CN102924800B - Polyethylene resin composition for weathering resistance agriculture film, and preparation method thereof - Google Patents

Polyethylene resin composition for weathering resistance agriculture film, and preparation method thereof Download PDF

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CN102924800B
CN102924800B CN201110228041.2A CN201110228041A CN102924800B CN 102924800 B CN102924800 B CN 102924800B CN 201110228041 A CN201110228041 A CN 201110228041A CN 102924800 B CN102924800 B CN 102924800B
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uldpe
low density
preparation
weather
ultra
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CN102924800A (en
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徐典宏
曹凤霞
何连成
朱晶
白竞冰
陈红
翟云芳
王月霞
魏绪玲
梁天珍
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China Petroleum and Natural Gas Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92561—Time, e.g. start, termination, duration or interruption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention provides a linear low density polyethylene (LLDPE) resin composition for a weathering resistance agriculture film and a preparation method thereof. The resin composition comprises, by weight of LLDPE, (1) 100% of LLDPE, (2) 0.05-0.3% of a compound cross-linking aid, and (3) 10-30% of ultra-low density polyethylene (ULDPE) weathering resistance master batch. With the composition, a broad width shed plastic film (a width of more than or equal to 8 m and a thickness of more than or equal to 80 mum) can be blown out without any blending, fisheyes on the surface of the shed plastic film are less, weathering resistance is excellent, and natural damage can not occur after the shed plastic film continuously covers a greenhouse for more than 40 months. The present invention further provides a preparation method for the resin composition, wherein the preparation method has advantages of short procedure, simple process, low development cost, stable product quality and the like.

Description

A kind of polyethylene resin composition and preparation method thereof for weathering resistance plastic sheeting for farm use
Technical field
The present invention relates to a kind of polyethylene resin composition and preparation method thereof, be specifically related to the agricultural canopy film resin combination with excellent weather resistance take linear low density polyethylene as base resin.
Background technology
Agricultural plastic film is extremely important to agricultural modernization, closely bound up with national economy, effectively alleviates the contradiction of agriculture production and development, has brought material benefit to peasant.At present, China is one of maximum country of agricultural plastic film production and consumption, wherein the polyvinyl resin consumption of agricultural canopy film exceedes more than 1,200,000 tons, particularly agricultural canopy film annual polyvinyl resin consumption in west area has reached 500,000 tons, and agricultural canopy film has become one of important applied field of polyethylene (PE) resin.
At present, first of the output of China's agricultural canopy film and the area coverage Jun Ju world.But the developmental level of the current agricultural canopy film of China, compared with advanced international standard, still has very large gap, not only show in quantity, kind, and show in the performance index such as weathering resistance, the transparency, anti-droplet.Abroad, agricultural canopy film be absolutely almost long lifetime plastic sheeting for farm use, can detain canopy use and reach 18 months nature breakage does not occur, and the common agricultural canopy film of China cannot reach this requirement.This generally adopts hp-ldpe/linear low density polyethylene (LDPE/LLDPE) blending resin mainly due to domestic agricultural canopy film covering material, and wherein LDPE molecular weight is low, molecular weight distribution is wide; LLDPE is made up of ethene and 1-butylene copolymerization, side chain is short, branch is many, catalyst residue amount is high, when being subject under the impact of the factors such as sunlight, temperature, wind-force, easily there is chain rupture in the molecular chain of LDPE and LLDPE, easily occurs " backboard effect " (phenomenon that canopy film easily ftractures at skeleton place).The difference of the resin grade of blending, mixing proportion makes its agricultural canopy film quality uneven in addition, has greatly shortened the work-ing life of agricultural canopy film.Therefore, in the Application and Development of agripast canopy film, improve the work-ing life of agricultural canopy film for save energy, saving manpower, minimizing environmental pollution, reduce farmer's burdens all very favourable.
