CN101962453B - Polyethylene greenhouse film resin composition and preparation method thereof - Google Patents
Polyethylene greenhouse film resin composition and preparation method thereof Download PDFInfo
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- CN101962453B CN101962453B CN2009100890568A CN200910089056A CN101962453B CN 101962453 B CN101962453 B CN 101962453B CN 2009100890568 A CN2009100890568 A CN 2009100890568A CN 200910089056 A CN200910089056 A CN 200910089056A CN 101962453 B CN101962453 B CN 101962453B
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Abstract
The invention discloses a polyethylene greenhouse film resin composition, which is calculated by linear low density polyethylene in weight percent, and comprises the following components: 1) linear low density polyethylene the melt flow rate of which is 0.7-3.0g/10min; 2) 5-15% of low-pressure polyethylene the melt flow rate of which is 0.01-0.1g/10min; 3) 0.1-0.5% of tert-butyl hydroperoxide; and 4) 0.03-0.07% of dicumyl peroxide. The composition can stably blow a wide greenhouse film on a common film blowing unit which is not transformed, wherein, the thickness of the wide greenhouse film is more than or equal to 80 mu m, and the width of the wide greenhouse film is more than or equal to 8m; the product has no crystallization point on the appearance, has high tearing strength, and can resist 7-8 grade sand wind, wherein, the wind power is 17.2-20.7m/s, and is especially suitable for the laying of the central and western regions in which the sandstorm occurs frequently. The invention also further discloses a preparation method of the composition.
Description
Affiliated technical field
The present invention relates to a kind of polyethylene green house film resin combination and preparation method thereof, be specifically related to a kind of little cross-linking modified polyethylene green house film resin combination and preparation method thereof.
Background technology
China is a large agricultural country, and the production of plastic sheeting for farm use occupies critical role in China's plastics industry.Plastic sheeting for farm use mainly is divided into two kinds of mulch film and canopy films by function, and in recent years, the agricultural greenhouse booth of China obtains widespread use, and is very urgent to the demand that high-performance canopy film is resin dedicated.At present, China is the maximum country of agricultural canopy film production and consumption, and its consumption is about 1.6 times of other All Countries summation.According to incompletely statistics; China has had nearly thousand families of plastic sheeting for farm use manufacturing enterprise that big small-scale does not wait, and its canopy film throughput is more than 1,000,000 tons, and actual YO is above 1,200,000 tons; Particularly the annual consumption of west area canopy film has reached 500,000 tons, and the agricultural canopy film area coverage is more than 4,000,000,000 mu.In recent years; Along with excessively developing natural resources of causing of population expansion, excessive deforestation, excessively the land reclamation causes the global greenhouse effect aggravation; Make north China become the sandstorm high-incidence season in every year 4, May, common instantaneous wind-force reaches 7 to 8 grades.This diastrous weather causes warmhouse booth large-area being packed to occur, this to the west area have a poor foundation, not rich peasant is a kind of deathblow.
At present, mainly to adopt LDPE PP Pipe Compound, LDPE/LLDPE blending resin be that raw material is produced in the production of domestic canopy film.LDPE PP Pipe Compound performance requriements is high, and the production difficulty is bigger, and is therefore domestic more common with resinous blending production canopy film.But the physical mechanical strength of the canopy film that the LDPE/LLDPE blend composition is produced is on the low side, and particularly cross direction tear strength is little, under the quick-fried mal-condition that takes place frequently of China's western region sand and dust, lays to be prone to be packed phenomenon.In addition, the difference of mixing proportion makes its canopy film quality uneven.
