CN115431484B - Method and system for recycling EPE three-layer co-extrusion composite adhesive film rim charge - Google Patents
Method and system for recycling EPE three-layer co-extrusion composite adhesive film rim charge Download PDFInfo
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- CN115431484B CN115431484B CN202211064790.0A CN202211064790A CN115431484B CN 115431484 B CN115431484 B CN 115431484B CN 202211064790 A CN202211064790 A CN 202211064790A CN 115431484 B CN115431484 B CN 115431484B
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 238000001125 extrusion Methods 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000004064 recycling Methods 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 77
- 239000002245 particle Substances 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 150000002978 peroxides Chemical class 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 claims abstract description 26
- 238000004513 sizing Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 18
- 239000000155 melt Substances 0.000 claims description 15
- 238000003490 calendering Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 5
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- HTCRKQHJUYBQTK-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-yloxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)CC HTCRKQHJUYBQTK-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 230000002776 aggregation Effects 0.000 abstract description 8
- 238000004220 aggregation Methods 0.000 abstract description 8
- 230000004580 weight loss Effects 0.000 abstract description 8
- 238000000465 moulding Methods 0.000 abstract description 7
- 238000004806 packaging method and process Methods 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004804 winding Methods 0.000 description 11
- 230000007246 mechanism Effects 0.000 description 9
- 206010049040 Weight fluctuation Diseases 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000001723 carbon free-radicals Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention relates to the technical field of solar packaging adhesive films, and discloses a recycling method and a recycling system of EPE three-layer co-extrusion composite adhesive film rim charge. The recovery method comprises the following steps: crushing the EPE composite adhesive film rim charge to obtain millimeter-sized rim charge particles; adding the rim charge particles, a peroxide initiator and a grafting agent with carbon-carbon double bonds into a double-screw extruder, and extruding and granulating after in-situ crosslinking and grafting reaction under the melting condition to obtain rim charge particles; uniformly mixing the rim charge particles with the EVA material mixed with the auxiliary agent to obtain a mixed material; and adding the mixed material into an EVA single screw extruder, plasticizing to obtain an EVA sizing material, and carrying out coextrusion and extension molding on the EVA sizing material and the POE sizing material to obtain the EPE composite adhesive film. The recovery method solves the problem of material clamping of the small screw device and the problem of local aggregation of POE resin, can effectively avoid large melt pressure fluctuation and gram weight loss of the composite adhesive film in the extruder caused by improper rim charge recovery method, and reduces production cost.
Description
Technical Field
The invention relates to the technical field of solar packaging adhesive films, in particular to a recycling method and recycling system of EPE three-layer co-extrusion composite adhesive film rim charge.
Background
The traditional solar photovoltaic module is a single-glass module of an aluminum back surface field passivation single-sided battery, and the adopted packaging adhesive film is mainly an EVA adhesive film. However, the technology of reducing cost and enhancing efficiency and surfing the internet at low price is common in the industry, so that the improvement of the conversion efficiency of the photovoltaic module enters an acceleration period, and the technology of the photovoltaic module is an efficient era, and the double-sided double-glass module is one of the efficient photovoltaic modules. From the power station income analysis, the double-sided assembly can achieve 10% increase, so that the whole investment income rate is greatly improved. Obviously, the double-sided double-glass assembly is a development trend in the future, and is one of means for reducing the electricity cost of enterprises.
Most of the battery plates used by the existing double-sided assembly are double-sided battery plates of P-type Perc, N-type Pert and N-type Topcon, and when the battery plates are packaged by adopting a traditional EVA adhesive film, serious PID problems are easy to generate, so that power attenuation is caused. The power attenuation of the back surface of the EVA film packaged double-sided double-glass assembly reaches 20-40% under the conditions of-1500V and 192h, and the power attenuation of the front surface of the EVA film packaged double-sided double-glass assembly exceeds 5%. In order to solve the PID problem, POE glued films are currently commonly adopted to package double-sided double-glass assemblies.
However, the POE adhesive film is prone to problems such as air bubbles, slipping and merging during lamination of the photovoltaic module, which can lead to reduction of the packaging yield of the photovoltaic module; and moreover, the ageing delamination risk of the photovoltaic module packaged by the POE adhesive film is higher than that of the photovoltaic module packaged by the EVA adhesive film, and the reliability is inferior to that of the EVA adhesive film. Moreover, the POE adhesive film is more expensive than the EVA adhesive film, so that the manufacturing cost of the photovoltaic module can be increased. In order to solve the problems brought by POE films, an EVA/POE/EVA (EPE) three-layer co-extrusion composite film is generated, and the composite film not only solves the PID problem of the EVA film, but also solves the problems of aging delamination, air bubbles, slipping and merging of the POE film. The existing EPE three-layer co-extrusion composite adhesive film is applied on a large scale, is a development trend of the photovoltaic packaging adhesive film in the future, and the market share of the EPE three-layer co-extrusion composite adhesive film is increased year by year.