In prior art, about the report of organo-peroxide modification LLDPE a lot.The cumyl superoxide that adds 100～200ppm as USA4578431 in LLDPE (MFR 2g/10min) carries out extrusion reaction, and gained resin can be blow molded into the film of 25 μ m.ZL03137608.8 is at LLDPE (C 4～C 8alpha olefin copolymer) in add ditertiary butyl peroxide, be under 0.3wt%～0.6wt%, to carry out crosslinked extrused reaction at its consumption, make one and be suitable for blowing the canopy film resin composition of 8000 × 0.08mm specification.JP 1113411 (A) proposes to react in the n-heptane solution of tert-butyl peroxide and LLDPE, the good micro-crosslinked LLDPE of acquisition processibility.US4614764 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.JP1113411 adds UV light absorber in LLDPE and ethene-vinyl acetate (EVA) blending resin, prepares weather-proof film.CN1056696A, in Low Density Polyethylene (LDPE) and ethene-vinyl acetate (EVA) blending resin, adds the master batch of being made by UV light absorber, photostabilizer, oxidation inhibitor and other processing aid, prepares weather-proof film.CN90101638.1 provides a kind of and in main polyolefin blends, has added photostabilizer, oxidation inhibitor, visible ray conditioning agent and other processing aid at polyethylene or take polyethylene, and extrusion-blown modling becomes to have the warmhouse booth film manufacturing method of weathering resistance.
Above-mentioned patent is single resin to be carried out cross-linking modified substantially, and emphasis just improves the melt strength of resin, improves its processing characteristics, but limited in the amplitude that improves aspect agricultural canopy film weathering resistance.At present, agricultural canopy film uses in producing at home LDPE, LLDPE base resin weather resistance are low, cause agricultural canopy film short work-ing life, the persistence that the ageing-resistant system simultaneously adding exists is unreasonable, auxiliary agent kind is many, production cost is high, auxiliary agent uses are short, the problem such as migration easily occurs and separate out.
Summary of the invention
The object of the invention is to provide a kind of linear low density polyethylene canopy film resin composition.Said composition is that the wide cut canopy film (thickness >=80 μ m, fabric width >=8m) of raw material production has good weathering resistance, can detain continuously canopy nature breakage does not occur for 40 months above.The present invention further proposes the preparation method of composition.
Take the weight of linear low density polyethylene (LLDPE) as absolutely, resin combination of the present invention comprises:
1) 100% LLDPE;
2) 0.05%～0.3% composite crosslinking coagent;
3) the weather-proof master batch of 10%～30% ultra-low density polyethylene (ULDPE);
Wherein said composite crosslinking coagent is tertbutyl peroxide (TBHP) and the composite composition of dibenzoyl peroxide (BPO), and the mass ratio of two kinds of crosslinking coagents is TBHP/BPO=30: 1～5: 1.
The blend that the weather-proof master batch of described ULDPE is made up of grafts (ULDPE-g-VA) and the dispersion agent of ULDPE, composite light stabilizer, ULDPE and vinyl acetate between to for plastic.Polymkeric substance ULDPE is made by vapor phase process, solution method or high-pressure process copolymerization by ethene and a-alkene (propylene, butylene, hexene and octene), the multipolymer of optimal ethylene and butylene, wherein density: 0.860～0.915g/cm 3; Melt flow rate (MFR) (MFR) is: 0.1～20g/10min.Described melt flow rate (MFR) (MFR) is at 190 ℃, the measured value under 2.16Kg load.
The compound system that composite light stabilizer is made up of quencher and radical scavenger.Quencher is organic nickel compound, as: two (3, 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel (Irgastab 2002), 2, 2-thiobis (the tertiary octyl phenol oxygen of 4-base) nickel-n-Butyl Amine 99 complex compound (UV-1084), 2, 2-thiobis (the tertiary octyl phenol oxygen of 4-base) nickel (AM-101), dioctyl dithiocarbamic acid nickel (AM-108), N, one in N-nickel dibutyl dithiocarbamate (NBC), organic nickel compound is because of the toxicity problem of heavy metal ion, its consumption should be strict controlled in 0.01%～0.04% (by the weight percent meter of ULDPE).
