CN102350794A - Method for preparing polyolefin-based barrier material product - Google Patents
Method for preparing polyolefin-based barrier material product Download PDFInfo
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- CN102350794A CN102350794A CN2011101637615A CN201110163761A CN102350794A CN 102350794 A CN102350794 A CN 102350794A CN 2011101637615 A CN2011101637615 A CN 2011101637615A CN 201110163761 A CN201110163761 A CN 201110163761A CN 102350794 A CN102350794 A CN 102350794A
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Abstract
The invention discloses a novel method for preparing a polyolefin-based barrier material product, which is characterized in that: a micro-layered coextrusion method is combined with the methods such as mold pressing, injection molding, blow molding or extrusion molding and the like to prepare the polyolefin-based barrier material products with different shapes. The micro-layered coextrusion can effectively control a lamellar morphological structure and a length-diameter ratio of a barrier phase, and the mold pressing, the injection molding, the blow molding or the extrusion molding has diversity, so the method not only can compensate the single type of the product which is prepared through the micro-layered coextrusion method, but also overcomes the defect that in the traditional mold pressing, the injection molding, the blow molding or the extrusion molding, a lamella blend of the product cannot be molded on an original position. The prepared polyolefin-based barrier material product has a parallel lamella structure, the lamella structure of the high aspect ratio of the barrier phase can greatly lengthen a diffusion path of small molecules, so the barrier property of the material can be greatly improved, or the consumption of the barrier polymer can be remarkably reduced on the premise of reaching the same barrier effect, and the cost can be saved. At the same time, the mechanical property of the material can be remarkably improved.
Description
Technical field
The present invention relates to a kind of technology of preparing of polymer matrix composite goods, the apparatus of saying so more specifically has the polymer of high obstructing performance to improve the polyolefin barrier property, prepares the method for plastic products.
Background technology
Along with the emergence of China's plastics package industry, characteristics are widely used as packing barrier material to polyolefin such as polyethylene, polypropylene owing to its good processing properties, mechanical property and light weight be inexpensive etc.Polyolefin is a non-polar polymer, and water and polar solvent are had excellent barrier properties, but relatively poor to the barrier property of non-polar gas such as oxygen and oil product and solvent.Therefore in actual use, polyolefine material usually can not satisfy our demand, and we need carry out blending and modifying to the polymer that non-polar gas and solvent have excellent barrier properties to it with some, to improve polyolefinic materials with high barrier property.As everyone knows, the barrier property of blend polymer is closely related with its obstruct morphosis mutually.As a rule, intercepting the island structure be spherical mutually improves not obvious to the barrier property of material.Be alternately when polyolefin intercepts phase material that the pantostrat shape distributes, or when intercepting the sheet distribution that in polyolefin substrate, is mutual superposition, the barrier property of blend increased substantially.Before a kind of morphosis be through forcing little molecule to see through the barrier property of infiltration coefficient extremely low obstruct the raising mutually material, then a kind of form improves barrier property through prolonging micromolecular the evolving path.
At present, prepare the method that this obstruct is the polymer barrier composite goods of pantostrat shape alternately or parallel sheet structure distribution mutually and mainly contain following four kinds:
Extrude the blend blow molding process: this process can make barrier polymer original position in the extrusion-blown modling process form laminated structure; But processing conditions there is extremely harsh requirement; All can influence the morphosis that intercepts in the goods mutually, thereby influence the barrier property of material like type and the gap of the mouth mould of two component proportionings and ratio of viscosities, processing temperature, screw speed and shaping area, temperature, blow-up ratio and the cooling velocity of mouthful mould.
Multilayer dry type complex technique: this technology is to utilize compatilizer that several films are bonded together to process laminated film.Its structure normally skin is BOPP (biaxial tension PP), BOPET (biaxial tension PET), and the intermediate layer is PA, PVDC, EVOH or aluminium foil, and seal is CPP (curtain coating PP) in the heat, high temperature resistantly also can use PE if need not.The barrier property of multilayer dry type laminated film is relevant with Obstruct membrane and adhesive.This technology mainly relies on the research and development of Obstruct membrane, needs post forming in the process, and the smell of used adhesive is big, and is big with healthy harm to environment, and costs an arm and a leg, and cost is high, so people tend to utilize the coextru-lamination technology gradually.
