CN106905714A - A kind of Graphene modified flame retardant type bamboo moulding material, preparation method and applications - Google Patents
A kind of Graphene modified flame retardant type bamboo moulding material, preparation method and applications Download PDFInfo
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Abstract
The invention discloses flame retardant type bamboo moulding material, preparation method and applications that a kind of Graphene is modified, belong to 3D printing technical field of material, the modified flame retardant type bamboo moulding material of the Graphene includes following raw material：Waste plastic, bamboo powder, PLA, two polyphosphate sodiums, stearyl acrylate acid esters, Graphene, surfactant, conditioning agent, propellant, crosslinking agent, catalyst, plasticizer, dispersant, tackifier, curing agent, antioxidant, heat stabilizer, antiager, fire retardant, smoke suppressant, the modified flame retardant type bamboo moulding material of the Graphene are made through steps such as over cleaning, drying, crushing, activation, mixing, extruding.The modified flame retardant type bamboo moulding material good flame retardation effect of Graphene of the invention, strong shock resistance, toughness is strong, is a kind of excellent fire-retardant Graphene modified bamboo moulding material of performance, can be applicable, and has significant economic and social benefit.
Description
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of modified flame retardant type bamboo modeling of Graphene
Material, preparation method and applications.
【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 bamboo matter sense, more friendliness.
The Geim and Novoselov of Man Chesidun universities of Britain in 2004 peel off high starch breeding and obtain solely by adhesive tape
Since vertical two-dimensional graphene (Gra-phene, GN) crystal for existing, it is extremely concerned that Graphene has become material science
One of study hotspot.The graphite of Graphene, actually monoatomic layer, it possesses the two-dimensional structure and excellent power of uniqueness
, thermodynamics, optically and electrically performance.
Graphene be at present it is most thin in the world be but also most hard nano material, it is almost fully transparent, to inhale
2.3% light is received, thermal conductivity factor is up to 5300W/mk, higher than CNT and diamond.Graphene is one kind by carbon atom
The new material of the individual layer laminated structure of composition, high with intensity, specific surface area is big, chemical reactivity high, the spy of fillibility high
Point.
Current polypropylene composites are little as the document of 3D printing material.
China Patent Publication No. a kind of PP composite material for 102276920A is disclosed, using glass fibre, toughness reinforcing
Agent, coupling agent, antioxidant, lubricant, Nucleating Agent on Pp are modified, the tool intensity of modified PP composite material
It is higher and creep-resistant property is preferable.But its compatibility and heat distortion temperature to PP composite material is modified few, it is impossible to very well
Ground meets printing demand.
A kind of China Patent Publication No. processing procedure of composite material of plant fiber for 101781472A is disclosed, its addition coupling
Agent is uniformly mixed mixing material with high pass filter muller into mixing material, adds lubrication prescription to be mixed into micelle and make compound
It is used finished material, and modified material has weight saving, is difficult the small characteristic of thermal deformation, thermal shrinkage force.But its compatibility
It is not high, it is impossible to meet 3D printing demand well.
Single performance boost can not meet performance need of the 3D printing technique to polypropylene composites
Ask, be badly in need of a kind of new polypropylene composites and widely applied in 3D printing technique.
【The content of the invention】
The present invention provides a kind of Graphene modified flame retardant type bamboo moulding material, preparation method and applications, existing to solve
Polypropylene composites heat distortion temperature be modified low, mechanical property and flame retardant effect difference the problems such as.Stone of the invention
The modified flame retardant type bamboo moulding material good flame retardation effect of black alkene, strong shock resistance, toughness is strong, is a kind of excellent fire-retardant graphite of performance
Alkene modified bamboo moulding material, can be applicable, and have significant economic and social benefit.
To solve above technical problem, the present invention uses following technical scheme：
A kind of modified flame retardant type bamboo moulding material of Graphene, in units of weight portion, including following raw material：Waste plastic
165-224 parts, bamboo powder 100-153 parts, PLA 40-54 parts, two polyphosphate sodium 30-42 parts, stearyl acrylate acid esters 24-30
Part, Graphene 2-4 parts, surfactant 1-1.6 parts, conditioning agent 0.4-0.8 parts, propellant 0.3-0.5 parts, crosslinking agent 0.5-
0.8 part, catalyst 0.3-0.5 parts, plasticizer 0.4-0.7 parts, dispersant 0.3-0.5 parts, tackifier 0.3-0.4 parts, curing agent
1-2 parts, antioxidant 0.2-0.4 parts, heat stabilizer 0.2-0.4 parts, antiager 0.8-1.5 parts, fire retardant 1.3-1.8 parts, suppression cigarette
Agent 1-1.5 parts；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
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 catalyst is vanadic anhydride.
Preferably, the plasticizer is citrate.
Preferably, the dispersant is Dispersant MF.
