CN1468698A - In-situ fibril method of recovering waste thermoplastic plastics - Google Patents
In-situ fibril method of recovering waste thermoplastic plastics Download PDFInfo
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- CN1468698A CN1468698A CNA031351867A CN03135186A CN1468698A CN 1468698 A CN1468698 A CN 1468698A CN A031351867 A CNA031351867 A CN A031351867A CN 03135186 A CN03135186 A CN 03135186A CN 1468698 A CN1468698 A CN 1468698A
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Abstract
The present invention is in-situ fibrillation method of recovering waste thermoplastic plastics. Washed and dried waste thermoplastic engineering plastics and waste thermoplastic common plastics are mixed in certain ratio; the mixture is molten, extruded and stretched in selected technological conditions; and the stretched material strips are forced cooled in cooling water tank and pelletized to obtain the in-situ reinforced and toughened plastic alloy with excellent comprehensive performance. The said production process has low cost and high production efficiency, solves the environmental pollution caused by waste plastics and utilizes the resource of waste plastics in high additional value.
Description
One, technical field
The invention belongs to waste and old thermoplastic recovery and utilization technology field, is a kind of method of utilizing the waste and old thermoplastic of in-situ micro-fibril recovery.
Two, background technology
Plastics are widely used in the national economy industry-by-industry with advantage such as its light weight, corrosion-resistant, easy processing, cost be low, easy to use.The plastic products annual production is all more than 1.5 hundred million tons, and every year is also with 10% speed increase.Because the main component of plastics is the big molecules with number of chemical structure and chain structure, it in use can wear out, and degraded or crosslinked takes place, thereby makes its combination property deterioration etc. become the waste plastics that can not re-use.And use the discarded plastics in back, and according to State Bureau of Environmental Protection, Ministry of Agriculture's statistics, every year, only the non-returnable container product just reached more than 5,000 ten thousand tons, and the field plastic sheeting for farm use reaches 8,000,000 tons, adds that other waste plastic can reach more than hundred million tons.Discarded amount is so big, and recovery utilization rate is less than 20%, and this not only makes resource can not get sufficient regeneration, also can cause a large amount of pollutions to environment.Therefore, the technics of reclaim of plastic waste utilization has caused people's extensive attention as a major issue that needs to be resolved hurrily.
The technics of reclaim of plastic waste Study on Technology is mainly reflected in two aspects.
The one, with the waste or used plastics energy, comprise and utilize heat energy that its burning produces and its catalytic pyrolysis is become gasoline equal energy source product.Many western developed countries mainly are the heat energy [R.J.Ehring, Munich.Plastics Recycling, New York, 1992] that utilizes its burning to produce to the technics of reclaim of plastic waste utilization.This respect technical research mainly concentrates on aspects such as waste or used plastics early time treatment equipment, later stage burning facility and heat energy trans-utilization equipment.Incinerating method has saved waste or used plastics and miscellaneous work such as has separated in earlier stage, but mass disposal waste or used plastics and house refuse, but equipment investment is bigger, and cost is higher.It is exactly by catalyst that the waste or used plastics catalytic pyrolysis is become gasoline equal energy source product, and at high temperature its catalytic pyrolysis is become olefines fuel oil [topaz favour etc., macromolecule circular, 62 pages of 2000 the 3rd phases].