In the prior art, the report of relevant organo-peroxide modification LLDPE is a lot.The cumyl superoxide that in LLDPE (MFR 2g/10min), adds 100～200ppm like US A4578431 carries out extrusion reaction, and the gained resin can be blow molded into the film of 25 μ m.(>=15g/10min) LLDPE carries out modification to clear 64-65146, and product is difficult for curling when the production casting films, is easy to processing to high melt flow rate(MFR) through adding linking agent.CN 97119782.2 is at LLDPE (C
4～C
8Alpha olefin copolymer) in add hydroperoxide, be to carry out extrusion reaction under 500～10000ppm at its consumption, make a kind of resin combination that is suitable for blowing the ultra-thin mulch film of thickness≤10 μ m.ZL 03137608.8 is at LLDPE (C
4～C
8Alpha olefin copolymer) in add ditertiary butyl peroxide, be to carry out crosslinked extrused reaction under 0.3～0.6wt% at its consumption, make a kind of canopy film resin compsn that is suitable for blowing 8000 * 0.08mm specification.React in the n-heptane solution of JP 1113411 (A) proposition tert-butyl peroxide and LLDPE, obtain the good little crosslinked LLDPE of processibility.FR19840005549 adopts one or more superoxide and fused LLDPE reaction at least, prepares the resin that is suitable for extruding with blow molding.US 4614764 (A) adopts a kind of LLDPE and another kind of through the LLDPE of organo-peroxide modification blend, and preparation is suitable for the resin combination of blown film.Above-mentioned patent is single resin to be carried out little cross-linking modified basically, and emphasis improves the melt strength of resin, improves its processing characteristics.
Summary of the invention
The object of the invention provides a kind of polyethylene green house film resin combination.Said composition be the raw material product wide cut canopy film of giving birth to (thickness >=80um, fabric width 8～12m) has high-tear strength, it is quick-fried to resist 7～8 grades of sand and dust.The present invention further proposes the preparation of compositions method.
Weight in linear low density polyethylene is a hundred per cent, and resin combination of the present invention comprises:
1) linear low density polyethylene melt flow rate(MFR) 0.7～3.0g/10min;
2) low pressure polyethylene melt flow rate(MFR) 0.01～0.1g/10min of 5～15%;
3) 0.1～0.5% tertbutyl peroxide;
4) 0.03～0.07% Di Cumyl Peroxide 99,
Described melt flow rate(MFR) (MFR) is at 190 ℃, the measured value under the 2.16Kg load, and linear low density polyethylene (LLDPE) is the copolymerization product of ethene and 1-butylene.
LLDPE and HDPE can be powdery or granular resin, for reaching the better mixing effect, are that powdered resin is good to have at least a kind of in two kinds of resins.
Tertbutyl peroxide (TBHP), Di Cumyl Peroxide 99 (DCP) are the commercially available prod, and the half life temperature of superoxide is because of manufacturer's difference difference slightly, transformation period T=257～269 of general TBHP ℃/1min; Transformation period T=169～175 of DCP ℃/1min.
Preparation of compositions can be carried out in Banbury mixer, kneader, screw extrusion press, and temperature of reaction is 145～230 ℃, reaction times 3～5min.Wherein be best with the screw extrusion press.Also can add thermo-stabilizer and oxidation inhibitor as required in the preparation process, be per-cent in the weight of LLDPE, and add-on is 0.05～0.2%.
When adopting screw rod to extrude, can put in the forcing machine again and react earlier with resin and various auxiliary agent pre-mixing; Also can various auxiliary agents progressively be joined in the resin, extrude preparation through reactivity.A kind of method in back has more operability in industry.Its preparation main points comprise: 1) at laterally disposed liquid feed mouth of forcing machine opening for feed and auxiliary charging opening, see accompanying drawing 1; 2) solid-state DCP uses earlier a small amount of xylene soluble, again with the TBHP proportional mixing of liquid state after, progressively add in the forcing machine through liquid sampling device; 3) powdery or granular HDPE, a spot of granular or powdery LLDPE, thermo-stabilizer, oxidation inhibitor are carried out mixed at high speed, mixture gets into forcing machine through auxiliary feed ports; 4) surplus LLDPE is directly added by the forcing machine charging opening; 5) 185～230 ℃ of 145～165 ℃ of feeding section temperature, the fluxing zone temperature of twin screw extruder, 190～200 ℃ of head temperatures; Reaction times 3～5min.
