CN111116980B - Controllable cracking process of crosslinked EVA material - Google Patents
Controllable cracking process of crosslinked EVA material Download PDFInfo
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- CN111116980B CN111116980B CN201911264083.4A CN201911264083A CN111116980B CN 111116980 B CN111116980 B CN 111116980B CN 201911264083 A CN201911264083 A CN 201911264083A CN 111116980 B CN111116980 B CN 111116980B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/17—Amines; Quaternary ammonium compounds
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to the regeneration and recovery of high polymer materials, in particular to a controllable cracking process of a crosslinked EVA material. A controllable cracking process of a crosslinked EVA material comprises the following steps: 1) Crushing waste EVA materials, and sieving EVA powder with a sieve of 20-60 meshes; 2) Adding a polymerization inhibitor, a compatibilizer, an antioxidant and a filler into the EVA powder obtained in the step 1), and mixing; 3) Adding the material obtained in the step 2) into a reaction device, preheating, cracking and cooling, and controlling the temperature of a cracking section to be 250-450 ℃ to obtain the catalyst. By adopting the special process and components, the invention can obtain the cracking product with any melt index by adjusting the process, so that the waste EVA material is effectively recycled, the problem of environmental pollution caused by a large amount of waste crosslinked EVA material is relieved, simultaneously, huge resource waste is avoided, and the invention conforms to the current concept of green environmental protection and sustainable development.
Description
Technical Field
The invention relates to the technical field of regeneration and recovery of high polymer materials, in particular to a controllable cracking process of a crosslinked EVA material.
Background
The crosslinked foamed material of ethylene-vinyl acetate copolymer (EVA) has the advantages of high flexibility, impact resistance, weather resistance, solarization resistance and the like, and is widely applied to the fields of sound insulation, vibration reduction, heat preservation, toys, sports shoe materials and the like. But a large amount of leftover materials and waste materials are generated in the production and use processes, wherein the existence of cross-linking bonds causes that the waste materials are difficult to directly utilize. Many countries can only adopt an energy recovery method, and burn to generate electricity, but the pollution caused by the method can not be accepted, and the method causes great resource waste.
At present, a part of EVA cross-linked materials can be recycled through mechanochemical decrosslinking of EVA cross-linked wastes, but the obtained recycled EVA cross-linked materials often have the problems of too high or too low melt index, ideal products are difficult to obtain, the recycling rate is not high, and the industrialization requirement cannot be met.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a controlled cracking process for crosslinking EVA material, comprising the following steps:
1) Crushing waste EVA materials, and sieving EVA powder with a sieve of 20-60 meshes;
2) Adding a polymerization inhibitor, a compatibilizer, an antioxidant and a filler into the EVA powder obtained in the step 1), and mixing;
3) Adding the material obtained in the step 2) into a reaction device, preheating, cracking and cooling, and controlling the temperature of a cracking section to be 250-450 ℃ to obtain the catalyst.
As a preferred technical scheme of the invention, the step 2) comprises the following components in parts by weight: 60 to 110 portions of EVA powder, 0.05 to 0.2 portion of polymerization inhibitor, 7 to 18 portions of compatibilizer, 0.08 to 0.35 portion of antioxidant and 12 to 25 portions of filler.
As a preferable technical scheme, the polymerization inhibitor is selected from one or more of diphenylamine, hydroquinone, p-benzoquinone, ferric trichloride, m-dinitrobenzene and 2, 5-di-tert-butylhydroquinone.
As a preferable technical scheme of the invention, the polymerization inhibitor is 2, 5-di-tert-butylhydroquinone and/or p-benzoquinone.
As a preferable technical scheme of the invention, the weight ratio of the 2, 5-di-tert-butyl hydroquinone to the p-benzoquinone is (2-4): 1.
as a preferable technical scheme of the invention, the compatibilizer is one or more selected from polyolefin elastomer, chlorinated polyethylene, acrylonitrile-styrene copolymer, polypropylene grafted maleic anhydride, ethylene propylene diene monomer grafted maleic anhydride and polyolefin elastomer grafted maleic anhydride.
As a preferred technical scheme of the invention, the antioxidant is selected from one or more of phenolic antioxidant, amine antioxidant, sulfur compound antioxidant and organic metal salt antioxidant.
