CN106916469A - A kind of environment-friendly materials with high tensile, preparation method and applications - Google Patents
A kind of environment-friendly materials with high tensile, preparation method and applications Download PDFInfo
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Abstract
The invention discloses a kind of environment-friendly materials with high tensile, preparation method and applications, the environment-friendly materials include following raw material：Graphene, waste plastic, neoprene, PLA, four PA 800Ks, the phenyl propyl ketone of 2 hydroxyl, 4 octyloxy two, cyclobutenyl bis-stearamides, ethylene glycol monostearate, tributoxyethyl phosphate, three (2, 4 di-tert-butyl-phenyls) phosphite ester, polyvinyl chloride fibre, vinal, surfactant, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, curing agent, antioxidant, stabilizer, antiager, fire retardant, smoke suppressant, the environment-friendly materials are through over cleaning, drying, crush, activation, mixing, what the steps such as extruding were made.Material wear ability of the invention obtained and tensile strength are substantially better than the plastic material of prior art, while during material of the invention can be applied to 3D printing article of footwear.
Description
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of environmentally friendly material with high tensile
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.
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.
White pollution is the environmental pollution that global urban has, and can see what is largely discarded everywhere in various public places
Plastic products, they come from nature, are manufactured by the mankind, are but difficult to be dissolved by natural when being finally attributed to the Nature, from
And have impact on the ecological environment of the Nature.From the angle for economizing on resources, because plastic products main source is to face exhaustion
Petroleum resources, should reclaim as far as possible, but because the production cost of recycling at this stage is far above direct production cost, existing
It is difficult under condition of market economy.Therefore, how waste plastic is processed, becomes a kind of problem.
【The content of the invention】
The present invention provides a kind of environment-friendly materials with high tensile, preparation method and applications, to solve discarded modeling
Expect the problem for the treatment of.The wearability and tensile strength of the obtained environment-friendly materials with high tensile of the invention are substantially better than existing
There is the plastic material of technology, while during material of the invention can be applied to 3D printing article of footwear.
To solve above technical problem, the present invention uses following technical scheme：
A kind of environment-friendly materials with high tensile, preparation method and applications, it is in units of weight portion including following
Raw material：Graphene 2-4 parts, waste plastic 60-112 parts, neoprene 32-80 parts, PLA 34-55 parts, four PA 800K 17-
22 parts, phenyl propyl ketone 16-23 parts of 2- hydroxyl -4- octyloxies two, 18-30 parts of cyclobutenyl bis-stearamides, ethylene glycol monostearate
9-14 parts, tributoxyethyl phosphate 14-19 parts, three phosphite ester 10-17 parts of (2,4- di-tert-butyl-phenyls), polyvinyl chloride it is fine
Dimension 5-10 parts, vinal 4-8 parts, surfactant 1.2-1.8 parts, conditioning agent 0.6-1 parts, propellant 0.4-0.6 parts,
Crosslinking agent 0.4-0.8 parts, compatilizer 0.6-1.2 parts, bridging agent 0.6-1.2 parts, catalyst 0.3-0.6 parts, plasticizer 0.4-0.8
Part, dispersant 0.3-0.5 parts, tackifier 0.3-0.6 parts, curing agent 1.2-2.5 parts, antioxidant 0.3-0.5 parts, stabilizer 0.2-
0.4 part, antiager 1-1.6 parts, fire retardant 1.5-2 parts, smoke suppressant 2-4 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 compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
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 stabilizer is modified alta-mud heat stabilizer；
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 present invention also provides a kind of preparation method of the environment-friendly materials with high tensile, comprises the following steps：
S1：Dried after waste plastic is cleaned to water content≤0.8%, will then dry plastics and neoprene mixed powder
200-300 mesh sieve is crossed after broken, plastics powder is obtained；
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 activation plastics powder obtained in step S2
Amount powder, PLA, four PA 800Ks, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard
Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyvinyl chloride fibre, polyvinyl alcohol are fine
Dimension, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, in microwave power
It is 320-360W, temperature is 135-142 DEG C, and rotating speed is obtained mixture I to stir 2.8-4.2h under 200-400r/min；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4
Agent, is 76-80 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.6-2h under 150-250r/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 environment-friendly materials with high tensile are obtained.
