CN103160013B - Metallocene polyethylene resin composition for greenhouse film and preparation method thereof - Google Patents
Metallocene polyethylene resin composition for greenhouse film and preparation method thereof Download PDFInfo
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- CN103160013B CN103160013B CN201110419931.1A CN201110419931A CN103160013B CN 103160013 B CN103160013 B CN 103160013B CN 201110419931 A CN201110419931 A CN 201110419931A CN 103160013 B CN103160013 B CN 103160013B
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- 239000011342 resin composition Substances 0.000 title claims abstract description 47
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 61
- 229920013716 polyethylene resin Polymers 0.000 title claims description 6
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims abstract description 96
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 30
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 29
- 238000005469 granulation Methods 0.000 claims description 24
- 230000003179 granulation Effects 0.000 claims description 24
- 238000001125 extrusion Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- -1 dimethyl-2,5-di-t-butyl hexane peroxides Chemical class 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical group CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000007664 blowing Methods 0.000 abstract description 24
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 230000006378 damage Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000000428 dust Substances 0.000 abstract description 2
- 229920000578 graft copolymer Polymers 0.000 abstract description 2
- 239000004576 sand Substances 0.000 abstract description 2
- 241000251468 Actinopterygii Species 0.000 abstract 1
- 238000004880 explosion Methods 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 description 20
- 230000003078 antioxidant effect Effects 0.000 description 20
- 239000004744 fabric Substances 0.000 description 20
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 14
- 235000013539 calcium stearate Nutrition 0.000 description 14
- 239000008116 calcium stearate Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a metallocene polyethylene greenhouse film resin composition, which comprises the following components in percentage by weight of mLLDPE: 100 percent of mLLDPE, 0.07-0.2 percent of compound crosslinking assistant and 10-25 percent of ULDPE graft, wherein the ULDPE graft is a graft copolymer which grafts styrene monomer to the main chain of ULDPE under the action of initiator, and the composition can be used for blowing a wide greenhouse film with high tearing strength and excellent weather resistance without any blending. The surface of the shed film has few fish eyes, can continuously buckle the shed for more than 900 days without natural damage and can resist the sand dust explosion of 7-8 levels.
Description
Technical field
The present invention relates to a kind of metallocene polyethylene greenhouse film resin composition, be specifically related to resin based on metallocene linear low density polyethylene (mLLDPE), by organo-peroxide and the modification of second component ULDPE-g-St grafts, prepare that tear strength is high, the agricultural wide cut canopy film resin composition and method of making the same of good weatherability.
Background technology
China is a large agricultural country, is one of country that agricultural plastic film usage quantity is maximum in the world, and wherein the annual consumption of canopy film has reached more than 700,000 tons, and agricultural canopy film occupies very important status in China's plastics industry.At present, the developmental level of China's agricultural canopy film is compared with advanced international standard, still have very large gap, these gaps are mainly manifested in that domestic common canopy film tear strength is low and weathering resistance is bad, 7 to 8 grades, NORTHWEST CHINA area sandstorm weather cannot be resisted, this diastrous weather causes warmhouse booth to occur large-arealy being packed, and this has a poor foundation concerning west area, be a kind of deathblow not rich peasant.
Metallocene linear-low density polyethylene (mLLDPE) has been able to develop rapidly since the suitability for industrialized production realized first by american exxon (Exxon) company the nineties in 20th century.This mainly have benefited from mLLDPE adopt be there is single-activity center, catalytic activity is high, show the metallocene catalyst of outstanding catalysis in a homogeneous system, make mLLDPE compared with conventional linear polyethylene resin (LLDPE): to have high physical mechanical strength, excellent anti tear and anti-puncture performance, optical transparence is good.Thus, mLLDPE in agricultural canopy film by a large amount of application.But mLLDPE molecular structure feature determines that its melt strength is low, cause showing in extrusion-blown modling complete processing: mouth mould place " stick-slip phenomenon " is obvious, easily piles film, film bubble swings, and bubble stability is poor, cannot blow separately the wide greenhouse films of excellent performance.Secondly, when under the impact being subject to the factors such as sunlight, temperature, wind-force, easily there is chain rupture in the molecular chain of mLLDPE, easily occurs " backboard effect " (canopy film is easily in phenomenon of skeleton place cracking).So just significantly limit the application development space of mLLDPE in agricultural canopy film field.
