CN1511871A - Polyvinyl/montmorillonite composite separate material - Google Patents
Polyvinyl/montmorillonite composite separate material Download PDFInfo
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- CN1511871A CN1511871A CNA021590303A CN02159030A CN1511871A CN 1511871 A CN1511871 A CN 1511871A CN A021590303 A CNA021590303 A CN A021590303A CN 02159030 A CN02159030 A CN 02159030A CN 1511871 A CN1511871 A CN 1511871A
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- polyethylene
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- montmorillonite
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Abstract
The composite polyethylene/montmorillonite obstructing material consists of polyethylene in 100 portions, organic montmorillonite in 0.5-30 portions and compatilizer in 1-10 portions. The composite material is prepared with the materials and through mixing, and extruding and pelletizing in a screw extruder at 170-250 deg.c. The composite material has excellent obstructing performance, and is suitable for preparing various product via blowing, extruding, injecting or other process.
Description
Technical field: the present invention relates to a kind of composite polyethylene material, particularly relate to a kind of compound barrier material of polyethylene/montmorillonite with excellent barrier properties.
Background technology: polyethylene has good snappiness and processing characteristics, therefore, be widely used in wrapping material, according to estimates, polyethylene accounts for more than half in Plastic Packaging Materials, but poly gas barrier property is relatively poor, and people adopt the whole bag of tricks to improve the barrier property of polyethylene to gas, and main method has: 1. surface-coated, fluoridize or process for treating surface such as sulfonation; 2. multi-layer co-extruded technology; 3. blending and modifying technology.
Process for treating surface is very limited because of serious environment pollution; Multi-layer co-extruded technological investment is big, complex process, and the product cost height, this has limited the popularization of this technology equally; The blending technology counter investment is few, and production technology is simple, is particularly suitable for medium and small sized enterprises.Mainly contain PE/PA (polyethylene/nylon), PE/EVOH (polyethylene/vinyl-vinyl alcohol copolymer), PE/UHWPE obstruct systems such as (polyethylene/ultrahigh molecular weight polyethylene(UHMWPE)s) in the present blending technology, the obstruct principle of these systems is: polyethylene forms external phase in matrix material, and barrier materials such as PA, EVOH form the stratiform disperse phase in external phase, the existence of a large amount of laminate structures in the matrix material, make the diffusion path of penetrant molecule become circuitous, thereby its barrier property is improved.Even the dispersions in polyethylene such as PA or EVOH are very even in this method, but, more after a little while, are difficult to reach the ideal barrier property at content, and when content increases, mechanical property reduced greatly because its laminate structure size is bigger.
Chinese patent CN1247203A has reported a kind of preparation of barrier polyblend, use HDPE to be body material in this method, AS (vinylbenzene-acrylonitrile) is as barrier material, and HDPE-g-AS (high-density polycthylene grafted vinylbenzene-acrylonitrile), LDPE-g-AS (grafted low density polyethylene vinylbenzene-acrylonitrile) or CPE-g-AS (chlorinatedpolyethylene graft phenylethene-acrylonitrile) are as expanding material; Chinese patent CN1067702C has reported a kind of isolation-type polyolefin multicomponent composite that contains high density polyethylene(HDPE) (HDPE), ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE), viscosity modifier, interface modifier, free radical terminator, peroxide decomposer, carbon black.UHMW-PE is the high viscoelastic body of semi-solid in this patent under molten state, does not almost have flowability, and its is difficult to and HDPE melt blending, and above-mentioned patent does not relate to clay.
The matrix material that polyolefine and polynite polymerization preparation is arranged in the prior art, as the described nanoclay composite polyolefine material of patent CN1289786A (open day is April 4 calendar year 2001), but this material has only improved the intensity of material, heat-resisting, ageing resistance, and do not mention the barrier property that improves matrix material; And for example the described olefin polymerization nanometer composite material of patent CN1293692A (open day is May 2 calendar year 2001) has improved polyolefinic elongation at break, yield strength and breaking tenacity, does not also mention the barrier property that improves matrix material.
Summary of the invention: the polyethylene/montmorillonite matrix material that provides a kind of barrier property good is provided the object of the invention, and its preparation method is simple.