In the compsn of the present invention, on the one hand, select two kinds of decomposition temperatures to differ bigger peroxide cross-linking system; The melt strength that can appropriateness improves resin through control reaction temperature; Improve processing characteristics, it is excessively crosslinked to avoid single use DCP to be prone to, and film surface is prone to form " brilliant point "; Or single use TBHP consumption is excessive, is unfavorable for problems such as environmental protection.On the other hand, the base resin system of small amount of H DPE/LLDPE, the mechanical property of resin increases than LLDPE; Simultaneously, extrude through reactivity, little crosslinking reaction takes place in two kinds of resins under the effect of superoxide, and the resin enhancement is more remarkable.This synergy; Make compsn have lower MFR (≤0.4g/10mi) with higher density (>=0.921g/cm3); Can on common blown film unit, stably blow out wide cut canopy film (thickness>=80um, fabric width>=8m), solved the problem that LLDPE blown film film bubble is piled up or swung without any transformation; And product appearance does not have brilliant point basically; Tear strength can be resisted 7～strong gale husky (wind-force 17.2～20.7 meter per seconds) far above common commercially available LDPE/LLDPE agricultural canopy film simultaneously, is particularly suitable for laying in the central and west regions that sandstorm takes place frequently.
Figure of description
The twin screw extruder apparatus sketch of Fig. 1 production resin combination of the present invention
1-charging opening; 2-auxiliary charging opening; 3-liquid feed mouth;
4-venting port; 5-head
Embodiment
1, raw material
1) resin
2) superoxide
Tertbutyl peroxide transformation period T=264 ℃/1min, the auxiliary reagent factory, Lanzhou
Di Cumyl Peroxide 99 transformation period T=170 ℃/1min, the auxiliary reagent factory, Lanzhou
3) auxiliary agent
Oxidation inhibitor B561 Switzerland vapour Bagong department
Calcium stearate Yangtse River in Chongqing chemical plant
2, performance test standard
Melt flow rate(MFR) MFR (g/10min) GB/T3682-2000
Density (g/cm
3) GB/T1033-1986
Film stretching intensity GB/T1040-1992
Film elongation at break GB/T1040-1992
Film tear strength GB/T16578
3, equipment and instrument
Φ 34 twin screw extruders are long/directly=34/1 German Lestreiz company
Plunger type metering pump range: 0～100 liter of/hour U.S. Paasche Fei De company
The fast mixing machine of 10 risings Fuxin plastics machinery factory
120 3 layers of compound inflation film manufacturing machine of Φ Dalian rubber and plastics machine factory
4. embodiment and Comparative Examples
1) canopy film resin preparation of compositions
Φ 34 twin screw extruders of producing with German Lestreiz company are reactor drum, and the LLDPE resin is added by charging opening 1; LLDPE, HDPE, oxidation inhibitor, the thermo-stabilizer of getting 5wt% mixes 3 minutes in high-speed mixer after, join in the spiral side direction feeder, get into forcing machines through auxiliary charging opening 2; Select the TB/DCP of different proportionings, earlier solid-state DCP is used a small amount of xylene soluble, mix the back again with TBHP and inject plunger type metering pump, be added dropwise to by liquid feed mouth 3; The reaction devolatilization can realize at venting port 4 places of forcing machine; Reaction mass finally by head 5 extrude, granulation obtains resin combination.Concrete composition of raw materials and preparation technology see table (1) and table (2).