Application of the environment-friendly materials with high tensile in 3D printing article of footwear.
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) wearability and tensile strength of the obtained environment-friendly materials with high tensile of the present invention are substantially better than existing
The plastic material of technology, adds Graphene to improve the intensity of plastic cement, Graphene high lubricating effect, therefore can improve in plastic cement
The rub resistance of plastic cement；Polyvinyl chloride fibre can cause that the wearability of plastic cement is significantly improved with the addition of vinal,
Improve the corrosion resistance of plastic cement so that the crocking resistance of plastic cement increases；
(3) during material of the invention can be applied to 3D printing article of footwear, and the plastic material of prior art may not apply to
In 3D printing article of footwear.
【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 environment-friendly materials with high tensile, in units of weight portion, including following raw material：
Graphene 2-4 parts, waste plastic 60-112 parts, neoprene 32-80 parts, PLA 34-55 parts, four PA 800K 17-22 parts,
Phenyl propyl ketone 16-23 parts of 2- hydroxyl -4- octyloxies two, 18-30 parts of cyclobutenyl bis-stearamides, ethylene glycol monostearate 9-14
Part, tributoxyethyl phosphate 14-19 parts, three phosphite ester 10-17 parts of (2,4- di-tert-butyl-phenyls), polyvinyl chloride fibre 5-
10 parts, vinal 4-8 parts, surfactant 1.2-1.8 parts, conditioning agent 0.6-1 parts, propellant 0.4-0.6 parts, crosslinking
Agent 0.4-0.8 parts, compatilizer 0.6-1.2 parts, bridging agent 0.6-1.2 parts, catalyst 0.3-0.6 parts, plasticizer 0.4-0.8 parts,
Dispersant 0.3-0.5 parts, tackifier 0.3-0.6 parts, curing agent 1.2-2.5 parts, antioxidant 0.3-0.5 parts, stabilizer 0.2-0.4
Part, antiager 1-1.6 parts, fire retardant 1.5-2 parts, smoke suppressant 2-4 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 compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
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 stabilizer is modified alta-mud heat stabilizer；
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 described environment-friendly materials with high tensile, comprises the following steps：
S1：Dried after waste plastic is cleaned to water content≤0.8%, will then dry plastics and neoprene mixed powder
200-300 mesh sieve is crossed after broken, plastics powder is obtained；
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 activation plastics powder obtained in step S2
Amount powder, PLA, four PA 800Ks, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard
Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyvinyl chloride fibre, polyvinyl alcohol are fine
Dimension, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, in microwave power
It is 320-360W, temperature is 135-142 DEG C, and rotating speed is obtained mixture I to stir 2.8-4.2h under 200-400r/min；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4
Agent, is 76-80 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.6-2h under 150-250r/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 environment-friendly materials with high tensile are obtained, it is described with high tensile
Environment-friendly materials are applied in 3D printing article of footwear.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of environment-friendly materials with high tensile, in units of weight portion, including following raw material：3.2 parts of Graphene,
90 parts of waste plastic, 60 parts of neoprene, 45 parts of PLA, 20 parts of four PA 800K, the phenyl propyl ketone 20 of 2- hydroxyl -4- octyloxies two
Part, 25 parts of cyclobutenyl bis-stearamides, 12 parts of ethylene glycol monostearate, 16 parts of tributoxyethyl phosphate, three (2,4- bis- uncles
Butyl phenyl) 15 parts of phosphite ester, 8 parts of polyvinyl chloride fibre, 6 parts of vinal, 1.5 parts of surfactant, conditioning agent
0.8 part, 0.5 part of propellant, 0.6 part of crosslinking agent, 1 part of compatilizer, 1 part of bridging agent, 0.5 part of catalyst, plasticizer 0.6 part, point
0.4 part of powder, 0.5 part of tackifier, 1.8 parts of curing agent, 0.4 part of antioxidant, 0.3 part of stabilizer, 1.5 parts of antiager, fire retardant
1.8 parts, 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 compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
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 stabilizer is modified alta-mud heat stabilizer；
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, 11 parts of aluminum oxide,
10 parts of antimony oxide, 8 parts of lead oxide, 10 parts of bentonite, 1.6 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, 1.8 parts of stearic acid；