Radical scavenger is selected the hindered amine as light stabilizer (HALS) with space steric effect, as: the one in Tinuvin123, Tinuvin622, Tinuvin791, Tinuvin328, Tinuvin326, GW-540, GW-480, GW-544, CH944, its consumption is 0.1%～0.5% (by the weight percent meter of ULDPE).This compound system can reduce the excited state functional group in the molecular resin after cross-linking modified with reactive behavior effectively, promptly catch free radical R, ROO that linking agent produces, destroy the growth of living chain, improve the stability of base resin molecular structure, reached the work-ing life that extends resin.
ULDPE-g-VA is grafted to grafted monomer the graft copolymer on ULDPE main chain under the effect of initiator; initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate (TBPA), tertbutyl peroxide, 2; 5-dimethyl-2; one in 5-di-t-butyl hexane peroxide (BPDH), ditertiary butyl peroxide (DTBP), dicumyl peroxide (DCP), diisopropylbenzenehydroperoxide (DBHP), benzoyl peroxide or peroxide di-t-butyl, preferably adopts dicumyl peroxide (DCP).Grafted monomer is selected from polymerization-grade vinyl acetate between to for plastic (VA).
Dispersion agent can be wherein a kind of or composite such as sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax, white oil, preferably adopts white oil.
The weather-proof agglomerate preparation method of ULDPE provided by the invention comprises:
(1) preparation method of ULDPE-g-VA grafts:
ULDPE high-speed mixing 5～10min by the vinyl acetate between to for plastic of 5～10 parts (VA) with 100 parts places 5～10h by the material mixing in encloses container; Then initiator and the acetone of getting 0.01～0.1 part are within 1: 10～1: 20, to be mixed with mixing solutions by weight, again by mixing solutions and the mixture high-speed mixing 5～10min placing, finally by carrying out melting graft reaction in twin screw extruder, 160～200 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain VA percentage of grafting and be 2%～7% ULDPE-g-VA grafts.
(2) preparation of the weather-proof master batch of ULDPE
Together with the ULDPE of 100 parts and the ULDPE-g-VA grafts of 4～10 parts, the dispersion agent of 0.5～1.0 part, put in super mixer high-speed mixing 3～5min; And then add the composite light stabilizer of 0.11～0.54 part, high-speed mixing 5～10min; Mixed material is added to twin screw extruder, 165～210 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, obtains the weather-proof master batch of ULDPE.
LLDPE described in composition adopts the ethene prepared of efficient ziegler-natta catalyst systems and the copolymerization product of 1-butylene, MFR:0.7～3.0g/10min; Density: 0.915～0.925g/cm 3.In the present invention, LLDPE can be powdery or granular resin, but for reaching better mixed effect with powdered resin the best.
Composite crosslinking coagent described in composition is that TBHP and BPO are by the composite composition of different ratios.Wherein the scope of total add-on of composite crosslinking coagent is that the optimum mixture ratio of 0.05%～0.3%, two kinds of crosslinking coagents is TBHP/BPO=25: 1～10: 1.Two kinds of superoxide are commercially available prod, and its half life temperature is because of manufacturer's slightly difference of difference, transformation period T=246～267 of general TBHP ℃/1min; Transformation period T=131～134 of BPO ℃/1min.
The used in amounts of general BPO is strictly controlled, its consumption can not exceed 0.03%, in composition preparation process, processing temperature can not exceed 230 ℃ in addition, otherwise degree of crosslinking is uncontrollable, be prone to the excessively crosslinked gel that produces, agricultural canopy film surface is prone to " brilliant point ", its tear strength and weathering resistance not only do not improve, cause on the contrary mechanics mechanical property variation, brittle fracture occurs, also there will be the problems such as processing units damage and environmental protection simultaneously.
The preparation of resin combination of the present invention also can be carried out in Banbury mixer, kneader, forcing machine, but take twin screw extruder as best.
