CN106752057A - A kind of preparation technology of utilization waste plastic synthesizing environment-friendly plastic material - Google Patents
A kind of preparation technology of utilization waste plastic synthesizing environment-friendly plastic material Download PDFInfo
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Abstract
The invention discloses a kind of preparation technology of utilization waste plastic synthesizing environment-friendly plastic material, belong to 3D printing technical field of material, the environment friendly plastic rubber material of the utilization waste plastic synthesis includes following raw material：Graphene, waste plastic, maleic anhydride grafting ethylene propylene diene rubber, PLA, two polyphosphate sodiums, 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, polyimide fiber, glass fibre, auxiliary agent, the environment friendly plastic rubber material of utilization waste plastic synthesis is made through steps such as over cleaning, drying, crushing, activation, mixing, extruding.The wearability and tensile strength of the environment friendly plastic rubber material using waste plastic synthesis of the invention obtained are substantially better than the plastic material of prior art, while during plastic 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 one kind is using the modeling of waste plastic synthesizing environment-friendly
The preparation technology of glue material.
【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 preparation technology of utilization waste plastic synthesizing environment-friendly plastic material, to solve at waste plastic
The problem of reason.The wearability and tensile strength of the obtained environment friendly plastic rubber material using waste plastic synthesis of the invention are substantially better than
The plastic material of prior art, while during plastic 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 preparation technology of utilization waste plastic synthesizing environment-friendly plastic material, comprises the following steps：
S1：Dried after waste plastic 63-116 parts is cleaned to water content≤0.8%, will then dry plastics and maleic acid
200-300 mesh sieve is crossed after acid anhydride grafting 35-82 parts of co-grinding of ethylene propylene diene rubber, plastics powder is obtained；
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：By Graphene 2.2-4.5 parts of crushing, 200-300 mesh sieve is crossed, powder is obtained, gained powder is in magnetic field intensity
It is 7000-8200GS, ultrasonic power is 520-650W, temperature is 52-56 DEG C, under rotating speed is 200-300r/min, stirs 42-
55min, is obtained Graphene energy powder；
S4：Under nitrogen protection, to Graphene energy obtained in addition step S3 in activation plastics powder obtained in step S2
Amount powder, PLA 36-58 parts, two polyphosphate sodium 34-45 parts, 2- hydroxyl -4- octyloxies two phenyl propyl ketone 18-25 parts, cyclobutenyls
Bis-stearamides 20-32 parts, ethylene glycol monostearate 10-15 parts, tributoxyethyl phosphate 15-20 parts, three (2,4- bis- uncles
Butyl phenyl) phosphite ester 12-18 parts, polyimide fiber 6-12 parts, glass fibre 4-8 parts, conditioning agent 0.6-1 parts, generation
Agent 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, be 300-350W in microwave power, and temperature is
138-145 DEG C, rotating speed is obtained mixture I to stir 3-4h under 200-400r/min；
S5：To 1.2-2.5 parts of curing agent of addition, antioxidant 0.3-0.5 parts, stabilizer in mixture I obtained in step S4
0.2-0.4 parts, antiager 1-1.6 parts, fire retardant 1.5-2 parts, smoke suppressant 2-4 parts, be 76-80 DEG C in temperature, and rotating speed is 150-
1.6-2h is stirred under 250r/min, mixture II is obtained；
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 plastic rubber material using waste plastic synthesis is obtained.
Preferably, surfactant described in step S2 is Pluronic F68.
Preferably, conditioning agent described in step S4 is ACR, and the propellant is aerogel generating agent, and the crosslinking agent is
Crosslinking aid S AC-100.
Preferably, compatilizer described in step S4 is that maleic anhydride is grafted compatilizer, and the bridging agent is acrylic acid type frame
Bridge agent.
Preferably, catalyst described in step S4 is vanadic anhydride, and the plasticizer is citrate.
Preferably, dispersant described in step S4 is Dispersant MF, and the tackifier are butyl trimethoxy silane.
Preferably, curing agent described in step S5 is epoxylite curing agent, and the antioxidant is antioxidant 1098.
Preferably, stabilizer described in step S5 is modified alta-mud heat stabilizer, and the antiager is BASF UV-
234 antiagers.