The coextru-lamination technology: this technology is divided into two kinds of tradition multi-layer co-extruded and microbedding coextrusion again.Tradition is multi-layer co-extruded to be the technology of the moulding composite article developed the sixties in 20th century; It directly adopts the plastic raw materials more than 2 kinds; After making every kind of plastics fusion plastification respectively through several extruders; Get in the same mouthful of mould and (perhaps pass through distributor; Inlet port mould after the plastics that each extruder is supplied with converge); Pass through further processed then, make multi-layer compound film.It is usually used in preparing the continuous stratiform composite product of two or more polymer stacks.But three above extruders of traditional multi-layer co-extruded needs, equipment is complicated with mouthful mould, and investment is high, and floor space is big, and the number of plies is many more, and this problem is outstanding more.
If only need prepare the alternately laminar composite goods of stack of 2 kinds of polymerizations, adopt emerging microbedding coextrusion just can avoid this problem.The microbedding coextrusion only needs two extruders.Two kinds of polymer add from two extruders respectively, and two strands of polymer melts converge the back at junction station and get into the layering superpositing unit, the cutting-unsteady flow-superimposed effect of the runner through the layering superpositing unit force two fluid streams alternately stack form continuous layer structure.The method can prepare micron even nano level tens to several thousand layers laminar composite goods.
But tradition is multi-layer co-extruded all to have a common limitation with the microbedding coextrusion, and that is exactly the goods that can only be used to prepare simple shape such as composite pipe, laminated film, sheet material, optical fiber, electric wire, cable, thereby has limited the range of application of coextrusion.In actual production; Many complex-shaped goods are through mold pressing, injection moulding, blowing or extrusion molding preparation; And these traditional forming methods can't provide enough strong pressure field, and stress field and velocity field are difficult to obtain desirable layer structure through the original position method of formation.
To the disadvantage of the polyolefin-based barrier material method of above preparation, we with microbedding coextrusion technology and mold pressing, injection moulding, blowing, processing molding method such as extrude and combine, adopt two-step method to prepare polyolefin-based barrier material.This method has made full use of the effective control action of microbedding coextrusion technology to lamellar morphology, and mold pressing, injection moulding, blowing, the characteristics that processing molding method can prepare the complicated shape goods such as extrudes.
Summary of the invention
The objective of the invention is to the present situation for preparing polyolefin-based barrier material article process at present; A kind of method of new polyolefin-based barrier material goods of preparation is provided, and the polyolefin-based barrier material goods of prior art for preparing kind is single to solve, the problem of simple shape.
The method of the polyolefin-based barrier material goods of preparation disclosed by the invention; Its substance is; At first prepare the continuous stratified material that micron order polyolefin layer and layer of barrier polymer are alternately arranged with the microbedding co-extrusion device; Then these continuous stratified materials are carried out granulation, granule size is controlled voluntarily.Because the barrier polymer layer thickness that the microbedding co-extrusion forms is a micron order, and the granule size after the granulation is the millimeter level, so the obstruct after the granulation still has great draw ratio mutually.Next is to utilize mold pressing, injection moulding, blowing or manufacturing process such as extrude and under specific temperature, microbedding coextrusion pellet is carried out the machine-shaping goods, thereby obtains having the polyolefin-based barrier material goods of the high obstructing performance of complicated shape.
The method of the polyolefin-based barrier material goods of preparation disclosed by the invention, its concrete technical scheme may further comprise the steps:
(1) polyolefin and fusing point drop into the two extruders of microbedding co-extrusion equipment respectively greater than the barrier polymer of at least 10 ℃ of polyolefin fusing points, through melting, conflux, cutting, unsteady flow, superimposed, extrude and make continuous stratiform sheet material or the film that polyolefin and barrier polymer multilayer are alternately arranged;
(2) alternately the continuous stratiform sheet material or the film of arrangement are processed into microbedding coextrusion pellet with comminutor to the multilayer that step (1) is made;
(3) microbedding coextrusion pellet is adopted mold pressing, injection moulding, blowing or extrusion way carry out product molding, the product molding temperature is between the fusing point of polyolefin and barrier polymer, or at the fusing point place of barrier polymer, or on the fusing point of barrier polymer.