In prior art, about the method improving processing capability of metallocene polyethylene has: 1). by polymer blending, select that structure is close, processing characteristics that the general polyethylene of good processability or other polymkeric substance improve metallocene PE.If: CN101323674A is by 90% polyethylene and 9% glyceryl monooleate and 1%2.5-methyl-2.5 bishexane blend graft at 200 DEG C, then in three layers of Coextruded blown unit, blow out longevity polar shed film with high-pressure polyethylene (HDPE) and linear low density polyethylene (LLDPE) and mLLDPE blending.CN1384139A adds 50 ~ 90wt% high-pressure polyethylene in 10 ~ 50wt%mLLDPE, prepares angle tear strength high, and thickness is 0.02 ~ 0.045mm canopy film.Document " research of metallocene PE wide cut blowing moulding greenhouse film " (Chinese Plastics, 16 volume 1 phases in 2002,45-50 page) to describe mLLDPE and LDPE blended, solve the processing problems such as mLLDPE melt viscosity is large, melt strength is low, blowing goes out thickness 0.06mm ~ 0.08mm, the wide cut canopy film of folding footpath 4000mm ~ 5000mm.2). by the processing characteristics of aggregation process modification metallocene PE resin.As: CN1927897A adds the oxidation inhibitor of 0.1 ~ 3 weight part in mLLDPE (100 weight part), force chemical reactor is put into after mixing, under 15 ~ 35 DEG C of conditions, carry out chemical reaction handling, preparing can at the generally general mLLDPE resin extruded, inject smooth forming process on processing units.3). utilize Reaction extrusion technology, by the processing characteristics of micro-cross-linking modified metallocene PE resin.As: the wide cut canopy film adding the peroxidized t-butyl perbenzoate preparation folding footpath 8000mm of 0.05 ~ 0.35wt% di-tert-butyl hydrogen peroxide and 0.005 ~ 0.041wt% in CN201010114242.5 in mLLDPE.
Above-mentioned patent and document are intended to the melt strength of raising mLLDPE resin and improve its blown film processing characteristics.But some problems is there is in raising mLLDPE speciality for green house film tear strength and weathering resistance, mainly the blending resin trade mark is many, base resin mechanical property is low, auxiliary agent kind is many, preparation technology's long flow path, production cost are high, auxiliary agent utilize high efficiency and persistence poor.Easily cause the quality of mLLDPE canopy film uneven like this, the problems such as work-ing life is short, tearing toughness is low.
Summary of the invention
The object of the invention is to provide a kind of metallocene polyethylene greenhouse film resin composition and preparation method thereof.Said composition any blending just need not can blow out the wide cut canopy film (fabric width >=8, thickness >=60 μm) that tear strength is high and weathering resistance is excellent.This canopy film surface " flake " less, canopy can be detained continuously within more than 900 days, do not occur that nature is damaged and can to resist 7 ~ 8 grades of sand and dust quick-fried.The present invention proposes the preparation method of composition further.
A kind of Metallocene polyethylene resin composition, in the weight of mLLDPE for a hundred per cent, comprising:
(1)mLLDPE 100％
(2) composite crosslinking coagent 0.07 ~ 0.2%
(3) ULDPE-g-St grafts 10% ~ 25%
Composite crosslinking coagent described in composition is 2,5-dimethyl-2,5-di-t-butyl hexane peroxide (BPDH) and dibenzoyl peroxide (BPO) composite composition, and the mixing quality ratio of BPDH and BPO is 25: 1 ~ 5: 1.
