CN103756075A - Method for preparation of thermoplastic elastomer from waste rubber and waste plastics - Google Patents
Method for preparation of thermoplastic elastomer from waste rubber and waste plastics Download PDFInfo
- Publication number
- CN103756075A CN103756075A CN201310700335.XA CN201310700335A CN103756075A CN 103756075 A CN103756075 A CN 103756075A CN 201310700335 A CN201310700335 A CN 201310700335A CN 103756075 A CN103756075 A CN 103756075A
- Authority
- CN
- China
- Prior art keywords
- waste
- rubber
- thermoplastic elastomer
- weight
- weight parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a method for preparation of a thermoplastic elastomer from waste rubber and waste plastics. The method comprises the steps of: according to the following material composition requirements, weighing the materials and adding them into a plasticizing machine to perform uniform plasticizing, and carrying out dynamic vulcanization reaction through a conical screw machine, thus obtaining the thermoplastic elastomer. The materials include: 30-70 parts by weight of rubber powder, 30-70 parts by weight of waste plastics, 20-50 parts by weight of a compatibilizer, 1-10 parts by weight of a plasticizer, 20-40 parts by weight of vegetable oil, 0.1-2 parts by weight of zinc oxide, 0.2-5 parts by weight of a homogenizing agent, 10-40 parts by weight of a filler and 1-10 parts by weight of other auxiliaries. The method provided by the invention can prepare the waste rubber and waste plastics into the thermoplastic elastomer through a dynamic vulcanization process. The whole production process is carried out under environmental protection conditions, and discharges no waste gas and wastewater. The method not only can realize reasonable reusing of waste rubber and waste plastics, but is also implemented under atmospheric pressure, so that the energy consumption can be effectively reduced, and the equipment and people are relatively safe. The method provided by the invention uses the existing automated equipment to conduct continuous production, and can effectively reduce the human labor.
Description
Technical field
The present invention relates to a kind of waste rubber and used plastics method for thermoplastic elastomer of utilizing.
Background technology
Since entering 21 century, one of many problems that the mankind face are exactly the processing of solid waste.Because polymer materials is not easy to decompose under general environment, processing Polymer wastes has become a serious environmental problem.
In the last few years, China's Economic development was rapid, and people's lives also improve year by year, had driven the rapid growth of each side consumption simultaneously.In the time of Growth of Consumption, also driven the generation of various consumption refuses, wherein maximum is exactly waste rubber and plastic waste.Waste rubber and plastic waste all belong to the macromolecular compound of difficult degradation, and the rubber of China and petroleum resources are all very limited, if waste rubber and plastic waste are changed into a kind of useful material through chemical technology, the novel material changing on the one hand can Substitute For Partial rubber and plastics, solid waste can also be disposed on the other hand, so this is a very significant thing.
Rubber is mathematical in the vital role of contemporary society, at new China's initial stage, is once being decided to be strategic stockpile, also fails to find at present a material for instead of rubber completely.But the rubber sources of China is not abundant, and major part still relies on import.Since 2002, China became continuously rubber in the world and consumes maximum country, and the consumption of rubber accounts for 30% left and right of world's rubber-consumer amount, and the natural rubber of while 80%, 46% synthetic rubber rely on import.Add the cross-link bond and the stablizer that due to waste rubber self, exist, so be difficult under field conditions (factors) be degraded, as long-term, overstock not processed and will cause serious environmental pollution.Will cause so dual harm: wasted resource, polluted environment.In the face of such present situation, the resource utilization recycling of research rubber and plastics is very significant.
In these years, the development of automobile industry drives burning the wind of Rubber Industry.The consumption of rubber is year after year soaring, and the doughnut of simultaneously scrapping also hits new peak continuously.As long as automobile, plane tyre have 1% tire wear, whole tire just can not continue to use.The tire number of scrapping every year is in the world hundred million of 14-15, and according to incompletely statistics, the China at present conservative owning amount of automobile is 100,000,000 left and right, and damaged tire is with the speed increase of annual 8%-10%.More than 860 ten thousand tons of the raw damaged tires of China's common property in 2010, the quantity of 2011 has reached more than 960 ten thousand tons, adds up to 2.76 hundred million.These quantity do not comprise other rubber item, as the tire of bicycle motorcycle, other rubber item etc.
At present, the method for rubber sources recycling is mainly heat energy utilization, is ground into rubber powder and produces reclaimed rubber both at home and abroad.Wherein developed country is main mainly with heat energy utilization, using waste rubber, as fuel, provide heat energy, this is a kind of simple disposable method of utilizing, and resource cannot recirculation, and the flue dust producing while processing burning needs great economic input purify to avoid environmental pollution.Rubber powder be mainly used in prepare regenerated rubber, modifying asphalt, make plastic cement race track, composite coating etc., rubber powder is gone back imperfection in the application of China, if rubber powder modified asphalt is still in the exploratory stage, so the rubber powder of the overwhelming majority is all applied to, prepares regenerated rubber.The production of regenerated rubber at present still exists serious secondary pollution, and the performance of the regenerated rubber of gained is also unsatisfactory.
Plastics are requisite macromolecular materials in people's daily life.Since the first plastics come out, had the history of over one hundred year so far, plastic industry development is very rapid, and simultaneously increasing waste material has also caused serious pollution to environment, and China has promulgated " plastic limit " for this reason.At present China has become the first big country of plastics-production and consumption in the world, and within 2010, the annual consumption of China's plastics is 6,500 ten thousand tons, is about 1/4 of world's plastics aggregate consumption.