Preferably, fire retardant described in step S5 is in units of weight portion, including following raw material：Ethylene glycol ether acetate
60-68 parts, Miglyol 812N 25-28 parts, 22-24 parts of NPE ammonium sulfate, PPOX triol
18-22 parts, 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.
Preferably, smoke suppressant described in step S5 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
Part.
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 plastic rubber material using waste plastic synthesis of the present invention are substantially excellent
In the plastic material of prior art, Graphene is added to improve the intensity of plastic cement in plastic cement, Graphene high lubricating effect, therefore
The rub resistance of plastic cement can be improved；Polyimide fiber can cause that the wearability of plastic cement is significantly carried with the addition of glass fibre
Height, improves the corrosion resistance of plastic cement so that the crocking resistance of plastic cement increases；
(3) during plastic material of the invention can be applied to 3D printing article of footwear, and the plastic material of prior art can not be answered
For 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 plastic rubber material of the utilization waste plastic synthesis is in units of weight portion including following
Raw material：Graphene 2.2-4.5 parts, waste plastic 63-116 parts, maleic anhydride grafting 35-82 parts of ethylene propylene diene rubber, PLA
36-58 parts, two polyphosphate sodium 34-45 parts, phenyl propyl ketone 18-25 parts of 2- hydroxyl -4- octyloxies two, cyclobutenyl bis-stearamides 20-
32 parts, ethylene glycol monostearate 10-15 parts, tributoxyethyl phosphate 15-20 parts, three (2,4- di-tert-butyl-phenyl) phosphorous
Acid esters 12-18 parts, polyimide fiber 6-12 parts, glass fibre 4-8 parts, surfactant 1.2-1.8 parts, conditioning agent 0.6-1
Part, 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 part, 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 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, 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 environment friendly plastic rubber material of described utilization waste plastic synthesis, comprises the following steps：
S1：Dried after waste plastic is cleaned to water content≤0.8%, then will drying plastics and maleic anhydride grafting three
200-300 mesh sieve is crossed after first EP rubbers co-grinding, 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, two polyphosphate sodiums, 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, polyimide fiber, glass fibre, tune
Section agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, are 300- in microwave power
350W, temperature is 138-145 DEG C, and rotating speed is obtained mixture I to stir 3-4h 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 plastic rubber material using waste plastic synthesis is obtained, it is described using discarded modeling
Expect that the environment friendly plastic rubber material of synthesis is 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 plastic rubber material of utilization waste plastic synthesis, in units of weight portion, including following raw material：Graphene
3.5 parts, 90 parts of waste plastic, maleic anhydride grafting 60 parts of ethylene propylene diene rubber, 45 parts of PLA, 40 parts of two polyphosphate sodium, 2-
22 parts of two phenyl propyl ketone of hydroxyl -4- octyloxies, 26 parts of cyclobutenyl bis-stearamides, 13 parts of ethylene glycol monostearate, tricresyl phosphate fourth
18 parts of epoxide ethyl ester, three 15 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, 8 parts of polyimide fiber, 6 parts of glass fibre, table
1.5 parts of face activating agent, 0.8 part of conditioning agent, 0.5 part of propellant, 0.6 part of crosslinking agent, 1 part of compatilizer, 1 part of bridging agent, catalyst
0.5 part, 0.6 part of plasticizer, 0.4 part of dispersant, 0.5 part of tackifier, 1.8 parts of curing agent, 0.4 part of antioxidant, stabilizer 0.3
Part, 1.5 parts of antiager, 1.8 parts of fire retardant, 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 environment friendly plastic rubber material of described utilization waste plastic synthesis, comprises the following steps：
S1：It is 0.8% to be dried after waste plastic is cleaned to water content, then will drying plastics and maleic anhydride grafting three
200 mesh sieve are crossed after first EP rubbers co-grinding, 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, two polyphosphate sodiums, 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, polyimide fiber, glass fibre, tune
Section agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, be in microwave power
320W, temperature is 142 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 plastic rubber material using waste plastic synthesis, the utilization waste plastic synthesis is obtained
Environment friendly plastic rubber material be applied in 3D printing article of footwear.
