CN102350794B - Method for preparing polyolefin-based barrier material product - Google Patents
Method for preparing polyolefin-based barrier material product Download PDFInfo
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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, say that more specifically apparatus has the polymer of high obstructing performance to improve polyolefin barrier property, prepares the method for plastic products.
Background technology
Along with the emergence of China's plastics package industry, because its good processing characteristics, mechanical property and light weight be inexpensive etc., feature is widely used as packing barrier material to the polyolefin such as polyethylene, polypropylene.Polyolefin is non-polar polymer, and water and polar solvent are had to excellent barrier properties, but poor to the barrier property of the non-polar gas such as oxygen and oil product and solvent.Therefore in actual use, polyolefine material usually can not meet our demand, and we need to carry out blending and modifying to it with the polymer that some have excellent barrier properties to non-polar gas and solvent, to improve polyolefinic materials with high barrier property.As everyone knows, the barrier property of blend polymer is closely related with the morphosis of its obstruct phase.As a rule, intercepting the island structure that is mutually spherical improves not obvious to the barrier property of material.Be alternatively successive layers shape and distribute when polyolefin intercepts phase material, or intercept sheet when distribution that is mutual stack in polyolefin substrate, can make the barrier property of blend increase substantially.Front a kind of morphosis is the barrier property that improves mutually material by forcing little molecule to see through the extremely low obstruct of infiltration coefficient, and then a kind of form improves barrier property by extending micromolecular the evolving path.
At present, prepare the method that this obstruct is the polymer barrier composite goods of alternatively successive layers shape or parallel sheet structure distribution mutually and mainly contain lower four kinds:
Extrude blend blow molding process: this process can make barrier polymer form laminated structure at extrusion-blown modling process situ, but processing conditions is had to extremely harsh requirement, as temperature, blow-up ratio and the cooling velocity of the mouth type of mould of two component proportionings and ratio of viscosities, processing temperature, screw speed and shaping area and gap, mouthful mould all can affect the morphosis that intercepts phase in goods, thereby affect the barrier property of material.
Multilayer dry type complex technique: this technique is to utilize compatilizer that several films are bonded together and make laminated film.Its structure normally skin is BOPP (biaxial tension PP), BOPET (biaxial tension PET), and intermediate layer is PA, PVDC, EVOH or aluminium foil, and in heat, sealing is CPP (curtain coating PP), if without the high temperature resistant PE that also can use.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 process, and the smell of adhesive used is large, large to environment and healthy harm, and expensive, and cost is high, and therefore people tend to utilize coextru-lamination technology gradually.
Coextru-lamination technology: this technology is divided into again two kinds of the multi-layer co-extruded and microbedding coextrusion of tradition.Tradition is multi-layer co-extruded is the technology of the moulding composite article developed the sixties in 20th century, it directly adopts plastic raw materials of more than two kinds, make respectively after every kind of plastics fusion plastification by several extruders, enter in same mouthful of mould and (or pass through distributor, inlet port mould after the plastics that each extruder is supplied with converge), then through further processing processing, make multi-layer compound film.It is usually used in preparing the continuous stratiform composite product that two or more polymer superpose.But more than three extruder of traditional multi-layer co-extruded needs, equipment and a mouthful mould complexity, invest highly, and floor space is large, and the number of plies is more, and this problem is more outstanding.
If only need to prepare the alternately laminar composite goods of stack of 2 kinds of polymerizations, adopt emerging microbedding coextrusion just can avoid this problem.Microbedding coextrusion only needs two extruders.Two kinds of polymer add from two extruders respectively, and two strands of polymer melts enter layering superpositing unit after junction station converges, the cutting-unsteady flow-superimposed effect of the runner by layering superpositing unit force two fluid streams alternately stack form continuous layer structure.The method can be prepared the laminar composite goods of even nano level tens to several thousand layers of micron.
But the multi-layer co-extruded and microbedding coextrusion of tradition has a common limitation, that is exactly can only be for the preparation of the goods of the 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 prepared by mold pressing, injection moulding, blowing or extrusion molding, and these traditional forming methods cannot provide enough strong pressure field, stress field and velocity field, be difficult to obtain desirable layer structure by original position method of formation.