China generally adopts landfill, burning and three kinds of modes of recycling to the processing mode of mixed waste plastic at present.Landfill disposal is still the major way of China's Treatment of Waste Plastics till now, is about 93% of plastic waste total amount.This is mainly due to this mode less investment, simple, but such processing mode hazardness is very large, and the one, landfill needs a large amount of soils, thereby waste is a large amount of, ploughs; The 2nd, plastic waste needs centuries just may be degraded completely in soil, and a large amount of like this arable lands can only be fallen into disuse for a long time; The 3rd, plastic waste, through without poisoning processing, may not accompany the pollutents such as heavy metal, bacterium, virus in plastic waste, and prolonged permeation also can polluted underground water resource.So this processing form of landfill is just conceived to short-term interests, not for long-term interest is considered, this mode should be forbidden as far as possible.The plastic waste burning accounts for 2% of total amount, burns this processing mode more reasonable than simple landfill, first burns very high heat energy can be provided, and the macromolecular material after secondly burning is more easily landfilled.The very most plastic waste of developed country adopts this kind of mode.But burn and need to build perfect incinerator, invest greatlyr, macromolecular material is difficult for perfect combustion meeting and emits a large amount of toxic and harmfuls, plastic waste also easily lumps when burning, and these problems are all restricting the development of burning disposal plastic waste.At present China in Shanghai, Xi'an, zhejiang and other places is provided with waste incineration station.Recycling is current best processing mode.The recycling of plastic waste is divided into physics regeneration and chemical regeneration at present.Physics regeneration utilize the method for physics by waste plastics recycling, as melt-processed, straight forming processing etc. again.The basic non-secondary pollution of this method, resource utilization are very high, but very high to the requirement of plastic waste, and plastic waste must be single, it is few to adhere to pollutent.Chemical regeneration makes plastic waste by chemical operation such as thermolysis, catalytic pyrolysis, gasifications the Chemicals such as industrial chemicals, plastic monomer, fuel oil, combustion gas.Chemical regeneration running cost is lower, and secondary pollution is also less, but also higher to the requirement of raw material.
And the utilization of two kinds of waste material resourcebilities is prepared to thermoplastic elastomer by chemical technology, it will be very significant something.
Patent CN88101416 discloses a kind of method of utilizing reclaimed rubber and polyethylene to prepare thermoplastic elastomer, but the production cost of reclaimed rubber is higher, use for polyethylene be not to discarded poly utilization again, do not solve the recycling problem of waste rubber or plastics.Patent 200410022630.5 discloses one and has utilized the elastomeric method of preparing thermoplastic elastomer by using waste vulcanized rubber, wherein add polyolefin plastics as blend, but same, the polyolefin plastics of its use is not waste plastic, do not solve equally the recycling problem of waste plastic, and the performance of the thermoplastic elastomer obtaining is barely satisfactory.Due to the reason of the degradations such as ductility after the aging and finished product processing sizing of plastics itself, waste plastic again utilize difficulty often higher, as the recovery agglomeration technique to waste polyethylene must be take 90% new polyethylene as raw material, only can add a small amount of waste material of 10%, and must just can make finished product through second melting.There is larger difficulty in the direct recycling of visible plastic waste, develops its technique directly recycling and have more practical significance.
Summary of the invention
What the object of this invention is to provide a kind of high-efficiency environment friendly utilizes waste rubber, the used plastics method for thermoplastic elastomer, and the thermoplastic elastomer that uses the method to prepare has good physicals, and can realize the resource recycling of solid waste.
The present invention adopts following technical scheme:
Method of the present invention comprises the following steps:
Step 1: according to the requirement of following material composition, take material and add in plasticizing machine and mix plasticizing, and to be stirred to temperature be 80 ~ 120 ℃;
Step 2: while hot gained material is imported in conical screw machine, rubber is reacted with plastics generation dynamic vulcanization, controlling high-temperature temperature is 140 ~ 180 ℃, the temperature of controlling cooling unit is 20 ~ 40 ℃, main control system rotating speed is 50 ~ 200 revs/min of per minutes, and controlling reinforced rotating speed is 10 ~ 50 revs/min of per minutes; After discharging is cooling, both obtained thermoplastic elastomer;
Described material composition comprises: rubber powder 30 ~ 70 weight parts, plastic waste 30 ~ 70 weight parts, expanding material 20 ~ 50 weight parts, fluidizer 1 ~ 10 weight part, industry oil 20 ~ 40 weight parts, zinc oxide 0.1 ~ 2 weight part, leveler 0.2 ~ 5 weight part, filler 10 ~ 40 weight parts, other auxiliary agent 1 ~ 10 weight parts.
Further, waste rubber of the present invention is waste tyre rubber powder or useless acrylonitrile-butadiene rubber powder, and described plastic waste is useless high density polyethylene(HDPE) or waste polyvinyl chloride.
Further, the weight ratio of rubber powder of the present invention and plastic waste powder is 2:1.
Further, fluidizer of the present invention is selected from one or more in PTC-R, RV1 or RV2.
Further, expanding material of the present invention is selected from one or more in polyolefin elastomer, ethylene-vinyl acetate copolymer or chlorinatedpolyethylene.
Further, industry oil of the present invention is selected from one or more in acidification oil, aromatic hydrocarbon oil, naphthenic oil or paraffin oil.
Further, filler of the present invention is selected from one or more in carbon black, white carbon black or calcium carbonate.
Further, other auxiliary agents of the present invention comprise anti-aging agent and/or promotor.
Further, the generation system of vulcanization reaction of the present invention is selected from sulfur cross-linking system, peroxide vulcanizing system, resin cure system or low Sulfur and the shared vulcanization system of superoxide.
