CN106751630A - A kind of printing consumables with high impact-resistance and preparation method thereof - Google Patents

A kind of printing consumables with high impact-resistance and preparation method thereof Download PDF

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CN106751630A
CN106751630A CN201710143549.XA CN201710143549A CN106751630A CN 106751630 A CN106751630 A CN 106751630A CN 201710143549 A CN201710143549 A CN 201710143549A CN 106751630 A CN106751630 A CN 106751630A
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parts
agent
mixture
printing consumables
high impact
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冯可发
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Guangxi Feng Da Three Dimensional Technology Co Ltd
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Guangxi Feng Da Three Dimensional Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/28Treatment by wave energy or particle radiation
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer 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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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

The invention discloses a kind of printing consumables with high impact-resistance and preparation method thereof, belong to 3D printing technical field of material, the printing consumables with high impact-resistance includes following raw material:Dolomite dust, corn stalk powder, waste plastic, PLA, four PA 800Ks, stearyl acrylate acid esters, surfactant, conditioning agent, propellant, coupling agent, catalyst, plasticizer, dispersant, tackifier, softening agent, curing agent, antioxidant, heat stabilizer, antiager, fire retardant, smoke suppressant, the printing consumables with high impact-resistance are made through steps such as over cleaning, drying, crushing, activation, mixing, extruding.Printing consumables good flame retardation effect of the invention, impact resistance and toughness are strong, are a kind of excellent printing consumables of performance, can be applicable, and have significant economic and social benefit.

Description

A kind of printing consumables with high impact-resistance and preparation method thereof
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of printing with high impact-resistance Consumptive material and preparation method thereof.
【Background technology】
3D printing is also called rapid shaping technique, also referred to as increases material manufacturing technology, is that one kind does not need conventional tool, fixture And lathe, but based on mathematical model file, successively printed using the material with adhesion such as metal dust or plastics To manufacture the technology of arbitrary shape article.The article that 3D printer can be manufactured is a lot, such as aircraft, pistol, for another example food, human body Organ, toy for children etc..3D printing technique is an important breakthrough of world's manufacturing technology field over the past two decades.It is mechanic The multidisciplinary technology such as journey, computer technology, Numeric Control Technology, material science it is integrated.It is to beat that 3D printing is most difficult to most crucial technology Print the exploitation of material.Therefore developing more various multi-functional 3D printing material turns into focus of the future studies with application and pass Key.3D printing material of the invention is a kind of new material, has the performance of bamboo wood and plastics concurrently, for 3D printing provides more materials Selection in terms of material.
Polypropylene has nontoxic, tasteless, and mechanical property is good, and easy processing is corrosion-resistant, and melt temperature is relatively low, and good fluidity is cold But speed is fast, all meets requirement of the 3D printing technique to polymeric material the advantages of transparent easy dyeing, and pp material is originated Extensively, price is low;Bamboo fiber/PP composite material causes its double grading for having bamboo wood and plastics concurrently, bamboo fiber plus Enter reduce further polyacrylic condensation shrinkage factor, and the article for printing has woodiness touch, more friendliness.
Wood plastic composite (WPC), is a kind of main by material based on timber or cellulose and answering that plastics are made Condensation material, exactly makes a certain proportion of wood-fibred (such as wood powder, powder of straw, cotton stalk powder, bamboo powder, shell powder) by pretreatment A kind of new material being combined into thermoplastic polymer resin or other materials;The new material not only environmental protection but also tool There is good mechanical stability, but the two big raw material wood-fibreds and polyolefin that constitute wood plastic composite are all inflammability materials Material, is that this composite is also combustible material, and it is materials application development to assign the good fire resistance of wood plastic composite The need for;The individually fire-retardant research to timber and wood-fibred has a lot, typically there is phosphorus-nitrogenated flame retardant;Boron flame retardant;It is halogen Fire retardant;Other inorganic salts etc.;But it is main based on phosphorus-nitrogenated flame retardant, it is considered to be optimum wood fire retardant, phosphorus, Two kinds of elements of nitrogen play synergy in wood fire retardant and improve flame retardant effect;But these fire retardants almost have one jointly The characteristics of, it is exactly the thermal degradation temperature for significantly reducing wood-fibred, this may result in the processing that cannot carry out composite;It is right Also many in the research of polyolefin flame-retardant, its flame resistant method is frequently with halogen containing flame-retardant and antimony oxide (Sb2O3) coordinate make With;Metal hydroxides (Al (OH)3、Mg(OH)2) fire retardant;Expansibility flame-proof agent;Ammonium polyphosphate flame retardant etc.;Halogen-free flameproof The focus of polyolefin flame-retardant research, expanding fire retardant polyolefin/Wood Fiber Composites are carried out it is dual it is fire-retardant be that this is combined The focus of the fire-retardant research of material;But the addition of fire retardant often deteriorates the mechanical property of composite, therefore to fire-retardant multiple The research of the research flame-proof composite material of condensation material will simultaneously study interface compatibility, heat endurance and anti-flammability, to be managed The flame-proof composite material thought.
