CN104774481A - Recycling preparation method and applications of metallocene thermo-plastic elastormer foaming body - Google Patents
Recycling preparation method and applications of metallocene thermo-plastic elastormer foaming body Download PDFInfo
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- CN104774481A CN104774481A CN201410009371.6A CN201410009371A CN104774481A CN 104774481 A CN104774481 A CN 104774481A CN 201410009371 A CN201410009371 A CN 201410009371A CN 104774481 A CN104774481 A CN 104774481A
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Abstract
The invention discloses a recycling preparation method and applications of a metallocene thermo-plastic elastormer foaming body, and belongs to the technical field of foam materials. Raw materials comprise a metallocene thermo-plastic elastormer, an ethylene acetic ether copolymer, a polyolefin elastomer, a reclaimed material, a foaming agent, a bridging agent, an active agent, and zinc oxide. The preparation method comprises following steps: the raw materials above are mixed; an obtained mixture is subjected to plastifying and pelleting, or slicing for further processing; and vulcanization molding is carried out so as to obtain the metallocene thermo-plastic elastormer foaming body. Large-scale industrialized production can be realized; cost is low; recycling can be realized; waste material output is reduced; natural resources are saved; production cost is reduced; the recycling preparation method is friendly to the environment; and the metallocene thermo-plastic elastormer foaming body is prepared via the recycling preparation method, so that raw material resources are extensive, and organic unification of economic benefit with environmental protection benefit is realized effectively.
Description
Technical field:
The present invention relates to foam material technical field, be specifically related to a kind of metallocene hot elastico-plastic body foam cycling and reutilization and preparation method thereof and application.
Background technology:
Along with the enhancing gradually that people's environment protection and resources conservation are realized, to footwear material, dress materials, in the auxiliary material of small stores, sports goods, box material, foam material proposes more and more higher requirement.Traditional foam material is mainly with PVC, PU, EVA etc. are prepared from for base material adds auxiliary agent, EVA starting material are mainly plasticated after granulation high-temperature fusion by its preparation method, banburying unit banburying granulation obtains foaming master batch, then penetrate, produce sheet and be placed on sulfuration on vulcanizing press at foam the outward product that obtains and melting of mould and obtain goods, this relevant foam plasticity-is good, tool workability, after foaming, density of material is little, mechanical property is good, therefore be also most footwear material on market, dress materials, small stores, the auxiliary material of sports goods, the main selection of box material, especially in sports shoes, the end or shoe-pad are widely adopted especially.
Large and difference of compressive displacement are shunk in the foam material existence such as general PVC, PU, EVA, tensile strength is low, the critical defects such as high bounce-back is inadequate, typical processing units is not easy processing, fittings particularly in foam material production process is many, categorised collection difficulty is large, easily causes the wasting of resources and environmental problem, is difficult to realize " low-carbon (LC) ", " Sustainable development " suitability for industrialized production pattern in its preparation process.
Summary of the invention:
The object of this invention is to provide preparation method and the application of a kind of metallocene hot elastico-plastic body foam cycling and reutilization, it can large-scale industrial production, low, the capable of circulation recycling of cost, employing can reduce waste material rubbish output and can save again natural resources, reduce the environmental friendliness mode of production cost, recycling method prepares metallocene hot elastico-plastic body foam, both open up raw-material channel, effectively achieve again the organic unity of economic benefit and environmental benefit.
In order to solve the problem existing for background technology, the present invention is by the following technical solutions: its raw material composition comprises the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, polyolefin elastomer, reclaimed materials, whipping agent, bridging agent, promoting agent and zinc oxide, and the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, polyolefin elastomer, reclaimed materials, whipping agent, bridging agent, promoting agent and zinc oxide percentage composition content are 60: 30: 20: 20-5: 2-10: 1.0: 0.5-2.5: 1-1.5 preferably 50: 40: 30: 15-10: 2-2.5: 0.6-0.8: 1-1.5: 1-2 more preferably 50: 30: 20: 10-5: 1.5: 1.0: 0.5: 1.2.