However, the rim charge generated in the production process of the EPE three-layer co-extrusion composite adhesive film (EPE composite adhesive film for short) is difficult to recycle. The main reason is that: firstly, the existing photovoltaic packaging adhesive film production enterprises are mostly provided with a small screw device arranged at a side feeding port of an EVA single screw extruder 11 as shown in figure 1 for recycling adhesive film rim charge, and the recycling method is as follows: in the process of three-layer co-extrusion molding of the EPE composite adhesive film, the on-line cut rim charge is pulled into a small screw device, and the rim charge is directly fed into an EVA single screw extruder 11 through melt extrusion of a small screw extruder 8 and is mixed with new sizing material in a melt manner so as to enter the next process for preparing the EPE composite adhesive film (the device shown in fig. 1 and a method for recycling the rim charge of the adhesive film by adopting the device, and particularly, refer to a method for recycling the rim charge of the EVA adhesive film and a device thereof provided by publication No. CN 102248682A). The method has the advantages that the added rim charge is large in size, the material dispersing plasticizing capacity of the single-screw extruder is poor, and when the rim charge with the large size is directly recycled to the EVA single-screw extruder through the small screw device, the rim charge cannot be uniformly dispersed in the EVA single-screw extruder, so that the fluctuation of the melt pressure of the extruder is large, and the gram weight fluctuation range of the produced adhesive film is large; and because the rim charge size is great, the problem of card material is still produced easily to little screw rod device, leads to the rim charge to stay longer in the screw rod, and the friction time of heated and screw rod is longer, and the rim charge can take place the crosslinking reaction by oneself to lead to the extrusion in-process to produce crosslinked crystal point easily, and then produce glued membrane waste material.
Secondly, because EVA is polar resin and POE is nonpolar resin, the compatibility of the two is poor, and in an EVA single screw extruder, the POE resin in the rim charge and the molecular chains of the EVA resin are mutually exclusive and cannot be well compatible, so that the POE resin is locally aggregated; the fluid state and the melt pressure of the POE resin are different from those of the EVA resin in a molten state, and the fluidity of the EVA resin is higher than that of the POE resin, so that local aggregation of the POE resin in an extruder easily causes large integral melt pressure fluctuation.
The superposition of the two reasons leads to larger fluctuation of melt pressure in the extruder and larger fluctuation range of gram weight of the EPE composite adhesive film. In order to avoid the problems, the existing EPE composite adhesive film production enterprises either do not recycle rim charge or make the gram weight of the whole EPE composite adhesive film larger so as to solve the existing situations of insufficient gram weight and unqualified gram weight; however, both methods greatly increase the production cost of the EPE composite adhesive film, and prevent future large-scale application of the EPE three-layer co-extrusion composite adhesive film to a certain extent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a recycling method and a recycling system of EPE three-layer co-extrusion composite adhesive film rim charge, which not only solve the problems of cross-linked crystal points and adhesive film waste generated by clamping materials of a small screw device, but also solve the problem of local aggregation of POE resin, can effectively avoid large melt pressure fluctuation in an extruder and gram weight loss of the composite adhesive film caused by improper rim charge recycling method, and reduce the production cost of the composite adhesive film.
Based on the above, the invention discloses a recycling method of EPE three-layer co-extrusion composite adhesive film rim charge, which comprises the following steps:
s1, crushing the rim charge of the cut EPE composite adhesive film to a millimeter level by a crusher to obtain rim charge particles containing EVA resin and POE resin;
s2, adding the rim charge particles, a peroxide initiator and a grafting agent with carbon-carbon double bonds into a double-screw extruder, initiating by the peroxide initiator in a molten state, carrying out an in-situ crosslinking reaction on EVA resin and POE resin in the rim charge particles, carrying out an in-situ grafting reaction on the POE resin and the grafting agent with carbon-carbon double bonds, and extruding and granulating after the reaction to obtain rim charge particles;
s3, uniformly mixing the rim charge particles with the prefabricated EVA material mixed with the auxiliary agent according to the weight ratio to obtain a mixed material;
and S4, adding the mixed material into an EVA single-screw extruder, and performing melt plasticization to obtain an EVA sizing material, so that the EVA sizing material and the POE sizing material are subjected to coextrusion and calendaring to obtain the EPE composite adhesive film.