Positively effect of the present invention comprises:
The present invention can be prepared into thermoplastic elastomer by waste rubber and plastic waste by Technology of Dynamic Vulcanized, and whole production process is carried out under the condition of environmental protection, and without waste gas, discharge of wastewater.
The present invention can realize the rationalization recycling of waste old, plastic waste.
The present invention uses existing automatic equipment, can continuous automatic production, can effectively reduce manpower work.
The present invention carries out under normal pressure, effectively reduces energy consumption, and equipment and the person are comparatively safe.
The prepared thermoplastic elastomer of the present invention can be a kind of plastic waste and a kind of waste rubber, also can be multiple waste rubber and plastic waste blend.
The present invention is prepared has certain physicals, and repeatedly used thermoplastic elastomer.
The prepared thermoplastic elastomer of the present invention can be applicable to the fields such as footwear material, sealed strip.
The prepared thermoplastic elastomer of the present invention is used waste rubber, used plastics standby, therefore cheap, is easy to get.
Embodiment
Rubber powder in various embodiments of the present invention is tire glue powder or rubber item rubber powder.Plastic waste can be Industry Waste plastics, reworked material.Can be that single waste rubber and single plastic waste blend can be also multiple blend.
In various embodiments of the present invention, the effect of fluidizer is: interrupt the cross-link bond of rubber, make rubber powder recover plasticity.Preferably, fluidizer is selected one or more in PTC-R, RV1 or RV2.Wherein PTC-R is that Hebei Rui Wei Science and Technology Ltd. produces, can be by commercially available acquisition.Wherein RV1 is that Hebei Rui Wei Science and Technology Ltd. produces, can be by commercially available acquisition.Wherein RV2 is that Hebei Rui Wei Science and Technology Ltd. produces, can be by commercially available acquisition.
In various embodiments of the present invention, the effect of expanding material is: in plastics phase and Young's modulus transitional region of rubber phase interface formation, play transitional function, increase the consistency of plastics and rubber.Can select, solubilizing agent can be one or more in polyolefin elastomer, ethylene-vinyl acetate copolymer or chlorinatedpolyethylene, and each compound all can obtain by commercially available mode.
In various embodiments of the present invention, the effect of industry oil is: play effect softening and increase processing characteristics.Can select, solubilizing agent can be one or more in acidification oil, aromatic hydrocarbon oil, naphthenic oil or paraffin oil, and each compound all can obtain by commercially available mode.
In various embodiments of the present invention, the effect of leveler is: make the more even of each mixing of materials.Can select the leveler that the leveler using in various embodiments of the present invention is produced for German STRUKTOL company.
In various embodiments of the present invention, the effect of filler is: the physicals that improves thermoplastic elastomer.Can select, filler can be one or more in carbon black, white carbon black or calcium carbonate, and each compound all can obtain by commercially available mode.
Other auxiliary agents in various embodiments of the present invention be mainly promotor and or anti-aging agent, it does not have conclusive effect to waste rubber and used plastics for the processing method of thermoplastic elastomer, just can promote the quality of gained thermoplastic elastomer.The anti-aging agent that can select is selected ketoamine, N-Phenyl beta naphthylamine, Ursol D or antioxidant D.Promotor is selected from vulkacit D (vulkacit D), DM(2,2'-dithio-bis-benzothiazole), M(2-thiol benzothiazole) or TMTD(tetramethyl-thiuram disulfide), each compound all can obtain by commercially available mode.
In various embodiments of the present invention, the effect of vulcanization system is: rubber and plastics are realized dynamic vulcanization under mechanical shear stress, and limit blend becomes sulfuration.
Waste Crumb rubber of the present invention is the granular or meal that waste rubber obtains after fragmentation, for the size of rubber powder, there is no special requirement, can not serve as restriction condition of the present invention.Particle diameter is less still can increase pretreated cost for follow-up light-catalyzed reaction is more fully more efficient, and the rubber powder that preferred various embodiments of the present invention adopt is 50-60 object rubber powder.
The plastic waste powder that plastic waste of the present invention becomes through fragmentation for plastic waste, preferably carries out plastic waste powder and solubilizing agent to obtain major ingredient with rubber powder blend again after blend.
Embodiment 1:
Proportioning: major ingredient 100 weight parts [tire glue powder 70 weight parts, POE (polyethylene octene elastomer) 15 weight parts, high density polyethylene(HDPE) 15 weight parts], RV2 2 weight parts, carbon black 15 weight parts, acidification oil 10 weight parts, WS sulfuration resin 15 weight parts, S 0.5 weight part, Vulcanization accelerator TMTD 1 weight part, captax 1 weight part, antioxidant D 0.5 weight part, leveler 0.5 weight part, zinc oxide 1 weight part.
(1) high-speed stirring is mixed: by above formula rate, pour into successively in homogenizer and start to stir, make RV2 evenly be wrapped in shoddy particle surface, through immersional wetting, infiltrate in rubber powder granule; Its whipping temp is set as 100 ℃, and frequency setting is 50Hz, when temperature rises to 95 ℃ of left and right, reduces speed now, and stirs 5min and discharges material again.
(2) discharge the material having stirred from homogenizer, pour into while hot in conical double screw extruder, by mechanical shearing effect, continue reaction, make rubber and plastics generation dynamic vulcanization, by the cooperation of various auxiliary agents and the effect of mechanical shearing, rubber grain is dispersed in the matrix of plastics, forms the thermoplastic elastomer with certain performance.Then from conical double-screw material out, directly enter upper and lower two roller mill slice.(wherein: the engine speed of conical screw extruder is made as 200 revs/min, electric current 57A, reinforced rotating speed is made as 30 revs/min, electric current 2A, the design temperature in Si Ge district is respectively 140 ℃-160 ℃-160 ℃-40 ℃; Actual temperature is respectively 136 ℃-159 ℃-162 ℃-40 ℃).