In technique scheme, can be polyethylene, polypropylene and the copolymer of the two thereof as the polyolefin of matrix phase; Barrier polymer as intercepting phase is the polymer of fusing point greater than at least 10 ℃ of polyolefin fusing points, and is concrete optional from polyamide (nylon), polyester, ethylene-vinyl alcohol copolymer and polyvinylidene chloride.Generally select for use a kind of conduct wherein to intercept phase.As the polyolefin of matrix phase with as the barrier polymer content ratio that intercepts mutually, 50% the scope of being not less than in the polyolefin mass content can combination in any.In order to improve the compatibility of polyolefin and barrier polymer, can in polyolefin or barrier polymer, add the compatilizer of material gross mass 2-20%.Compatilizer can be selected polycthylene grafted maleic anhydride for use, or polypropylene grafted maleic anhydride.
In technique scheme; The microbedding coextrusion technology that is adopted is the laminated structure generation phase of barrier polymer; Polyolefin and barrier polymer drop into the two extruders of microbedding coextrusion equipment respectively; By the number of change layering unit and the rotating speed of screw rod; Can regulate the bed thickness of barrier polymer in the 0.001mm-0.1mm scope; Again because microbedding coextrusion product sheet material or film can be processed into the microbedding coextrusion pellet of different size by comminutor; The length and width size of microbedding coextrusion pellet is generally 1-4mm, regulates the purpose that intercepts the phase draw ratio thereby can arrive easily.
In technique scheme; Microbedding coextrusion pellet moulded products can adopt mold pressing, injection moulding, blowing or method such as extrude; In the process of machine-shaping goods; Forming temperature can be between the fusing point of polyolefin and barrier polymer; Or at the fusing point place of barrier polymer, or on the fusing point of barrier polymer.Because obstruct phase bed thickness is a micron order, even not fusion also has machinability, this just provides possibility under the barrier polymer fusing point, carrying out moulding and keeping the original laminated structure that intercepts phase.The different optimal process temperature that forming method adopted is different.Such as when being shaped to compression molding, optimum processing temperature is between two melting point polymers, because this moment, barrier polymer did not have fusion, remains with can making its original sheet structural integrity that in the microbedding coextrusion, forms; When being shaped to micro-injection mo(u)lding; Best processing temperature is on the fusing point of barrier polymer; Though because barrier polymer fusion this moment, but still possibly keep laminated structure or large scale aggregation and do not disperseed to be bead, subsequently under the effect of injection moulding shearing force by further stretching.
In technique scheme, the microbedding coextrusion pellet that uses in material that uses in the microbedding co-extrusion and the processing and forming all needs dried, is dried to relative moisture content＜0.02%.
The method for preparing polyolefin barrier material goods disclosed by the invention is characterized in microbedding coextrusion technology and mold pressing, injection moulding, blowing, processing molding method such as extrudes and combine, and prepares the goods of polyolefin-based barrier material.Because the microbedding coextrusion can be controlled lamellar morphology structure and the draw ratio that intercepts phase effectively, and the goods of conventional moulded, injection moulding, blowing or extrusion molding have diversity.Therefore any processing mode among microbedding coextrusion and the latter is combined, it is single both to have remedied the product type that the microbedding coextrusion prepares, and has solved conventional moulded, injection moulding, blowing again or has extruded the shortcoming of more difficult formed in situ goods sheet blend.
Experimental result shows; Compare with conventional method; The polyolefin barrier material of the present invention's preparation has parallel laminated structure; The laminated structure that intercepts the high length-diameter ratio of phase can prolong micromolecular the evolving path significantly; Thereby, practiced thrift cost reaching the consumption that significantly reduces barrier polymer under the prerequisite of same barriering effect.And the mechanical property of material is improved.
The present invention has following characteristics and advantage:
At the fusing point of only requiring barrier polymer on the material choice greater than polyolefinic fusing point more than 10 ℃.The collocation of two kinds of polymer flexibly, less demanding to ratio of component and ratio of viscosities.
2. the laminated structure form and the draw ratio that intercept phase all have controllability.
3. very convenient owing to utilizing mold pressing, injection moulding, blowing or extrusion molding to prepare different complicated shape goods; Only need more mold exchange, therefore utilize the present invention can prepare the compound barrier articles of polymer that difform minute barrier polymer distributes in the form of sheets in polyolefin substrate.