Described ULDPE-g-St grafts is the graft copolymer be grafted to by grafted monomer under the effect of initiator on ultra-low density polyethylene (ULDPE) main chain; initiator was selected from octanoic acid ter-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, dicumyl peroxide, diisopropylbenzenehydroperoxide (DBHP), benzoyl peroxide or peroxide di-t-butyl, preferably adopts dicumyl peroxide (DCP).Grafted monomer is selected from polymerization-grade vinylbenzene (St), vinylbenzene purity > 99.0%.Polymkeric substance ULDPE is obtained 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, its Midst 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 DEG C, the measured value under 2.16Kg load.
The preparation method of described ULDPE-g-St grafts is: by the vinylbenzene (St) of 10 ~ 20 weight parts and the ULDPE high-speed mixing 5 ~ 10min of 100 weight parts, the material mixed is placed 12 ~ 24h in encloses container; Then getting the initiator of 0.3 ~ 1.0 weight part and acetone is be mixed with mixing solutions at 1: 2 ~ 1: 4 by weight, again by mixing solutions and the mixture high-speed mixing 5 ~ 10min placed, melting graft reaction is carried out finally by twin screw extruder, temperature of reaction 160 ~ 210 DEG C, reaction times 5 ~ 10min, extrude, cool, granulation, obtain the ULDPE-g-St grafts that styrene-grafted rate is 6% ~ 9%.
Metallocene linear-low density polyethylene (mLLDPE) described in composition is to adopt single site catalysts---polyethylene prepared by metallocene catalysis system, can be ethene and butene-1, hexene-1 copolymerization and obtaining, also can be obtained by ethylene homo.Weight-average molecular weight M
w: 6 ~ 15 × 10
4, molecular weight distribution MWD :≤2.2, density: 0.865 ~ 0.941g/cm
3, melt flow rate (MFR): 0.5 ~ 10g/10min.
MLLDPE described in composition can be powdery or granular resin, but best with powdered resin for reaching better mixed effect.
Composite crosslinking coagent described in composition is the composite composition that BPDH and BPO carries out different ratios.Wherein the scope of total add-on of composite crosslinking coagent is the best mixing quality ratio of 0.07 ~ 0.2%, two kinds of crosslinking coagents is BPDH/BPO=20: 1 ~ 8: 1.The half life temperature of superoxide is slightly difference because of the difference of manufacturer, transformation period T=175 ~ 189 of general BPDH DEG C/1min; Transformation period T=131 ~ 134 of BPO DEG C/1min.
The used in amounts of general BPO strictly controls, its consumption can not more than 0.03%, in composition preparation process, processing temperature can not more than 230 DEG C in addition, otherwise degree of crosslinking is uncontrollable, easily occurring excessively crosslinked generation gel, easily there is " flake " in agricultural canopy film surface, its tear strength and weathering resistance not only do not improve, cause mechanics mechanical degradation on the contrary, 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, but is the best with twin screw extruder.
Particularly, the preparation method of resin combination provided by the invention comprises: add solvent after being first mixed in proportion by two kinds of crosslinking coagents, add the mLLDPE accounting for total amount 5% ~ 10% (wt) again, then after high-speed mixing 3 ~ 5min, make premix masterbatch; Then residue mLLDPE, premix masterbatch and ULDPE-g-St grafts are joined in forcing machine together by charging opening and carry out extrusion reaction, temperature of reaction is 155 ~ 210 DEG C, reaction times is 1 ~ 3min, extrude, cool, granulation, obtained metallocene linear-low density polyethylene canopy film resin composition.
The present invention also can add a certain amount of thermo-stabilizer and oxidation inhibitor in the preparation process of ULDPE-g-St grafts and resin combination, its total add-on be 0.1% ~ 0.5% (in the weight of mLLDPE for absolutely).