Preferably, the tackifier are butyl trimethoxy silane.
Preferably, the curing agent is epoxylite curing agent.
Preferably, the antioxidant is antioxidant 1098.
Preferably, the heat stabilizer is Dythal.
Preferably, the antiager is BASF UV-234 antiagers.
The present invention also provides a kind of preparation method of the modified flame retardant type bamboo moulding material of Graphene, 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：Graphene is crushed, 200-300 mesh sieve is crossed, powder is obtained, gained powder is 7000- in magnetic field intensity
8200GS, ultrasonic power is 520-650W, and temperature is 52-56 DEG C, under rotating speed is 200-300r/min, stirs 42-55min,
Graphene energy powder is obtained；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activated plastics powder obtained in step S2
Amount powder, bamboo powder, PLA, two polyphosphate sodiums, stearyl acrylate acid esters, conditioning agent, propellant, crosslinking agent, catalyst, plasticising
Agent, dispersant, tackifier, microwave power be 260-270W, temperature be 132-140 DEG C, rotating speed be 200-400r/min under stir
3-4h is mixed, mixture I is obtained；
S5：To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S4
Fumicants, is 72-75 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.8-2.2h 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；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 190-200 DEG C, rotating speed in temperature
Under for 125-140r/min, through extruding strand, the modified flame retardant type bamboo moulding material of Graphene is obtained.
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 bamboo powder filled polypropylene, is made the modified flame retardant type bamboo moulding material of Graphene so that product has
There are bamboo matter sense, more friendliness, can Partial digestion, more low-carbon environment-friendly；
(3) the modified flame retardant type bamboo moulding material good flame retardation effect of Graphene of the invention, strong shock resistance, toughness is strong,
It is a kind of excellent fire-retardant Graphene modified bamboo moulding material of performance, can be applicable, there is 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 modified flame retardant type bamboo moulding material of the Graphene, in units of weight portion, including following original
Material：Waste plastic 165-224 parts, bamboo powder 100-153 parts, PLA 40-54 parts, two polyphosphate sodium 30-42 parts, stearyl acrylates
Acid esters 24-30 parts, Graphene 2-4 parts, surfactant 1-1.6 parts, conditioning agent 0.4-0.8 parts, propellant 0.3-0.5 parts, friendship
0.5-0.8 parts of agent of connection, catalyst 0.3-0.5 parts, plasticizer 0.4-0.7 parts, dispersant 0.3-0.5 parts, tackifier 0.3-0.4
Part, curing agent 1-2 parts, antioxidant 0.2-0.4 parts, heat stabilizer 0.2-0.4 parts, antiager 0.8-1.5 parts, fire retardant 1.3-
1.8 parts, smoke suppressant 1-1.5 parts；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
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 modified flame retardant type bamboo moulding material of the Graphene, 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：Graphene is crushed, 200-300 mesh sieve is crossed, powder is obtained, gained powder is 7000- in magnetic field intensity
8200GS, ultrasonic power is 520-650W, and temperature is 52-56 DEG C, under rotating speed is 200-300r/min, stirs 42-55min,
Graphene energy powder is obtained；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activated plastics powder obtained in step S2
Amount powder, bamboo powder, PLA, two polyphosphate sodiums, stearyl acrylate acid esters, conditioning agent, propellant, crosslinking agent, catalyst, plasticising
Agent, dispersant, tackifier, microwave power be 260-270W, temperature be 132-140 DEG C, rotating speed be 200-400r/min under stir
3-4h is mixed, mixture I is obtained；
S5：To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S4
Fumicants, is 72-75 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.8-2.2h 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；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 190-200 DEG C, rotating speed in temperature
Under for 125-140r/min, through extruding strand, the modified flame retardant type bamboo moulding material of Graphene, the modified resistance of the Graphene is obtained
Combustion type bamboo moulding material is applied in 3d printings.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of modified flame retardant type bamboo moulding material of Graphene, in units of weight portion, including following raw material：Discarded modeling
202 parts of material, 125 parts of bamboo powder, 48 parts of PLA, 36 parts of two polyphosphate sodium, 27 parts of stearyl acrylate acid esters, 3 parts of Graphene, surface
1.3 parts of activating agent, 0.6 part of conditioning agent, 0.4 part of propellant, 0.7 part of crosslinking agent, 0.4 part of catalyst, 0.6 part of plasticizer, dispersion
0.4 part of agent, 0.3 part of tackifier, 1.6 parts of curing agent, 0.3 part of antioxidant, 0.3 part of heat stabilizer, 1.2 parts of antiager, fire retardant
1.6 parts, 1.3 parts of smoke suppressant；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
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 modified flame retardant type bamboo moulding material of the Graphene, 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：Graphene is crushed, 200 mesh sieve are crossed, powder is obtained, gained powder is 7600GS, ultrasound in magnetic field intensity
Wave power is 580W, and temperature is 55 DEG C, and rotating speed is obtained Graphene energy powder under 200r/min, to stir 50min；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activated plastics powder obtained in step S2
Amount powder, bamboo powder, PLA, two polyphosphate sodiums, stearyl acrylate acid esters, conditioning agent, propellant, crosslinking agent, catalyst, plasticising
Agent, dispersant, tackifier, are 265W in microwave power, and temperature is 136 DEG C, and rotating speed is obtained mixed to stir 3.5h under 300r/min
Compound I；
S5：To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S4
Fumicants, is 73 DEG C in temperature, and rotating speed is obtained mixture II to stir 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；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 195 DEG C in temperature, rotating speed is
Under 132r/min, through extruding strand, the modified flame retardant type bamboo moulding material of Graphene, the modified flame retardant type bamboo of the Graphene is obtained
Moulding material is applied in 3d printings.