The present invention is a body material with polyethylene (PE), and as disperse phase, adopting anhydrides grafted polyethylene or EVA is compatilizer through the polynite of intercalation processing.
Specifically, polyethylene/montmorillonite matrix material of the present invention comprises following composition: 100 parts of polyvinyl resins (A); 0.5～30 parts of polynites (B); 1～10 part of compatilizer (C)).Above-mentioned A, B, C component number average are by weight.
As mentioned above, according to the present invention, this polyethylene composition comprises A, B, C component.
As the polyvinyl resin of A component, but the melt flow rate (MFR) of using for technical grade (MFR) is the polyvinyl resin of 0.1-20g/10min.
As the polynite of B component is organo montmorillonite through intercalation processing, and its interlayer has Na
+, Ca
2+, Mg
2+Exist etc. the interchangeability positively charged ion; The sheet interlayer spacing of polynite own is about 1 nanometer, is swollen through intercalation processing sheet interlayer spacing, and what have can reach 2.5 to 3 nanometers, and the macromole that helps polymkeric substance like this is inserted into the sheet interlayer of polynite, obtains nano composite material.At present, the domestic and external organo montmorillonite that the intercalation processing is all arranged.
Compatilizer as the C component is anhydrides grafted polyethylene or EVA (ethylene/vinyl acetate multipolymer), and anhydrides grafted polyethylene or EVA can be the polyethylene of maleic anhydride graft, EVA, acrylic anhydride grafted polyethylene or the acrylic anhydride grafted EVA of maleic anhydride graft.
The best portion rate of component A, B, C is 20: 5: 1.
If needed, the present invention also can add dispersion agent, as polyethylene wax or Poly Propylene Wax.
Obstruct principle of the present invention is: polynite is a kind of natural laminate structure, and its interlayer has Na
+, Ca
2+, Mg
2+Exist etc. the interchangeability positively charged ion, pass through intercalation processing, positively charged ion between organic ammonium salt and cheating engaging layer exchanges, the interlamellar spacing of polynite is stretched, make organ-mmt simultaneously, interaction between fused polyethylene macromolecular chain and intercalator (as the cetyl chloride ammonium) organic group can be injected the interlayer of polynite, and under the effect of shearing force, make the laminate structure of polynite be dissociated into one lamella, it is evenly distributed in the fused polyethylene matrix, reach the dispersion of nanoscale, the existence of a large amount of nano-lamellar structures in the polyethylene, make oxygen, carbonic acid gas, gas molecules such as water vapour are when passing through, and the path is full of twists and turns, greatly reduces poly gas permeation rate.Matrix material combines rigidity, the thermotolerance of inorganics with toughness, the processibility of polymkeric substance simultaneously, and performance of composites is improved greatly.
Under 170 ℃～250 ℃ conditions of processing temperature, behind above-mentioned A, B, three kinds of components of C (with other component that adds as required) uniform mixing, adopt the screw rod extruding pelletization promptly to obtain the compound barrier material of polyethylene/montmorillonite of the present invention.The temperature of forcing machine is 170-250 ℃, and screw speed is 100-300rpm.
Embodiment:
Below, with the invention will be further described with Comparative Examples in conjunction with the embodiments.But the present invention is not subjected to the restriction of embodiment content.
Embodiment 1.
100 parts of melt flow rate (MFR)s polyvinyl resin that is 2g/10min, the organo montmorillonite (commercially available getting final product) of 3 parts of intercalation processing are mixed in high speed agitator, on twin screw extruder, carry out granulation, the temperature of forcing machine is set at: 210 ℃ in a district, 220 ℃ in two districts, 215 ℃ in three districts, 210 ℃ of heads, screw speed is 240rpm, obtain barrier composite behind the granulating and drying, carry out blown film then on inflation film manufacturing machine, its performance test sees the following form.
Embodiment 2
With 100 parts of melt flow rate (MFR)s polyethylene that is 7g/10min, the organo montmorillonite of 8 parts of intercalation processing, 2 parts of maleic anhydride grafted polyethylenes, in high speed agitator, mix, on twin screw extruder, carry out granulation, other condition is with embodiment 1.
Embodiment 3.
With 100 parts of melt flow rate (MFR)s polyethylene that is 0.5/10min, the organo montmorillonite of 15 parts of intercalation processing, 4 parts of maleic anhydride graft EVA, in high speed agitator, mix, on twin screw extruder, carry out granulation, other condition is with embodiment 2.