The 2nd, with the waste or used plastics resource, promptly through chemical modification or with other material blend, make its performance reach the degree that can re-use, it is re-used as raw material, or reclaims monomer through catalytic degradation.The technology of this respect mainly comprises following several respects: (1) waste or used plastics blend capacity increasing modifying recovery technology.This class recovery technology mainly is with waste or used plastics and other plastics or material blend, improves the mechanical property of waste or used plastics, makes useful goods.As [ARC ' 96 Technol.Spark Recycl.SPE Recycl.Div such as Richardson, Annu.Recycl.Conf.Proc.3rd, 1996, p.117] with ABS and waste or used plastics blend, improved the toughness and the intensity of polyethylene (PE), polypropylene (PP) and polystyrene general-purpose plastics such as (PS), made waste or used plastics reach the purpose of utilizing again.Park etc. [Polym.Recycl.1996,2 (4): 277] have increased substantially the blend hot strength with the waste and old high density polyethylene (HDPE) of haloflex (CPE) increase-volume (HDPE)/polyvinyl chloride (PVC) blend.[New Front such as Kale, Proc.IUPAC Int.Symp.Adv.Polym.Sci.Technol.1998,2:750] waste and old PETG (PET) is doped in the new high density polyethylene (HDPE), and adding bulking agent ethylene-acrylic acid copolymer is blow molded into film, improved the non-oxidizability and the processing characteristics of density polyethylene film with high, and the film of making there is the same outward appearance of paper.The wood-fibred that [J.Appl.Polym.Sci., 1997,66:1561] such as topaz favour, Liao Bing crosses with coupling agent treatment strengthens waste polyethylene, polypropylene and polyvinyl chloride, can increase substantially the hot strength and the impact strength of goods.(2) waste or used plastics chemical modification recovery technology.Become the waste and old polystyrol chemical modification polystyrene from aggressiveness as [CN, 1163913A.1998] such as topaz favours, make the MPS aqueous microemulsion of water emulsification.Inagaki etc. [JP, 10101734.1998] make sulfonated polystyrene with the waste and old polystyrol sulfonation, it as the magnetic pipe recording material adhesive specially.Yang Zhen [Huan-jing Kexue, 1997,18 (2): 43], Woo[Catal.Today, 1998,40 (1): 121] etc. invented the method and apparatus that from waste and old PS, reclaims monomer styrene.[New Front.Proe.IUPAC Int.Symp.Adv.Polym.Sci.Technol.1998 such as Kullkarni, 2:1073] utilize ester exchange reaction, with waste and old PETG and 1,4-butanediol, 1,6-hexylene glycol etc. carries out ester exchange, can be made into the poly-terephthalic acids alkylene of high added value.Gebauer etc. [Kunststoffe, 1998,88 (2): 228] utilize degradation reaction, and waste polyolefine class waste plastics is made paraffin, and made paraffin melting point is at 50 ℃～58 ℃, and contain side chain seldom.(3) others.Tsuji etc. [Semento Konkurito Ronbunshu, 1997,51:524] wherein contain 80% thermoplasticity waste or used plastics with the build concrete that waste plastics is made, and have the thermoplasticity of adding.Nosker etc. [WO, 9808896.1998] make the railway bed support fitting to waste and old high density polyethylene (HDPE) and glass fibre coextrusion, have very high intensity and modulus.Dehlig etc. [Semento Konkurito Ronbunshu, 1997,51:524] make construction cement deckle board with waste plastics, glass fibre and bonding jumper blend moulding, are promoted the use of widely in Germany.Shimano etc. [Proc.Am.Soc.Compos.Tech.Conf, 1997,12th:985] are cut into thin waste plastics plate or plastics phone card fibrous, then they are filled in the cement concrete, can obviously improve the bending strength of cement concrete.Wen Xinxiang etc. [CN, 1143127.1997] make door and window for building with waster terylene, useless high density polyethylene (HDPE), glass fibre and adhesive blend, and this door and window has splendid corrosion resistance and intensity preferably, but poor toughness.
Although researched and developed so many technology that respectively have its characteristics to can be used for the technics of reclaim of plastic waste utilization, and some of them have produced good economic benefit, still in practical application, on the whole, still there is such or such shortcoming to some extent in existing technics of reclaim of plastic waste technology.As some chemical recovery methods, particularly by the method for chemical method with waste polymer macromolecular cleavage acquisition micromolecular compound, its removal process complexity, the expense height, productive rate is low; Incinerating method not only equipment investment is big, will form waste to resource, and only is applicable to inflammable plastics; Directly the method by pulverizing, screening, utilize although simply be suitable for, can only be made low value-added product.In addition, cracking prepares little molecular method and incinerating method also can discharge the harmful three wastes product, causes environmental pollution.
Three, summary of the invention
The objective of the invention is the deficiency at prior art, a kind of method of utilizing the waste and old thermoplastic of in-situ micro-fibril recovery is provided, the removal process of this method is pollution-free, reclaims product added value height, can use in the field of requirements at the higher level.