4. the present invention can also reduce the consumption of barrier polymer, thereby reduce cost under the prerequisite that guarantees same barriering effect significantly.
5. the present invention compares with the conventional dry MULTILAYER COMPOSITE, can not produce in the production process stimulation or poisonous gas, health environment-friendly, cost is lower.
The specific embodiment
Below through embodiment the present invention is further specifically described.Be necessary to be pointed out that at this following examples only are used for the present invention is done further explanation; Can not be interpreted as restriction to protection domain of the present 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.
Constituent content umber or percentage among following each embodiment are mass content umber or percentage except that specifying.
Embodiment 1
High density polyethylene (HDPE), nylon 6 and polycthylene grafted maleic anhydride mass ratio are 70: 25: 5; Polycthylene grafted maleic anhydride and nylon 6 add an extruder in the microbedding co-extrusion equipment together; Process the microbedding coextrusion pellet that obtains through microbedding co-extrusion and pellet; Length and width are 2mm; The thickness of 6 of nylon is 0.01mm in the microbedding coextrusion pellet; Forming method is compression molding, and when forming temperature was 200 ℃, the oxygen permeability coefficient of goods was 2.7cm
3Cm10
-16/ cm
2Pas compares than the goods of commonsense method preparation, and barrier property has improved 115 times.
Embodiment 2
The mass ratio of polypropylene, ethylene-vinyl alcohol copolymer and polypropylene grafted maleic anhydride is 65: 15: 20; Polypropylene and polypropylene grafted maleic anhydride add an extruder in the microbedding co-extrusion equipment together; Process the microbedding coextrusion pellet that obtains through microbedding co-extrusion and pellet; Length and width are 4mm; The thickness of ethylene-vinyl alcohol copolymer sheet is 0.02mm in the microbedding coextrusion pellet; Forming method is injection moulding, and when forming temperature was 220 ℃, the oxygen permeability coefficient of goods was 3.2cm
3Cm10
-16/ cm
2Pas compares than the goods of commonsense method preparation, and barrier property has improved 95 times, and impact strength has improved 6 times.
Embodiment 3
The mass ratio of LLDPE, ethylene-vinyl alcohol copolymer and polycthylene grafted maleic anhydride is 70: 25: 10; Ethylene-vinyl alcohol copolymer and polycthylene grafted maleic anhydride add an extruder in the microbedding co-extrusion equipment together; Process the microbedding coextrusion pellet that obtains through microbedding co-extrusion and pellet; Length and width are 1mm; The thickness of ethylene-vinyl alcohol copolymer sheet is 0.005mm in the microbedding coextrusion pellet; Forming method is blow molding; When forming temperature was 230 ℃, the oxygen permeability coefficient of goods was 1.7cm
3Cm10
-16/ cm
2Pas compares than the goods of commonsense method preparation, and barrier property has improved 90 times.
Embodiment 4
The mass ratio of polypropylene, PETG and polypropylene grafted maleic anhydride is 82: 15: 3; Polypropylene and polypropylene grafted maleic anhydride add an extruder in the microbedding co-extrusion equipment together; Process the microbedding coextrusion pellet that obtains through microbedding co-extrusion and pellet; Length and width are 2mm; The thickness of PETG sheet is 0.01mm in the microbedding coextrusion pellet; Forming method is injection moulding, and when forming temperature was 250 ℃, the oxygen permeability coefficient of goods was 6.7cm
3Cm10
-16/ cm
2Pas compares than the goods of commonsense method preparation, and barrier property has improved 70 times, and impact strength has improved 5 times.
Embodiment 5
The mass ratio of high density polyethylene (HDPE), PETG and polycthylene grafted maleic anhydride is 70: 22: 8; PETG and polycthylene grafted maleic anhydride add an extruder in the microbedding co-extrusion equipment together; Process the microbedding coextrusion pellet that obtains through microbedding co-extrusion and pellet; Length and width are 3mm; The thickness of PETG sheet is 0.005mm in the microbedding coextrusion pellet; Forming method is extrusion molding; When forming temperature was 250 ℃, the oxygen permeability coefficient of goods was 3.3cm
3Cm10
-16/ cm
2Pas compares than the goods of commonsense method preparation, and barrier property has improved 77 times, and impact strength has improved 3 times.