In the invention, a peroxide initiator is adopted, and after the peroxide (-O-) contained in the peroxide initiator is heated in a melt extrusion temperature environment (such as 130-160 ℃) of a double-screw extruder, bond breakage can be quickly generated, the peroxide is split into two oxygen free radicals (O-), the oxygen free radicals have stronger activity, carbon-carbon bonds (C-C) of EVA resin and POE resin can be oxidized, the EVA resin and the POE resin can both form the carbon free radicals (C-), the carbon free radicals of the EVA resin and the carbon free radicals of the POE resin are mutually reacted and combined, so that a copolymerization addition reaction occurs, in-situ crosslinking reaction of the EVA resin and the POE resin is realized, the molecular chains of the EVA resin and the POE resin are connected together, and the problem of local aggregation of the POE resin is weakened; furthermore, in the process of recycling the rim charge, the fluctuation range of the melt pressure of the extruder can be reduced, so that the fluctuation range of the gram weight of the EPE composite adhesive film (namely the EPE composite adhesive film containing the rim charge) prepared by recycling the rim charge is reduced, and the gram weight loss of the EPE composite adhesive film is reduced.
Further, through addition polymerization reaction between carbon free radicals of the POE resin and carbon double bonds of the grafting agent, in-situ grafting reaction of the POE resin and the grafting agent with the carbon double bonds is realized, so that a compatilizer (such as POE-g-GMA compatilizer) of the POE resin grafting agent is obtained, and therefore, molecular chains of the POE resin and molecular chains of the EVA resin are further connected together in a molten state in a bridging connection mode of the compatilizer, repulsion between the molecular chains of the POE resin and the EVA resin is reduced, and compatibility between the molecular chains of the POE resin is improved, so that local aggregation of the POE resin in an extruder is further avoided; furthermore, in the process of recycling the rim charge, the fluctuation range of the melt pressure of the extruder can be further reduced, the fluctuation range of the gram weight of the EPE composite adhesive film containing the rim charge is further reduced, and the gram weight loss of the EPE composite adhesive film is greatly reduced.
Preferably, in the step S1, the width of the cut rim charge of the EPE composite adhesive film is 1-15cm; the rim charge is long strip-shaped, and the length of the short side of the rim charge is the width of the rim charge. The width of the rim charge is controlled within 1-15cm, so that the effect and the rate of crushing are prevented from being influenced by the overlarge width of the rim charge, and the rim charge is more convenient and quicker to crush.
Preferably, the length of the rim charge particles in millimeter level is 12-18mm, the width is 2-4mm, and the height is 2-4mm, and the rim charge particles are cylindrical particles with smaller volume, regular shape and uniform size; therefore, the problems of material clamping and no discharging at the feed inlet of the double-screw extruder caused by oversized rim charge particles can be prevented, the recovery quality is improved, and the fluctuation range of the melt pressure is further reduced.
Preferably, in step S2, the peroxide initiator is one or more of tert-amyl peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and tert-butyl peroxy-2-ethylhexyl carbonate.
Further preferably, the peroxide initiator is used in an amount of 0.05 to 0.2% by mass of the rim charge particles.
Preferably, in the step S2, the grafting agent with a carbon-carbon double bond is one or more of glycidyl methacrylate, maleic anhydride and vinyltrimethoxysilane.
Further preferably, the grafting agent is used in an amount of 0.5 to 2% by mass of the rim charge particles.
Preferably, in step S2, the temperature in the twin-screw extruder is 130-160 ℃; the double-screw extruder is provided with a double weightless scale, so that the peroxide initiator and the grafting agent added into the double-screw extruder can be accurately weighed.
Preferably, in step S2, the rim charge particles are cylindrical particles having a length of 3mm±0.5mm and an equivalent diameter of 2.8mm±0.5 mm.
Further preferably, the melt index of the rim charge particles is 5-12g/10min.
Preferably, in step S3, the weight ratio of the rim charge particles to the EVA material mixed with the auxiliary agent is 0.5-1.5: 10.
Preferably, in step S3, the time for mixing the rim charge particles and the EVA material mixed with the auxiliary agent is 20-30min, the mixing mode is stirring, and the stirring speed is 15-25r/min.
According to the invention, if the rim charge particles manufactured in the step S2 are not uniformly mixed with the prefabricated EVA materials mixed with the auxiliary agent according to the weight ratio, but are directly added into the EVA single-screw extruder in the step S4, the rim charge particles are unevenly mixed in the EVA rubber material, so that the fluctuation range of melt pressure in the EVA single-screw extruder is increased, and the fluctuation range of gram weight of the obtained EPE composite adhesive film is increased.