Particularly, the preparation method of polyethylene resin composition provided by the invention comprises: after first two kinds of crosslinking coagents are composite in proportion, add solvent, add again and account for the powdery LLDPE that gross weight is 5%～10% (wt), then, after high-speed mixing 3～5min, make premix masterbatch; Then remaining powdery LLDPE, premix masterbatch and the weather-proof master batch of ULDPE are joined together and in forcing machine, carried out extrusion reaction by charging opening, temperature of reaction is 165～220 ℃, reaction times is 2～5min, extrudes, cooling, granulation, makes polyethylene resin composition.
The present invention also can add a certain amount of thermo-stabilizer and oxidation inhibitor in the preparation process of the weather-proof master batch of ULDPE and polyethylene greenhouse film resin composition, and its total add-on is 0.2%～0.5% (take the weight of LLDPE as per-cent).Wherein, oxidation inhibitor can be one or several compounds in phenols, hindered amines, phosphite ester kind antioxidant, and its consumption is 0.1%～0.2%.Thermo-stabilizer can be stearates, and as Zinic stearas, calcium stearate etc., consumption is generally 0.1%～0.3%.
In resin combination preparation process of the present invention, in composite crosslinking coagent, add solvent, described solvent is the one in toluene, dimethylbenzene, acetone, and its add-on is 2～4 times of composite crosslinking coagent weight.
In composition of the present invention, on the one hand, low, the intermolecular freeboard of ULDPE density in the weather-proof master batch of ULDPE is large, degree of crystallinity is low, it is larger to have and more complete spherocrystal, will reduce refraction and the range of light in resin; Simultaneously again because short-chain branch in molecular structure is many, and there is certain crosslinked action with crosslinking coagent, in molecular structure, can form more physical crosslinking point, can greatly improve the weathering resistance of base resin.Secondly, ULDPE-g-VA grafts has improved the consistency of resin and photostabilizer, has improved the dispersion effect of photostabilizer in resin; ULDPE-g-VA grafts has certain adsorption to photostabilizer in addition, has avoided the migration of photostabilizer in resin and has separated out problem, has greatly improved persistence and the high efficiency of photostabilizer.Like this, ULDPE and photostabilizer can produce certain positive cooperativity, and this has fairly obvious effect to improving the weathering resistance of agricultural canopy film base resin, has reached with minimum add-on, minimum cost and has obtained best weathering resistance.
On the other hand, select two kinds of transformation period to differ the composite cross-linking system of larger superoxide composition, can effectively control cross-linked speed and the crosslinking degree of base resin, realize the micro-crosslinked of molecular structure, guaranteeing under the prerequisite of base resin basic physical properties, linking agent just can reach the desired melt strength of blowing wide cut canopy film (thickness >=80um, fabric width >=8m) in the time of few additive.Avoid to greatest extent a kind of superoxide of independent use to occur excessively crosslinked or crosslinked not enough simultaneously, easily caused film surface to occur " brilliant point " or cannot blow separately the problem of wide cut canopy film.Like this, make said composition on the common blown film unit without any transformation, can stably blow out the wide cut canopy film (thickness >=80 μ m with excellent weather resistance without any blending, fabric width >=8m), can detain continuously canopy and nature breakage not occur above in 40 months, be particularly suitable for west area long in the sunshine duration, awful weather and lay.
Embodiment
1, raw material
1) resin
Figure BDA0000082227940000051
Figure BDA0000082227940000061
2) superoxide
Transformation period T=264 ℃/1min of tertbutyl peroxide (TBHP), Lanzhou auxiliary reagent factory
Transformation period T=133 ℃/1min of dibenzoyl peroxide (BPO), Lanzhou auxiliary reagent factory
Transformation period T=170 ℃/1min of dicumyl peroxide (DCP), Lanzhou auxiliary reagent factory
Transformation period T=160 ℃/1min of t-butyl peroxy-acetate (TBPA), Lanzhou auxiliary reagent factory
3) auxiliary agent
2, performance test standard
Figure BDA0000082227940000064
3, equipment and instrument
Φ 67 twin-screw extrusion captain/footpath=34/1 German Lestreiz companies
10 liters of high-speed mixer Fuxin plastics machinery factories
120 3 layers of compound inflation film manufacturing machine Dalian rubber and plastics machine factory of Φ
Embodiment and comparative example
Enumerate following examples invention effect of the present invention is described, but protection scope of the present invention is not limited in these embodiment, in composition, each component is in the parts by weight of base resin LLDPE.