(3) use mill slice, roll spacing is adjusted to minimum, and slice roll spacing is 2mm.
(4) its physicals is surveyed in compression molding
According to national standards such as GB/T528-2009, measure the physicalies such as its tensile strength, tensile yield, tension set.
The thin slice pressing is pressed into to be about 2mm thick, is cut into the rectangular sheet (each two) that is about 300mm × 200mm with scissors, put into vulcanizing press moulding 10 minutes, condition of molding is: 160 ℃, and 20MPa.Taking-up is put into chilling press and is cooled to room temperature, then after 24 hours, surveys its physicals.
(5) survey its physicals
By the physicals of the thermoplastic elastomer of state's mapping, be: Shao A hardness is 82, tensile strength is 14.42MPa, and tensile yield is 278.84%, and tensile set is 40%.5 the aging conservation rates of back draft intensity that turn refining are continuously 91.98%, and tensile yield conservation rate is 91.84%.
Embodiment 2:
Proportioning: major ingredient 100 weight parts (Ethylene Propylene Terpolymer rubber powder 60 weight parts, VAMax 20 weight parts, waste polypropylene 20 weight parts), RV2 2 weight parts (take major ingredient as 100 weight parts), carbon black 15 weight parts, acidification oil 10 weight parts, WS sulfuration resin 15 weight parts, S 1.5 weight parts, captax 0.5 weight part, altax 0.5 weight part, antioxidant D 0.5 weight part, leveler 0.5 weight part, zinc oxide 0.5 weight part.
(1) high-speed stirring is mixed: by above formula rate, pour into successively in homogenizer and start to stir, make RV2 evenly be wrapped in shoddy particle surface, through immersional wetting, infiltrate in rubber powder granule; Its whipping temp is set as 100 ℃, and frequency setting is 50Hz, when temperature rises to 95 ℃ of left and right, reduces speed now, and stirs 5min and discharges material again.
(2) discharge the material having stirred from homogenizer, pour into while hot in parallel equidirectional two-screw forcing machine, by mechanical shearing effect, continue reaction, make rubber and plastics generation dynamic vulcanization, by the cooperation of various auxiliary agents and the effect of mechanical shearing, rubber grain is dispersed in the matrix of plastics, forms the thermoplastic elastomer with certain performance.Then from twin screw material out, directly enter upper and lower two roller mill slice.(wherein: the engine speed of parallel equidirectional two-screw forcing machine is made as 270 turn/57A, reinforced rotating speed is made as 30 turn/2A, and the design temperature in Si Ge district is respectively 150 ℃-170 ℃-170 ℃-40 ℃; Actual temperature is respectively 145 ℃-171 ℃-172 ℃-40 ℃).
(3) use mill slice, roll spacing is adjusted to minimum, and slice roll spacing is 2mm.
(4) its physicals is surveyed in compression molding
According to national standards such as GB/T528-2009, measure the physicalies such as its tensile strength, tensile yield, tension set.
The thin slice pressing is pressed into to be about 2mm thick, is cut into the rectangular sheet (each two) that is about 300mm × 200mm with scissors, put into vulcanizing press moulding 10 minutes, condition of molding is: 160 ℃, and 20MPa.Taking-up is put into chilling press and is cooled to room temperature, then after 24 hours, surveys its physicals.
(5) survey its physicals
By the physicals of the thermoplastic elastomer of state's mapping, be: Shao A hardness is 74, tensile strength is 10.52MPa, and tensile yield is 258.84%, and tensile set is 50%.5 the aging conservation rates of back draft intensity that turn refining are continuously 92.18%, and tensile yield conservation rate is 92.12%.
Embodiment 3:
Proportioning: major ingredient 100 weight parts (nitrile rubber powder 50 weight parts, chlorinatedpolyethylene 20 weight parts, waste polyvinyl chloride 30 weight parts), RV2 1.5 weight parts (take major ingredient as 100 weight parts), carbon black 10 weight parts, acidification oil 20 weight parts, WS sulfuration resin 15 weight parts, DCP 1.5 weight parts, antioxidant D 0.5 weight part, leveler 0.5 weight part, zinc oxide 1.5 weight parts.
(1) high-speed stirring is mixed: by above formula rate, pour into successively in homogenizer and start to stir, make RV2 evenly be wrapped in shoddy particle surface, through immersional wetting, infiltrate in rubber powder granule; Its whipping temp is set as 110 ℃, and frequency setting is 50Hz, when temperature rises to 100 ℃ of left and right, reduces speed now, and stirs 5min and discharges material again.
(2) discharge the material having stirred from homogenizer, pour into while hot in conical double screw extruder, by mechanical shearing effect, continue reaction, make rubber and plastics generation dynamic vulcanization, by the cooperation of various auxiliary agents and the effect of mechanical shearing, rubber grain is dispersed in the matrix of plastics, forms the thermoplastic elastomer with certain performance.Then from twin screw material out, directly enter upper and lower two roller mill slice.(wherein: the engine speed of conical screw extruder is made as 150 revs/min, electric current 57A, reinforced rotating speed is made as 25 revs/min, electric current 2A, the design temperature in Si Ge district is respectively 150 ℃-170 ℃-170 ℃-20 ℃; Actual temperature is respectively 146 ℃-168 ℃-171 ℃-20 ℃).
(3) use mill slice, roll spacing is adjusted to minimum, and slice roll spacing is 2mm.