The method of utilizing the waste and old thermoplastic of in-situ micro-fibril recovery provided by the invention is characterized in that with weight portion being that 60～95 parts the waste and old general-purpose plastics of thermoplasticity, 5～40 parts the waste and old engineering plastics of thermoplasticity are undertaken by following processing step and condition:
(1) drying will clean after the processing the waste and old engineering plastics of thermoplasticity 80～120 ℃ dry 8～24 hours down, control moisture content＜0.01%;
(2) mixing is just stirred the waste and old engineering plastics of the cooled thermoplasticity of drying at normal temperatures by proportioning with the waste and old general-purpose plastics of thermoplasticity and is mixed;
(3) melting mixing is extruded the material that will be just mixes to place draw ratio is 25～35 extruder melting mixing and extrude 175～280 ℃ of extrusion temperatures, 260～280 ℃ of die temperatures, 50～200 rev/mins of extruder screw rotating speeds;
(4) the material bar that will extrude that stretches stretches under normal temperature air, and draw ratio is controlled to be 1～50;
(5) forcing material bar after cooling will stretch to immerse water temperature is to force to cool off in 0～20 ℃ the cooling bath;
(6) pelletizing cooled material bar is through the pelleter pelletizing.
The present invention is divided into two classes with thermoplastic, it is the waste and old general-purpose plastics of the low thermoplasticity of melt processing temperature, the waste and old engineering plastics of the thermoplasticity that melt processing temperature is high, and both pairings are processed by " melt extruding-hot-stretch-quenching " provided by the invention method according to a certain percentage, in process, the waste and old engineering plastics of the thermoplasticity that melt processing temperature is high original position under shearing and tensile force field action forms the fento of micron order or submicron order, and by quick cooling fento is preserved, obtaining final products of the present invention---in-situ micro-fibril strengthens toughness reinforcing recovery plastic alloy (in-situmicrofiber reinforced and toughened recycled plastic alloys).Because the fento that in-situ micro-fibril strengthens in the toughness reinforcing recovery plastic alloy can play the humidification of similar macroscopic fibres in fibre reinforced composites, thereby make the combination property that reclaims plastic product, particularly mechanical property and heat resistance significantly improve, the also alternative common engineering plastics of the product that has (as ABS) use, and become a kind of high-performance, high value added product.
For boundary strength, the effect of stable phase form that increases waste and old general-purpose plastics of thermoplasticity and the waste and old engineering plastics of thermoplasticity, the present invention also can add weight portion when just mixing be 0～10 part interface modifier.Interface modifier is selected at least a in ethylene-vinyl acetate copolymer, maleic anhydride grafted polyethylene and the ethylene propylene diene rubber for use, and the weight percent content of vinylacetate should be 7～30% in the used ethylene-vinyl acetate copolymer.
The used waste and old general-purpose plastics of thermoplasticity of the present invention is at least a in polyethylene, polypropylene, the polystyrene, preferably polyethylene, polypropylene.
The used waste and old engineering plastics of thermoplasticity of the present invention are at least a in PETG, polybutylene terephthalate (PBT), polyamide, Merlon, the polyphenylene sulfide.
Method provided by the invention can adopt general device of plastic processing to implement, and employed capital equipment is single screw extrusion machine or double screw extruder, flat and mouth mould and draw-gear that runner seamlessly transits.
Plastic shaping method moulding various products such as the in-situ micro-fibril that obtains with the inventive method strengthens toughness reinforcing recovery plastic alloy can be with injection moulding, extrude, compacting are as plastic delivery hose, electric elements, auto-parts etc.The basic demand of moulding is: need before the processing and forming material is carried out drying, baking temperature is 80～100 ℃, and the time is 8～18 hours, if adopt vacuum be-0.040～-the vacuum drying oven drying of 0.08Mpa, then drying time desirable lower bound, but need 8 hours at least; The processing and forming maximum temperature must be controlled at below 220 ℃, to guarantee that in molding process the waste and old engineering plastics fento of the thermoplasticity that established processing temperature is high is not melted, and still can be present in the material with fibre morphology.
The present invention has the following advantages:
1, reclaim simple, the enforcement easily of technology, less demanding to equipment, production cost is lower, promotes easily.
2, raw material sources extensively, be easy to get, cheap, both solved the waste or used plastics problem of environment pollution caused, make resource obtain the regeneration of high added value again.
3, do not produce three wastes in the production process, belong to cleaning, greenization production method environment and human body harmful.
4, widely applicable, the waste or used plastics of most kinds all can adopt this technology to recycle.