Embodiment 1
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, the ULDPE high-speed mixing 6min by the vinyl acetate between to for plastic of 6 parts (VA) with 100 parts places 10hr by the material mixing in encloses container; Then the acetone of getting 0.02 part of DCP and 0.3 part is put into beaker and is mixed, then the solution mixing is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing, 0.15 part of antioxidant 1010,0.15 part of calcium stearate; Finally the material mixing is joined in Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, after reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 2.8%).
(2) preparation of the weather-proof master batch of ULDPE: the weight percent meter of pressing ULDPE, 2.8%), put in high-speed mixer high-speed mixing 5min together with the white oil 5# of 0.6 part by the ULDPE of 100 parts and the ULDPE-g-VA grafts of 5 parts (percentage of grafting:; And then add the hindered amine as light stabilizer CH944 of 0.2 part and 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.01 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; After reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch a of ULDPE.
(3) preparation of polyethylene resin composition: after 0.002 part of BPO and 0.05 part of TBHP are mixed with 0.2 part of acetone solvent, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 11 parts of weather-proof master batch a of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.15 part of oxidation inhibitor B561,0.15 part of calcium stearate joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 2
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 1.
(3) preparation of polyethylene resin composition: after 0.005 part of BPO and 0.12 part of TBHP are mixed with 0.3 part of acetone solvent, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 13 parts of weather-proof master batch a of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.15 part of oxidation inhibitor B561,0.2 part of calcium stearate joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 3
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 1.
(3) preparation of polyethylene resin composition: after 0.008 part of BPO and 0.17 part of TBHP are mixed with 0.4 part of acetone solvent, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 15 parts of weather-proof master batch a of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 4
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 1.
(3) preparation of polyethylene resin composition: after 0.009 part of BPO and 0.18 part of TBHP are mixed with 0.4 part of acetone solvent, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 17 parts of weather-proof master batch a of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 5
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 1.
(3) preparation of polyethylene resin composition: after 0.012 part of BPO and 0.22 part of TBHP are mixed with 0.5 part of acetone solvent, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 19 parts of weather-proof master batch a of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 6
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, the ULDPE high-speed mixing 6min by the vinyl acetate between to for plastic of 8 parts (VA) with 100 parts places 10hr by the material mixing in encloses container; Then the acetone of getting 0.03 part of DCP and 0.4 part is put into beaker and is mixed, then the solution mixing is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing, 0.15 part of antioxidant 1010,0.15 part of calcium stearate; Finally the material mixing is joined in Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, after reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 3.9%).
(2) preparation of the weather-proof master batch of ULDPE: the weight percent meter of pressing ULDPE, 3.9%), put in high-speed mixer high-speed mixing 5min together with the whiteruss of 0.8 part by the ULDPE of 100 parts and the ULDPE-g-VA grafts of 7 parts (percentage of grafting:; And then add 2002,0.15 parts of oxidation inhibitor B561 of quencher, the 0.15 part of calcium stearate of 791 and 0.02 part of the hindered amine as light stabilizer Tinuvin of 0.4 part, high-speed mixing 10min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; After reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch b of ULDPE.
(3) preparation of polyethylene resin composition: after 0.014 part of BPO and 0.15 part of TBHP are mixed with 0.4 part of xylene solvent, then add 7 parts of LLDPE (7042) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 21 parts of weather-proof master batch b of ULDPE and premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 7
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 6.