(4) its physicals is surveyed in compression molding
According to national standards such as GB/T528-2009, measure the physicalies such as its tensile strength, tensile yield, tension set.
The thin slice pressing is pressed into to be about 2mm thick, is cut into the rectangular sheet (each two) that is about 300mm × 200mm with scissors, put into vulcanizing press moulding 10 minutes, condition of molding is: 160 ℃, and 20MPa.Taking-up is put into chilling press and is cooled to room temperature, then after 24 hours, surveys its physicals.
(5) survey its physicals
By the physicals of the thermoplastic elastomer of state's mapping, be: Shao A hardness is 83, tensile strength is 14.82MPa, and tensile yield is 258.48%, and tensile set is 51%.5 the aging conservation rates of back draft intensity that turn refining are continuously 92.63%, and tensile yield conservation rate is 90.22%.
Embodiment 4:
Proportioning: major ingredient 100 weight parts (tire glue powder 30 weight parts, Ethylene Propylene Terpolymer rubber powder 30 weight parts, POE 10 weight parts, waste polyethylene 10 weight parts, VAMax 10 weight parts, waste polypropylene 10 weight parts), RV2 2 weight parts (take major ingredient as 100 weight parts), carbon black 15 weight parts, acidification oil 10 weight parts, WS sulfuration resin 5 weight parts, S 1.5 weight parts, captax 0.5 weight part, altax 0.5 weight part, antioxidant D 0.5 weight part, leveler 0.5 weight part, zinc oxide 2 weight parts.
(1) high-speed stirring is mixed: by above formula rate, pour into successively in homogenizer and start to stir, make RV2 evenly be wrapped in shoddy particle surface, through immersional wetting, infiltrate in rubber powder granule; Its whipping temp is set as 100 ℃, and frequency setting is 50Hz, when temperature rises to 95 ℃ of left and right, reduces speed now, and stirs 5min and discharges material again.
(2) discharge the material having stirred from homogenizer, pour into while hot in parallel equidirectional two-screw forcing machine, by mechanical shearing effect, continue reaction, make rubber and plastics generation dynamic vulcanization, by the cooperation of various auxiliary agents and the effect of mechanical shearing, rubber grain is dispersed in the matrix of plastics, forms the thermoplastic elastomer with certain performance.Then from twin screw material out, directly enter upper and lower two roller mill slice.(wherein: the engine speed of parallel equidirectional two-screw forcing machine is made as 250 turn/57A, reinforced rotating speed is made as 30 turn/2A, and the design temperature in Si Ge district is respectively 150 ℃-170 ℃-170 ℃-40 ℃; Actual temperature is respectively 145 ℃-171 ℃-172 ℃-40 ℃).
(3) use mill slice, roll spacing is adjusted to minimum, and slice roll spacing is 2mm.
(4) its physicals is surveyed in compression molding
According to national standards such as GB/T528-2009, measure the physicalies such as its tensile strength, tensile yield, tension set.
The thin slice pressing is pressed into to be about 2mm thick, is cut into the rectangular sheet (each two) that is about 300mm × 200mm with scissors, put into vulcanizing press moulding 10 minutes, condition of molding is: 160 ℃, and 20MPa.Taking-up is put into chilling press and is cooled to room temperature, then after 24 hours, surveys its physicals.
(5) survey its physicals
By the physicals of the thermoplastic elastomer of state's mapping, be: Shao A hardness is 84, tensile strength is 8.52MPa, and tensile yield is 200.11%, and tensile set is 60%.5 aging conservation rates of back draft intensity of back mixing are 85.28% continuously, and tensile yield conservation rate is 84.25%.
Embodiment 5:
Proportioning: major ingredient 100 weight parts (tire glue powder 20 weight parts, Ethylene Propylene Terpolymer rubber powder 20 weight parts, nitrile rubber powder 20 weight parts, POE 10 weight parts, waste polyethylene 10 weight parts, VAMax 10 weight parts, waste polypropylene 10 weight parts, chlorinatedpolyethylene 10 weight parts, waste polyvinyl chloride 10 weight parts), RV2 2 weight parts (take major ingredient as 100 weight parts), carbon black 15 weight parts, acidification oil 10 weight parts, WS sulfuration resin 5 weight parts, S 1.5 weight parts, captax 0.5 weight part, altax 0.5 weight part, antioxidant D 0.5 weight part, leveler 0.5 weight part, zinc oxide 1.2 weight parts.
(1) high-speed stirring is mixed: by above formula rate, pour into successively in homogenizer and start to stir, make RV2 evenly be wrapped in shoddy particle surface, through immersional wetting, infiltrate in rubber powder granule; Its whipping temp is set as 110 ℃, and frequency setting is 50Hz, when temperature rises to 115 ℃ of left and right, reduces speed now, and stirs 5min and discharges material again.
(2) discharge the material having stirred from homogenizer, pour into while hot in conical double screw extruder, by mechanical shearing effect, continue reaction, make rubber and plastics generation dynamic vulcanization, by the cooperation of various auxiliary agents and the effect of mechanical shearing, rubber grain is dispersed in the matrix of plastics, forms the thermoplastic elastomer with certain performance.Then from twin screw material out, directly enter upper and lower two roller mill slice.(wherein: the engine speed of conical double screw extruder is made as 170 revs/min, electric current 57A, reinforced rotating speed is made as 25 revs/min, electric current 2A, the design temperature in Si Ge district is respectively 170 ℃-190 ℃-190 ℃-30 ℃; Actual temperature is respectively 169 ℃-191 ℃-189 ℃-30 ℃).
(3) use mill slice, roll spacing is adjusted to minimum, and slice roll spacing is 2mm.