5, owing to original position in process has formed fortifying fibre, making has product combination property height than application fields.Be mainly reflected in following aspect:
(1) in-situ micro-fibril strengthens toughness reinforcing recovery plastic alloy and has good workability, can be the same as thermoplastic, and by injection moulding, the method processing and forming such as extrude, more than the production efficiency height of traditional macro fiber-reinforced resin matrix compound material.
(2) wild phase is soft thermoplastic fento, friction, wearing and tearing to equipment in the process are little, overcome macroscopic fibres reinforced composites such as glass fibre shortcoming big in molding process, thereby can prolong the service life of contour machining equipment the wearing and tearing of equipment.
(3) in-situ micro-fibril strengthens toughness reinforcing recovery plastic alloy and has good comprehensive performances, and higher mechanical strength, hear resistance and other physical and mechanical properties can be widely used in fields such as plastic conduit, household electrical appliance, automobile and motorcycle, electric elements.
Four, description of drawings
Fig. 1 strengthens the electron scanning micrograph of toughness reinforcing recovery plastic alloy for embodiment 1 gained in-situ micro-fibril; Fig. 2 strengthens the electron scanning micrograph of toughness reinforcing recovery plastic alloy for embodiment 5 gained in-situ micro-fibrils; Fig. 3 strengthens the electron scanning micrograph of toughness reinforcing recovery plastic alloy for embodiment 8 gained in-situ micro-fibrils; Fig. 4 strengthens the electron scanning micrograph of toughness reinforcing recovery plastic alloy for embodiment 10 gained in-situ micro-fibrils; Fig. 5 strengthens the electron scanning micrograph of toughness reinforcing recovery plastic alloy for embodiment 11 gained in-situ micro-fibrils; Fig. 6 strengthens the electron scanning micrograph of toughness reinforcing recovery plastic alloy for embodiment 12 gained in-situ micro-fibrils.
Five, the specific embodiment
Providing embodiment below is to specifically describe of the present invention; be necessary to be pointed out that at this following examples only are used for that the present invention is further illustrated; can not be interpreted as limiting the scope of the invention; this art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
Embodiment 1～12
(1) dry at first with clean in the table one the waste and old engineering plastics component of thermoplasticity selected for use after handling 80～120 ℃ dry 8～24 hours down, control moisture wherein is below 0.01%.
(2) mixing is just stirred the waste and old engineering plastics of the cooled thermoplasticity of drying at normal temperatures by proportioning with the waste and old general-purpose plastics of thermoplasticity and is mixed, or add a certain amount of interface modifier again and stir at normal temperatures and mix, if the waste and old engineering plastics of the thermoplasticity of selecting for use contain PETG, polybutylene terephthalate (PBT), also can add catalyst, embodiment 5 and 8 catalyst that add are dibutyltin oxide;
(3) melting mixing is extruded the material that will be just mixes to place draw ratio is 25, mouth mould inlet is 45 degree, flow channel length is a melting mixing and extruding in 10～20 millimeters the extruder, the extruder barrel temperature is 175～280 ℃, die temperature is 260～280 ℃, and the screw speed of extruder is 50～200 rev/mins;
(4) the material bar that will extrude that stretches carries out hot-stretch under normal temperature air, and draw ratio is controlled to be 1～50;
(5) forcing cooling that the material bar behind the drawn is immersed water temperature is to force cooling in 0～20 ℃ the bosh;
(6) pelletizing cooled material bar is through the pelleter pelletizing.
Table one
| Embodiment | Waste and old general-purpose plastics | Waste and old engineering plastics | Interface modifier and catalyst |
| ???1 | PE:85 part | PET:15 part | |
| ???2 | PE:85 part | PET:15 part | EVA:3 part |
| ???3 | PE:75 part | PA66:15 part; PET:10 part | MAHgPE:5 part |
| ???4 | PE:75 part | PC:10 part | EVA:5 part |
| ???5 | PP:90 part | PET:10 part | EVA:3 part; DBTO:0.5 part |
| ???6 | PP:75 part | PA6:15 part; PC:10 part | MAHgPE:5 part |
| ???7 | PP:80 part | PC:20 part | |
| ???8 | PE:30 part; PP:40 part | PET:10 part; PC:15 part PA6:5 part | EVA:4 part; MAHgPE:2 part; DBTO:0.5 part; EPDM:2 part |
| ???9 | PE:40 part; PP:30 part | PA66:30 part | |
| ???10 | PE:40 part; PP:30 part | PET:20 part; PA66:10 part | |
| ???11 | PE:30 part; PP:45 part | PET:10 part; PC:15 part | EVA:2.5 part; MAHgPE:2 part EPDM:5 part |
| ???12 | PE:20 part; PP:50 part | PET:10 part; PC:15 part PA6:5 part | EVA:2.5 part; MAHgPE:2 part |
Annotate: PE is a polyethylene in the table; PP is a polypropylene; PET is a PETG; PA is a polyamide; PC is a Merlon; EVA is an ethylene-vinyl acetate copolymer; MAHgPE is a maleic anhydride grafted polyethylene; DBTO is a dibutyltin oxide; EPDM is an ethylene propylene diene rubber.