The invention also discloses a recycling system for the recycling method of the EPE three-layer co-extrusion composite adhesive film rim charge, which comprises the following steps:
the co-extrusion forming device is used for co-extruding and calendaring the EVA rubber material and the POE rubber material to prepare an EPE composite adhesive film;
the winding mechanism is connected with the discharge port of the co-extrusion forming device and is used for winding the EPE composite adhesive film;
the traction device is connected with the winding mechanism and used for drawing out the rim charge cut from the EPE composite adhesive film;
the crusher is connected with the output end of the traction device and is used for crushing the rim charge of the pulled EPE composite adhesive film so as to obtain rim charge particles containing EVA resin and POE resin;
the double-screw extruder is connected with a discharge port of the crusher and is used for carrying out in-situ crosslinking reaction and in-situ grafting reaction on the rim charge particles, the peroxide initiator and the grafting agent with carbon-carbon double bonds under melting, and then extruding and granulating to obtain rim charge particles;
the mixing device is connected with the discharge port of the double-screw extruder and is used for uniformly mixing the rim charge particles and the prefabricated EVA material mixed with the auxiliary agent according to the weight ratio so as to obtain a mixed material;
the co-extrusion forming device comprises an EVA single-screw extruder, and a discharge port of the mixing device is connected with a feed port of the EVA single-screw extruder, so that the mixed material is melted and plasticized in the EVA single-screw extruder to obtain the EVA sizing material containing the rim charge.
Compared with the prior art, the invention at least comprises the following beneficial effects:
1. according to the invention, the rim charge of the EPE composite adhesive film sequentially passes through the crusher and the double-screw extruder to prepare rim charge particles, the volume is smaller, the shape is regular, the particle size of all rim charge particles is uniform, the rim charge particles and EVA materials mixed with additives are uniformly mixed, and then the rim charge particles and EVA materials mixed with additives are directly added into the EVA single-screw extruder, so that the problems of uneven rim charge dispersion and material clamping of a small screw device are avoided, the melt pressure fluctuation range of the extruder can be reduced, the gram weight fluctuation range of the EPE composite adhesive film prepared by recycling the rim charge can be reduced, the gram weight loss of the EPE composite adhesive film is reduced, and the problems of cross-linked crystal points and adhesive film waste caused by material clamping of the small screw device are solved.
2. In the invention, a part of peroxide initiator can trigger EVA resin and POE resin to generate in-situ crosslinking reaction, so that the molecular chain of EVA resin and the molecular chain of POE resin are connected together, thereby weakening the problem of local aggregation of POE resin; and the other part of peroxide initiator can initiate in-situ grafting reaction of grafting agent with carbon-carbon double bond and POE resin to generate POE grafted glycidyl methacrylate compatilizer, POE grafted maleic anhydride compatilizer or POE grafted silane compatilizer in situ, so that the molecular chain of the POE resin and the molecular chain of the EVA resin are further connected together in a molten state in a bridging connection mode of the compatilizer, the rejection between the molecular chains is reduced, the compatibility between the molecular chains is improved, and further, the local aggregation of the POE resin in the EVA single-screw extruder is further avoided. Therefore, through the cooperation of the in-situ crosslinking reaction and the in-situ grafting reaction, the melt pressure fluctuation range of the EVA single-screw extruder can be greatly reduced in the process of recycling the rim charge, so that the gram weight fluctuation range of the EPE composite adhesive film containing the rim charge is greatly reduced, and the gram weight loss of the EPE composite adhesive film is greatly reduced.
In summary, the recovery method solves the problems of cross-linking crystal points and adhesive film waste generated by clamping materials of a small screw device and local aggregation of POE resin through the synergistic effect of the steps S1, S2 and S3, can effectively avoid large fluctuation of melt pressure in an extruder and large fluctuation range of gram weight of the produced EPE composite adhesive film containing the rim charge caused by improper rim charge recovery method, and can effectively reduce the gram weight loss of the produced EPE composite adhesive film containing the rim charge, further improve the yield and reduce the production cost of the composite adhesive film. The method has simple and practical process and high industrial application value.
Drawings
Fig. 1 is a schematic structural diagram of a recycling system of EPE three-layer co-extrusion composite film rim charge of comparative example 1.
Fig. 2 is a schematic structural diagram of a recycling system of EPE three-layer co-extrusion composite film rim charge of comparative example 2.
FIG. 3 is a schematic structural diagram of a recycling system of EPE three-layer co-extrusion composite adhesive film rim charge according to the present invention.
Reference numerals illustrate: a coextrusion molding apparatus 1; an EVA single screw extruder 11; a first host 111; a first hopper 112; a coextrusion die 12; a calender 13; a winding mechanism 2; a traction device 3; a crusher 4; a twin-screw extruder 5; a mixing device 6; a premixing device 7; a small screw extruder 8; a second host 81; a second hopper 82.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
Example 1
The recycling method of the EPE three-layer co-extrusion composite adhesive film rim charge comprises the following steps:
s1, crushing the rim charge of the cut EPE composite adhesive film to millimeter level by a crusher 4 to obtain rim charge particles containing EVA resin and POE resin.