The hot elastico-plastic body of described metallocene is the resin adopting high-pressure process manufacturing technology to produce, and be the homogeneous polymer of structure, its hardness is mixed by one or more mixtures in 27-45D;
The number-average molecular weight of described ethylene ethyl acetate multipolymer is 400-4000, preferred 800-2000, and in described ethylene ethyl acetate multipolymer, the mass percentage of vinyl acetic monomer (VA) is 10-50%, preferred 18-26%;
The number-average molecular weight of described polyolefin elastomer is 400-4000, preferred 600-2000;
Described reclaimed materials is selected from the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, the polyethylene of polyolefin elastomer or ethylene ethyl acetate multipolymer outer packaging bag, medicament polyethylene packaging bag is through crusher, after being broken into fritter, regrind into 30-200 object fine powder, metallocene hot elastico-plastic body foam, corner after EVA, OBC, PE foaming, and defective work in-process reclaim pulverizing, regrind into 30-200 object fine powder;
Described whipping agent is one or more mixing in Cellmic C 121,4,4-oxos this sulfonyl hydrazide two, p-toluene sulfonyl hydrazide, sodium bicarbonate;
Described bridging agent is selected from least one in dicumyl peroxide (DCP), sulphur and ditertiary butyl peroxide, preferred dicumyl peroxide;
Described promoting agent is selected from least one in stearic acid, magnesiumcarbonate and calcium oxide, preferred stearic acid;
Described zinc oxide is selected from least one in active zinc flower order number 1000--3000 order, zinc carbonate, preferential oxidation zinc.
Plasticate after preparation method of the present invention comprises the steps: aforementioned each component to mix granulation or slice for subsequent use, sulfidization molding, obtains described foam.In vulcanisation step described in the method, temperature is 165-195 DEG C, preferred 170-185 DEG C, more preferably 175 DEG C, and the time is 5 ~ 45 minutes, preferred 6-10 minute, more preferably 7 minutes;
More even in order to make each component be mixed to get, before described vulcanisation step, the mode mixed in described mixing step can be mixing, it comprises the steps: recycling powder particle and ethylene ethyl acetate multipolymer, first in this step mixing, temperature is no more than 70 degree, descend the hot elastico-plastic body of metallocene again, polyolefin elastomer, simultaneously by whipping agent, bridging agent, promoting agent and zinc oxide one remove carry out in refining machine mixing, banburying unit banburying granulation obtains foaming master batch, banburying unit banburying granulation obtains foaming master batch, Banbury mixer prilling temperature 110-130 DEG C, banburying time 10-15min, two roller opens refining, temperature 90-100 DEG C of rolling 5-7min, play triangle bag 3-5 time, granulation or to be pressed into sheet stock for subsequent use, setting 170 DEG C-190 DEG C times is 5 ~ 20 minutes, vulcanizer or inject to mould by pipeline, then be brewed in mould outgoing and obtain foam.
The present invention can large-scale industrial production, low, the capable of circulation recycling of cost, employing can reduce waste material rubbish output and can save again natural resources, reduce the environmental friendliness mode of production cost, recycling method prepares metallocene hot elastico-plastic body foam, both open up raw-material channel, effectively achieve again the organic unity of economic benefit and environmental benefit.
Embodiment:
This embodiment is by the following technical solutions: its raw material composition comprises the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, polyolefin elastomer, reclaimed materials, whipping agent, bridging agent, promoting agent and zinc oxide, and the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, polyolefin elastomer, reclaimed materials, whipping agent, bridging agent, promoting agent and zinc oxide percentage composition content are 60: 30: 20: 20-5: 2-10: 1.0: 0.5-2.5: 1-1.5 preferably 50: 40: 30: 15-10: 2-2.5: 0.6-0.8: 1-1.5: 1-2 more preferably 50: 30: 20: 10-5: 1.5: 1.0: 0.5: 1.2.