Wood plastic composite has preferable machinability, beautiful, generous while anticorrosive, however, its defect is in Not good enough in its mechanical property, therefore, people seek solution route, once someone was re-introduced into stone flour in wood plastic composite, used In shaping stone wood plastic composite, however, the problems such as due to interface compatibility, the mechanical performance of the composite for finally giving compared with Difference.
【The content of the invention】
The present invention provides a kind of printing consumables with high impact-resistance and preparation method thereof, to solve in the prior art The addition of fire retardant can deteriorate the mechanical property of wood plastic composite, and introduce stone flour for being molded stone wood plastic composite, by The problems such as interface compatibility, the problems such as the mechanical performance of the composite for finally giving is poor.Printing consumables resistance of the invention Fuel efficiency fruit is good, and impact resistance and toughness are strong, are a kind of excellent printing consumables of performance, can be applicable, have it is significant economical and Social benefit.
To solve above technical problem, the present invention uses following technical scheme:
A kind of preparation method of the printing consumables with high impact-resistance, comprises the following steps:
S1:Dried after waste plastic 78-118 parts is cleaned to water content≤0.8%, 200-300 mesh is crossed after then crushing Sieve, is obtained plastic powders;
S2:It is 70-74 DEG C in temperature to 1.2-1.8 parts of surfactant is added in plastic powders obtained in step S1, turns Speed is obtained activated plastics powder to activate 1.2-1.8h under 150-180r/min;
S3:Under nitrogen protection, to 96-160 parts of dolomite dust of addition, corn in activated plastics powder obtained in step S2 Powder of straw 55-88 parts, PLA 84-112 parts, four PA 800K 22-30 parts, 25-32 parts of stearyl acrylate acid esters, conditioning agent 0.5-1 parts, propellant 0.4-0.6 parts, coupling agent 0.6-0.9 parts, catalyst 0.3-0.5 parts, plasticizer 0.4-0.7 parts, dispersion Agent 0.3-0.5 parts, tackifier 0.3-0.4 parts, softening agent 0.3-0.5 parts, be 252-278W in microwave power, and temperature is 132- 148 DEG C, rotating speed is obtained mixture I to stir 3.2-4.8h under 300-400r/min;
S4:To 1-2 parts of curing agent of addition, antioxidant 0.2-0.4 parts, heat stabilizer in mixture I obtained in step S3 0.2-0.4 parts, antiager 1.2-1.8 parts, fire retardant 1-1.5 parts, smoke suppressant 0.9-1.3 parts, be 76-78 DEG C, rotating speed in temperature To stir 2-2.5h under 100-200r/min, mixture II is obtained;
S5:Mixture II obtained in step S4 is put into screw extruding forming machine, is 212-225 DEG C, rotating speed in temperature Under for 120-135r/min, through extruding strand, the printing consumables with high impact-resistance is obtained.
Preferably, the surfactant is Pluronic F68;
The conditioning agent is JINHASS conditioning agents;
The propellant is aerogel generating agent;
The coupling agent is titanate coupling agent;
The catalyst is vanadic anhydride;
The plasticizer is citrate;
The dispersant is Dispersant MF;
The tackifier are butyl trimethoxy silane;
The softening agent is polyester fiber;
The curing agent is epoxylite curing agent;
The antioxidant WINGSTAYL antioxidant;
The heat stabilizer is Dythal;
The antiager is BASF UV-234 antiagers;
The fire retardant is in units of weight portion, including following raw material:Ethylene glycol ether acetate 60-68 parts, the sad last of the ten Heavenly stems Acid glycerol three ester 25-28 parts, 22-24 parts of NPE ammonium sulfate, 18-22 parts of PPOX triol, urea 14- 16 parts, aluminum oxide 10-12 parts, antimony oxide 9-11 parts, lead oxide 7-10 parts, bentonite 8-12 parts, bleeding agent 1-2 parts;
The smoke suppressant is in units of weight portion, including following raw material:Tributyltin oxide 32-42 parts, lead hydroxide 16- 21 parts, diatomite 12-20 parts, aluminium hydroxide 8-10 parts, ammonium octamolybdate 4-6 parts, stearic acid 1.5-2 parts.