The width of the rim charge of the cut EPE composite adhesive film is 12cm; the length of the millimeter-sized rim charge particles is 15mm, the width is 3mm, and the height is 3mm.
S2, adding the rim charge particles, a peroxide initiator and a grafting agent with carbon-carbon double bonds into a double-screw extruder 5 with a temperature zone of 130-160 ℃ and a double-weightless scale, initiating by the peroxide initiator in a molten state to enable EVA resin and POE resin in the rim charge particles to carry out in-situ crosslinking reaction, enabling the POE resin and the grafting agent with carbon-carbon double bonds to carry out in-situ grafting reaction, and carrying out the whole reaction in the double-screw extruder 5, and carrying out extrusion granulation by the double-screw extruder 5 to obtain rim charge particles. The rim charge particles are cylindrical particles with the length of 3mm plus or minus 0.5mm and the equivalent diameter of 2.8mm plus or minus 0.5 mm; and the melt index of the rim charge particles is 10.4g/10min.
Wherein the peroxide initiator is tert-butyl peroxy-2-ethylhexyl carbonate, and the addition amount of the peroxide initiator is 0.05% of the mass of the rim charge particles.
Wherein the grafting agent with carbon-carbon double bond is maleic anhydride, and the addition amount of the grafting agent is 0.5 percent of the mass of the rim charge particles.
S3, mixing the rim charge particles with the prefabricated EVA material mixed with the auxiliary agent according to the weight ratio of 1:10, stirring for 20min at a rotating speed of 20r/min to obtain a mixed material.
Wherein, the prefabricated EVA material mixed with the auxiliary agent is an EVA mixture semi-finished product obtained after EVA particles and the auxiliary agent are mixed in a normal EPE production process; the auxiliary agent comprises a conventional initiator, a crosslinking assistant, a coupling agent, an ultraviolet stabilizer and an antioxidant.
And S4, adding the mixed material into an EVA single screw extruder 11, performing melt plasticization to obtain an EVA rubber material, and performing coextrusion and calendaring molding on the EVA rubber material and a POE rubber material in a normal EPE production process to obtain the EPE composite adhesive film.
The recycling method of the edge material of the EPE three-layer co-extrusion composite adhesive film in the embodiment, referring to fig. 3, comprises the following steps:
the co-extrusion molding device 1 is used for co-extruding and calendaring EVA rubber and POE rubber to prepare an EPE composite adhesive film;
the winding mechanism 2 is connected with the discharge port of the co-extrusion molding device 1 and is used for winding the EPE composite adhesive film;
the traction device 3 is connected with the winding mechanism 2 and is used for drawing out the rim charge cut from the EPE composite adhesive film;
the crusher 4 is connected with the output end of the traction device 3 and is used for crushing the rim charge of the pulled EPE composite adhesive film to obtain rim charge particles containing EVA resin and POE resin (see step S1);
the double-screw extruder 5 is connected with the discharge port of the crusher 4 and is used for carrying out in-situ crosslinking reaction and in-situ grafting reaction on the rim charge particles, the peroxide initiator and the grafting agent with carbon-carbon double bonds under the melting condition, and then extruding and granulating the rim charge particles to obtain rim charge particles (see step S2);
the mixing device 6 is connected with the discharge port of the double-screw extruder 5 and is used for uniformly mixing the rim charge particles and the prefabricated EVA material mixed with the auxiliary agent according to the weight ratio to obtain a mixed material (see step S3);
the co-extrusion molding device 1 comprises an EVA single-screw extruder 11, wherein a discharge port of the mixing device 6 is connected with a feed port of the EVA single-screw extruder 11, so that the mixed material is melted and plasticized in the EVA single-screw extruder 11 to obtain a new EVA sizing material (see step S4); and then the new EVA sizing material and the new POE sizing material are subjected to coextrusion and calendaring molding by utilizing the coextrusion molding device 1 to prepare the new EPE composite adhesive film. Thus, by using the recycling system of fig. 3 and repeating steps S1-S4 of the recycling method, the cut edge material of the EPE composite adhesive film can be recycled.
Specifically, referring to fig. 3, the recycling system further includes a premixing device 7 (for prefabricating the EVA material mixed with the auxiliary agent), and a feed inlet of the mixing device 6 is connected to a discharge outlet of the premixing device 7 to feed the EVA material mixed with the auxiliary agent into the mixing device 6.