Strengthen the physical and mechanical properties of toughness reinforcing recovery plastic alloy for the in-situ micro-fibril of investigating the present invention's preparation, the in-situ micro-fibril of gained is strengthened toughness reinforcing recovery plastic alloy place injection machine, Shooting Technique condition injection moulding routinely becomes GB11997-89 specified standard test bars and carries out following performance test:
Tensile property: press the test of GB1040-79 regulation, rate of extension is 50 millimeters/minute;
Impact strength: press the test of GB1843-89 regulation, span is 40 millimeters;
Heat distortion temperature (Vicat softening point): press the test of GB1634-79 regulation;
Table two is the part in-situ micro-fibril and strengthens toughness reinforcing recovery plastic alloy and pure polyolefin and general engineering plastic ABS some performance comparison according to above-mentioned method of testing test.
Also adopt SEM that the form that prepared part in-situ micro-fibril strengthens toughness reinforcing recovery plastic alloy is observed in addition, photo is seen accompanying drawing.
Table two
| Description of materials | Hot strength (MPa) | Impact strength (kJ/M 2) | Vicat softening point (℃) | Stretch modulus (MPa) |
| Pure PE material | ????19.5 | ??15.0 | ????126 | ????900 |
| Pure PP material | ????33.6 | ??12.5 | ????142 | ????1209 |
| Embodiment 2 products | ????32.5 | ??5.6 | ????131 | ????1457 |
| Embodiment 3 products | ????34.6 | ??5.8 | ????133 | ????1564 |
| Embodiment 6 products | ????42.3 | ??4.6 | ????144 | ????1768 |
| Embodiment 8 products | ????44.1 | ??4.9 | ????145 | ????1879 |
| Embodiment 10 products | ????40.1 | ??4.1 | ????136 | ????1689 |
| Embodiment 12 products | ????46.2 | ??4.9 | ????136 | ????1736 |
Claims (6)
1. a method of utilizing the waste and old thermoplastic of in-situ micro-fibril recovery is characterized in that with weight portion be 60～95 parts the waste and old general-purpose plastics of thermoplasticity, 5～40 parts the waste and old engineering plastics of thermoplasticity, is undertaken by following processing step and condition:
(1) drying will clean after the processing the waste and old engineering plastics of thermoplasticity 80～120 ℃ dry 8～24 hours down, control moisture content＜0.01%;
(2) mixing is just stirred the waste and old engineering plastics of the cooled thermoplasticity of drying at normal temperatures by proportioning with the waste and old general-purpose plastics of thermoplasticity and is mixed;
(3) melting mixing is extruded the material that will be just mixes to place draw ratio is 25～35 extruder melting mixing and extrude 175～280 ℃ of extruder barrel temperature, 260～280 ℃ of die temperatures, 50～200 rev/mins of extruder screw rotating speeds;
(4) the material bar that will extrude that stretches carries out hot-stretch under normal temperature air, and draw ratio is controlled to be 1～50;
(5) forcing material bar after cooling will stretch to immerse water temperature is to force to cool off in 0～20 ℃ the cooling bath;
(6) pelletizing cooled material bar is through the pelleter pelletizing.
2. the method for utilizing the waste and old thermoplastic of in-situ micro-fibril recovery according to claim 1 is characterized in that also can adding weight portion and is 0～10 part interface modifier when just mixing.
3. the method for utilizing the waste and old thermoplastic of in-situ micro-fibril recovery according to claim 2 is characterized in that used interface modifier is at least a in ethylene-vinyl acetate copolymer, maleic anhydride grafted polyethylene and the ethylene propylene diene rubber.