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, first the composite cross-linking system of a kind of low activity and highly active organo-peroxide composition is selected, effectively can control cross-linked speed and the crosslinking degree of resin, ensure that linking agent appropriateness when few additive improves the melt strength of resin, blowing wide cut canopy film (fabric width >=8m can be reached, thickness >=60 μm) requirement, a kind of organo-peroxide of single use is avoided not to be occur excessively being cross-linked, cause consumption excessive exactly, film surface " flake " is many, and be unfavorable for safety, environmental protection, the problems such as modification cost.Secondly, along with adding of second component ULDPE-g-St grafts makes phenyl ring be incorporated into well in the molecular chain structure of base resin, improve the tearing toughness of base resin significantly.Secondly, in ULDPE molecular structure, short-chain branch is many, there is the feature of larger and more complete spherocrystal, and also there is certain crosslinked action with crosslinking coagent, can form more physical crosslinking point in the molecular structure, this synergy makes ULDPE-g-St grafts have the weathering resistance of base resin and tear strength obviously to improve effect.In addition, because ULDPE density is low, intermolecular freeboard is large, and short-chain branch is many, makes molecular chain produce larger rebound resilience and avoids, because the introducing of benzene ring structure is for the destruction of base resin ductility, maintaining canopy film to ductile requirement.Make said composition can have without the common blown film unit of any transformation can stably be blown out without the need to any blending wide cut canopy film (fabric width >=8m that tear strength is high and weathering resistance is excellent like this, thickness >=60 μm), 7 ~ 8 grades of sandstorms can be resisted and detain canopy continuously and nature breakage not occur in more than 900 days, be particularly suitable for laying in the west area that sandstorm takes place frequently and the sunshine duration is long.
Embodiment
(1) raw material
1) resin
2) organo-peroxide
BPDH transformation period T=186 DEG C/1min, Lanzhou auxiliary reagent factory
BPO transformation period T=133 DEG C/1min, Lanzhou auxiliary reagent factory
DCP transformation period T=171 DEG C/1min, Hao Hua chemical plant, Shanghai
TBPA transformation period T=160 DEG C/1min, Lanzhou auxiliary reagent factory
3) other auxiliary agent
Antioxidant 1010 Switzerland vapour Bagong department
Calcium stearate Yangtse River in Chongqing chemical plant
Zinic stearas Yangtse River in Chongqing chemical plant
(2) performance test standard
(3) equipment and instrument
The German Lestreiz company in Φ 67 twin-screw extrusion captain/footpath=34/1
10 liters of high-speed mixer Fuxin plastics machinery factories
Φ 120 3 layers of compound inflation film manufacturing machine Dalian rubber and plastics machine factory
Embodiment and comparative example
Enumerate following examples so that invention effect of the present invention to be described, but protection scope of the present invention is not limited in these embodiments, in composition, each component is with the weight parts of base resin mLLDPE.
Embodiment 1
(1) preparation of ULDPE-g-St grafts: by the ULDPE high-speed mixing 7min of the vinylbenzene of 11 parts (St) with 100 parts, the material mixed is placed 19hr in encloses container; Then the acetone getting 0.4 part of DCP and 1.0 part is put into beaker and is mixed, then the solution mixed is put into 10L high-speed mixer, high-speed mixing 6min together with the mixture placed, 0.15 part of antioxidant 1010,0.15 part of calcium stearate; Finally joined in Φ 67 twin screw extruder by the material mixed, screw zones temperature of reaction (DEG C) is followed successively by: 160, and 175,180,190,200,210,200,190,180; Carry out melting graft reaction, after reaction 5min, extrude, cool, granulation, obtained ULDPE-g-St grafts (percentage of grafting: 5.9%).