Specifically, referring to fig. 3, the EVA single screw extruder 11 is provided with a first hopper 112 for feeding and a first host 111 located at the front end of the EVA single screw extruder 11, the discharge port of the mixing device 6 is connected to the first hopper 112 of the EVA single screw extruder 11, and the first host 111 is used for driving the EVA single screw extruder 11 to work.
Specifically, referring to fig. 3, the co-extrusion molding apparatus 1 further includes a POE single screw extruder for preparing POE compound (POE single screw extruder belongs to a conventional equipment used in a normal EPE production process, is not substantially associated with the recovery method of the present invention, and is not illustrated in detail, and is not illustrated in the recovery system diagram), a co-extrusion die 12, and a calender 13; the discharge port of the POE single screw extruder and the discharge port of the EVA single screw extruder 11 are both connected with the co-extrusion die head 12, so that the POE sizing material and the EVA sizing material share the co-extrusion die head 12; and the co-extrusion die head 12 is connected with the calender 13, and the EVA sizing material and the POE sizing material are subjected to co-extrusion and calendaring molding in sequence through the cooperation of the co-extrusion die head 12 and the calender 13 so as to obtain the EPE composite adhesive film.
Example 2
The recovery method and recovery system of the edge material of the EPE three-layer co-extrusion composite adhesive film in this embodiment refer to embodiment 1, and the difference from embodiment 1 is that:
in the step S2 of the recovery method, the peroxide initiator is tert-butyl peroxy-2-ethylhexyl carbonate and tert-amyl peroxy-2-ethylhexyl carbonate, and the addition amount of the peroxide initiator and the peroxide initiator is 0.05% of the mass of the rim charge particles; the grafting agent with carbon-carbon double bond is vinyl trimethoxy silane, and the addition amount of the grafting agent is 2% of the mass of the rim charge particles; the melt index of the obtained rim charge particles was 8.3g/10min.
Example 3
The recovery method and recovery system of the edge material of the EPE three-layer co-extrusion composite adhesive film in this embodiment refer to embodiment 1, and the difference from embodiment 1 is that:
in the step S2 of the recovery method, the peroxide initiator is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, and the addition amount of the peroxide initiator is 0.15% of the mass of the rim charge particles; the grafting agent with carbon-carbon double bond is glycidyl methacrylate, and the addition amount of the grafting agent is 1% of the mass of the rim charge particles; the melt index of the obtained rim charge particles was 5.1g/10min.
Comparative example 1
An EPE three-layer co-extrusion composite film rim charge recycling system of this comparative example, see fig. 1, includes: the device comprises a coextrusion forming device 1, a winding mechanism 2, a traction device 3 and a small screw device; wherein the co-extrusion molding apparatus 1 comprises an EVA single screw extruder 11, a POE single screw extruder (the POE single screw extruder belongs to conventional equipment used in a normal EPE production process and is not described in detail), a co-extrusion die head 12 and a calender 13; the connection and the function of the coextrusion device 1, the winding mechanism 2 and the traction device 3 are basically described in embodiment 1. The recovery system of this comparative example is different from that of example 1 in that:
instead of the crusher 4, twin-screw extruder 5 and mixing device 6 of fig. 3, a small screw device is provided; referring to fig. 1, the small screw device comprises a small screw extruder 8, a second hopper 82 for feeding, and a second main machine 81 for driving the small screw extruder 8 to operate; the output end of the traction device 3 is connected with a second hopper 82, and the discharge port of the small screw extruder 8 is connected with the side material port of the EVA single screw extruder 11.
Based on this, a recycling method of EPE three-layer co-extrusion composite film rim charge of this comparative example, see fig. 1, is different from the recycling method of example 1 in that:
directly conveying the rim charge of the cut EPE composite adhesive film to a small screw device through a traction device 3 for melt extrusion, directly adding the rim charge into an EVA single screw extruder 11 (the EVA single screw extruder 11 is added with a prefabricated EVA material mixed with an auxiliary agent), and obtaining an EVA sizing material through melt plasticization; and then the EVA sizing material and the POE sizing material prepared by using the POE single-screw extruder are subjected to coextrusion and calendaring molding in sequence to prepare the EPE composite adhesive film.
Comparative example 2
An EPE three-layer co-extrusion composite film edge trim recycling system of this comparative example, see fig. 2, includes: the device comprises a co-extrusion forming device 1, a winding mechanism 2, a traction device 3, a crusher 4 and a double-screw extruder 5, wherein the co-extrusion forming device 1 comprises an EVA single-screw extruder 11, and the EVA single-screw extruder 11 is provided with a first hopper 112 for feeding and a first host 111 positioned at the front end of the EVA single-screw extruder 11; the co-extrusion molding apparatus 1 further includes a POE single screw extruder (POE single screw extruder belongs to a conventional apparatus used in a normal EPE production process, and thus not described in detail), a co-extrusion die 12, and a calender 13; the connection and the function of the co-extrusion molding device 1, the winding mechanism 2, the traction device 3, the crusher 4 and the twin-screw extruder 5 are basically described in the embodiment 1. The recovery system of this comparative example is different from that of example 1 in that:
the mixing device 6 of fig. 3 is not included, see fig. 2, and the discharge port of the twin-screw extruder 5 is directly connected to the first hopper 112 of the EVA single-screw extruder 11.