(3) preparation of polyethylene resin composition: after 0.017 part of BPO and 0.14 part of TBHP are mixed with 0.4 part of xylene solvent, then add 7 parts of LLDPE (7042) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 23 parts of weather-proof master batch b of ULDPE and premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 8
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 6.
(3) preparation of polyethylene resin composition: after 0.02 part of BPO and 0.26 part of TBHP are mixed with 0.6 part of acetone solvent, then add 7 parts of LLDPE (7042) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 25 parts of weather-proof master batch b of ULDPE and premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 9
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 6.
(3) preparation of polyethylene resin composition: after 0.022 part of BPO and 0.23 part of TBHP are mixed with 0.6 part of acetone solvent, then add 7 parts of LLDPE (7042) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 27 parts of weather-proof master batch b of ULDPE and premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Embodiment 10
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, the ULDPE high-speed mixing 6min by the vinyl acetate between to for plastic of 9 parts (VA) with 100 parts places 10hr by the material mixing in encloses container; Then the acetone of getting 0.04 part of TBPA and 0.6 part is put into beaker and is mixed, then the solution mixing is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing, 0.15 part of antioxidant 1010,0.15 part of calcium stearate; Finally the material mixing is joined in Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, after reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 4.2%).
(2) preparation of the weather-proof master batch of ULDPE: the weight percent meter of pressing ULDPE, 4.2%), put in high-speed mixer high-speed mixing 5min together with the white oil 5# of 0.9 part by the ULDPE of 100 parts and the ULDPE-g-VA grafts of 8 parts (percentage of grafting:; And then add the hindered amine as light stabilizer CH944 of 0.5 part and the quencher AM-101 of 0.03 part, 0.15 part of oxidation inhibitor B561,0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; After reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch c of ULDPE.
(3) preparation of polyethylene resin composition: after 0.007 part of BPO and 0.2 part of TBHP are mixed with 0.4 part of xylene solvent, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 29 parts of weather-proof master batch c of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of calcium stearate joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 1
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 1.
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 1, difference is not add in composition preparation process BPO, the add-on of TBHP is 0.052 part, that is: 0.052 part of TBHP is mixed with 0.2 part of acetone solvent after, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 11 parts of weather-proof master batch a of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.15 part of oxidation inhibitor B561,0.15 part of calcium stearate joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 2
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 1.
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 2, difference is not add in composition preparation process TBHP, the add-on of BPO is 0.125 part, that is: 0.125 part of BPO is mixed with 0.3 part of acetone solvent after, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 13 parts of weather-proof master batch a of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.15 part of oxidation inhibitor B561,0.2 part of calcium stearate joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 3
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 1.
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 3, difference is that the add-on of the weather-proof master batch a of ULDPE in composition preparation process is 6 parts, that is: 0.008 part of BPO and 0.17 part of TBHP are mixed with 0.4 part of acetone solvent after, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 6 parts of weather-proof master batch a of ULDPE and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 4
(1) preparation of the weather-proof master batch of ULDPE: difference is not add ULDPE-g-VA grafts in the weather-proof master batch preparation process of ULDPE, and other processes are identical with embodiment 1, make the weather-proof master batch of ULDPE (a-1).
(2) preparation of polyethylene resin composition: other condition is identical with embodiment 4, difference is that the weather-proof master batch of the ULDPE adding in composition preparation process is not containing ULDPE-g-VA grafts, 17 parts of the add-ons of the weather-proof master batch of ULDPE (a-1), that is: 0.009 part of BPO and 0.18 part of TBHP are mixed with 0.4 part of acetone solvent after, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 17 parts of weather-proof master batches of ULDPE (a-1) and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 5
The preparation of polyethylene resin composition: difference is not add the weather-proof master batch a of ULDPE in resin combination preparation process, and other processes are identical with embodiment 5.The canopy film properties of its composition blowing is in table 1.
Comparative example 6
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE is completely identical with embodiment 6.