As a preferable technical scheme of the invention, the filler is selected from one or more of sodium carbonate, calcium carbonate, magnesium carbonate, titanium dioxide, bentonite, diatomite, double hydroxide and montmorillonite.
As a preferable technical scheme of the invention, the screw rotating speed of the cracking section is 300-500 rpm, and the time is 2.7-3 min.
In a second aspect, the invention provides a pyrolyzed EVA material that may be prepared by the above method.
Has the beneficial effects that: according to the controllable cracking process, by adopting special process conditions and components, the inherent problems that the thermal cracking process is difficult to control and the product utilization rate is low are solved, so that the waste EVA materials are effectively recycled, the problem of environmental pollution caused by a large amount of waste crosslinked EVA materials is relieved, huge resource waste is avoided, and the controllable cracking process conforms to the current green, environment-friendly and sustainable development concepts; on the other hand, under a proper process condition, through the mutual synergistic action of a plurality of components in the system, dynamic balance exists among reactions such as degradation, free radical polymerization, crosslinking and the like in the system, so that the controllable cracking of the crosslinked EVA material is realized, and the cracked EVA material has high recovery rate. In addition, the invention can obtain cracking products with any melt index by adjusting the process, has wider application prospect and can greatly reduce the cost.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The words "preferred," "more preferred," "most preferred," and the like in this disclosure mean embodiments of the invention that may, in some instances, provide some benefit. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In order to solve the above problems, the first aspect of the present invention provides a controlled cracking process for crosslinking EVA material, comprising the following steps:
1) Crushing waste EVA materials, and sieving EVA powder with a sieve of 20-60 meshes;
2) Adding a polymerization inhibitor, a compatibilizer, an antioxidant and a filler into the EVA powder obtained in the step 1), and mixing;
3) Adding the material obtained in the step 2) into a reaction device, preheating, cracking and cooling, and controlling the temperature of a cracking section to be 250-450 ℃ to obtain the catalyst.
In a preferred embodiment, the step 2) comprises the following components in parts by weight: 60 to 110 portions of EVA powder, 0.05 to 0.2 portion of polymerization inhibitor, 7 to 18 portions of compatibilizer, 0.08 to 0.35 portion of antioxidant and 12 to 25 portions of filler.
Step 1)
The waste EVA materials of the invention include, but are not limited to, flexible packaging films, woven products, polymer packaging containers, packaging bags, foam packaging materials, foamed shoe materials, functional greenhouse films, hot melt adhesives, electric wires and cables, toys, gaskets, medical devices, refrigerator ducts, gas pipes, containers and digital product shell components.
The pulverization method of the present invention is not particularly limited as long as the desired EVA powder can be obtained without impairing the object of the present invention, and various pulverization methods conventionally used by those skilled in the art can be used.
The EVA powder sieved by the sieve with the sieve size of 20-60 meshes is the EVA material crushed by the sieve with the sieve size of 20-60 meshes, and the part which can leak from the sieve meshes is the needed EVA powder.
Step 2)
In a preferred embodiment, the mixing speed of the present invention is 450 to 650rpm; the mixing time is 5-15min.
Polymerization inhibitor
The polymerization inhibitor of the present invention is an industrial aid, and is generally used for preventing polymerization from proceeding. The inhibitor molecule reacts with the chain radical to form a non-radical species or a low-activity radical that cannot initiate, thereby terminating the polymerization.
In a preferred embodiment, the polymerization inhibitor of the present invention is selected from one or more of diphenylamine, hydroquinone, p-benzoquinone, ferric trichloride, m-dinitrobenzene, and 2, 5-di-tert-butylhydroquinone.
In a preferred embodiment, the polymerization inhibitor of the present invention is 2, 5-di-tert-butylhydroquinone and/or p-benzoquinone.
The 2, 5-di-tert-butylhydroquinone, also known as 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone or 2, 5-di-tert-butyl-1, 4-dihydroxybenzene is white to light yellow crystalline powder, is easily soluble in ethanol, benzene, acetone and carbon disulfide, is insoluble in water, and has a molecular formula C 14 H 22 O 2 The molecular weight is 222.32, and the CAS number is 88-58-4.