Embodiment 6
The mass ratio of metallocene PE, nylon 6 and polycthylene grafted maleic anhydride is 70: 25: 5; Metallocene PE and polycthylene grafted maleic anhydride add an extruder in the microbedding co-extrusion equipment together; Process the microbedding coextrusion pellet that obtains through microbedding co-extrusion and pellet; Length and width are 4mm; The thickness of 6 of nylon is 0.04mm in the microbedding coextrusion pellet,, forming method is compression molding; When forming temperature was 180 ℃, the oxygen permeability coefficient of goods was 9.2cm
3Cm10
-16/ cm
2Pas compares than the goods of commonsense method preparation, and barrier property has improved 85 times, and impact strength has improved 4 times.
Claims (10)
1. method for preparing polyolefin-based barrier material goods is characterized in that may further comprise the steps:
(1) polyolefin and fusing point drop into the two extruders of microbedding co-extrusion equipment respectively greater than the barrier polymer of at least 10 ℃ of polyolefin fusing points, through melting, conflux, cutting, unsteady flow, superimposed, extrude and make continuous stratiform sheet material or the film that polyolefin and barrier polymer multilayer are alternately arranged;
(2) alternately the continuous stratiform sheet material or the film of arrangement are processed into microbedding coextrusion pellet with comminutor to the multilayer that step (1) is made;
(3) microbedding coextrusion pellet is adopted mold pressing, injection moulding, blowing or extrusion way carry out product molding, the product molding temperature is between the fusing point of polyolefin and barrier polymer, or at the fusing point place of barrier polymer, or on the fusing point of barrier polymer.
2. according to the method for the polyolefin-based barrier material goods of the said preparation of claim 1, it is characterized in that said polyolefin is selected from polyethylene, polypropylene and the copolymer of the two.
3. according to the method for the polyolefin-based barrier material goods of the said preparation of claim 2, it is characterized in that the mass content of polyolefin in polyolefin-based barrier material is greater than 50%.
4. according to the method for the polyolefin-based barrier material goods of the said preparation of claim 1, it is characterized in that said barrier polymer is selected from polyamide, polyester, ethylene-vinyl alcohol copolymer and polyvinylidene chloride.
5. according to the method for the polyolefin-based barrier material goods of the said preparation of one of claim 1 to 4; The relative moisture content of microbedding coextrusion pellet that it is characterized in that being used for polyolefin, the barrier polymer of microbedding co-extrusion processing and be used for product molding processing is all less than 0.02%.
6. according to the method for the polyolefin-based barrier material goods of the said preparation of one of claim 1 to 4, it is characterized in that the length and width of said microbedding coextrusion pellet are of a size of 1-4mm.
7. according to the method for the polyolefin-based barrier material goods of the said preparation of claim 5, it is characterized in that the length and width of said microbedding coextrusion pellet are of a size of 1-4mm.
8. according to the method for the polyolefin-based barrier material goods of the said preparation of one of claim 1 to 4, it is characterized in that one of polyolefin and barrier polymer contain the compatilizer of polyolefin-based barrier material gross mass 2-20%.
9. according to the method for the polyolefin-based barrier material goods of the said preparation of claim 5, it is characterized in that one of polyolefin and barrier polymer contain the compatilizer of polyolefin-based barrier material gross mass 2-20%.