Preferably, the preparation method of the fire retardant, comprises the following steps:
A () adds NPE ammonium sulfate, water 320-400 parts in microwave reactor, be in speed of agitator 8-12min is stirred under 300-500r/min, mixture A is obtained;
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in step a Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 200-400r/ in speed of agitator Min, microwave power is 350-400W, and temperature is obtained mixture B to stir 1.3-1.8h at 92-96 DEG C, and the bleeding agent is to ooze Saturating agent JFC;
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, be 4000-5000r/ in rotating speed Centrifugal drying is obtained fire retardant to water content≤1% under min.
Preferably, the preparation method of the smoke suppressant, comprises the following steps:
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring Rotating speed is 300-400r/min, and microwave power is 200-250W, and temperature is obtained mixture to stir 1-1.5h at 110-120 DEG C C;
(B) after mixture C obtained in step A being cooled into room temperature, sediment is filtered, is 4000-5000r/ in rotating speed Centrifugal drying is obtained smoke suppressant to water content≤1% under min.
The invention has the advantages that:
(1), using conventional waste plastic, source is wide, and price is low, has widened the selection of 3D printing material feedstock for the present invention Scope, while for effective treatment of waste plastic provides new approach;
(2) present invention uses stone flour and Wood flour filled polypropylene, is made the printing consumables with high impact-resistance so that Product has woodiness touch, more friendliness, can Partial digestion, more low-carbon environment-friendly;
(3) printing consumables good flame retardation effect of the invention, impact resistance and toughness are strong, are a kind of excellent printing consumptions of performance Material, can be applicable, and have significant economic and social benefit.
【Specific embodiment】
For ease of more fully understanding the present invention, it is illustrated by following examples, these embodiments belong to of the invention Protection domain, but do not limit the scope of the invention.
In embodiment, the printing consumables with high impact-resistance, in units of weight portion, including following original Material:Dolomite dust 96-160 parts, corn stalk powder 55-88 parts, waste plastic 78-118 parts, PLA 84-112 parts, four poly- phosphorus Sour potassium 22-30 parts, 25-32 parts of stearyl acrylate acid esters, surfactant 1.2-1.8 parts, conditioning agent 0.5-1 parts, propellant 0.4-0.6 parts, coupling agent 0.6-0.9 parts, catalyst 0.3-0.5 parts, plasticizer 0.4-0.7 parts, dispersant 0.3-0.5 parts, increasing Stick 0.3-0.4 parts, softening agent 0.3-0.5 parts, curing agent 1-2 parts, antioxidant 0.2-0.4 parts, heat stabilizer 0.2-0.4 parts, Antiager 1.2-1.8 parts, fire retardant 1-1.5 parts, smoke suppressant 0.9-1.3 parts;
The surfactant is Pluronic F68;
The conditioning agent is JINHASS conditioning agents;
The propellant is aerogel generating agent;
The coupling agent is titanate coupling agent;
The catalyst is vanadic anhydride;
The plasticizer is citrate;
The dispersant is Dispersant MF;
The tackifier are butyl trimethoxy silane;
The softening agent is polyester fiber;
The curing agent is epoxylite curing agent;
The antioxidant WINGSTAYL antioxidant;
The heat stabilizer is Dythal;
The antiager is BASF UV-234 antiagers;
The fire retardant is in units of weight portion, including following raw material:Ethylene glycol ether acetate 60-68 parts, the sad last of the ten Heavenly stems Acid glycerol three ester 25-28 parts, 22-24 parts of NPE ammonium sulfate, 18-22 parts of PPOX triol, urea 14- 16 parts, aluminum oxide 10-12 parts, antimony oxide 9-11 parts, lead oxide 7-10 parts, bentonite 8-12 parts, bleeding agent 1-2 parts;
The smoke suppressant is in units of weight portion, including following raw material:Tributyltin oxide 32-42 parts, lead hydroxide 16- 21 parts, diatomite 12-20 parts, aluminium hydroxide 8-10 parts, ammonium octamolybdate 4-6 parts, stearic acid 1.5-2 parts;
The preparation method of the printing consumables with high impact-resistance, comprises the following steps:
S1:Dried after waste plastic is cleaned to water content≤0.8%, 200-300 mesh sieve is crossed after then crushing, be obtained Plastic powders;