Said benzene isQuinone, also known as benzoquinone, p-phenylenediamine, p-quinone, 1, 4-benzoquinone or 1, 4-benzenedione, is golden yellow prismatic crystal, has melting point of 115-117 deg.C and density of 1.318g/cm 3 (20 ℃) and the molecular formula is C 6 H 4 O 2 The molecular weight is 108.09, the CAS number is 106-51-4, can be sublimated and distilled along with water gas, can be dissolved in hot water, ethanol and ether, and has carbonyl, carbon-carbon double bonds and conjugated double bonds in the molecule, so that carbonyl addition, carbon-carbon double bond addition and 1, 4-addition of the conjugated double bonds can occur.
In a preferred embodiment, the weight ratio of 2, 5-di-tert-butylhydroquinone to p-benzoquinone in the present invention is (2 to 4): 1.
the inventor finds that during the thermal cracking process, thermal degradation and radical polymerization reaction exist at the same time, and the activity of the radical has important influence on the radical polymerization reaction, so that the controllability of the thermal cracking reaction is influenced. The polymerization inhibitor molecule forms non-radical matter or low activity radical incapable of initiating through reaction with chain radical, so as to inhibit the polymerization effectively.
The inventor also finds that the 2, 5-di-tert-butyl hydroquinone has a certain slow polymerization effect by terminating the polymerization reaction through the chain transfer reaction with free radicals; and p-benzoquinone and chain free radicals generate polymerization inhibition through addition reaction, so that the free radical polymerization rate is inhibited. Through the mutual synergistic effect of the polymerization inhibitor 2, 5-di-tert-butylhydroquinone and p-benzoquinone, the free radical polymerization reaction can be effectively regulated and controlled, so that the thermal degradation and the free radical polymerization can be dynamically balanced, and the controllable cracking of the crosslinked EVA material is realized.
Bulking agent
The compatibilizer provided by the invention refers to an auxiliary agent which can play a role in softening or enhancing the processing performance.
In a preferred embodiment, the compatibilizer of the present invention is one or more selected from polyolefin elastomer, chlorinated polyethylene, acrylonitrile-styrene copolymer, polypropylene grafted maleic anhydride, ethylene propylene diene monomer grafted maleic anhydride, and polyolefin elastomer grafted maleic anhydride.
In a more preferred embodiment, the compatibilizer of the present invention is polypropylene grafted maleic anhydride.
The polypropylene grafted maleic anhydride is prepared by extruding and grafting maleic anhydride through reaction of polypropylene. A strong polar side group is introduced into a nonpolar molecular main chain, and the maleic anhydride grafted polypropylene can be used as a bridge for improving the adhesion and compatibility of polar materials and nonpolar materials.
In a preferred embodiment, the polypropylene grafted maleic anhydride of the present invention can be obtained commercially, for example, the commercially available polypropylene grafted maleic anhydride includes but is not limited to the product of model A-669K available from Shenzhen golden technischen Limited.
Antioxidant
The antioxidants of the present invention, also known as antioxidants, are chemical substances that, when present in only small amounts in a polymer system, retard or inhibit the progress of the polymer oxidation process, thereby preventing polymer aging and extending its useful life.
In a preferred embodiment, the antioxidant of the present invention is selected from one or more of phenolic antioxidants, amine antioxidants, sulfur-containing compounds, and organic metal salt antioxidants.
Examples of phenolic antioxidants include: hydroquinone, thiobisphenol, triphenol, 2, 6-tertiary butyl-4-methylphenol and 2, 6-di-tert-butyl-p-cresol.
Examples of amine antioxidants include: butyl diphenylamine, 4' -dioctyl diphenylamine, diphenylamine and p-phenylenediamine.
As examples of the sulfur compound antioxidant, there may be mentioned: cool thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate.
As examples of the organic metal salt antioxidant, there can be cited: zinc dialkyldithiophosphate, copper dialkyldithiophosphate, molybdenum diisooctyldithiophosphate, molybdenum carbamate.
In a more preferred embodiment, the antioxidant of the present invention is 4,4' -dioctyldiphenylamine.
The 4,4 '-dioctyl diphenylamine is also called 4,4' -diisooctyl diphenylamine, 4-octyl-N- (4-octylphenyl) aniline, petroleum antioxidant V-81, octyl diphenylamine, antioxidant ODA, antioxidant T5570 or antioxidant ODA, and the molecular formula is C 28 H 43 N, molecular weight 393.65, CAS number 101-67-7.
Packing
The filler, also called filler, additive or filler, refers to a solid substance capable of improving material performance, or increasing capacity and weight and reducing material cost.