(4) its physicals is surveyed in compression molding
According to national standards such as GB/T528-2009, measure the physicalies such as its tensile strength, tensile yield, tension set.
The thin slice pressing is pressed into to be about 2mm thick, is cut into the rectangular sheet (each two) that is about 300mm × 200mm with scissors, put into vulcanizing press moulding 10 minutes, condition of molding is: 160 ℃, and 20MPa.Taking-up is put into chilling press and is cooled to room temperature, then after 24 hours, surveys its physicals.
(5) survey its physicals
By the physicals of the thermoplastic elastomer of state's mapping, be: Shao A hardness is 85, tensile strength is 6.89MPa, and tensile yield is 180.36%, and tensile set is 68%.5 aging conservation rates of back draft intensity of back mixing are 88.62% continuously, and tensile yield conservation rate is 85.95%.
Embodiment 6 ~ 12
Investigate the impact of waste Crumb rubber additional proportion for the thermoplastic elastomer making, the difference of embodiment 6 ~ 12 is only to add the amount difference of rubber powder, in major ingredient, the ratio of plastic waste and expanding material CPE is 1:1, according to the amount of table 1, add shoddy, the addition of various auxiliary material auxiliary agents is identical with embodiment 1, the each district of the conical double-screw temperature of selecting is respectively 160 ℃-180 ℃-180 ℃-40 ℃, and feed rate is 30r/min, engine speed 120r/min.In mill, be pressed into sheet, after cutting, 160 ℃ of compacted under 5min slices, and survey its physicals by method described in 3.2.2.Acquired results is in Table 1.
Table 1 embodiment 6 ~ 12
As can be seen from Table 1, along with the minimizing of rubber powder content, Shore A hardness, tensile set constantly increase, in dynamic vulcanization, forming rubber phase all the time by vulcanized rubber particles is that disperse phase is dispersed in the external phase of plastics phase composite, rubber powder content is higher, and plastics phase content is just fewer, while being subject to like this stretching action of external force, have more powerful plastics just more fragile mutually, thereby affect tensile strength, the tensile yield of thermoplastic elastomer.Contrary plastic content is too much, can improve the hardness of TPV, and tensile strength also improves thereupon, but be to provide elastic caoutchouc, will diminish mutually, and crosslinked rubber particles becomes sparse, makes the reduction of tensile yield.Rubber powder content is when 40%-60%, and prepared thermoplastic elastomer physicals is better, and now, the weight ratio of rubber powder and plastic waste is about 2:1.
Claims (9)
1. utilize waste rubber and the used plastics method for thermoplastic elastomer, it is characterized in that comprising the following steps:
Step 1: according to the requirement of following material composition, take material and add in plasticizing machine and mix plasticizing, and to be stirred to temperature be 80 ~ 120 ℃;
Step 2: while hot gained material is imported in conical screw machine, rubber is reacted with plastics generation dynamic vulcanization, controlling high-temperature temperature is 140 ~ 180 ℃, the temperature of controlling cooling unit is 20 ~ 40 ℃, main control system rotating speed is 50 ~ 200 revs/min of per minutes, and controlling reinforced rotating speed is 10 ~ 50 revs/min of per minutes; After discharging is cooling, both obtained thermoplastic elastomer;
Described material composition comprises: rubber powder 30 ~ 70 weight parts, plastic waste 30 ~ 70 weight parts, expanding material 20 ~ 50 weight parts, fluidizer 1 ~ 10 weight part, industry oil 20 ~ 40 weight parts, zinc oxide 0.1 ~ 2 weight part, leveler 0.2 ~ 5 weight part, filler 10 ~ 40 weight parts, other auxiliary agent 1 ~ 10 weight parts.
2. a kind of waste rubber and used plastics of utilizing according to claim 1, for the method for thermoplastic elastomer, is characterized in that described waste rubber is waste tyre rubber powder or useless acrylonitrile-butadiene rubber powder, and described plastic waste is useless high density polyethylene(HDPE) or waste polyvinyl chloride.
3. a kind of waste rubber and used plastics of utilizing according to claim 1, for the method for thermoplastic elastomer, is characterized in that described rubber powder and the weight ratio of plastic waste powder are 2:1.
4. a kind of waste rubber and used plastics of utilizing according to claim 1, for the method for thermoplastic elastomer, is characterized in that described fluidizer is selected from one or more in PTC-R, RV1 or RV2.
5. a kind of waste rubber and used plastics of utilizing according to claim 1, for the method for thermoplastic elastomer, is characterized in that described expanding material is selected from one or more in polyolefin elastomer, ethylene-vinyl acetate copolymer or chlorinatedpolyethylene.
6. a kind of waste rubber and used plastics of utilizing according to claim 1, for the method for thermoplastic elastomer, is characterized in that described industry oil is selected from one or more in acidification oil, aromatic hydrocarbon oil, naphthenic oil or paraffin oil.
7. a kind of waste rubber and used plastics of utilizing according to claim 1, for the method for thermoplastic elastomer, is characterized in that described filler is selected from one or more in carbon black, white carbon black or calcium carbonate.
8. a kind of waste rubber, used plastics method for thermoplastic elastomer of using according to claim 1, is characterized in that other described auxiliary agents comprise anti-aging agent and/or promotor.