S2:It it is 70-74 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 150- 1.2-1.8h is activated under 180r/min, activated plastics powder is obtained;
S3:Under nitrogen protection, in activated plastics powder obtained in step S2 add dolomite dust, corn stalk powder, PLA, four PA 800Ks, stearyl acrylate acid esters, conditioning agent, propellant, coupling agent, catalyst, plasticizer, dispersant, increasing Stick, softening agent, microwave power be 252-278W, temperature be 132-148 DEG C, rotating speed be 300-400r/min under stir 3.2- 4.8h, is obtained mixture I;
S4:To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S3 Fumicants, is 76-78 DEG C in temperature, and rotating speed is obtained mixture II to stir 2-2.5h under 100-200r/min;
The preparation method of the fire retardant, comprises the following steps:
A () adds NPE ammonium sulfate, water 320-400 parts in microwave reactor, be in speed of agitator 8-12min is stirred under 300-500r/min, mixture A is obtained;
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in step a Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 200-400r/ in speed of agitator Min, microwave power is 350-400W, and temperature is obtained mixture B to stir 1.3-1.8h at 92-96 DEG C, and the bleeding agent is to ooze Saturating agent JFC;
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, be 4000-5000r/ in rotating speed Centrifugal drying is obtained fire retardant to water content≤1% under min;
The preparation method of the smoke suppressant, comprises the following steps:
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring Rotating speed is 300-400r/min, and microwave power is 200-250W, and temperature is obtained mixture to stir 1-1.5h at 110-120 DEG C C;
(B) after mixture C obtained in step A being cooled into room temperature, sediment is filtered, is 4000-5000r/ in rotating speed Centrifugal drying is obtained smoke suppressant to water content≤1% under min;
S5:Mixture II obtained in step S4 is put into screw extruding forming machine, is 212-225 DEG C, rotating speed in temperature Under for 120-135r/min, through extruding strand, the printing consumables with high impact-resistance is obtained, it is described with high impact-resistant energy The printing consumables of power is applied in 3d printings.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of printing consumables with high impact-resistance, in units of weight portion, including following raw material:Dolomite 130 parts of powder, 75 parts of corn stalk powder, 98 parts of waste plastic, 100 parts of PLA, 56 parts of four PA 800K, stearyl acrylate acid esters 28 parts, 1.5 parts of surfactant, 0.8 part of conditioning agent, 0.5 part of propellant, 0.8 part of coupling agent, 0.4 part of catalyst, plasticizer 0.6 part, 0.5 part of dispersant, 0.3 part of tackifier, 0.4 part of softening agent, 1.5 parts of curing agent, 0.3 part of antioxidant, heat stabilizer 0.3 Part, 1.5 parts of antiager, 1.3 parts of fire retardant, 1 part of smoke suppressant;
The surfactant is Pluronic F68;
The conditioning agent is JINHASS conditioning agents;
The propellant is aerogel generating agent;
The coupling agent is titanate coupling agent;
The catalyst is vanadic anhydride;
The plasticizer is citrate;
The dispersant is Dispersant MF;
The tackifier are butyl trimethoxy silane;
The softening agent is polyester fiber;
The curing agent is epoxylite curing agent;
The antioxidant WINGSTAYL antioxidant;
The heat stabilizer is Dythal;
The antiager is BASF UV-234 antiagers;
The fire retardant is in units of weight portion, including following raw material:65 parts of ethylene glycol ether acetate, caprylic capric are sweet Oily 27 parts of three ester, 23 parts of NPE ammonium sulfate, 20 parts of PPOX triol, 15 parts of urea, 12 parts of aluminum oxide, 10 parts of antimony oxide, 8 parts of lead oxide, 10 parts of bentonite, 1.5 parts of bleeding agent;
The smoke suppressant is in units of weight portion, including following raw material:38 parts of tributyltin oxide, 18 parts of lead hydroxide, 16 parts of diatomite, 9 parts of aluminium hydroxide, 5 parts of ammonium octamolybdate, 1.7 parts of stearic acid;
The preparation method of the printing consumables with high impact-resistance, comprises the following steps:
S1:It is 0.8% to be dried after waste plastic is cleaned to water content, and 200 mesh sieve are crossed after then crushing, and plastics are obtained Powder;
S2:It it is 72 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 170r/min Lower activation 1.5h, is obtained activated plastics powder;