Based on this, a recycling method of EPE three-layer co-extrusion composite film rim charge of this comparative example, see fig. 2, is different from the recycling method of example 1 in that:
in the step S2, only the rim charge particles obtained in the step S1 are added into the twin-screw extruder 5 without adding a peroxide initiator and a grafting agent having a carbon-carbon double bond, so that the in-situ crosslinking reaction and the in-situ grafting reaction are not performed in the twin-screw extruder 5 in the step S2, and only melt extrusion granulation is performed to obtain the rim charge particles in the step S2 of the comparative example;
step S3 is omitted;
in step S4, the rim charge particles in step S2 are directly added into an EVA single screw extruder 11 (a prefabricated EVA material mixed with an auxiliary agent is added into the EVA single screw extruder 11), and are melted and plasticized to obtain an EVA compound, so that the EVA compound and POE compound are co-extruded and calendared to obtain the EPE composite adhesive film.
Comparative example 3
The method and system for recycling the edge material of the EPE three-layer co-extrusion composite adhesive film in the comparative example refer to the embodiment 1, and the difference from the embodiment 1 is that:
in the recycling method of the EPE three-layer co-extrusion composite adhesive film rim charge of the comparative example, in the step S2, only rim charge particles obtained in the step S1 are added into the double-screw extruder 5, and a peroxide initiator and a grafting agent with carbon-carbon double bonds are not added, so that in-situ crosslinking reaction and in-situ grafting reaction are not carried out in the double-screw extruder 5 of the step S2, and only melt extrusion granulation is carried out, so that rim charge particles of the step S2 of the comparative example are obtained.
Performance testing
Testing the current fluctuation range and the pre-net pressure fluctuation range of the EVA single-screw extruder 11 in the recovery methods of examples 1-3 and comparative examples 1-3, testing the gram weight fluctuation range of the EPE composite adhesive film containing the rim charge prepared in the recovery methods of examples 1-3 and comparative examples 1-3, and observing the conditions of the clamping material and the cross-linking crystal point in the rim charge recovery process; the test results are shown in table 1 below:
TABLE 1
From the data in Table 1 for comparative example 1 and examples 1-3, it can be seen that:
compared with the method for recycling the rim charge of the EPE composite adhesive film by adopting the small screw device in the comparative example 1, the recycling method of the embodiments 1-3 of the invention reduces the current fluctuation range of the EVA single screw extruder 11 by 66.7%, reduces the pre-net pressure fluctuation range of the EVA single screw extruder 11 by 75% (the reduction of the current fluctuation range and the pre-net pressure fluctuation range of the extruder indicates that the melt pressure fluctuation range of the extruder is reduced), reduces the gram weight fluctuation range of the EPE composite adhesive film containing the rim charge by 65%, and solves the problems of material clamping and cross-linking crystal points.
From the data in table 1 for comparative example 1 (without steps S1-S3 and with a small screw device for rim charge granulation), comparative example 2 (with step S1, granulation with step S2 only and without in situ crosslinking and grafting of step S2 and without step S3), comparative example 3 (with steps S1 and S3 and granulation with step S2 only and without in situ crosslinking and grafting of step S2) and examples 1-3 it can be seen that:
according to the recycling method disclosed by the invention, the rim charge particles which are smaller in volume, regular in shape and uniform in size are crushed and prepared (see step S1), the double-screw extruder 5 carries out in-situ crosslinking reaction and in-situ grafting reaction and pelletizes (step S2), the prepared rim charge particles and the prepared EVA material mixed with the auxiliary agent are uniformly mixed according to the weight ratio (step S3), the three steps can reduce the current fluctuation range of the EVA single-screw extruder 11, the pre-net pressure fluctuation range and the gram weight fluctuation range of the prepared rim charge-containing EPE composite adhesive film, the three steps have a synergistic enhancement effect, and the current fluctuation range of the EVA single-screw extruder 11, the pre-net pressure fluctuation range and the gram weight fluctuation range of the prepared rim charge-containing EPE composite adhesive film in the rim charge recycling process of the EPE composite adhesive film can be effectively reduced, so that the gram weight loss of the prepared rim charge-containing EPE composite adhesive film is effectively reduced, and the production cost is further reduced.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the scope of the embodiments of the invention.