Embodiment 2
A kind of modified flame retardant type bamboo moulding material of Graphene, in units of weight portion, including following raw material：Discarded modeling
165 parts of material, 100 parts of bamboo powder, 40 parts of PLA, 30 parts of two polyphosphate sodium, 24 parts of stearyl acrylate acid esters, 2 parts of Graphene, surface
1 part of activating agent, 0.4 part of conditioning agent, 0.3 part of propellant, 0.5 part of crosslinking agent, 0.3 part of catalyst, 0.4 part of plasticizer, dispersant
0.3 part, 0.3 part of tackifier, 1 part of curing agent, 0.2 part of antioxidant, 0.2 part of heat stabilizer, 0.8 part of antiager, fire retardant 1.3
Part, 1 part of smoke suppressant；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
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 modified flame retardant type bamboo moulding material of the Graphene, 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：Graphene is crushed, 200 mesh sieve are crossed, powder is obtained, gained powder is 7000GS, ultrasound in magnetic field intensity
Wave power is 520W, and temperature is 52 DEG C, and rotating speed is obtained Graphene energy powder under 200r/min, to stir 55min；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activated plastics powder obtained in step S2
Amount powder, bamboo powder, PLA, two polyphosphate sodiums, stearyl acrylate acid esters, conditioning agent, propellant, crosslinking agent, catalyst, plasticising
Agent, dispersant, tackifier, are 260W in microwave power, and temperature is 132 DEG C, and rotating speed is obtained mixing to stir 4h under 200r/min
Thing I；
S5：To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S4
Fumicants, is 72 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, 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；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 190 DEG C in temperature, rotating speed is
Under 125r/min, through extruding strand, the modified flame retardant type bamboo moulding material of Graphene, the modified flame retardant type bamboo of the Graphene is obtained
Moulding material is applied in 3d printings.
Embodiment 3
A kind of modified flame retardant type bamboo moulding material of Graphene, in units of weight portion, including following raw material：Discarded modeling
224 parts of material, 153 parts of bamboo powder, 54 parts of PLA, 42 parts of two polyphosphate sodium, 30 parts of stearyl acrylate acid esters, 4 parts of Graphene, surface
1.6 parts of activating agent, 0.8 part of conditioning agent, 0.5 part of propellant, 0.8 part of crosslinking agent, 0.5 part of catalyst, 0.7 part of plasticizer, dispersion
0.5 part of agent, 0.4 part of tackifier, 2 parts of curing agent, 0.4 part of antioxidant, 0.4 part of heat stabilizer, 1.5 parts of antiager, fire retardant 1.8
Part, 1.5 parts of smoke suppressant；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
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 modified flame retardant type bamboo moulding material of the Graphene, 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：Graphene is crushed, 300 mesh sieve are crossed, powder is obtained, gained powder is 8200GS, ultrasound in magnetic field intensity
Wave power is 650W, and temperature is 56 DEG C, and rotating speed is obtained Graphene energy powder under 300r/min, to stir 42min；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activated plastics powder obtained in step S2
Amount powder, bamboo powder, PLA, two polyphosphate sodiums, stearyl acrylate acid esters, conditioning agent, propellant, crosslinking agent, catalyst, plasticising
Agent, dispersant, tackifier, are 270W in microwave power, and temperature is 140 DEG C, and rotating speed is obtained mixing to stir 3h under 400r/min
Thing I；
S5：To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression in mixture I obtained in step S4
Fumicants, is 75 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.8h 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；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 200 DEG C in temperature, rotating speed is
Under 140r/min, through extruding strand, the modified flame retardant type bamboo moulding material of Graphene, the modified flame retardant type bamboo of the Graphene is obtained
Moulding material is applied in 3d printings.