4. the method for utilizing the waste and old thermoplastic of in-situ micro-fibril recovery according to claim 3, the weight percent content that it is characterized in that vinylacetate in the used ethylene-vinyl acetate copolymer is 7～30%.
5. according to claim 1 or 2 or the 3 or 4 described methods of utilizing the waste and old thermoplastic of in-situ micro-fibril recovery, it is characterized in that the waste and old general-purpose plastics of used thermoplasticity is at least a in polyethylene, polypropylene, the polystyrene.
6. according to claim 1 or 2 or the 3 or 4 described methods of utilizing the waste and old thermoplastic of in-situ micro-fibril recovery, it is characterized in that the waste and old engineering plastics of used thermoplasticity are at least a in PETG, polybutylene terephthalate (PBT), polyamide, Merlon, the polyphenylene sulfide.
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| CN100441627C (en) * | 2005-03-23 | 2008-12-10 | 中山大学 | Microfiber technology process of preparing nanometer composite inorganic particle/polymer material |
| CN101863632A (en) * | 2010-06-03 | 2010-10-20 | 朱成锁 | Process for prolonging service life of roads |
| CN102532831A (en) * | 2012-02-22 | 2012-07-04 | 东莞市拓展实业有限公司 | Method for preparing ABS (Acrylonitrile-Butadiene-Styrene)/PET (Polyethylene Terephthalate) alloy material by using in-situ fiber forming method |
| CN103665721A (en) * | 2013-12-04 | 2014-03-26 | 中塑联新材料科技湖北有限公司 | Modifier for regenerating and processing hybrid waste plastic bottle/barrel/kettle materials and usage method |
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| CN103897205A (en) * | 2014-04-02 | 2014-07-02 | 四川大学 | Hydrophilic modification master batch on surface of polystyrene product and preparation method of master batch |
| CN106497057A (en) * | 2016-09-21 | 2017-03-15 | 沈阳化工大学 | A kind of isomerism cross-linking method of crosslinking agent of structure containing Sakyamuni is modified to reclaim PPS and preparation method thereof |
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2003
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| CN100441627C (en) * | 2005-03-23 | 2008-12-10 | 中山大学 | Microfiber technology process of preparing nanometer composite inorganic particle/polymer material |
| CN101863632A (en) * | 2010-06-03 | 2010-10-20 | 朱成锁 | Process for prolonging service life of roads |
| CN102532831A (en) * | 2012-02-22 | 2012-07-04 | 东莞市拓展实业有限公司 | Method for preparing ABS (Acrylonitrile-Butadiene-Styrene)/PET (Polyethylene Terephthalate) alloy material by using in-situ fiber forming method |
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| CN103665620A (en) * | 2013-12-04 | 2014-03-26 | 中塑联新材料科技湖北有限公司 | Modifier for regeneration processing of mixed waste plastic tube material and usage method thereof |
| CN103665621A (en) * | 2013-12-04 | 2014-03-26 | 中塑联新材料科技湖北有限公司 | Modifier for regeneration processing of mixed waste plastic plate / sheet material and usage method thereof |
| CN103665720A (en) * | 2013-12-04 | 2014-03-26 | 中塑联新材料科技湖北有限公司 | Modifier for generating and processing hybrid waste plastic net/wire/thread materials and usage method |
| CN103665722A (en) * | 2013-12-04 | 2014-03-26 | 中塑联新材料科技湖北有限公司 | Modifier for regeneration processing of mixed waste plastic foil / bag material and usage method thereof |
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| CN103878901A (en) * | 2014-03-27 | 2014-06-25 | 苏州益群模具有限公司 | Smelting process for injection molding material |
| CN103897205A (en) * | 2014-04-02 | 2014-07-02 | 四川大学 | Hydrophilic modification master batch on surface of polystyrene product and preparation method of master batch |
| CN106497057A (en) * | 2016-09-21 | 2017-03-15 | 沈阳化工大学 | A kind of isomerism cross-linking method of crosslinking agent of structure containing Sakyamuni is modified to reclaim PPS and preparation method thereof |
| CN114106464A (en) * | 2021-12-27 | 2022-03-01 | 镇江市元润电子有限公司 | Production process of green environment-friendly modified polypropylene plastic particles |
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