Embodiment 4.
With 100 parts of melt flow rate (MFR)s polyethylene that is 10g/10min, the organo montmorillonite of 20 parts of intercalation processing, 5 parts of acrylic anhydride grafting EVA, in high speed agitator, mix, on twin screw extruder, carry out granulation, other condition is with embodiment 3.
Embodiment 5.
With 100 parts of melt flow rate (MFR)s polyethylene that is 7g/10min, the organo montmorillonite of 25 parts of intercalation processing, 5 parts of maleic anhydride grafted polyethylenes, in high speed agitator, mix, on twin screw extruder, carry out granulation, other condition is with embodiment 4.
Comparative Examples
Polyethylene in the Comparative Examples is 100 parts of polyethylene that melt flow rate (MFR) is 7g/10min.
Comparative Examples and embodiment 1～5 test result see the following form:
| Polyethylene (part) | Polynite (part) | Grafted polyethylene/EVA (part) | Tensile strength MPa | Elongation % | OTR oxygen transmission rate m 3·/cm 2·s·P ????a | Water vapor transmission rate (WVTR) gcm/cm 2?·s ????·Pa | |
| Comparative Examples | ??100 | ??0 | ????0 | ?11.5 | ????100 | ??1.52×10 -13 | ??1.66×10 -14 |
| Embodiment 1 | ??100 | ??3 | ????0 | ?11.2 | ????99 | ??1.26×10 -13 | ??1.26×10 -14 |
| Embodiment 2 | ??100 | ??8 | ????2 | ?10.0 | ????95 | ??1.13×10 -13 | ??1.08×10 -14 |
| Embodiment 3 | ??100 | ??15 | ????4 | ?9.0 | ????90 | ??0.94×10 -13 | ??0.86×10 -14 |
| Embodiment 4 | ??100 | ??20 | ????5 | ?8.5 | ????81 | ??0.75×10 -13 | ??0.69×10 -14 |
| Embodiment 5 | ??100 | ??25 | ????5 | ?8.0 | ????72 | ??0.61×10 -13 | ??0.56×10 -14 |
By the result in the table as can be seen, the barrier property of polyethylene composition of the present invention is better than Comparative Examples, is a kind of comparatively ideal polyethylene barrier material, and particularly effect is remarkable aspect blocking oxygen, water vapour.This material is suitable for blowing, extrude or forming method such as injection prepare have good barrier properties can product.
Claims (6)
1, the compound barrier material of a kind of polyethylene/montmorillonite is characterized in that described matrix material comprises following composition:
(A) 100 parts of polyvinyl resins (by weight)
(B) polynite 0.5-30 part (by weight)
(C) compatilizer 1-10 part (by weight)
2, the compound barrier material of polyethylene/montmorillonite according to claim 1 is characterized in that the melt flow rate (MFR) (MFR) of described polyvinyl resin (A) is 0.1-20g/10min.
3, the compound barrier material of polyethylene/montmorillonite according to claim 1 is characterized in that described polynite (B) is the organic montmorillonoid of intercalation processing.
4, the compound barrier material of polyethylene/montmorillonite according to claim 1 is characterized in that described compatilizer (C) is anhydrides grafted polyethylene or ethylene/vinyl acetate multipolymer (EVA).
5, the compound barrier material of polyethylene/montmorillonite according to claim 1 is characterized in that the best portion rate of described each component polyvinyl resin (A), polynite (B), compatilizer (C) is 20: 5: 1.