S3:Under nitrogen protection, in activated plastics powder obtained in step S2 add dolomite dust, corn stalk powder, PLA, four PA 800Ks, stearyl acrylate acid esters, conditioning agent, propellant, coupling agent, catalyst, plasticizer, dispersant, increasing Stick, softening agent, are 265W in microwave power, and temperature is 142 DEG C, and rotating speed is obtained mixture to stir 4.2h under 300r/min Ⅰ;
S4:To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S3 Fumicants, is 76-78 DEG C in temperature, and rotating speed is obtained mixture II to stir 2.2h under 100r/min;
The preparation method of the fire retardant, comprises the following steps:
A () adds NPE ammonium sulfate, 380 parts of water in microwave reactor, be 400r/ in speed of agitator 10min is stirred under min, mixture A is obtained;
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in step a Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 300r/min in speed of agitator, micro- Wave power is 380W, and temperature is obtained mixture B to stir 1.7h at 95 DEG C, and the bleeding agent is penetrating agent JFC;
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, in the case where rotating speed is 4500r/min Centrifugal drying to water content is 1%, and fire retardant is obtained;
The preparation method of the smoke suppressant, comprises the following steps:
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring Rotating speed is 300r/min, and microwave power is 220W, and temperature is obtained mixture C to stir 1.2h at 110 DEG C;
(B) after mixture C obtained in step A being cooled into room temperature, sediment is filtered, in the case where rotating speed is 4500r/min Centrifugal drying to water content is 1%, and smoke suppressant is obtained;
S5:Mixture II obtained in step S4 is put into screw extruding forming machine, is 213 DEG C in temperature, rotating speed is Under 130r/min, through extruding strand, the printing consumables with high impact-resistance, the beating with high impact-resistance is obtained Print consumptive material is applied in 3d printings.
Embodiment 2
A kind of printing consumables with high impact-resistance, in units of weight portion, including following raw material:Dolomite 96 parts of powder, 55 parts of corn stalk powder, 78 parts of waste plastic, 84 parts of PLA, 22 parts of four PA 800K, stearyl acrylate acid esters 25 Part, 1.2 parts of surfactant, 0.5 part of conditioning agent, 0.4 part of propellant, 0.6 part of coupling agent, 0.3 part of catalyst, plasticizer 0.4 It is part, 0.3 part of dispersant, 0.3 part of tackifier, 0.3 part of softening agent, 1 part of curing agent, 0.2 part of antioxidant, 0.2 part of heat stabilizer, anti- 1.2 parts of old agent, 1 part of fire retardant, 0.9 part of smoke suppressant;
The surfactant is Pluronic F68;
The conditioning agent is JINHASS conditioning agents;
The propellant is aerogel generating agent;
The coupling agent is titanate coupling agent;
The catalyst is vanadic anhydride;
The plasticizer is citrate;
The dispersant is Dispersant MF;
The tackifier are butyl trimethoxy silane;
The softening agent is polyester fiber;
The curing agent is epoxylite curing agent;
The antioxidant WINGSTAYL antioxidant;
The heat stabilizer is Dythal;
The antiager is BASF UV-234 antiagers;
The fire retardant is in units of weight portion, including following raw material:60 parts of ethylene glycol ether acetate, caprylic capric are sweet Oily 25 parts of three ester, 22 parts of NPE ammonium sulfate, 18 parts of PPOX triol, 14 parts of urea, 10 parts of aluminum oxide, 9 parts of antimony oxide, 7 parts of lead oxide, 8 parts of bentonite, 1 part of bleeding agent;
The smoke suppressant is in units of weight portion, including following raw material:32 parts of tributyltin oxide, 16 parts of lead hydroxide, 12 parts of diatomite, 8 parts of aluminium hydroxide, 4 parts of ammonium octamolybdate, 1.5 parts of stearic acid;
The preparation method of the printing consumables with high impact-resistance, comprises the following steps:
S1:It is 0.6% to be dried after waste plastic is cleaned to water content, and 200 mesh sieve are crossed after then crushing, and plastics are obtained Powder;
S2:It it is 70 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 150r/min Lower activation 1.8h, is obtained activated plastics powder;