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 6, difference is not add in composition preparation process the weather-proof master batch b of ULDPE, but add ULDPE (4404G), 21 parts of the add-ons of ULDPE (4404G), that is: 0.014 part of BPO and 0.15 part of TBHP are mixed with 0.4 part of xylene solvent after, then add 7 parts of LLDPE (7042) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 21 parts of ULDPE (4404G) and premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 7
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE: other condition is identical with embodiment 6, difference is not add quencher 2002 in the weather-proof master batch preparation process of ULDPE, the add-on of hindered amine as light stabilizer Tinuvin 791 is 0.42 part, 3.9%), put in high-speed mixer high-speed mixing 5min together with the whiteruss of 0.8 part that is: by the ULDPE of 100 parts and the ULDPE-g-VA grafts of 7 parts (percentage of grafting:; And then add 791,0.15 parts of oxidation inhibitor B561 of hindered amine as light stabilizer Tinuvin of 0.42 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; After reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch of ULDPE (b-1).
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 7, difference is that the weather-proof master batch of the ULDPE adding in composition preparation process is not containing quencher 2002,23 parts of the add-ons of the weather-proof master batch of ULDPE (b-1), that is: 0.017 part of BPO and 0.14 part of TBHP are mixed with 0.4 part of xylene solvent after, then add 7 parts of LLDPE (7042) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 23 parts of weather-proof master batches of ULDPE (b-1) and premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 8
(1) preparation of ULDPE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE: other condition is identical with embodiment 6, difference is not add hindered amine as light stabilizer Tinuvin 791 in the weather-proof master batch preparation process of ULDPE, the add-on of quencher 2002 is 0.42 part, 3.9%), put in high-speed mixer high-speed mixing 5min together with the whiteruss of 0.8 part that is: by the ULDPE of 100 parts and the ULDPE-g-VA grafts of 7 parts (percentage of grafting:; And then add 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.42 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; After reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch of ULDPE (b-2).
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 8, difference is that the weather-proof master batch of the ULDPE adding in composition preparation process is not containing hindered amine as light stabilizer Tinuvin 791,25 parts of the add-ons of the weather-proof master batch of ULDPE (b-2), that is: 0.02 part of BPO and 0.26 part of TBHP are mixed with 0.6 part of acetone solvent after, then add 7 parts of LLDPE (7042) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 25 parts of weather-proof master batches of ULDPE (b-2) and premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 9
(1) preparation of the weather-proof master batch of ULDPE: difference is not add ULDPE-g-VA grafts in the weather-proof master batch preparation process of ULDPE, and other processes are identical with embodiment 6, make the weather-proof master batch of ULDPE (b-3).
(2) preparation of polyethylene resin composition: other condition is identical with embodiment 9, difference is that the weather-proof master batch of the ULDPE adding in composition preparation process is not containing ULDPE-g-VA grafts, 27 parts of the add-ons of the weather-proof master batch of ULDPE (b-3), that is: 0.022 part of BPO and 0.23 part of TBHP are mixed with 0.6 part of acetone solvent after, then add 7 parts of LLDPE (7042) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 27 parts of weather-proof master batches of ULDPE (b-3) and premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
Comparative example 10
The preparation of polyethylene resin composition: difference is not add in resin combination preparation process the weather-proof master batch c of ULDPE, but add ULDPE (4404G), 29 parts of the add-ons of ULDPE (4404G), that is: 0.007 part of BPO and 0.2 part of TBHP are mixed with 0.4 part of xylene solvent after, then add 5 parts of LLDPE (101AA) powder resin, in 10 liters of high-speed mixers, mix 3min, make premix masterbatch; Take out 29 parts of ULDPE (4404G) and premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of calcium stearate joins in Φ 67 twin screw extruders together with charging opening, screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; After reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition 120 3 layers of compound blown film unit blowing up wide cut canopy processed film of Φ (fabric width 8m, thickness be 80 μ m), the canopy film properties of its composition blowing is in table 1.