The hot elastico-plastic body of described metallocene is the resin adopting high-pressure process manufacturing technology to produce, and be the homogeneous polymer of structure, its hardness is mixed by one or more mixtures in 27-45D;
The number-average molecular weight of described ethylene ethyl acetate multipolymer is 400-4000, preferred 800-2000, and in described ethylene ethyl acetate multipolymer, the mass percentage of vinyl acetic monomer (VA) is 10-50%, preferred 18-26%;
The number-average molecular weight of described polyolefin elastomer is 400-4000, preferred 600-2000;
Described reclaimed materials is selected from the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, the polyethylene of polyolefin elastomer or ethylene ethyl acetate multipolymer outer packaging bag, medicament polyethylene packaging bag is through crusher, after being broken into fritter, regrind into 30-200 object fine powder, metallocene hot elastico-plastic body foam, corner after EVA, OBC, PE foaming, and defective work in-process reclaim pulverizing, regrind into 30-200 object fine powder;
Described whipping agent is one or more mixing in Cellmic C 121,4,4-oxos this sulfonyl hydrazide two, p-toluene sulfonyl hydrazide, sodium bicarbonate;
Described bridging agent is selected from least one in dicumyl peroxide (DCP), sulphur and ditertiary butyl peroxide, preferred dicumyl peroxide;
Described promoting agent is selected from least one in stearic acid, magnesiumcarbonate and calcium oxide, preferred stearic acid;
Described zinc oxide is selected from least one in active zinc flower order number 1000--3000 order, zinc carbonate, preferential oxidation zinc.
Plasticate after the preparation method of this embodiment comprises the steps: aforementioned each component to mix granulation or slice for subsequent use, sulfidization molding, obtains described foam.In vulcanisation step described in the method, temperature is 165-195 DEG C, preferred 170-185 DEG C, more preferably 175 DEG C, and the time is 5 ~ 45 minutes, preferred 6-10 minute, more preferably 7 minutes;
More even in order to make each component be mixed to get, before described vulcanisation step, the mode mixed in described mixing step can be mixing, it comprises the steps: recycling powder particle and ethylene ethyl acetate multipolymer, first in this step mixing, temperature is no more than 70 degree, descend the hot elastico-plastic body of metallocene again, polyolefin elastomer, simultaneously by whipping agent, bridging agent, promoting agent and zinc oxide one remove carry out in refining machine mixing, banburying unit banburying granulation obtains foaming master batch, banburying unit banburying granulation obtains foaming master batch, Banbury mixer prilling temperature 110-130 DEG C, banburying time 10-15min, two roller opens refining, temperature 90-100 DEG C of rolling 5-7min, play triangle bag 3-5 time, granulation or to be pressed into sheet stock for subsequent use, setting 170 DEG C-190 DEG C times is 5 ~ 20 minutes, vulcanizer or inject to mould by pipeline, then be brewed in mould outgoing and obtain foam.
This embodiment can large-scale industrial production, low, the capable of circulation recycling of cost, employing can reduce waste material rubbish output and can save again natural resources, reduce the environmental friendliness mode of production cost, recycling method prepares metallocene hot elastico-plastic body foam, both open up raw-material channel, effectively achieve again the organic unity of economic benefit and environmental benefit.
This embodiment not only has the performance compared with light weight, its foam performance and mechanical property excellent, expansion ratio is high; bubble is even, and rebound effect is good, and density is good; excellent in durability; both the good tensile properties of foam material such as realizing footwear material, excellent compression set performance, shock resistance had been ensure that; again reduce the foam material Raw usage quantitys such as footwear material; realize resource utilization to greatest extent, environmental friendliness, low-carbon (LC) reduces production cost, improves large-scale industrial production efficiency.