S3:Under nitrogen protection, in activated plastics powder obtained in step S2 add dolomite dust, corn stalk powder, PLA, four PA 800Ks, stearyl acrylate acid esters, conditioning agent, propellant, coupling agent, catalyst, plasticizer, dispersant, increasing Stick, softening agent, are 252W in microwave power, and temperature is 132 DEG C, and rotating speed is obtained mixture to stir 4.8h under 300r/min Ⅰ;
S4:To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S3 Fumicants, is 76 DEG C in temperature, and rotating speed is obtained mixture II to stir 2.5h under 100r/min;
The preparation method of the fire retardant, comprises the following steps:
A () adds NPE ammonium sulfate, 320 parts of water in microwave reactor, be 300r/ in speed of agitator 12min is stirred under min, mixture A is obtained;
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in step a Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 200r/min in speed of agitator, micro- Wave power is 350W, and temperature is obtained mixture B to stir 1.8h at 92 DEG C, and the bleeding agent is penetrating agent JFC;
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, in the case where rotating speed is 4000r/min Centrifugal drying to water content is 0.9%, and fire retardant is obtained;
The preparation method of the smoke suppressant, comprises the following steps:
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring Rotating speed is 300r/min, and microwave power is 200W, and temperature is obtained mixture C to stir 1.5h at 110 DEG C;
(B) after mixture C obtained in step A being cooled into room temperature, sediment is filtered, in the case where rotating speed is 4000r/min Centrifugal drying to water content is 0.8%, and smoke suppressant is obtained;
S5:Mixture II obtained in step S4 is put into screw extruding forming machine, is 212 DEG C in temperature, rotating speed is Under 120r/min, through extruding strand, the printing consumables with high impact-resistance, the beating with high impact-resistance is obtained Print consumptive material is applied in 3d printings.
Embodiment 3
A kind of printing consumables with high impact-resistance, in units of weight portion, including following raw material:Dolomite 160 parts of powder, 88 parts of corn stalk powder, 118 parts of waste plastic, 112 parts of PLA, 30 parts of four PA 800K, stearyl acrylate acid 32 parts of ester, 1.8 parts of surfactant, 1 part of conditioning agent, 0.6 part of propellant, 0.9 part of coupling agent, 0.5 part of catalyst, plasticizer 0.7 part, 0.5 part of dispersant, 0.4 part of tackifier, 0.5 part of softening agent, 2 parts of curing agent, 0.4 part of antioxidant, heat stabilizer 0.4 Part, 1.8 parts of antiager, 1.5 parts of fire retardant, 1.3 parts of smoke suppressant;
The surfactant is Pluronic F68;
The conditioning agent is JINHASS conditioning agents;
The propellant is aerogel generating agent;
The coupling agent is titanate coupling agent;
The catalyst is vanadic anhydride;
The plasticizer is citrate;
The dispersant is Dispersant MF;
The tackifier are butyl trimethoxy silane;
The softening agent is polyester fiber;
The curing agent is epoxylite curing agent;
The antioxidant WINGSTAYL antioxidant;
The heat stabilizer is Dythal;
The antiager is BASF UV-234 antiagers;
The fire retardant is in units of weight portion, including following raw material:68 parts of ethylene glycol ether acetate, caprylic capric are sweet Oily 28 parts of three ester, 24 parts of NPE ammonium sulfate, 22 parts of PPOX triol, 16 parts of urea, 12 parts of aluminum oxide, 11 parts of antimony oxide, 10 parts of lead oxide, 12 parts of bentonite, 2 parts of bleeding agent;
The smoke suppressant is in units of weight portion, including following raw material:42 parts of tributyltin oxide, 21 parts of lead hydroxide, 20 parts of diatomite, 10 parts of aluminium hydroxide, 6 parts of ammonium octamolybdate, 2 parts of stearic acid;
The preparation method of the printing consumables with high impact-resistance, comprises the following steps:
S1:It is 0.6% to be dried after waste plastic is cleaned to water content, and 300 mesh sieve are crossed after then crushing, and plastics are obtained Powder;
S2:It it is 74 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 180r/min Lower activation 1.2h, is obtained activated plastics powder;
S3:Under nitrogen protection, in activated plastics powder obtained in step S2 add dolomite dust, corn stalk powder, PLA, four PA 800Ks, stearyl acrylate acid esters, conditioning agent, propellant, coupling agent, catalyst, plasticizer, dispersant, increasing Stick, softening agent, are 278W in microwave power, and temperature is 148 DEG C, and rotating speed is obtained mixture to stir 3.2h under 400r/min Ⅰ;