The preparation method of the described environment-friendly materials with high tensile, comprises the following steps：
S1：It is 0.8% to be dried after waste plastic is cleaned to water content, will then dry plastics and neoprene mixed powder
200 mesh sieve are crossed after broken, plastics powder is obtained；
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, 200-300 mesh sieve is crossed, powder is obtained, gained powder is 7500GS in magnetic field intensity,
Ultrasonic power is 600W, and temperature is 55 DEG C, and rotating speed is obtained Graphene energy powder under 200r/min, to stir 48min；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activation plastics powder obtained in step S2
Amount powder, PLA, four PA 800Ks, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard
Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyvinyl chloride fibre, polyvinyl alcohol are fine
Dimension, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, in microwave power
It is 340W, temperature is 140 DEG C, and rotating speed is obtained mixture I to stir 3.5h under 300r/min；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4
Agent, is 78 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.8h under 220r/min；
The preparation method of the fire retardant, comprises the following steps：
A () adds NPE ammonium sulfate, 350 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 1.5h 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 1.3h 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 135r/min, through extruding strand, the environment-friendly materials with high tensile, the environmentally friendly material with high tensile are obtained
Material is applied in 3D printing article of footwear.
Embodiment 2
A kind of environment-friendly materials with high tensile, in units of weight portion, including following raw material：2.2 parts of Graphene,
62 parts of waste plastic, 33 parts of neoprene, 34 parts of PLA, 17 parts of four PA 800K, the phenyl propyl ketone 16 of 2- hydroxyl -4- octyloxies two
Part, 18 parts of cyclobutenyl bis-stearamides, 9 parts of ethylene glycol monostearate, 14 parts of tributoxyethyl phosphate, three (2,4- bis- uncles
Butyl phenyl) 10 parts of phosphite ester, 5 parts of polyvinyl chloride fibre, 4 parts of vinal, 1.3 parts of surfactant, conditioning agent
0.6 part, 0.4 part of propellant, 0.4 part of crosslinking agent, 0.6 part of compatilizer, 0.6 part of bridging agent, 0.3 part of catalyst, plasticizer 0.4
It is part, 0.3 part of dispersant, 0.3 part of tackifier, 1.2 parts of curing agent, 0. part of antioxidant, 0.2 part of stabilizer, 1 part of antiager, fire-retardant
1.5 parts of agent, 2 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 compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
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 stabilizer is modified alta-mud heat stabilizer；
The antiager is BASF UV-234 antiagers；
The fire retardant is in units of weight portion, including following raw material：62 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：34 parts of tributyltin oxide, 16 parts of lead hydroxide,
12 parts of diatomite, 8 parts of aluminium hydroxide, 4 parts of ammonium octamolybdate, 1.6 parts of stearic acid；
The preparation method of the described environment-friendly materials with high tensile, comprises the following steps：
S1：It is 0.7% to be dried after waste plastic is cleaned to water content, will then dry plastics and neoprene mixed powder
200 mesh sieve are crossed after broken, plastics powder is obtained；
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, 200-300 mesh sieve is crossed, powder is obtained, gained powder is 7000GS in magnetic field intensity,
Ultrasonic 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 activation plastics powder obtained in step S2
Amount powder, PLA, four PA 800Ks, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard
Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyvinyl chloride fibre, polyvinyl alcohol are fine
Dimension, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, in microwave power
It is 320W, temperature is 135 DEG C, and rotating speed is obtained mixture I to stir 4.2h under 200r/min；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4
Agent, is 76 DEG C in temperature, and rotating speed is obtained mixture II to stir 2h under 150r/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 0.8%, 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 environment-friendly materials with high tensile, the environmentally friendly material with high tensile are obtained
Material is applied in 3D printing article of footwear.