9. a kind of waste rubber, used plastics method for thermoplastic elastomer of using according to claim 1, the generation system that it is characterized in that wherein said vulcanization reaction is selected from sulfur cross-linking system, peroxide vulcanizing system, resin cure system or low Sulfur and superoxide shares vulcanization system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310700335.XA CN103756075A (en) | 2013-12-19 | 2013-12-19 | Method for preparation of thermoplastic elastomer from waste rubber and waste plastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310700335.XA CN103756075A (en) | 2013-12-19 | 2013-12-19 | Method for preparation of thermoplastic elastomer from waste rubber and waste plastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103756075A true CN103756075A (en) | 2014-04-30 |
Family
ID=50523412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310700335.XA Pending CN103756075A (en) | 2013-12-19 | 2013-12-19 | Method for preparation of thermoplastic elastomer from waste rubber and waste plastics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103756075A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327342A (en) * | 2014-11-26 | 2015-02-04 | 重庆可益荧新材料有限公司 | Thermoplastic elastomer and preparation method thereof |
| CN105037964A (en) * | 2015-08-28 | 2015-11-11 | 广州敬信高聚物科技有限公司 | Thermoplastic elastomer and preparation method thereof |
| CN105153504A (en) * | 2015-07-24 | 2015-12-16 | 石家庄瑞威橡胶科技有限公司 | Rubber softening oil |
| CN105400051A (en) * | 2015-12-21 | 2016-03-16 | 常熟市久昇电器有限公司 | Environment-friendly migration-resistant refrigerator door sealing strip |
| KR20160126259A (en) * | 2015-04-23 | 2016-11-02 | 금오공과대학교 산학협력단 | Thermoplastic vulcanized composite and the preparing method thereof |
| CN106633262A (en) * | 2016-12-12 | 2017-05-10 | 俞扬池 | Regenerated rubber material |
| CN106750698A (en) * | 2016-12-09 | 2017-05-31 | 俞杨许 | A kind of environment-friendlyregenerated regenerated rubber material |
| CN107602985A (en) * | 2017-09-29 | 2018-01-19 | 南京晟强橡塑有限公司 | A kind of rubber plastic pipe |
| CN108276631A (en) * | 2018-01-25 | 2018-07-13 | 赵国营 | Modified rubber powder and preparation method thereof |
| CN108485017A (en) * | 2018-04-04 | 2018-09-04 | 江蔓青 | A kind of high-performance is given up rubber and plastic base pitch energy hole infiltrating irrigation and preparation method thereof |
| CN109161083A (en) * | 2018-09-12 | 2019-01-08 | 安徽微威胶件集团有限公司 | A kind of rubber doping polyethylene shock absorption material and preparation method thereof |
| CN110041643A (en) * | 2019-05-05 | 2019-07-23 | 天津永高塑业发展有限公司 | A kind of seal for pipe joints soft polyvinyl chloride composition and preparation method thereof |
| CN110092974A (en) * | 2018-01-27 | 2019-08-06 | 东莞市诚欣精密模具有限公司 | A kind of Portable shoe sole Recipe with oil resistant corrosion resistance |
| CN112321922A (en) * | 2020-11-09 | 2021-02-05 | 仇帅康 | Regenerated high-molecular elastic material and preparation method thereof |
| CN113072762A (en) * | 2021-04-23 | 2021-07-06 | 明浩塑胶科技(昆山)有限公司 | Environment-friendly flange barrel based on petrochemical waste recycling and preparation method thereof |
| CN114015131A (en) * | 2021-11-24 | 2022-02-08 | 亚罗斯建材（江苏）有限公司 | Preparation process of novel rubber-plastic material with low density and high elasticity |
| CN114989510A (en) * | 2022-05-26 | 2022-09-02 | 泉州南京大学环保产业研究院 | Reclaimed rubber filler and application thereof in denitrification filter |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102222A (en) * | 1985-04-01 | 1986-08-06 | 中国科学院长春应用化学研究所 | Ethylene propylene rubber polypropylene thermoplastic elastomer and preparation method |
| CN1704446A (en) * | 2004-05-25 | 2005-12-07 | 昆明凤凰橡胶有限公司 | Process for preparing thermoplastic elastomer by using waste vulcanized rubber |
| CN101348584A (en) * | 2008-09-04 | 2009-01-21 | 南昌航空大学 | Method for preparing damping material from waste polystyrene plastic foam and waste rubber powder |
| CN103183856A (en) * | 2011-12-28 | 2013-07-03 | 荆门市格林美新材料有限公司 | Tire rubber powder modified recycled plastic and preparation method thereof |
-
2013
- 2013-12-19 CN CN201310700335.XA patent/CN103756075A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102222A (en) * | 1985-04-01 | 1986-08-06 | 中国科学院长春应用化学研究所 | Ethylene propylene rubber polypropylene thermoplastic elastomer and preparation method |
| CN1704446A (en) * | 2004-05-25 | 2005-12-07 | 昆明凤凰橡胶有限公司 | Process for preparing thermoplastic elastomer by using waste vulcanized rubber |
| CN101348584A (en) * | 2008-09-04 | 2009-01-21 | 南昌航空大学 | Method for preparing damping material from waste polystyrene plastic foam and waste rubber powder |
| CN103183856A (en) * | 2011-12-28 | 2013-07-03 | 荆门市格林美新材料有限公司 | Tire rubber powder modified recycled plastic and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈占勋编著: "《废旧高分子材料资源及综合利用》", 31 January 1998, 化学工业出版社出版 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327342A (en) * | 2014-11-26 | 2015-02-04 | 重庆可益荧新材料有限公司 | Thermoplastic elastomer and preparation method thereof |
| CN104327342B (en) * | 2014-11-26 | 2016-05-18 | 中北大学 | A kind of thermoplastic elastomer (TPE) and preparation method thereof |
| KR20160126259A (en) * | 2015-04-23 | 2016-11-02 | 금오공과대학교 산학협력단 | Thermoplastic vulcanized composite and the preparing method thereof |