In a preferred embodiment, the filler of the present invention is selected from one or more of sodium carbonate, calcium carbonate, magnesium carbonate, titanium dioxide, bentonite, diatomaceous earth, double hydroxide, and montmorillonite.
In a preferred embodiment, the filler of the present invention is titanium dioxide.
The titanium dioxide is white solid or powdery amphoteric oxide, is a white inorganic pigment, has no toxicity, optimal opacity, optimal whiteness and brightness, and is considered to be the best white pigment in the world nowadays. Meanwhile, titanium dioxide has better ultraviolet screening effect, is often used as a sun-screening agent to be doped into textile fibers, and superfine titanium dioxide powder is also added into sun-screening cream to prepare a sun-screening cosmetic.
In a preferred embodiment, the titanium dioxide of the present invention is commercially available, for example, commercially available titanium dioxide includes, but is not limited to, the product available from THR-218, inc.
Step 3)
In a preferred embodiment, the temperature of the preheating section is 170-230 ℃, the screw speed is 40-60 rpm, and the time is 0.8-1 min.
In a preferred embodiment, the screw speed of the cracking section of the present invention is 300 to 500rpm for 2.7 to 3min.
In a preferred embodiment, the temperature of the cooling section is 110-170 ℃, the screw speed is 40-70 rpm, and the time is 0.7-1 min.
Softening and compressing the material obtained in the step 2) through a preheating section; then cracking is carried out; then the cracked materials are transported to a cooling section for oxygen insulation and cooling, so that the EVA materials are prevented from being oxidized.
The inventor in the application unexpectedly finds that when 2, 5-di-tert-butyl hydroquinone and p-benzoquinone are used as polymerization inhibitors, the weight ratio of the two is controlled to be (2-4): 1, and simultaneously, when the temperature of the cracking section is controlled to be 250-450 ℃, the melt index of the cracking EVA material can be improved, and the recovery rate is higher. Probably because under the condition of certain temperature, the cross-linked EVA material is degraded to a certain extent and simultaneously generates a certain amount of free radicals, and under the condition of specific proportion, 2, 5-di-tert-butyl hydroquinone and p-benzoquinone are mutually synergistic, the cross-linked EVA material can generate proper inhibition effect on the free radicals in the system, so that dynamic balance exists among reactions such as degradation, free radical polymerization, cross-linking and the like in the system, thereby realizing the controllable cracking of the cross-linked EVA material, improving the melt index of the cracked EVA material and having higher recovery rate.
In a second aspect, the present invention provides a cleaved EVA material, which is prepared by the above method.
The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a controlled cracking process for a crosslinked EVA material, comprising the steps of:
1) Crushing the waste EVA packaging bags, and sieving EVA powder with a 40-mesh sieve;
2) Adding a polymerization inhibitor, a compatibilizer, an antioxidant and a filler into the EVA powder obtained in the step 1), and mixing;
3) Adding the material obtained in the step 2) into a reaction device, preheating, cracking and cooling, and controlling the temperature of a cracking section to be 350 ℃ to obtain the catalyst.
In the step 2), the composition comprises the following components in parts by weight: 90 parts of EVA powder, 0.12 part of polymerization inhibitor, 13 parts of compatibilizer, 0.2 part of antioxidant and 20 parts of filler.
The polymerization inhibitor is 2, 5-di-tert-butyl hydroquinone and p-benzoquinone.
The weight ratio of the 2, 5-di-tert-butylhydroquinone to the p-benzoquinone is 3:1.
the compatibilizer is polypropylene grafted maleic anhydride.
The purchasing merchant of the polypropylene grafted maleic anhydride is Shenzhen JinDasychun Co.
The antioxidant is 4,4' -dioctyl diphenylamine.
The filler is titanium dioxide.
The titanium dioxide purchasing merchant is Hezhou rich chemical industry Co., ltd, and the model is THR-218.
The rotation speed of the mixing in the step 2) is 550rpm; the mixing time was 10min.
And 3) the temperature of the preheating section in the step 3) is 200 ℃, the rotating speed of a screw is 50rpm, and the time is 1min.
The screw rotating speed of the cracking section in the step 3) is 400rpm, and the time is 3min.
And 3) the temperature of the cooling section in the step 3) is 140 ℃, the rotating speed of a screw is 50rpm, and the time is 1min.
Example 1 also provides a cleaved EVA material.