Embodiment 2
A kind of environment friendly plastic rubber material of utilization waste plastic synthesis, in units of weight portion, including following raw material：Graphene
2.3 parts, 64 parts of waste plastic, maleic anhydride grafting 36 parts of ethylene propylene diene rubber, 38 parts of PLA, 35 parts of two polyphosphate sodium, 2-
20 parts of two phenyl propyl ketone of hydroxyl -4- octyloxies, 20 parts of cyclobutenyl bis-stearamides, 11 parts of ethylene glycol monostearate, tricresyl phosphate fourth
16 parts of epoxide ethyl ester, three 12 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, 7 parts of polyimide fiber, 4 parts of glass fibre, table
1.3 parts of face activating agent, 0.6 part of conditioning agent, 0.4 part of propellant, 0.4 part of crosslinking agent, 0.6 part of compatilizer, 0.6 part of bridging agent, urge
0.3 part of agent, 0.4 part of plasticizer, 0.3 part of dispersant, 0.3 part of tackifier, 1.2 parts of curing agent, 0. part of antioxidant, stabilizer
0.2 part, 1 part of antiager, 1.5 parts of fire retardant, 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 environment friendly plastic rubber material of described utilization waste plastic synthesis, comprises the following steps：
S1：It is 0.7% to be dried after waste plastic is cleaned to water content, then will drying plastics and maleic anhydride grafting three
200 mesh sieve are crossed after first EP rubbers co-grinding, 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, two polyphosphate sodiums, 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, polyimide fiber, glass fibre, tune
Section agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, be in microwave power
300W, temperature is 138 DEG C, and rotating speed is obtained mixture I to stir 4h 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 plastic rubber material using waste plastic synthesis, the utilization waste plastic synthesis is obtained
Environment friendly plastic rubber material be applied in 3D printing article of footwear.
Embodiment 3
A kind of environment friendly plastic rubber material of utilization waste plastic synthesis, in units of weight portion, including following raw material：Graphene
4.2 parts, 115 parts of waste plastic, maleic anhydride grafting 80 parts of ethylene propylene diene rubber, 55 parts of PLA, 44 parts of two polyphosphate sodium, 2-
24 parts of two phenyl propyl ketone of hydroxyl -4- octyloxies, 30 parts of cyclobutenyl bis-stearamides, 14 parts of ethylene glycol monostearate, tricresyl phosphate fourth
20 parts of epoxide ethyl ester, three 18 parts of (2,4- di-tert-butyl-phenyl) phosphite esters, 12 parts of polyimide fiber, 8 parts of glass fibre, table
1.8 parts of face activating agent, 1 part of conditioning agent, 0.6 part of propellant, 0.8 part of crosslinking agent, 1.2 parts of compatilizer, 1.2 parts of bridging agent, catalysis
0.6 part of agent, 0.8 part of plasticizer, 0.5 part of dispersant, 0.6 part of tackifier, 2.5 parts of curing agent, 0.5 part of antioxidant, stabilizer 0.4
Part, 1.6 parts of antiager, 2 parts of fire retardant, 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 environment friendly plastic rubber material of described utilization waste plastic synthesis, comprises the following steps：
S1：It is 0.6% to be dried after waste plastic is cleaned to water content, then will drying plastics and maleic anhydride grafting three
300 mesh sieve are crossed after first EP rubbers co-grinding, 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, two polyphosphate sodiums, 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, polyimide fiber, glass fibre, tune
Section agent, propellant, crosslinking agent, compatilizer, bridging agent, catalyst, plasticizer, dispersant, tackifier, be in microwave power
350W, temperature is 145 DEG C, and rotating speed is obtained mixture I to stir 3h 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 plastic rubber material using waste plastic synthesis, the utilization waste plastic synthesis is obtained
Environment friendly plastic rubber material be 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 polyimide fiber wherein
And glass fibre.
