT resin 7-11 part, dibutyl phthalate 6-10 part, stearic acid 9-16 part, polyacrylamide 4-7
Part, specific syntheticses 12-20 part, fire retardant 8-12 part；
The specific syntheticses in units of weight portion, including following raw material：Initiator 3-5 part, catalyst 1-3 part, regulator
8-12 part, viscosifier 3-5 part, propellant 7-11 part, coupling agent 10-14 part, compatilizer 9-14 part, plasticizer 7-13 part, toughness reinforcing
Agent 8-12 part, antioxidant 6-12 part, flocculation agent 5-9 part, terminator 2-4 part, stabilizer 3-5 part；
The initiator is two isopropylformic acid. of azo（Acrylic acid ethylene glycol）Ester；
The catalyst is platinum catalyst；
The toughener is poly- propylene diene rubber；
The antioxidant is antioxidant 1076；
The flocculation agent is aluminium polychlorid；
The terminator is wood tar；
The stabilizer is organic tin stabilizer；
The fire retardant in units of weight portion, including following raw material：Triphenyl phosphate 23-28 part, alkyd resin 10-16 part,
Diammonium phosphate 11-14 part, aluminium hydroxide 7-12 part, antimony oxide 6-9 part, silane 5-8 part, kieselguhr 4-7 part, fatty alcohol
Polyoxyethylene ether 1-1.8 part；
The preparation method of described 3D printing glass fiber compound material, comprises the following steps：
S1：Glass fibre is infiltrated using coupling agent 560, just level fiberglass is obtained；
S2：Using duroplastss disintegrating machine, preliminary crushing is carried out to waste plastic, will followed by batch type plastic cleaning machine
The waste plastic for crushing carries out thoroughly cleaning, removes the dirt on surface, after natural air drying is selected, selected plastics is obtained；
S3：Selected plastics obtained in step S2 are placed in the Lowtemperaturepulverizer of nitrogen or dry ice, are -90--110 DEG C in temperature
Lower by plastic crushing 2-3h, obtain the plastic grains of 400-600 mesh after sieving；
S4：By plastic grains, stearic amide, metacetaldehyde, poly- carbon obtained in first level fiberglass, step S1 obtained in step S1
Acid esters, acrylic resin, PBT resin, dibutyl phthalate, stearic acid, polyacrylamide, specific syntheticses, fire retardant
Mixing, is warming up to 231-246 DEG C, and stirring under rotating speed is for 200-400r/min melts 2.5-3.5h, is subsequently cooled to room temperature, system
Obtain modified glass fibre 3D printing secondary-material；
The preparation method of the specific syntheticses, comprises the following steps：
（a）Propellant, coupling agent, initiator, catalyst, compatilizer, antioxidant mixing are warming up to 123-131 DEG C, are being turned
Speed is for reacting 52-78 min, prepared material A under 200-300r/min；
（b）To in material A obtained in step a, add regulator, flocculation agent, viscosifier 158-164 DEG C to be warming up to after mixing, turning
Speed is for reacting 128-212 min, prepared material B under 200-400r/min；
（c）To in material B obtained in step b, add plasticizer, toughener, terminator, stabilizer to be cooled to 126-135 after mixing
DEG C, 52-112 min is reacted under rotating speed is for 200-300r/min, specific syntheticses are obtained；
The preparation method of the fire retardant, comprises the following steps：
（1）Diammonium phosphate, water 120-150 part are added in microwave reactor, is stirred under speed of agitator is for 200-300r/min
9-12min is mixed, prepared mixture a；
（2）Triphenyl phosphate, alkyd resin, aluminium hydroxide, antimony oxide, silicon is added in mixture a obtained in step 1
Alkane, kieselguhr, fatty alcohol-polyoxyethylene ether, are 300-500r/min in speed of agitator, and microwave power is that 200-225W, temperature is
1.2-1.7h, prepared mixture b is stirred at 84-93 DEG C；
（3）Mixture b obtained in step 2 is cooled to after room temperature, precipitate is filtered, under rotating speed is for 3000-5000r/min
Centrifugal drying to water content≤3.2%, prepared fire retardant；
S5：Put after modified glass fibre 3D printing secondary-material obtained in step S4 is crushed at temperature is -92--118 DEG C
Enter in screw extruding forming machine, be 209-218 DEG C in temperature, rotating speed is under 210-434r/min, melt extrudes pelletize, prepared 3D
Printing glass fiber compound material.
2. 3D printing glass fiber compound material according to claim 1, it is characterised in that the regulator be.
3. 3D printing glass fiber compound material according to claim 1, it is characterised in that the viscosifier be
Methoxy silane.
4. 3D printing glass fiber compound material according to claim 1, it is characterised in that the propellant be
Propellant.
5. 3D printing glass fiber compound material according to claim 1, it is characterised in that the coupling agent be
560.
6. 3D printing glass fiber compound material according to claim 1, it is characterised in that the compatilizer be
Type compatilizer.
7. 3D printing glass fiber compound material according to claim 1, it is characterised in that the plasticizer be
Ester.
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| CN201610914382.8A CN106433178A (en) | 2016-10-20 | 2016-10-20 | Glass fiber composite material for 3D printing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610914382.8A CN106433178A (en) | 2016-10-20 | 2016-10-20 | Glass fiber composite material for 3D printing |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113501658A (en) * | 2021-08-02 | 2021-10-15 | 湖北嘉辐达节能科技股份有限公司 | Glass fiber composite material suitable for 3D printing and printing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479282A (en) * | 2014-12-11 | 2015-04-01 | 四川威玻股份有限公司 | Glass fiber composite material for 3D printing and preparation method of glass fiber composite material |
| CN105925003A (en) * | 2016-07-12 | 2016-09-07 | 广西南宁桂尔创环保科技有限公司 | Environment-friendly 3D printing material |
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2016
- 2016-10-20 CN CN201610914382.8A patent/CN106433178A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479282A (en) * | 2014-12-11 | 2015-04-01 | 四川威玻股份有限公司 | Glass fiber composite material for 3D printing and preparation method of glass fiber composite material |
| CN105925003A (en) * | 2016-07-12 | 2016-09-07 | 广西南宁桂尔创环保科技有限公司 | Environment-friendly 3D printing material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113501658A (en) * | 2021-08-02 | 2021-10-15 | 湖北嘉辐达节能科技股份有限公司 | Glass fiber composite material suitable for 3D printing and printing method |
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Application publication date: 20170222 |