For the disadvantage of preparing above polyolefin-based barrier material method, we by microbedding coextrusion technology and mold pressing, injection moulding, blowing, the processing molding method such as extrude and combine, adopt two-step method to prepare polyolefin-based barrier material.The method takes full advantage of the effective control action of microbedding coextrusion technology to lamellar morphology, and mold pressing, injection moulding, blowing, the feature that processing molding method can be prepared complicated shape goods such as extrudes.
Summary of the invention
The object of the invention is for the present situation of preparing at present polyolefin-based barrier material product method, a kind of new method of preparing polyolefin-based barrier material product is provided, prepares to solve prior art that polyolefin-based barrier material product kind is single, the problem of simple shape.
The method of preparing polyolefin-based barrier material product disclosed by the invention, its substance is, first prepare the continuous stratified material of micron order polyolefin layer and layer of barrier polymer alternative arrangement with microbedding co-extrusion device, then these continuous stratified materials are carried out to granulation, granule size is controlled voluntarily.The barrier polymer layer thickness forming due to microbedding co-extrusion is micron order, and granule size after granulation is grade, and therefore the obstruct after granulation still has great draw ratio mutually.Next is utilize mold pressing, injection moulding, blowing or the manufacturing process such as extrude, at specific temperature, microbedding coextrusion pellet is being carried out to machine-shaping goods, thereby obtains the polyolefin-based barrier material product of the high obstructing performance with complicated shape.
The method of preparing polyolefin-based barrier material product disclosed by the invention, its concrete technical scheme comprises the following steps:
(1) barrier polymer that polyolefin and fusing point are greater than at least 10 DEG C of polyolefin fusing points drops into respectively the two extruders of microbedding co-extrusion equipment, through melting, conflux, cutting, unsteady flow, superimposed, extrude the continuous stratiform sheet material or the film that make polyolefin and barrier polymer multilayer alternative arrangement;
(2) continuous stratiform sheet material or the film comminutor of multilayer alternative arrangement step (1) being made are processed into microbedding coextrusion pellet;
(3) adopt mold pressing, injection moulding, blowing or extrusion way to carry out product molding microbedding coextrusion pellet, product molding temperature is between polyolefin and the fusing point of 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; Be the polymer that fusing point is greater than at least 10 DEG C of polyolefin fusing points as the barrier polymer that intercepts phase, concrete optional from polyamide (nylon), polyester, ethylene-vinyl alcohol copolymer and polyvinylidene chloride.Generally select one wherein as intercepting phase.As the polyolefin of matrix phase with as the barrier polymer content ratio that intercepts phase, being not less than 50% scope can be combined in polyolefin mass content.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 Research of Grafting Malaic Anhydride Onto Polyethylene, or polypropylene grafted maleic anhydride.
In technique scheme, the laminated structure generation phase that the microbedding coextrusion technology adopting is barrier polymer, polyolefin and barrier polymer drop into respectively the two extruders of microbedding co-extrusion equipment, by changing the number of layering unit and the rotating speed of screw rod, can regulate in 0.001mm-0.1mm scope the bed thickness of barrier polymer, can be processed into again the microbedding coextrusion pellet of different size by comminutor due to microbedding coextrusion product sheet material or film, the length and width size of microbedding coextrusion pellet is generally 1-4mm, regulate thereby can arrive easily the object that intercepts phase draw ratio.
In technique scheme, microbedding coextrusion pellet moulded products can adopt mold pressing, injection moulding, blowing or the method such as extrude, in the process of machine-shaping goods, forming temperature can be between polyolefin and the fusing point of barrier polymer, or at the fusing point place of barrier polymer, or on the fusing point of barrier polymer.Be micron order owing to intercepting phase bed thickness, even if not melting also has machinability, this original laminated structure that just intercepts phase for carry out moulding reservation under barrier polymer fusing point provides may.The optimal process temperature difference that different forming methods adopts.Such as in the time being shaped to compression molding, optimum processing temperature is between two melting point polymers, because now barrier polymer does not have melting, can make its original sheet structural integrity forming and remain in microbedding coextrusion; In the time being shaped to micro-injection mo(u)lding, on the fusing point that best processing temperature is barrier polymer, although because now barrier polymer melting, but still may keep laminated structure or large scale aggregation and not be dispersed being bead, further be stretched under the effect of injection moulding shearing force subsequently.