Example 2
Embodiment 2 provides a controlled cracking process for crosslinked EVA materials, comprising the steps of:
1) Crushing the waste EVA packaging bags, and sieving EVA powder with a 40-mesh sieve;
2) Adding a polymerization inhibitor, a compatibilizer, an antioxidant and a filler into the EVA powder obtained in the step 1), and mixing;
3) Adding the material obtained in the step 2) into a reaction device, preheating, cracking and cooling, and controlling the temperature of a cracking section to be 250 ℃ to obtain the catalyst.
In the step 2), the composition comprises the following components in parts by weight: 60 parts of EVA powder, 0.05 part of polymerization inhibitor, 7 parts of compatibilizer, 0.08 part of antioxidant and 12 parts of filler.
The polymerization inhibitor is 2, 5-di-tert-butyl hydroquinone and p-benzoquinone.
The weight ratio of the 2, 5-di-tert-butyl hydroquinone to the p-benzoquinone is 3:1.
the compatibilizer is polypropylene grafted maleic anhydride.
The purchasing merchant of the polypropylene grafted maleic anhydride is Shenzhen JinDasychun Co.
The antioxidant is 4,4' -dioctyl diphenylamine.
The filler is titanium dioxide.
The titanium dioxide purchasing merchant is Hezhou Fengsho chemical company, the model of which is THR-218.
The mixing mode of the step 2) is mechanical stirring, and the rotating speed is 450rpm; the mixing time was 5min.
And 3) the temperature of the preheating section is 170 ℃, the rotating speed of a screw is 40rpm, and the time is 0.8min.
The screw rotating speed of the cracking section in the step 3) is 300rpm, and the time is 2.7min.
And 3) the temperature of the cooling section in the step 3) is 110 ℃, the rotating speed of the screw is 40rpm, and the time is 0.7min.
Example 2 also provides a cleaved EVA material.
Example 3
Embodiment 3 provides a controlled cracking process for crosslinked EVA materials, comprising the steps of:
1) Crushing the waste EVA packaging bags, and sieving EVA powder with a 40-mesh sieve;
2) Adding a polymerization inhibitor, a compatibilizer, an antioxidant and a filler into the EVA powder obtained in the step 1), and mixing;
3) Adding the material obtained in the step 2) into a reaction device, preheating, cracking and cooling, and controlling the temperature of a cracking section to be 450 ℃ to obtain the catalyst.
In the step 2), the composition comprises the following components in parts by weight: 110 parts of EVA powder, 0.2 part of polymerization inhibitor, 18 parts of compatibilizer, 0.35 part of antioxidant and 25 parts of filler.
The polymerization inhibitor is 2, 5-di-tert-butyl hydroquinone and p-benzoquinone.
The weight ratio of the 2, 5-di-tert-butylhydroquinone to the p-benzoquinone is 3:1.
the compatibilizer is polypropylene grafted maleic anhydride.
The purchasing merchant of the polypropylene grafted maleic anhydride is Shenzhen JinDasychun Co.
The antioxidant is 4,4' -dioctyl diphenylamine.
The filler is titanium dioxide.
The titanium dioxide purchasing merchant is Hezhou rich chemical industry Co., ltd, and the model is THR-218.
The mixing mode of the step 2) is mechanical stirring, and the rotating speed is 650rpm; the mixing time was 15min.
And 3) the temperature of the preheating section is 230 ℃, the rotating speed of a screw is 60rpm, and the time is 1min.
The screw rotating speed of the cracking section in the step 3) is 500rpm, and the time is 3min.
And 3) the temperature of the cooling section in the step 3) is 170 ℃, the rotating speed of the screw is 70rpm, and the time is 1min.
Example 3 also provides a cleaved EVA material.
Example 4
Embodiment 4 provides a controllable cracking process for a crosslinked EVA material, and further provides a cracked EVA material, which is similar to embodiment 1 in specific implementation manner, except that the amount of 2, 5-di-tert-butylhydroquinone is replaced with 0.
Example 5
Embodiment 5 provides a controllable cracking process for crosslinked EVA material, and a cracked EVA material, which is similar to embodiment 1, except that the amount of p-benzoquinone is replaced with 0.