Embodiment 3
A kind of environment-friendly materials with high tensile, in units of weight portion, including following raw material：3.8 parts of Graphene,
110 parts of waste plastic, 80 parts of neoprene, 55 parts of PLA, 22 parts of four PA 800K, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two
23 parts, 30 parts of cyclobutenyl bis-stearamides, 14 parts of ethylene glycol monostearate, 19 parts of tributoxyethyl phosphate, three (2,4- bis-
Tert-butyl-phenyl) 17 parts of phosphite ester, 10 parts of polyvinyl chloride fibre, 8 parts of vinal, 1.8 parts of surfactant, regulation
1 part of agent, 0.6 part of propellant, 0.8 part of crosslinking agent, 1.2 parts of compatilizer, 1.2 parts of bridging agent, 0.6 part of catalyst, plasticizer 0.8
Part, 0.5 part of dispersant, 0.6 part of tackifier, 2.5 parts of curing agent, 0.5 part of antioxidant, 0.4 part of stabilizer, 1.6 parts of antiager, resistance
2 parts of agent of combustion, 4 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 compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
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 stabilizer is modified alta-mud heat stabilizer；
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 described environment-friendly materials with high tensile, comprises the following steps：
S1：It is 0.6% to be dried after waste plastic is cleaned to water content, will then dry plastics and neoprene mixed powder
300 mesh sieve are crossed after broken, plastics powder is obtained；
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 activation plastics powder obtained in step S2
Amount powder, PLA, four PA 800Ks, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol list are hard
Resin acid ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyvinyl chloride fibre, polyvinyl alcohol are fine
Dimension, conditioning agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, in microwave power
It is 360W, temperature is 142 DEG C, and rotating speed is obtained mixture I to stir 2.8h under 400r/min；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, suppression cigarette in mixture I obtained in step S4
Agent, is 80 DEG C in temperature, and rotating speed is obtained mixture II to stir 1.6h under 250r/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 0.7%, 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 environment-friendly materials with high tensile, the environmentally friendly material with high tensile are obtained
Material is applied in 3D printing article of footwear.
Comparative example 1, a kind of Patent Application Publication " environment friendly plastic rubber material (publication number：CN106084757A) " embodiment 3 is made
The product for obtaining.
Comparative example 2, formula used is same as Example 3 with preparation method, and unique difference is not add Graphene wherein.
Comparative example 3, formula used is same as Example 3 with preparation method, and unique difference is not add polyvinyl chloride fibre wherein
And vinal.
Plastic material prepared by plastic material and comparative example 1-3 prepared by detection embodiment 1-3, it is as a result as shown in the table：
As seen from the above table, the wearability and tensile strength of the obtained environment-friendly materials with high tensile of the present invention are obvious
Better than the plastic material of comparative example 1-3.Graphene is added in plastic cement can improve the intensity of plastic cement, Graphene high lubricating effect,
The rub resistance of plastic cement can be improved；Polyvinyl chloride fibre can cause that the wearability of plastic cement is notable with the addition of vinal
Improve, improve the corrosion resistance of plastic cement so that the crocking resistance of plastic cement increases.In addition as can be seen from the above table, product of the invention
During product can be applied in 3D printing article of footwear, and the product of prior art may not apply to 3D printing article of footwear.