In technique scheme, the microbedding coextrusion pellet using in the material using in microbedding co-extrusion and processing and forming all needs dry processing, is dried to relative moisture content < 0.02%.
The method of preparing polyolefin barrier material product disclosed by the invention, is characterized in microbedding coextrusion technology and mold pressing, injection moulding, blowing, the processing molding method such as extrudes and combine, and prepares the goods of polyolefin-based barrier material.Because microbedding coextrusion can be controlled the lamellar morphology structure and the draw ratio that intercept phase effectively, and the goods of conventional moulded, injection moulding, blowing or extrusion molding have diversity.Therefore any processing mode in microbedding coextrusion and the latter is combined, both made up product type prepared by microbedding coextrusion single, solved again conventional moulded, injection moulding, blowing or extruded the shortcoming of more difficult formed in situ goods sheet blend.
Experimental result shows, compared with conventional method, polyolefin barrier material prepared by the present invention has parallel laminated structure, the laminated structure that intercepts the high length-diameter ratio of phase can significantly extend micromolecular the evolving path, thereby under the prerequisite that reaches same barriering effect, significantly reduce the consumption of barrier polymer, saved cost.And the mechanical property of material is improved.
The present invention has following features and advantage:
1. on selecting, raw material only requires that the fusing point of barrier polymer is greater than polyolefinic fusing point more than 10 DEG C.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 point of barrier polymer distributes in the form of sheets in polyolefin substrate.
4. the present invention can also, under the prerequisite of the same barriering effect of guarantee, significantly reduce the consumption of barrier polymer, thereby reduce costs.
5. the present invention is compared with conventional dry MULTILAYER COMPOSITE, in production process, can not produce stimulation or poisonous gas, health environment-friendly, cost is lower.
Detailed description of the invention
By the following examples the present invention is further described specifically.Be necessary to be pointed out that at this following examples are only for the present invention is described further; 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.
Constituent content umber or percentage in following each embodiment are mass content umber or percentage except special instruction.
Embodiment 1
High density polyethylene (HDPE), nylon 6 and Research of Grafting Malaic Anhydride Onto Polyethylene mass ratio are 70: 25: 5, Research of Grafting Malaic Anhydride Onto Polyethylene adds an extruder in microbedding co-extrusion equipment together with nylon 6, process through microbedding co-extrusion and pellet the microbedding coextrusion pellet obtaining, length and width are 2mm, in microbedding coextrusion pellet, the thickness of 6 of nylon is 0.01mm, forming method is compression molding, and when forming temperature is 200 DEG C, the oxygen permeability coefficient of goods is 2.7cm
3cm10
-16/ cm
2pas, the goods of preparing than commonsense method are compared, 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 adds an extruder in microbedding co-extrusion equipment together with polypropylene grafted maleic anhydride, process through microbedding co-extrusion and pellet the microbedding coextrusion pellet obtaining, length and width are 4mm, in microbedding coextrusion pellet, the thickness of ethylene-vinyl alcohol copolymer sheet is 0.02mm, forming method is injection moulding, and when forming temperature is 220 DEG C, the oxygen permeability coefficient of goods is 3.2cm
3cm10
-16/ cm
2pas, the goods of preparing than commonsense method are compared, 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 Research of Grafting Malaic Anhydride Onto Polyethylene is 70: 25: 10, ethylene-vinyl alcohol copolymer adds an extruder in microbedding co-extrusion equipment together with Research of Grafting Malaic Anhydride Onto Polyethylene, process through microbedding co-extrusion and pellet the microbedding coextrusion pellet obtaining, length and width are 1mm, in microbedding coextrusion pellet, the thickness of ethylene-vinyl alcohol copolymer sheet is 0.005mm, forming method is blow molding, when forming temperature is 230 DEG C, the oxygen permeability coefficient of goods is 1.7cm
3cm10
-16/ cm