| KR101675330B1 (en) * | 2015-04-23 | 2016-11-11 | 금오공과대학교 산학협력단 | Thermoplastic vulcanized composite and the preparing method thereof |
| CN105153504A (en) * | 2015-07-24 | 2015-12-16 | 石家庄瑞威橡胶科技有限公司 | Rubber softening oil |
| CN105037964A (en) * | 2015-08-28 | 2015-11-11 | 广州敬信高聚物科技有限公司 | Thermoplastic elastomer and preparation method thereof |
| CN105400051A (en) * | 2015-12-21 | 2016-03-16 | 常熟市久昇电器有限公司 | Environment-friendly migration-resistant refrigerator door sealing strip |
| CN106750698A (en) * | 2016-12-09 | 2017-05-31 | 俞杨许 | A kind of environment-friendlyregenerated regenerated rubber material |
| CN106633262A (en) * | 2016-12-12 | 2017-05-10 | 俞扬池 | Regenerated rubber material |
| CN107602985A (en) * | 2017-09-29 | 2018-01-19 | 南京晟强橡塑有限公司 | A kind of rubber plastic pipe |
| CN108276631A (en) * | 2018-01-25 | 2018-07-13 | 赵国营 | Modified rubber powder and preparation method thereof |
| CN110092974A (en) * | 2018-01-27 | 2019-08-06 | 东莞市诚欣精密模具有限公司 | A kind of Portable shoe sole Recipe with oil resistant corrosion resistance |
| CN108485017A (en) * | 2018-04-04 | 2018-09-04 | 江蔓青 | A kind of high-performance is given up rubber and plastic base pitch energy hole infiltrating irrigation and preparation method thereof |
| CN109161083A (en) * | 2018-09-12 | 2019-01-08 | 安徽微威胶件集团有限公司 | A kind of rubber doping polyethylene shock absorption material and preparation method thereof |
| CN110041643A (en) * | 2019-05-05 | 2019-07-23 | 天津永高塑业发展有限公司 | A kind of seal for pipe joints soft polyvinyl chloride composition and preparation method thereof |
| CN110041643B (en) * | 2019-05-05 | 2021-11-30 | 天津永高塑业发展有限公司 | Soft polyvinyl chloride composition for pipeline sealing and preparation method thereof |
| CN112321922A (en) * | 2020-11-09 | 2021-02-05 | 仇帅康 | Regenerated high-molecular elastic material and preparation method thereof |
| CN113072762A (en) * | 2021-04-23 | 2021-07-06 | 明浩塑胶科技(昆山)有限公司 | Environment-friendly flange barrel based on petrochemical waste recycling and preparation method thereof |
| CN114015131A (en) * | 2021-11-24 | 2022-02-08 | 亚罗斯建材（江苏）有限公司 | Preparation process of novel rubber-plastic material with low density and high elasticity |
| CN114989510A (en) * | 2022-05-26 | 2022-09-02 | 泉州南京大学环保产业研究院 | Reclaimed rubber filler and application thereof in denitrification filter |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103756075A (en) | Method for preparation of thermoplastic elastomer from waste rubber and waste plastics | |
| CN101864102B (en) | Compound type thermoplastic elastomer and preparation and application method thereof | |
| CN101717586B (en) | Concentrated composition of waste rubber composite modified pitch and preparation and use method | |
| CN101747637B (en) | Low-temperature environment-friendly rubber asphalt and preparation method thereof | |
| CN101200597A (en) | Method for preparing solid refuse composite modified asphalt | |
| CN104693819A (en) | Composite-SBS (Styrene Butadiene Styrene block polymer)-particle asphalt modifier with storage stability and aging resistance and preparation method thereof | |
| CN102863678B (en) | Special modified recycled polyethylene material for cables and preparation method of special modified recycled polyethylene material | |
| CN105017612A (en) | Modified waste polyethylene special material for pipeline and preparation method of modified waste polyethylene special material | |
| CN105175976B (en) | Composite toughening modifier and its preparation method and application | |
| CN101550276B (en) | Crumb rubber modified asphalt and prepration method thereof | |
| CN101948598B (en) | Method for preparing biodegradable membrane | |
| CN104710134B (en) | A kind of stable storing, ageing-resistant particle modified bituminous concretes of composite S BS and preparation method thereof | |
| CN103183898A (en) | Thermoplastic elastomer material for artificial lawn and preparation method thereof | |
| CN102408735A (en) | Composite asphalt modifier, composite modified asphalt and preparation method thereof | |
| CN101899178A (en) | Special material for drainage pipeline by modifying waste plastic and preparation method thereof | |
| CN104693595A (en) | Recycled material used for preparing vehicle bumper and preparation method of recycled material | |
| CN106519323A (en) | Method for preparing rubber powder/natural rubber liquid-phase mixed compound rubber | |
| CN101805524A (en) | Preparation method of waste rubber powder-modified asphalt with high-temperature storage property | |
| CN102501335B (en) | Novel process for reducing and regenerating waster rubber continuously | |
| CN102863677B (en) | Special modified recycled polyethylene material for pipes and pipe fittings and preparation method of special modified recycled polyethylene material | |
| CN109320978A (en) | A kind of asphalt mixed material modifier and preparation method thereof | |
| CN102229720B (en) | High impact polypropylene composition and preparation method thereof | |
| CN110387096A (en) | Regenerated PVC pipe preparation method can be recycled in one kind | |
| KR100969040B1 (en) | Recylcled thermoplastic elastomer using rubber waste and its preparation method | |
| CN105153504B (en) | A kind of rubber softening oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140430 |
|
| RJ01 | Rejection of invention patent application after publication |