The performance of table 1 polyethylene green house film and applicable cases
Figure BDA0000082227940000161
Figure BDA0000082227940000171
*heavy natural sunning place: Gansu Wuwei
*reference sample: commercially available Lan Hua HTC's film factory production LDPE/LLDPE (7: 3) blending material shed film (8000 × 0.08mm).

Claims (9)

1. a polyethylene resin composition, is characterized in that, take the weight of LLDPE as absolutely, comprising:
1) 100% LLDPE
2) 0.05%～0.3% composite crosslinking coagent
3) the weather-proof master batch of 10%～30% ultra-low density polyethylene
The blend that the weather-proof master batch of described ultra-low density polyethylene is made up of grafts and the dispersion agent of ultra-low density polyethylene, composite light stabilizer, ultra-low density polyethylene and vinyl acetate between to for plastic; The preparation method of the weather-proof master batch of described ultra-low density polyethylene comprises: together with 100 parts of ultra-low density polyethylenes, 4～10 parts of ultra-low density polyethylenes and the grafts of vinyl acetate between to for plastic, 0.5～1.0 part of dispersion agent, put in super mixer high-speed mixing 3～5min; And then add the composite light stabilizer of 0.11～0.54 part, high-speed mixing 5～10min; Mixed material is added to twin screw extruder, 165～210 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, obtains the weather-proof master batch of ultra-low density polyethylene; Described composite crosslinking coagent is tertbutyl peroxide and the composite composition of dibenzoyl peroxide, and the mass ratio of two kinds of crosslinking coagents is 30: 1～5: 1.
2. resin combination as claimed in claim 1, is characterized in that composite light stabilizer is made up of quencher and radical scavenger.
3. resin combination as claimed in claim 2, is characterized in that quencher is organic nickel compound.
4. resin combination as claimed in claim 2, is characterized in that radical scavenger is hindered amine as light stabilizer.
5. resin combination as claimed in claim 1, is characterized in that described dispersion agent is the one in sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax.
6. resin combination as claimed in claim 1, is characterized in that described ultra-low density polyethylene and the grafts of vinyl acetate between to for plastic are vinyl acetate between to for plastic to be grafted to the graft copolymer on ultra-low density polyethylene main chain under the effect of initiator.
7. resin combination as claimed in claim 6; it is characterized in that described initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate, tertbutyl peroxide, 2; 5-dimethyl-2, the one in 5-di-t-butyl hexane peroxide, dicumyl peroxide, diisopropylbenzenehydroperoxide, benzoyl peroxide or peroxide di-t-butyl.
8. resin combination as claimed in claim 1, the preparation method who it is characterized in that the grafts of described ultra-low density polyethylene and vinyl acetate between to for plastic comprises: by 5～10 parts of vinyl acetate between to for plastics and 100 parts of ultra-low density polyethylene high-speed mixing 5～10min, the material mixing is placed to 5～10h in encloses container; Then getting 0.01～0.1 part of initiator and acetone is within 1: 10～1: 20, to be mixed with mixing solutions by weight, again by mixing solutions and the mixture high-speed mixing 5～10min placing, finally by carrying out melting graft reaction in twin screw extruder, 160～200 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain vinyl acetate between to for plastic percentage of grafting and be 2%～7% ultra-low density polyethylene and the grafts of vinyl acetate between to for plastic.
9. the preparation method of a resin combination as claimed in claim 1, it is characterized in that comprising: after first two kinds of crosslinking coagents are composite in proportion, add solvent, add again that to account for gross weight be 5%～10% powdery LLDPE, then, after high-speed mixing 3～5min, make premix masterbatch; Then remaining powdery LLDPE, premix masterbatch and the weather-proof master batch of ultra-low density polyethylene are joined together and in forcing machine, carried out extrusion reaction by charging opening, temperature of reaction is 165～220 ℃, reaction times is 2～5min, extrudes, cooling, granulation, makes polyethylene resin composition.
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CN101143945A (en) * 2007-09-04 2008-03-19 上海新上化高分子材料有限公司 Color weatherable silane crosslinked polyethylene plastic and application thereof

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