S4:To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S3 Fumicants, is 78 DEG C in temperature, and rotating speed is obtained mixture II to stir 2h under 200r/min;
The preparation method of the fire retardant, comprises the following steps:
A () adds NPE ammonium sulfate, 400 parts of water in microwave reactor, be 500r/ in speed of agitator 8min is stirred under min, mixture A is obtained;
B () is to addition ethylene glycol ether acetate, Miglyol 812N, polyoxygenated in mixture A obtained in step a Propylene triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 400r/min in speed of agitator, micro- Wave power is 400W, and temperature is obtained mixture B to stir 1.3h at 96 DEG C, and the bleeding agent is penetrating agent JFC;
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, in the case where rotating speed is 5000r/min Centrifugal drying to water content is 0.7%, and fire retardant is obtained;
The preparation method of the smoke suppressant, comprises the following steps:
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in stirring Rotating speed is 400r/min, and microwave power is 250W, and temperature is obtained mixture C to stir 1h at 120 DEG C;
(B) after mixture C obtained in step A being cooled into room temperature, sediment is filtered, in the case where rotating speed is 5000r/min Centrifugal drying to water content is 0.8%, and smoke suppressant is obtained;
S5:Mixture II obtained in step S4 is put into screw extruding forming machine, is 225 DEG C in temperature, rotating speed is Under 135r/min, through extruding strand, the printing consumables with high impact-resistance, the beating with high impact-resistance is obtained Print consumptive material is applied in 3d printings.
After testing, its performance is as shown in the table for printing consumables with high impact-resistance prepared by the present embodiment 1-3:
As seen from the above table, printing consumables good flame retardation effect of the invention, impact resistance and toughness are strong, are that a kind of performance is excellent Printing consumables, can be applicable, have significant economic and social benefit.
Above content is confined to these explanations it cannot be assumed that the present invention is embodied, for the technical field of the invention Those of ordinary skill for, under the premise of present inventive concept is not departed from, some simple deduction or replace can also be made, all should When being considered as belonging to the scope of patent protection that claims by being submitted to of the present invention determine.

Claims (5)

1. a kind of preparation method of the printing consumables with high impact-resistance, it is characterised in that comprise the following steps:
S1:Dried after waste plastic 78-118 parts is cleaned to water content≤0.8%, 200-300 mesh sieve crossed after then crushing, Plastic powders are obtained;
S2:It it is 70-74 DEG C in temperature to 1.2-1.8 parts of surfactant is added in plastic powders obtained in step S1, rotating speed is 1.2-1.8h is activated under 150-180r/min, activated plastics powder is obtained;
S3:Under nitrogen protection, to 96-160 parts of dolomite dust of addition, maize straw in activated plastics powder obtained in step S2 Powder 55-88 parts, PLA 84-112 parts, four PA 800K 22-30 parts, 25-32 parts of stearyl acrylate acid esters, conditioning agent 0.5-1 Part, propellant 0.4-0.6 parts, coupling agent 0.6-0.9 parts, catalyst 0.3-0.5 parts, plasticizer 0.4-0.7 parts, dispersant 0.3- 0.5 part, tackifier 0.3-0.4 parts, softening agent 0.3-0.5 parts, be 252-278W in microwave power, and temperature is 132-148 DEG C, is turned Speed is obtained mixture I to stir 3.2-4.8h under 300-400r/min;
S4:To 1-2 parts of curing agent of addition, antioxidant 0.2-0.4 parts, heat stabilizer 0.2-0.4 in mixture I obtained in step S3 Part, antiager 1.2-1.8 part, fire retardant 1-1.5 parts, smoke suppressant 0.9-1.3 parts, temperature be 76-78 DEG C, rotating speed is 100- 2-2.5h is stirred under 200r/min, mixture II is obtained;
S5:Mixture II obtained in step S4 is put into screw extruding forming machine, is 212-225 DEG C in temperature, rotating speed is Under 120-135r/min, through extruding strand, the printing consumables with high impact-resistance is obtained.