After testing, its performance is as shown in the table for the flame retardant type bamboo moulding material that Graphene prepared by the present embodiment 1-3 is modified：
As seen from the above table, the modified flame retardant type bamboo moulding material good flame retardation effect of Graphene of the invention, strong shock resistance,
Toughness is strong, is a kind of excellent fire-retardant Graphene modified bamboo moulding material of performance, can be applicable, and has significant economic and society to imitate
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. the flame retardant type bamboo moulding material that a kind of Graphene is modified, it is characterised in that in units of weight portion, including following raw material：
Waste plastic 165-224 parts, bamboo powder 100-153 parts, PLA 40-54 parts, two polyphosphate sodium 30-42 parts, stearyl acrylate acid
Ester 24-30 parts, Graphene 2-4 parts, surfactant 1-1.6 parts, conditioning agent 0.4-0.8 parts, propellant 0.3-0.5 parts, crosslinking
Agent 0.5-0.8 parts, catalyst 0.3-0.5 parts, plasticizer 0.4-0.7 parts, dispersant 0.3-0.5 parts, tackifier 0.3-0.4 parts,
Curing agent 1-2 parts, antioxidant 0.2-0.4 parts, heat stabilizer 0.2-0.4 parts, antiager 0.8-1.5 parts, fire retardant 1.3-1.8
Part, smoke suppressant 1-1.5 parts；
The surfactant is Pluronic F68；
The conditioning agent is ACR；
The propellant is aerogel generating agent；
The crosslinking agent is crosslinking aid S AC-100；
The catalyst is vanadic anhydride；
The plasticizer is citrate；
The dispersant is Dispersant MF；
The tackifier are butyl trimethoxy silane；
The curing agent is epoxylite curing agent；
The antioxidant is antioxidant 1098；
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.
2. the preparation method of the modified flame retardant type bamboo moulding material of a kind of Graphene according to claim 1, it is characterised in that
Comprise the following steps：
S1：Dried after waste plastic is cleaned to water content≤0.8%, 200-300 mesh sieve is crossed after then crushing, plastics are obtained
Powder；
S2：It it is 70-74 DEG C in temperature to surfactant is added in plastic powders obtained in step S1, rotating speed is 150-180r/
1.2-1.8h is activated under min, activated plastics powder is obtained；
S3：Graphene is crushed, 200-300 mesh sieve is crossed, powder is obtained, gained powder is 7000-8200GS in magnetic field intensity,
Ultrasonic power is 520-650W, and temperature is 52-56 DEG C, and rotating speed is obtained graphite under 200-300r/min, to stir 42-55min
Alkene energy powder；
S4：Under nitrogen protection, to Graphene energy powder obtained in addition step S3 in activated plastics powder obtained in step S2
End, bamboo powder, PLA, two polyphosphate sodiums, stearyl acrylate acid esters, conditioning agent, propellant, crosslinking agent, catalyst, plasticizer,
Dispersant, tackifier, microwave power be 260-270W, temperature be 132-140 DEG C, rotating speed be 200-400r/min under stir 3-
4h, is obtained mixture I；
S5：To addition curing agent, antioxidant, heat stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4
Agent, is 72-75 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.8-2.2h under 100-200r/min；
S6：Mixture II obtained in step S5 is put into screw extruding forming machine, is 190-200 DEG C in temperature, rotating speed is
Under 125-140r/min, through extruding strand, the modified flame retardant type bamboo moulding material of Graphene is obtained.
3. the preparation method of the modified flame retardant type bamboo moulding material of Graphene according to claim 2, it is characterised in that step
The preparation method of fire retardant described in S5, 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 modified flame retardant type bamboo moulding material of Graphene according to claim 2, it is characterised in that step
The preparation method of smoke suppressant described in S5, 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. application of the modified flame retardant type bamboo moulding material of a kind of Graphene according to claim 1 in 3D printing.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086983A (en) * | 2014-07-28 | 2014-10-08 | 北京中科博益科技有限公司 | Graphene/nylon composite material as well as preparation method and application of graphene/nylon composite material |
| CN105176084A (en) * | 2015-10-28 | 2015-12-23 | 杨洋 | Composite 3D printing material and preparation method thereof |
| CN106467675A (en) * | 2016-09-27 | 2017-03-01 | 浙江农林大学 | A kind of new bamboo-plastic combined 3D printing material and preparation method thereof |
-
2017
- 2017-03-12 CN CN201710143561.0A patent/CN106905714A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086983A (en) * | 2014-07-28 | 2014-10-08 | 北京中科博益科技有限公司 | Graphene/nylon composite material as well as preparation method and application of graphene/nylon composite material |
| CN105176084A (en) * | 2015-10-28 | 2015-12-23 | 杨洋 | Composite 3D printing material and preparation method thereof |
| CN106467675A (en) * | 2016-09-27 | 2017-03-01 | 浙江农林大学 | A kind of new bamboo-plastic combined 3D printing material and preparation method thereof |
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