This embodiment adopts metallocene hot elastico-plastic body, ethylene ethyl acetate multipolymer (EVA), polyolefin elastomer (POE) and reclaimed materials to be main body sizing material, makes through mixing, granulation and injection sulfuration.The proportion of this foam is below 0.2, because its product weight is light, good springiness, good endurance, be applicable to and require higher goods as endurance quality, as: end lightweight in the footwear prepared with this foam, endurance quality are good, the end in the footwear of class and leisure of racing, in slipper material, there is important using value.Also other various footwear materials are applicable in addition, box material, automotive material, material of construction, wrapping material, dress materials, toy for children, advertisement goods, small stores, the application of the auxiliary material of various sports goods.
The above, be only the specific embodiment of the present invention and application, but protection scope of the present invention is not limited only to this; any based on the foam of the hot elastico-plastic body of metallocene and porous plastics, foam is preparing footwear material, case and bag; automotive material, material of construction, wrapping material; dress materials, toy for children, advertisement goods; small stores, the application of the auxiliary material of various sports goodss etc., and with the sole that described foam is the end; slippers, also belong to protection scope of the present invention.Any those skilled in the art are in the technical scope of patent diselosesll of the present invention, and the change expected easily, modification, combination, replacement, simplification all should be the substitute mode of equivalence, all should be encompassed in scope.
Embodiment: the metallocene hot elastico-plastic body foam of preparation production cycle recycling: the commodity of 50 weight parts are called the hot elastico-plastic body of metallocene, the commodity of 30 weight parts are called EVA7470, number-average molecular weight is the ethylene ethyl acetate multipolymer (wherein the mass percentage of vinyl acetic monomer (VA) is 26%) of 800-2000, the commodity of 20 weight parts are called POE8150, number-average molecular weight is the polyolefin elastomer of 600-2000 and the particle diameter of 10 weight parts is mixing in 50 object reclaimed materials powders input Banbury mixeies, the commodity of 1.5 weight parts are called the whipping agent Cellmic C 121 of AC6000 simultaneously, the bridging agent dicumyl peroxide (DCP) of 1.0 weight parts, the promoting agent stearic acid of 0.6 weight part and the zinc oxide of 1.2 weight parts drop in Banbury mixer mixing, in mixing process, melting temperature is 100-130 DEG C, mixing time is 12 minutes, mill temperature is no more than 80 degree.
After mixing, all raw materials are carried out discharge in 90 DEG C, thin-pass is continued at mill platform after discharge, then after granulating and drying, for subsequent use, inject mould postcure by ejaculator, curing temperature is 175 DEG C, and the time is 7 minutes, after shaping in shaping baking oven after sulfuration, obtain the metallocene hot elastico-plastic body foam of various body of the present invention.
Known after tested, the existing height bounce-back of a kind of metallocene provided by the invention hot elastico-plastic body foam, endurance quality has again by force the performance of lighter in weight, the foaming product be made up of it, good endurance, can meet endurance quality, bounce-back requires the material requirements of higher foaming product.
Claims (10)
1. the preparation method of metallocene hot elastico-plastic body foam cycling and reutilization and application, it is characterized in that its raw material composition comprises the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, polyolefin elastomer, reclaimed materials, whipping agent, bridging agent, promoting agent and zinc oxide, and the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, polyolefin elastomer, reclaimed materials, whipping agent, bridging agent, promoting agent and zinc oxide percentage composition content are 60: 30: 20: 20-5: 2-10: 1.0: 0.5-2.5: 1-1.5 preferably 50: 40: 30: 15-10: 2-2.5: 0.6-0.8: 1-1.5: 1-2 more preferably 50: 30: 20: 10-5: 1.5: 1.0: 0.5: 1.2.