2. the preparation method of the printing consumables with high impact-resistance according to claim 1, it is characterised in that described Surfactant is Pluronic F68;
The conditioning agent is JINHASS conditioning agents;
The propellant is aerogel generating agent;
The coupling agent is titanate coupling agent;
The catalyst is vanadic anhydride;
The plasticizer is citrate;
The dispersant is Dispersant MF;
The tackifier are butyl trimethoxy silane;
The softening agent is polyester fiber;
The curing agent is epoxylite curing agent;
The antioxidant WINGSTAYL antioxidant;
The heat stabilizer is Dythal;
The antiager is BASF UV-234 antiagers;
The fire retardant is in units of weight portion, including following raw material:Ethylene glycol ether acetate 60-68 parts, caprylic capric it is sweet Ester 25-28 parts of oil three, 22-24 parts of NPE ammonium sulfate, 18-22 parts of PPOX triol, urea 14-16 Part, aluminum oxide 10-12 parts, antimony oxide 9-11 parts, lead oxide 7-10 parts, bentonite 8-12 parts, bleeding agent 1-2 parts;
The smoke suppressant is in units of weight portion, including following raw material:Tributyltin oxide 32-42 parts, lead hydroxide 16-21 Part, diatomite 12-20 parts, aluminium hydroxide 8-10 parts, ammonium octamolybdate 4-6 parts, stearic acid 1.5-2 parts.
3. the preparation method of the printing consumables with high impact-resistance according to claim 2, it is characterised in that described The preparation method of fire retardant, comprises the following steps:
A () adds NPE ammonium sulfate, water 320-400 parts in microwave reactor, be 300- in speed of agitator 8-12min is stirred under 500r/min, mixture A is obtained;
B () is to addition ethylene glycol ether acetate, Miglyol 812N, PPOX in mixture A obtained in step a Triol, urea, aluminum oxide, antimony oxide, lead oxide, bentonite, bleeding agent, are 200-400r/min in speed of agitator, micro- Wave power is 350-400W, and temperature is obtained mixture B to stir 1.3-1.8h at 92-96 DEG C, and the bleeding agent is bleeding agent JFC;
C () filters sediment by after mixture B is cooled to room temperature obtained in step b, in the case where rotating speed is 4000-5000r/min Centrifugal drying is obtained fire retardant to water content≤1%.
4. the preparation method of the printing consumables with high impact-resistance according to claim 2, it is characterised in that described The preparation method of smoke suppressant, comprises the following steps:
(A) tributyltin oxide, lead hydroxide, diatomite, aluminium hydroxide, ammonium octamolybdate, stearic acid are mixed, in speed of agitator It is 300-400r/min, microwave power is 200-250W, and temperature is obtained mixture C to stir 1-1.5h at 110-120 DEG C;
(B) after mixture C obtained in step A being cooled into room temperature, sediment is filtered, in the case where rotating speed is 4000-5000r/min Centrifugal drying is obtained smoke suppressant to water content≤1%.
5. the printing consumables with high impact-resistance that prepared by a kind of method according to claim any one of 1-4.
CN201710143549.XA 2017-03-12 2017-03-12 A kind of printing consumables with high impact-resistance and preparation method thereof Pending CN106751630A (en)

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* Cited by examiner, † Cited by third party
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CN107141546A (en) * 2017-06-23 2017-09-08 广西南宁桂尔创环保科技有限公司 3D printing consumptive material prepared by a kind of high level cycling and reutilization waste rubber and preparation method thereof

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CN106398265A (en) * 2016-12-15 2017-02-15 广西筑梦三体科技有限公司 3D printing material of rape straw with high flexural modulus
CN106433179A (en) * 2016-11-11 2017-02-22 广西筑梦三体科技有限公司 Preparation method of novel printing plastic material
CN106433083A (en) * 2016-10-19 2017-02-22 黄宇 Graphene modified rubber material with high bending strength

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Publication number Priority date Publication date Assignee Title
CN106433083A (en) * 2016-10-19 2017-02-22 黄宇 Graphene modified rubber material with high bending strength
CN106433179A (en) * 2016-11-11 2017-02-22 广西筑梦三体科技有限公司 Preparation method of novel printing plastic material
CN106398265A (en) * 2016-12-15 2017-02-15 广西筑梦三体科技有限公司 3D printing material of rape straw with high flexural modulus

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Publication number Priority date Publication date Assignee Title
CN107141546A (en) * 2017-06-23 2017-09-08 广西南宁桂尔创环保科技有限公司 3D printing consumptive material prepared by a kind of high level cycling and reutilization waste rubber and preparation method thereof
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Application publication date: 20170531