(2) preparation of mLLDPE canopy film resin composition: after 0.07 part of BPDH and 0.003 part BPO is mixed with 0.2 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.15 part of antioxidant 1010,0.15 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 11 parts of ULDPE-g-St grafts (percentage of grafting: 5.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 2
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 1.
(2) preparation of mLLDPE canopy film resin composition: after 0.08 part of BPDH and 0.004 part BPO is mixed with 0.2 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.15 part of antioxidant 1010,0.15 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 13 parts of ULDPE-g-St grafts (percentage of grafting: 5.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 3
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 1.
(2) preparation of mLLDPE canopy film resin composition: after 0.09 part of BPDH and 0.005 part BPO is mixed with 0.2 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.2 part of antioxidant 1010,0.2 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 15 parts of ULDPE-g-St grafts (percentage of grafting: 5.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 4
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 1.
(2) preparation of mLLDPE canopy film resin composition: after 0.1 part of BPDH and 0.007 part BPO is mixed with 0.3 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.2 part of antioxidant 1010,0.2 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 17 parts of ULDPE-g-St grafts (percentage of grafting: 5.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 5
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 1.
(2) preparation of mLLDPE canopy film resin composition: after 0.12 part of BPDH and 0.008 part BPO is mixed with 0.3 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.2 part of antioxidant 1010,0.2 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 19 parts of ULDPE-g-St grafts (percentage of grafting: 5.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 6
(1) preparation of ULDPE-g-St grafts: by the ULDPE high-speed mixing 6min of the vinylbenzene of 16 parts (St) with 100 parts, the material mixed is placed 20hr in encloses container; Then the acetone getting 0.7 part of DCP and 1.6 part is put into beaker and is mixed, then the solution mixed is put into 10L high-speed mixer, high-speed mixing 6min together with the mixture placed, 0.2 part of antioxidant 1010,0.2 part of calcium stearate; Finally joined in Φ 67 twin screw extruder by the material mixed, screw zones temperature of reaction (DEG C) is followed successively by: 160, and 175,180,190,200,210,200,190,180; Carry out melting graft reaction, after reaction 5min, extrude, cool, granulation, obtained ULDPE-g-St grafts (percentage of grafting: 7.1%).
(2) preparation of mLLDPE canopy film resin composition: after 0.13 part of BPDH and 0.009 part BPO is mixed with 0.3 part of xylene solvent, then 7 parts of mLLDPE (ECD350) and 0.2 part of antioxidant 1010,0.2 part of Zinic stearas is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 20 parts of ULDPE-g-St grafts (percentage of grafting: 7.1%) join in Φ 67 twin screw extruder together with charging opening with 93 parts of mLLDPE (ECD350) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 7
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 6.
(2) preparation of mLLDPE canopy film resin composition: after 0.14 part of BPDH and 0.01 part BPO is mixed with 0.3 part of xylene solvent, then 7 parts of mLLDPE (ECD350) and 0.2 part of antioxidant 1010,0.2 part of Zinic stearas is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 21 parts of ULDPE-g-St grafts (percentage of grafting: 7.1%) join in Φ 67 twin screw extruder together with charging opening with 93 parts of mLLDPE (ECD350) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 8
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 6.
(2) preparation of mLLDPE canopy film resin composition: after 0.16 part of BPDH and 0.015 part BPO is mixed with 0.3 part of xylene solvent, then 7 parts of mLLDPE (ECD350) and 0.2 part of antioxidant 1010,0.2 part of Zinic stearas is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 22 parts of ULDPE-g-St grafts (percentage of grafting: 7.1%) join in Φ 67 twin screw extruder together with charging opening with 93 parts of mLLDPE (ECD350) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 9
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 6.