Table 1 composition of raw materials
Table 2 prepared in twin-screw extruder technology
2) blowing of canopy film and performance
The processing condition * of table 3 resin combination blowing moulding greenhouse film
| The film neck is " V " type | ||||||||||
| Embodiment 4 | 120 | 110 | 105 | 77 | 123 | 106 | 8.0 | 0.08 | 0 | The slight swing of film bubble film neck is " U " type |
| Embodiment 5 | 120 | 110 | 105 | 79 | 124 | 106 | 8.0 | 0.08 | 1 | The film bubble is " U " type than the stabilizing membrane neck |
| Embodiment 6 | 120 | 110 | 105 | 86 | 137 | 121 | 8.0 | 0.08 | 0 | Film bubble stabilizing membrane neck is " V " type |
| Comparative Examples 1 | 120 | 110 | 105 | 91 | 138 | 130 | 8.0 | 0.08 | 0 | The film bubble is " U " type than the stabilizing membrane neck |
| Comparative Examples 2 | 120 | 110 | 105 | 97 | 124 | 117 | 8.0 | 0.08 | 0 | Film bubble swing film forming difficulty |
| Comparative Examples 3 | 120 | 110 | 105 | 90 | 119 | 106 | 8.0 | 0.08 | 1 | The slight swing of film bubble film neck is " U " type |
| Comparative Examples 4 | 120 | 110 | 105 | 81 | 104 | 105 | 8.0 | 0.08 | 1 | Film bubble swing film forming difficulty |
| Comparative Examples 5 | 120 | 110 | 105 | 81 | 104 | 105 | 8.0 | 0.08 | 0 | Film bubble swing film forming difficulty |
| Comparative Examples 6 | 120 | 110 | 105 | 81 | 104 | 105 | 8.0 | 0.08 | 0 | Film bubble swing film forming difficulty |
| Comparative Examples 7 | 120 | 110 | 105 | 81 | 104 | 105 | 8.0 | 0.08 | 7 | The slight swing of film bubble film neck is " U " type |
| Comparative Examples 8 | 120 | 110 | 105 | 81 | 104 | 105 | 8.0 | 0.08 | 34 | The film bubble is prone to broken hole film forming difficulty |
* 120 3 layers of compound blown film unit of Φ of providing of Dalian rubber and plastics machine factory
The test result of canopy film resin composition properties and canopy film application performance.See table 4,5.
The physicals of table 4 resin combination
| Numbering | MFR (g/10min) | Density (g/cm 3) | Molten stream ratio * |
| Embodiment 1 | 0.31 | 0.932 | 61.3 |
| Embodiment 2 | 0.24 | 0.929 | 66.7 |
| Embodiment 3 | 0.17 | 0.941 | 81.2 |
| Embodiment 4 | 0.39 | 0.922 | 71.5 |
| Embodiment 5 | 0.31 | 0.927 | 76.4 |
| Embodiment 6 | 0.27 | 0.931 | 87.5 |
| Comparative Examples 1 | 0.37 | 0.928 | 54.7 |
| Comparative Examples 2 | 0.52 | 0.921 | 34.7 |
| Comparative Examples 3 | 0.43 | 0.923 | 44.1 |
| Comparative Examples 4 | 1.27 | 0.918 | 27.5 |
| Comparative Examples 5 | 0.84 | 0.920 | 26.9 |
| Comparative Examples 6 | 0.66 | 0.923 | 37.8 |
| Comparative Examples 7 | 0.19 | 0.919 | 67.5 |
| Comparative Examples 8 | 0.02 | 0.922 | 87.7 |
*Molten stream ratio: be the ratio of the melt flow rate(MFR) (MFR) of (2.16kg and 21.6kg) under two different loads, be used for the width of qualitative representation MWD.
The physicals and the applicable cases of table 5 canopy film
*Reference appearance: the commercially available orchidization production LDPE/LLDPE (7: 3) of film factory of HTC blending material shed film (8000 * 0.08mm)
Claims (6)
1. a polyethylene green house film resin combination is characterized in that the weight in linear low density polyethylene is a hundred per cent, and resin combination comprises:
1) linear low density polyethylene, its melt flow rate(MFR) 0.7～3.0g/10min;
2) 5～15% low pressure polyethylene, its melt flow rate(MFR) 0.01～0.1g/10min;
3) 0.1～0.5% tertbutyl peroxide;
4) 0.03～0.07% Di Cumyl Peroxide 99,
Described melt flow rate(MFR) is at 190 ℃, the measured value under the 2.16Kg load, and linear low density polyethylene is the copolymerization product of ethene and 1-butylene.
2. resin combination according to claim 1 is characterized in that having at least in linear low density polyethylene, the low pressure polyethylene a kind of powdered resin that is.
3. resin combination according to claim 1 is characterized in that the transformation period T=257～269 ℃/1min of tertbutyl peroxide; Transformation period T=169～175 of Di Cumyl Peroxide 99 ℃/1min.
4. preparation method who realizes one of the said resin combination of claim 1-3 is characterized in that preparation of compositions carries out in Banbury mixer, kneader or screw extrusion press, temperature of reaction is 145～230 ℃, reaction times 3～5min.