2. the preparation method of metallocene hot elastico-plastic body foam cycling and reutilization and application, it is characterized in that plasticating after its preparation method comprises the steps: aforementioned each component to mix granulation or slice for subsequent use, sulfidization molding, obtains described foam, in vulcanisation step described in the method, temperature is 165-195 DEG C, preferred 170-185 DEG C, more preferably 175 DEG C, the time is 5 ~ 45 minutes, preferred 6-10 minute, more preferably 7 minutes;
More even in order to make each component be mixed to get, before described vulcanisation step, the mode mixed in described mixing step can be mixing, it comprises the steps: recycling powder particle and ethylene ethyl acetate multipolymer, first in this step mixing, temperature is no more than 70 degree, descend the hot elastico-plastic body of metallocene again, polyolefin elastomer, simultaneously by whipping agent, bridging agent, promoting agent and zinc oxide one remove carry out in refining machine mixing, banburying unit banburying granulation obtains foaming master batch, banburying unit banburying granulation obtains foaming master batch, Banbury mixer prilling temperature 110-130 DEG C, banburying time 10-15min, two roller opens refining, temperature 90-100 DEG C of rolling 5-7min, play triangle bag 3-5 time, granulation or to be pressed into sheet stock for subsequent use, setting 170 DEG C-190 DEG C times is 5 ~ 20 minutes, vulcanizer or inject to mould by pipeline, then be brewed in mould outgoing and obtain foam.
3. the preparation method of metallocene according to claim 1 hot elastico-plastic body foam cycling and reutilization and application, it is characterized in that the hot elastico-plastic body of described metallocene is the resin adopting high-pressure process manufacturing technology to produce, be the homogeneous polymer of structure, its hardness is mixed by one or more mixtures in 27-45D.
4. the preparation method of metallocene according to claim 1 hot elastico-plastic body foam cycling and reutilization and application, it is characterized in that the number-average molecular weight of described ethylene ethyl acetate multipolymer is 400-4000, preferred 800-2000, in described ethylene ethyl acetate multipolymer, the mass percentage of vinyl acetic monomer is 10-50%, preferred 18-26%.
5. the preparation method of metallocene according to claim 1 hot elastico-plastic body foam cycling and reutilization and application, is characterized in that the number-average molecular weight of described polyolefin elastomer is 400-4000, preferred 600-2000.
6. the preparation method of metallocene according to claim 1 hot elastico-plastic body foam cycling and reutilization and application, it is characterized in that described reclaimed materials is selected from the hot elastico-plastic body of metallocene, ethylene ethyl acetate multipolymer, the polyethylene of polyolefin elastomer or ethylene ethyl acetate multipolymer outer packaging bag, medicament polyethylene packaging bag is through crusher, after being broken into fritter, regrind into 30-200 object fine powder, metallocene hot elastico-plastic body foam, EVA, OBC, corner after PE foaming, reclaim with defective work in-process and pulverize, regrind into 30-200 object fine powder.
7. the preparation method of metallocene according to claim 1 hot elastico-plastic body foam cycling and reutilization and application, it is characterized in that described whipping agent is one or more mixing in Cellmic C 121,4,4-oxos this sulfonyl hydrazide two, p-toluene sulfonyl hydrazide, sodium bicarbonate.
8. the preparation method of metallocene according to claim 1 hot elastico-plastic body foam cycling and reutilization and application, it is characterized in that described bridging agent is selected from least one in dicumyl peroxide (DCP), sulphur and ditertiary butyl peroxide, preferred dicumyl peroxide.
9. the preparation method of metallocene according to claim 1 hot elastico-plastic body foam cycling and reutilization and application, is characterized in that described promoting agent is selected from least one in stearic acid, magnesiumcarbonate and calcium oxide, preferred stearic acid.
10. the preparation method of metallocene according to claim 1 hot elastico-plastic body foam cycling and reutilization and application, is characterized in that described zinc oxide is selected from least one in active zinc flower order number 1000--3000 order, zinc carbonate, preferential oxidation zinc.
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| CN105175856A (en) * | 2015-08-28 | 2015-12-23 | 河南胜华电缆集团有限公司 | Regenerated polyolefine halogen-free flame-retardant environmental-friendly plastic foam and production method therefor |
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Application publication date: 20150715 |