The foregoing has outlined rather broadly the more detailed description of the invention in order that the detailed description of the invention that follows may be better understood, and in order that the present principles and embodiments may be better understood; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (7)
1. The recycling method of the EPE three-layer co-extrusion composite adhesive film rim charge is characterized by comprising the following steps of:
s1, crushing the rim charge of the cut EPE composite adhesive film to a millimeter level by a crusher to obtain rim charge particles containing EVA resin and POE resin; the length of the millimeter-sized rim charge particles is 12-18mm, the width is 2-4mm, and the height is 2-4mm;
s2, adding the rim charge particles, a peroxide initiator and a grafting agent with carbon-carbon double bonds into a double-screw extruder, initiating by the peroxide initiator in a molten state, carrying out an in-situ crosslinking reaction on EVA resin and POE resin in the rim charge particles, carrying out an in-situ grafting reaction on the POE resin and the grafting agent with carbon-carbon double bonds, and extruding and granulating after the reaction to obtain rim charge particles; the dosage of the peroxide initiator is 0.05-0.2% of the mass of the rim charge particles; the dosage of the grafting agent is 0.5-2% of the mass of the rim charge particles;
in the step S2, the rim charge particles are cylindrical particles with the length of 3mm plus or minus 0.5mm and the equivalent diameter of 2.8mm plus or minus 0.5 mm;
s3, uniformly mixing the rim charge particles with the prefabricated EVA material mixed with the auxiliary agent according to the weight ratio to obtain a mixed material;
in the step S3, the weight ratio of the rim charge particles to the EVA materials mixed with the auxiliary agent is 0.5-1.5:10;
s4, adding the mixed material into an EVA single-screw extruder, and performing melt plasticization to obtain an EVA sizing material, so that the EVA sizing material and a POE sizing material are subjected to coextrusion and calendaring to obtain an EPE composite adhesive film;
in the step S2, the temperature in the twin-screw extruder is 130-160 ℃.
2. The method for recycling the rim charge of the EPE three-layer co-extrusion composite adhesive film according to claim 1, wherein in the step S1, the width of the rim charge of the cut EPE composite adhesive film is 1-15cm.
3. The method for recycling the edge material of the EPE three-layer co-extrusion composite adhesive film according to claim 1, wherein in the step S2, the peroxide initiator is one or more of tert-amyl peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and tert-butyl peroxy-2-ethylhexyl carbonate.
4. The method for recycling the edge material of the EPE three-layer co-extrusion composite adhesive film according to claim 1, wherein in the step S2, the grafting agent with carbon-carbon double bonds is one or more of glycidyl methacrylate, maleic anhydride and vinyl trimethoxysilane.
5. The method for recycling the edge material of the EPE three-layer co-extrusion composite adhesive film according to claim 1, wherein in the step S2, the double-screw extruder is provided with a double-weightlessness scale.
6. The method for recycling the rim charge of the EPE three-layer co-extrusion composite adhesive film according to claim 1, wherein the melt index of the rim charge particles is 5-12g/10min.
7. The method for recycling the rim charge of the EPE three-layer co-extrusion composite adhesive film according to claim 1, wherein in the step S3, the mixing time of the rim charge particles and the EVA material mixed with the auxiliary agent is 20-30min, the mixing mode is stirring, and the stirring rotating speed is 15-25r/min.
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| CN101125943A (en) * | 2007-08-07 | 2008-02-20 | 刘明春 | Technique for manufacturing hollow plate raw material from modified fiberglass enhanced polypropylene waste plastic |
| CN210282854U (en) * | 2019-06-28 | 2020-04-10 | 广州爱科琪盛塑料有限公司 | Film rim charge recovery system |
| CN111793442A (en) * | 2020-07-17 | 2020-10-20 | 常州斯威克光伏新材料有限公司 | Three-layer co-extrusion composite adhesive film for packaging photovoltaic module and preparation method thereof |
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| EP1424181A1 (en) * | 2002-11-26 | 2004-06-02 | Tarkett Sommer S.A. | Method for recycling composite materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125943A (en) * | 2007-08-07 | 2008-02-20 | 刘明春 | Technique for manufacturing hollow plate raw material from modified fiberglass enhanced polypropylene waste plastic |
| CN210282854U (en) * | 2019-06-28 | 2020-04-10 | 广州爱科琪盛塑料有限公司 | Film rim charge recovery system |
| CN111793442A (en) * | 2020-07-17 | 2020-10-20 | 常州斯威克光伏新材料有限公司 | Three-layer co-extrusion composite adhesive film for packaging photovoltaic module and preparation method thereof |
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