5. according to the preparation method of the said resin combination of claim 4, it is characterized in that adding in the preparation process thermo-stabilizer and oxidation inhibitor, be per-cent in the weight of linear low density polyethylene, add-on is 0.05～0.2%.
6. according to the preparation method of the said resin combination of claim 5, it is characterized in that the main points that adopt screw extrusion press to prepare compsn comprise: 1) at laterally disposed liquid feed mouth of forcing machine opening for feed and auxiliary charging opening; 2) solid-state DCP uses earlier xylene soluble, again with the TBHP proportional mixing of liquid state after, progressively add in the forcing machine through the liquid feed mouth; 3) powdery or granular HDPE, a spot of granular or powdery LLDPE, thermo-stabilizer, oxidation inhibitor are carried out mixed at high speed, mixture gets into forcing machine through auxiliary charging opening; 4) surplus LLDPE is directly added by the forcing machine charging opening; 5) 185～230 ℃ of 145～165 ℃ of feeding section temperature, the fluxing zone temperature of twin screw extruder, 190～200 ℃ of head temperatures; Reaction times 3～5min.
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| CN2009100890568A CN101962453B (en) | 2009-07-22 | 2009-07-22 | Polyethylene greenhouse film resin composition and preparation method thereof |
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|---|---|---|---|
| CN2009100890568A CN101962453B (en) | 2009-07-22 | 2009-07-22 | Polyethylene greenhouse film resin composition and preparation method thereof |
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| CN101962453B true CN101962453B (en) | 2012-07-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102952310B (en) * | 2011-08-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Metallocene polyethylene agricultural film resin composition and its preparation method |
| CN102585328B (en) * | 2011-12-30 | 2015-03-25 | 上海雅竹化工材料有限公司 | Peroxide cross-linked polyolefin and preparation method thereof |
| EP2857165B1 (en) * | 2013-10-01 | 2019-03-13 | SABIC Global Technologies B.V. | Device and method for making masterbatch pellets for thermoplastic compositions |
| CN105968534A (en) * | 2016-07-04 | 2016-09-28 | 苏州云舒新材料科技有限公司 | PE film and preparation method thereof |
| CN106867093A (en) * | 2017-03-15 | 2017-06-20 | 江西乐富军工装备有限公司 | Military rotational moulding firearms pack composite material special |
| CN107501475A (en) * | 2017-08-16 | 2017-12-22 | 陕西理工大学 | Polyethylene green house film is modified the preparation method with grafting PE weatherability master batches |
| CN114350047A (en) * | 2021-12-31 | 2022-04-15 | 广东汇发塑业科技有限公司 | High-performance greenhouse film special for watermelons and Hami melons in Yueqiong areas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4614764A (en) * | 1985-03-06 | 1986-09-30 | Mobil Oil Corporation | Linear low density ethylene polymers blended with modified linear low density ethylene polymers |
| CN1566192A (en) * | 2003-06-18 | 2005-01-19 | 中国石油天然气股份有限公司 | Agricultural polyethylene resin composition |
| CN1760251A (en) * | 2005-09-29 | 2006-04-19 | 上海新上化高分子材料有限公司 | Crosslinkable peroxide, vinyon in low density, and preparation method |
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2009
- 2009-07-22 CN CN2009100890568A patent/CN101962453B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4614764A (en) * | 1985-03-06 | 1986-09-30 | Mobil Oil Corporation | Linear low density ethylene polymers blended with modified linear low density ethylene polymers |
| CN1566192A (en) * | 2003-06-18 | 2005-01-19 | 中国石油天然气股份有限公司 | Agricultural polyethylene resin composition |
| CN1760251A (en) * | 2005-09-29 | 2006-04-19 | 上海新上化高分子材料有限公司 | Crosslinkable peroxide, vinyon in low density, and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 李代叙等.HDPE/mLLDPE混炼后的性能与结构.《现代塑料加工应用》.2007,第19卷(第1期),第13页1.1部分，第15页2.4部分. * |
| 李代叙等.共混体系HDPE/m-LLDPE在动态保压注射成型中增强增韧的研究.《塑料工业》.2005,第33卷(第5期),第12页第1.1部分,第13页第1.4部分. * |
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