10. according to the method for the polyolefin-based barrier material goods of the said preparation of claim 7, it is characterized in that one of polyolefin and barrier polymer contain the compatilizer of polyolefin-based barrier material gross mass 2-20%.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102794832A (en) * | 2012-08-31 | 2012-11-28 | 江苏旭华圣洛迪建材有限公司 | Preparation process of micro-layer co-extruded WPC |
| CN102814958A (en) * | 2012-09-03 | 2012-12-12 | 四川大学 | Method for improving polyolefin gas barrier properties |
| CN103333394A (en) * | 2013-07-15 | 2013-10-02 | 四川大学 | Preparation method capable of designing polymer matrix functional film |
| CN103847198A (en) * | 2012-12-04 | 2014-06-11 | 浙江众成包装材料股份有限公司 | Propylene-based polymer multi-layer composite film, and preparation method, use and product thereof |
| CN105400053A (en) * | 2015-12-25 | 2016-03-16 | 广东威林工程塑料有限公司 | Micro permeability and low viscosity PE alloy material and preparation method thereof |
| CN104149443B (en) * | 2013-05-13 | 2016-04-20 | 浙江众成包装材料股份有限公司 | A kind of acrylic polymer containing composite tie layer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof |
| CN106832809A (en) * | 2017-01-06 | 2017-06-13 | 晋江市中辉印刷包装有限公司 | High-resistance anti-ultraviolet environment friendly PET composite soft packaging material and preparation method thereof |
| CN110938248A (en) * | 2019-12-16 | 2020-03-31 | 良和包装(浙江)有限公司 | High-barrier heat-resistant PE plastic bottle and preparation process thereof |
| CN112795120A (en) * | 2020-12-14 | 2021-05-14 | 中广核拓普（四川）新材料有限公司 | Modified polyethylene material, preparation method thereof, rat and ant prevention sheath and processing method thereof |
| CN113799286A (en) * | 2020-06-12 | 2021-12-17 | 四川大学 | Preparation method of polymer blend with controllable dispersed phase size and dimension |
| CN115028916A (en) * | 2022-06-08 | 2022-09-09 | 广州丽盈塑料有限公司 | High-barrier light plastic for plastic packaging container and preparation method thereof |
| CN115404566A (en) * | 2022-09-02 | 2022-11-29 | 江苏文明人造草坪有限公司 | Production process of high-performance mesh |
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| CN102794832A (en) * | 2012-08-31 | 2012-11-28 | 江苏旭华圣洛迪建材有限公司 | Preparation process of micro-layer co-extruded WPC |
| CN102814958A (en) * | 2012-09-03 | 2012-12-12 | 四川大学 | Method for improving polyolefin gas barrier properties |
| CN103847198A (en) * | 2012-12-04 | 2014-06-11 | 浙江众成包装材料股份有限公司 | Propylene-based polymer multi-layer composite film, and preparation method, use and product thereof |
| CN103847198B (en) * | 2012-12-04 | 2015-12-02 | 浙江众成包装材料股份有限公司 | A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof |
| CN104149443B (en) * | 2013-05-13 | 2016-04-20 | 浙江众成包装材料股份有限公司 | A kind of acrylic polymer containing composite tie layer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof |
| CN103333394A (en) * | 2013-07-15 | 2013-10-02 | 四川大学 | Preparation method capable of designing polymer matrix functional film |
| CN103333394B (en) * | 2013-07-15 | 2015-12-09 | 四川大学 | A kind of preparation method designing polymer-based carbon functional membrane |
| CN105400053B (en) * | 2015-12-25 | 2018-06-19 | 广东威林工程塑料有限公司 | A kind of micro- permeability low viscosity PE alloy materials and preparation method thereof |
| CN105400053A (en) * | 2015-12-25 | 2016-03-16 | 广东威林工程塑料有限公司 | Micro permeability and low viscosity PE alloy material and preparation method thereof |
| CN106832809A (en) * | 2017-01-06 | 2017-06-13 | 晋江市中辉印刷包装有限公司 | High-resistance anti-ultraviolet environment friendly PET composite soft packaging material and preparation method thereof |
| CN106832809B (en) * | 2017-01-06 | 2019-06-11 | 晋江市中辉印刷包装有限公司 | High-resistance anti-ultraviolet environment friendly PET composite soft packaging material and preparation method thereof |
| CN110938248A (en) * | 2019-12-16 | 2020-03-31 | 良和包装(浙江)有限公司 | High-barrier heat-resistant PE plastic bottle and preparation process thereof |
| CN113799286A (en) * | 2020-06-12 | 2021-12-17 | 四川大学 | Preparation method of polymer blend with controllable dispersed phase size and dimension |
| CN112795120A (en) * | 2020-12-14 | 2021-05-14 | 中广核拓普（四川）新材料有限公司 | Modified polyethylene material, preparation method thereof, rat and ant prevention sheath and processing method thereof |
| CN115028916A (en) * | 2022-06-08 | 2022-09-09 | 广州丽盈塑料有限公司 | High-barrier light plastic for plastic packaging container and preparation method thereof |
| CN115404566A (en) * | 2022-09-02 | 2022-11-29 | 江苏文明人造草坪有限公司 | Production process of high-performance mesh |
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