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：
| Pilot project | Wearability | Tensile strength (MPa) | In whether can be applied to 3D printing article of footwear |
| Embodiment 1 | It is excellent | 76.14 | It is |
| Embodiment 2 | It is excellent | 69.53 | It is |
| Embodiment 3 | It is excellent | 81.12 | It is |
| Comparative example 1 | It is good | 46.35 | It is no |
| Comparative example 2 | It is good | 53.46 | It is |
| Comparative example 3 | It is good | 62.42 | It is |
As seen from the above table, the wearability of the obtained environment friendly plastic rubber material using waste plastic synthesis of the present invention and stretching are strong
Degree is substantially better than the plastic material of comparative example 1-3.Graphene is added in plastic cement can improve the intensity of plastic cement, Graphene lubrication effect
It is really good, the rub resistance of plastic cement can be improved；Polyimide fiber can cause that the wearability of plastic cement shows with the addition of glass fibre
Write and 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, it is 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 (10)
1. a kind of preparation technology of utilization waste plastic synthesizing environment-friendly plastic material, it is characterised in that comprise the following steps：
S1：Dried after waste plastic 63-116 parts is cleaned to water content≤0.8%, then connect drying plastics and maleic anhydride
200-300 mesh sieve is crossed after branch 35-82 parts of co-grinding of ethylene propylene diene rubber, plastics powder is 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：By Graphene 2.2-4.5 parts of crushing, 200-300 mesh sieve is crossed, powder is obtained, gained powder is in magnetic field intensity
7000-8200GS, ultrasonic power is 520-650W, and temperature is 52-56 DEG C, under rotating speed is 200-300r/min, stirs 42-
55min, is obtained Graphene 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 36-58 part, two polyphosphate sodium 34-45 part, phenyl propyl ketone 18-25 parts of 2- hydroxyl -4- octyloxies two, cyclobutenyl pair firmly
20-32 parts of acyl amine, ethylene glycol monostearate 10-15 parts, tributoxyethyl phosphate 15-20 parts, three (2,4- di-t-butyls
Phenyl) phosphite ester 12-18 parts, polyimide fiber 6-12 parts, glass fibre 4-8 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
Modeling 0.4-0.8 part of agent, dispersant 0.3-0.5 parts, tackifier 0.3-0.6 parts, microwave power be 300-350W, temperature is 138-
145 DEG C, rotating speed is obtained mixture I to stir 3-4h under 200-400r/min；
S5：To 1.2-2.5 parts of curing agent of addition, antioxidant 0.3-0.5 parts, stabilizer 0.2- in mixture I obtained in step S4
0.4 part, antiager 1-1.6 parts, fire retardant 1.5-2 parts, smoke suppressant 2-4 parts, be 76-80 DEG C in temperature, and rotating speed is 150-250r/
1.6-2h is stirred under min, mixture II is obtained；
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 plastic rubber material using waste plastic synthesis is obtained.
2. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that step
Surfactant is Pluronic F68 described in rapid S2.
3. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that step
Conditioning agent described in rapid S4 is ACR, and the propellant is aerogel generating agent, and the crosslinking agent is crosslinking aid S AC-100.
4. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that step
Compatilizer described in rapid S4 is that maleic anhydride is grafted compatilizer, and the bridging agent is acrylic type bridging agent.
5. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that step
Catalyst described in rapid S4 is vanadic anhydride, and the plasticizer is citrate.
6. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that step
Dispersant described in rapid S4 is Dispersant MF, and the tackifier are butyl trimethoxy silane.
7. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that step
Curing agent described in rapid S5 is epoxylite curing agent, and the antioxidant is antioxidant 1098.
8. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that step
Stabilizer described in rapid S5 is modified alta-mud heat stabilizer, and the antiager is BASF UV-234 antiagers.
9. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that step
Fire retardant is in units of weight portion described in rapid S5, including following raw material：Ethylene glycol ether acetate 60-68 parts, caprylic capric
Triglycerides 25-28 parts, 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.
10. the preparation technology of utilization waste plastic synthesizing environment-friendly plastic material according to claim 1, it is characterised in that
Smoke suppressant described in step S5 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.
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| US20130116371A1 (en) * | 2011-11-08 | 2013-05-09 | Kenner Material & System Co., Ltd. | Thermally Conductive and Flame-Retarded Compositions |
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| CN1858101A (en) * | 2006-04-26 | 2006-11-08 | 南京聚隆化学实业有限责任公司 | Inorganic nano particle modified high performance recovery plastic and its preparing process |
| US20130116371A1 (en) * | 2011-11-08 | 2013-05-09 | Kenner Material & System Co., Ltd. | Thermally Conductive and Flame-Retarded Compositions |
| CN106147002A (en) * | 2016-07-25 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of novel environment friendly solar cell backboard material |
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