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 (3)
1. a kind of environment-friendly materials with high tensile, preparation method and applications, it is characterised in that with weight portion be single
Position, including following raw material：Graphene 2-4 parts, waste plastic 60-112 parts, neoprene 32-80 parts, PLA 34-55 parts, four
PA 800K 17-22 parts, phenyl propyl ketone 16-23 parts of 2- hydroxyl -4- octyloxies two, 18-30 parts of cyclobutenyl bis-stearamides, ethylene glycol
Monostearate 9-14 parts, tributoxyethyl phosphate 14-19 parts, three phosphite ester 10-17 parts of (2,4- di-tert-butyl-phenyls),
Polyvinyl chloride fibre 5-10 parts, vinal 4-8 parts, surfactant 1.2-1.8 parts, conditioning agent 0.6-1 parts, propellant
0.4-0.6 parts, crosslinking agent 0.4-0.8 parts, compatilizer 0.6-1.2 parts, bridging agent 0.6-1.2 parts, catalyst 0.3-0.6 parts, increasing
0.4-0.8 parts of agent of modeling, dispersant 0.3-0.5 parts, tackifier 0.3-0.6 parts, curing agent 1.2-2.5 parts, antioxidant 0.3-0.5
Part, stabilizer 0.2-0.4 parts, antiager 1-1.6 parts, fire retardant 1.5-2 parts, smoke suppressant 2-4 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 compatilizer is that maleic anhydride is grafted compatilizer；
The bridging agent is acrylic type bridging agent；
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 stabilizer is modified alta-mud heat stabilizer；
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. a kind of preparation method of the environment-friendly materials with high tensile according to claim 1, it is characterised in that bag
Include following steps：
S1：Dried after waste plastic is cleaned to water content≤0.8%, after will then drying plastics and neoprene co-grinding
200-300 mesh sieve is crossed, plastics powder is obtained；
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 activation plastics powder obtained in step S2
End, PLA, four PA 800Ks, the phenyl propyl ketone of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides, ethylene glycol monostearate
Ester, tributoxyethyl phosphate, three (2,4- di-tert-butyl-phenyl) phosphite esters, polyvinyl chloride fibre, vinal, tune
Section agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, are 320- in microwave power
360W, temperature is 135-142 DEG C, and rotating speed is obtained mixture I to stir 2.8-4.2h under 200-400r/min；
S5：To addition curing agent, antioxidant, stabilizer, antiager, fire retardant, smoke suppressant in mixture I obtained in step S4,
It it is 76-80 DEG C in temperature, rotating speed is obtained mixture II to stir 1.6-2h under 150-250r/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 environment-friendly materials with high tensile are obtained.
3. application of a kind of environment-friendly materials with high tensile according to claim 1 in 3D printing article of footwear.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885516A (en) * | 2019-12-17 | 2020-03-17 | 含山县仁盛鞋业有限公司 | Preparation method of wear-resistant plastic sandal material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176084A (en) * | 2015-10-28 | 2015-12-23 | 杨洋 | Composite 3D printing material and preparation method thereof |
| CN106009351A (en) * | 2016-06-28 | 2016-10-12 | 华蓥市高科德电子科技有限公司 | High-molecular polymer material for 3D printing and preparing method thereof |
| CN106496983A (en) * | 2016-11-17 | 2017-03-15 | 南宁梦幻三体环保科技有限公司 | A kind of graphene composite material of 3D printing |
-
2017
- 2017-03-26 CN CN201710186431.5A patent/CN106916469A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176084A (en) * | 2015-10-28 | 2015-12-23 | 杨洋 | Composite 3D printing material and preparation method thereof |
| CN106009351A (en) * | 2016-06-28 | 2016-10-12 | 华蓥市高科德电子科技有限公司 | High-molecular polymer material for 3D printing and preparing method thereof |
| CN106496983A (en) * | 2016-11-17 | 2017-03-15 | 南宁梦幻三体环保科技有限公司 | A kind of graphene composite material of 3D printing |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885516A (en) * | 2019-12-17 | 2020-03-17 | 含山县仁盛鞋业有限公司 | Preparation method of wear-resistant plastic sandal material |
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