Example 6
Embodiment 6 provides a controllable cracking process for a crosslinked EVA material, and further provides a cracked EVA material, which is the same as embodiment 1 in specific embodiment except that the weight ratio of 2, 5-di-tert-butylhydroquinone to p-benzoquinone is replaced with 1:2.
example 7
Embodiment 7 provides a controllable cracking process of a crosslinked EVA material, and further provides a cracked EVA material, which is the same as embodiment 1 in a specific embodiment except that the weight ratio of 2, 5-di-tert-butylhydroquinone to p-benzoquinone is replaced with 6:1.
example 8
Example 8 provides a controlled cracking process for crosslinked EVA material, and also provides a cracked EVA material, the specific implementation is the same as example 1, except that the temperature of the cracking zone is replaced by 100 ℃.
Example 9
Example 9 provides a controlled cracking process for crosslinked EVA material, and also provides a cracked EVA material, the specific implementation is the same as example 1, except that the temperature of the cracking zone is replaced with 550 ℃.
Evaluation of Properties
1. Melt index: referring to method A in GB/T3682-2000, the melt index of the sample before and after cracking is tested, the test temperature is 190 ℃, the load is 2.16kg, and the unit g/10min.
2. And (3) recovery rate: the recovery rate is calculated by the formula: the recovery rate (%) of the cracked EVA material is divided by the weight of the actually recovered cracked EVA material and the total weight of the waste EVA material multiplied by 100%.
Table 1 characterization of performance tests
As can be seen from Table 1, the cracked EVA material of the present invention has a high melt index and a high recovery rate, and is more suitable for the requirements of industrial production.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Where the claims recite a range of values, such ranges are intended to include all sub-ranges subsumed therein, and variations within the ranges are intended to be encompassed by the claims as appended hereto where possible.
Claims (3)
1. A controllable cracking process of a crosslinked EVA material is characterized by comprising the following steps:
1) Crushing the waste EVA material, and sieving the EVA powder with a 20-60 mesh sieve;
2) Adding a polymerization inhibitor, a compatibilizer, an antioxidant and a filler into the EVA powder obtained in the step 1), and mixing;
3) Adding the material obtained in the step 2) into a reaction device, preheating, cracking and cooling, and controlling the temperature of a cracking section to be 250-450 ℃ to obtain the catalyst;
in the step 2), the paint comprises the following components in parts by weight: 60-110 parts of EVA powder, 0.05-0.2 part of polymerization inhibitor, 7-18 parts of compatibilizer, 0.08-0.35 part of antioxidant and 12-25 parts of filler; the polymerization inhibitor is 2, 5-di-tert-butyl hydroquinone and p-benzoquinone, and the weight ratio is (2-4): 1; the compatibilizer is polypropylene grafted maleic anhydride; the antioxidant is an amine antioxidant; the filler is selected from one or more of sodium carbonate, calcium carbonate, magnesium carbonate, titanium dioxide, bentonite, diatomite, double hydroxide oxide and montmorillonite.
2. The controllable cracking process of the crosslinked EVA material of claim 1, wherein the screw rotation speed of the cracking section is 300-500 rpm and the time is 2.7-3 min.
3. A cracked EVA material prepared according to the controlled cracking process of any one of claims 1-2.
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| CN112852049A (en) * | 2021-02-01 | 2021-05-28 | 东莞市东塑高分子材料科技有限公司 | Production process and application of EVA foamed sole regenerated particles |
| CN115286752B (en) * | 2022-06-30 | 2023-12-22 | 合复新材料科技(无锡)有限公司 | Preparation method of polypropylene resin-EVA resin alloying graft |
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| CN104558697A (en) * | 2013-12-03 | 2015-04-29 | 张子亮 | Formula and preparation process of easily degradable natural material for shoes |
| CN104603190A (en) * | 2012-09-06 | 2015-05-06 | 耐克创新有限合伙公司 | Eva recycling method |
| CN106928733A (en) * | 2017-04-25 | 2017-07-07 | 武汉理工大学 | One kind solution crosslinked foaming EVA modified pitch and preparation method thereof |
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| CN104603190A (en) * | 2012-09-06 | 2015-05-06 | 耐克创新有限合伙公司 | Eva recycling method |
| CN104558697A (en) * | 2013-12-03 | 2015-04-29 | 张子亮 | Formula and preparation process of easily degradable natural material for shoes |
| CN106928733A (en) * | 2017-04-25 | 2017-07-07 | 武汉理工大学 | One kind solution crosslinked foaming EVA modified pitch and preparation method thereof |
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