2pas, the goods of preparing than commonsense method are compared, 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 adds an extruder in microbedding co-extrusion equipment together with polypropylene grafted maleic anhydride, process through microbedding co-extrusion and pellet the microbedding coextrusion pellet obtaining, length and width are 2mm, in microbedding coextrusion pellet, the thickness of PETG sheet is 0.01mm, forming method is injection moulding, and when forming temperature is 250 DEG C, the oxygen permeability coefficient of goods is 6.7cm
3cm10
-16/ cm
2pas, the goods of preparing than commonsense method are compared, 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 Research of Grafting Malaic Anhydride Onto Polyethylene is 70: 22: 8, PETG adds an extruder in microbedding co-extrusion equipment together with Research of Grafting Malaic Anhydride Onto Polyethylene, process through microbedding co-extrusion and pellet the microbedding coextrusion pellet obtaining, length and width are 3mm, in microbedding coextrusion pellet, the thickness of PETG sheet is 0.005mm, forming method is extrusion molding, when forming temperature is 250 DEG C, the oxygen permeability coefficient of goods is 3.3cm
3cm10
-16/ cm
2pas, the goods of preparing than commonsense method are compared, 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 Research of Grafting Malaic Anhydride Onto Polyethylene is 70: 25: 5, metallocene PE adds an extruder in microbedding co-extrusion equipment together with Research of Grafting Malaic Anhydride Onto Polyethylene, process through microbedding co-extrusion and pellet the microbedding coextrusion pellet obtaining, length and width are 4mm, in microbedding coextrusion pellet, the thickness of 6 of nylon is 0.04mm,, forming method is compression molding, when forming temperature is 180 DEG C, the oxygen permeability coefficient of goods is 9.2cm
3cm10
-16/ cm
2pas, the goods of preparing than commonsense method are compared, and barrier property has improved 85 times, and impact strength has improved 4 times.
Claims (7)
1. prepare a method for polyolefin-based barrier material product, it is characterized in that comprising the following steps:
(1) barrier polymer that polyolefin and fusing point are greater than at least 10 DEG C of polyolefin fusing points drops into respectively the two extruders of microbedding co-extrusion equipment, through melting, conflux, cutting, unsteady flow, superimposed, extrude the continuous stratiform sheet material or the film that make polyolefin and barrier polymer multilayer alternative arrangement, the compatilizer that one of polyolefin and barrier polymer contain polyolefin-based barrier material gross mass 2-20%;
(2) continuous stratiform sheet material or the film comminutor of multilayer alternative arrangement step (1) being made are processed into microbedding coextrusion pellet;
(3) adopt mold pressing, injection moulding, blowing or extrusion way to carry out product molding microbedding coextrusion pellet, product molding temperature is between polyolefin and the fusing point of 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 preparing polyolefin-based barrier material product described in claim 1, it is characterized in that described polyolefin is selected from polyethylene, polypropylene and the copolymer of the two.
3. according to the method for preparing polyolefin-based barrier material product described in 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 preparing polyolefin-based barrier material product described in claim 1, it is characterized in that described barrier polymer is selected from polyamide, polyester, ethylene-vinyl alcohol copolymer and polyvinylidene chloride.
5. according to the described method of preparing polyolefin-based barrier material product of one of claim 1 to 4, it is characterized in that polyolefin, barrier polymer for the processing of microbedding co-extrusion, and the relative moisture content of the microbedding coextrusion pellet of processing for product molding is all less than 0.02%.
6. according to the described method of preparing polyolefin-based barrier material product of one of claim 1 to 4, it is characterized in that the length and width of described microbedding coextrusion pellet are of a size of 1-4mm.
7. according to the method for preparing polyolefin-based barrier material product described in claim 5, it is characterized in that the length and width of described microbedding coextrusion pellet are of a size of 1-4mm.
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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 |
| 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 |
| 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 |
| 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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