6, the compound barrier material of polyethylene/montmorillonite according to claim 1 is characterized in that this barrier material is to form through extruding pelletization after with each component blend under 170-250 ℃ again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02159030 CN1227287C (en) | 2002-12-27 | 2002-12-27 | Polyvinyl/montmorillonite composite separate material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02159030 CN1227287C (en) | 2002-12-27 | 2002-12-27 | Polyvinyl/montmorillonite composite separate material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1511871A true CN1511871A (en) | 2004-07-14 |
| CN1227287C CN1227287C (en) | 2005-11-16 |
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|---|---|---|---|
| CN 02159030 Expired - Fee Related CN1227287C (en) | 2002-12-27 | 2002-12-27 | Polyvinyl/montmorillonite composite separate material |
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|---|---|
| CN (1) | CN1227287C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318498C (en) * | 2005-04-30 | 2007-05-30 | 浙江大学 | Nano composite material of polyethylene/montorillonite clay in high density and preparation method thereof |
| CN102336940A (en) * | 2011-07-20 | 2012-02-01 | 金发科技股份有限公司 | Composition of air-permeable film with low permeation volume and preparation method thereof |
| CN103450535A (en) * | 2013-07-25 | 2013-12-18 | 桐城市福润包装材料有限公司 | High-resistance antibacterial PE (polyethylene) film composite material |
| CN105061852A (en) * | 2015-07-31 | 2015-11-18 | 国家复合改性聚合物材料工程技术研究中心 | High oxygen barrier polyethylene/nylon 6 nanocomposite material and preparation method thereof |
| CN105885360A (en) * | 2016-04-29 | 2016-08-24 | 贵州省材料产业技术研究院 | High-barrier nano organic montmorillonite-polyethylene glycol terephthalate composite material and method for preparing same |
| CN107698844A (en) * | 2017-10-13 | 2018-02-16 | 武汉工程大学 | A kind of Gemini surface active organic modification montmonrillonite/composite polyethylene material and preparation method thereof |
| CN110802904A (en) * | 2019-10-17 | 2020-02-18 | 苏州同舟包装有限公司 | Multilayer high-barrier plastic uptake box and preparation method thereof |
| CN111019172A (en) * | 2019-12-31 | 2020-04-17 | 濮阳宏业高新科技发展有限公司 | Application of laminated silica in film processing |
| CN113121903A (en) * | 2021-04-12 | 2021-07-16 | 金富科技股份有限公司 | High-barrier plastic bottle cap and preparation method thereof |
| CN116178840A (en) * | 2023-02-13 | 2023-05-30 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
-
2002
- 2002-12-27 CN CN 02159030 patent/CN1227287C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318498C (en) * | 2005-04-30 | 2007-05-30 | 浙江大学 | Nano composite material of polyethylene/montorillonite clay in high density and preparation method thereof |
| CN102336940A (en) * | 2011-07-20 | 2012-02-01 | 金发科技股份有限公司 | Composition of air-permeable film with low permeation volume and preparation method thereof |
| CN103450535A (en) * | 2013-07-25 | 2013-12-18 | 桐城市福润包装材料有限公司 | High-resistance antibacterial PE (polyethylene) film composite material |
| CN105061852A (en) * | 2015-07-31 | 2015-11-18 | 国家复合改性聚合物材料工程技术研究中心 | High oxygen barrier polyethylene/nylon 6 nanocomposite material and preparation method thereof |
| CN105061852B (en) * | 2015-07-31 | 2017-11-24 | 国家复合改性聚合物材料工程技术研究中心 | Nano composite material of high oxygen barrier polyethylene nylon 6 and preparation method thereof |
| CN105885360A (en) * | 2016-04-29 | 2016-08-24 | 贵州省材料产业技术研究院 | High-barrier nano organic montmorillonite-polyethylene glycol terephthalate composite material and method for preparing same |
| CN107698844A (en) * | 2017-10-13 | 2018-02-16 | 武汉工程大学 | A kind of Gemini surface active organic modification montmonrillonite/composite polyethylene material and preparation method thereof |
| CN107698844B (en) * | 2017-10-13 | 2020-08-28 | 武汉工程大学 | Gemini surfactant organic modified montmorillonite/polyethylene composite material and preparation method thereof |
| CN110802904A (en) * | 2019-10-17 | 2020-02-18 | 苏州同舟包装有限公司 | Multilayer high-barrier plastic uptake box and preparation method thereof |
| CN111019172A (en) * | 2019-12-31 | 2020-04-17 | 濮阳宏业高新科技发展有限公司 | Application of laminated silica in film processing |
| CN113121903A (en) * | 2021-04-12 | 2021-07-16 | 金富科技股份有限公司 | High-barrier plastic bottle cap and preparation method thereof |
| CN116178840A (en) * | 2023-02-13 | 2023-05-30 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
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|---|---|
| CN1227287C (en) | 2005-11-16 |
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