(2) preparation of mLLDPE canopy film resin composition: after 0.16 part of BPDH and 0.02 part BPO is mixed with 0.3 part of xylene solvent, then 7 parts of mLLDPE (ECD350) and 0.2 part of antioxidant 1010,0.2 part of Zinic stearas is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 23 parts of ULDPE-g-St grafts (percentage of grafting: 7.1%) join in Φ 67 twin screw extruder together with charging opening with 93 parts of mLLDPE (ECD350) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Embodiment 10
(1) preparation of ULDPE-g-St grafts: by the ULDPE high-speed mixing 7min of the vinylbenzene of 18 parts (St) with 100 parts, the material mixed is placed 22hr in encloses container; Then the acetone getting 0.5 part of TBPA and 1.5 part is put into beaker and is mixed, then the solution mixed is put into 10L high-speed mixer, high-speed mixing 7min together with the mixture placed, 0.1 part of antioxidant 1010,0.2 part of calcium stearate; Finally joined in Φ 67 twin screw extruder by the material mixed, screw zones temperature of reaction (DEG C) is followed successively by: 160, and 175,180,190,200,210,200,190,180; Carry out melting graft reaction, after reaction 5min, extrude, cool, granulation, obtained ULDPE-g-St grafts (percentage of grafting: 7.9%).
(2) preparation of mLLDPE canopy film resin composition: after 0.17 part of BPDH and 0.022 part BPO is mixed with 0.4 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.2 part of antioxidant 1010,0.2 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 25 parts of ULDPE-g-St grafts (percentage of grafting: 7.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Comparative example 1
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 1.
(2) preparation of mLLDPE canopy film resin composition: other condition is identical with embodiment 1, difference is not add BPO in composition preparation process, the add-on of BPDH is 0.073 part, that is: after 0.073 part of BPDH being mixed with 0.2 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.15 part of antioxidant 1010,0.15 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 11 parts of ULDPE-g-St grafts (percentage of grafting: 5.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Comparative example 2
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 1.
(2) preparation of mLLDPE canopy film resin composition: other condition is identical with embodiment 1, difference is not add BPDH in composition preparation process, the add-on of BPO is 0.084 part, that is: after 0.084 part of BPO being mixed with 0.2 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.15 part of antioxidant 1010,0.15 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 13 parts of ULDPE-g-St grafts (percentage of grafting: 5.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Comparative example 3
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 1.
(2) preparation of mLLDPE canopy film resin composition: other condition is identical with embodiment 3, difference is not add BPDH and BPO in composition preparation process.Its composition blowing wide cut canopy film properties is in table 1.
Comparative example 4
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 1.
(2) preparation of mLLDPE canopy film resin composition: other condition is identical with embodiment 4, difference is the (percentage of grafting: 5.9%) add-on 4 parts of ULDPE-g-St grafts in composition preparation process, that is: after 0.1 part of BPDH and 0.007 part BPO being mixed with 0.3 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.2 part of antioxidant 1010,0.2 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 4 parts of ULDPE-g-St grafts (percentage of grafting: 5.9%) join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Comparative example 5
The preparation of mLLDPE canopy film resin composition: difference is not add ULDPE-g-St grafts in resin combination preparation process, and other processes are identical with embodiment 5.Its composition blowing wide cut canopy film properties is in table 1.
Comparative example 6
The preparation of mLLDPE canopy film resin composition: other condition is identical with embodiment 6, difference is not add ULDPE-g-St grafts in resin combination preparation process, but add ULDPE (4201G), ULDPE (4201G) add-on 20 parts, that is: after 0.13 part of BPDH and 0.009 part BPO being mixed with 0.3 part of xylene solvent, then 7 parts of mLLDPE (ECD350) and 0.2 part of antioxidant 1010,0.2 part of Zinic stearas is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then take out 20 parts of ULDPE (4201G) to join in Φ 67 twin screw extruder together with charging opening with 93 parts of mLLDPE (ECD350) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180,190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Comparative example 7
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 6.
(2) preparation of mLLDPE canopy film resin composition: other condition is identical with embodiment 7, difference is that the add-on of BPO in composition preparation process is 0.031 part, that is: after 0.14 part of BPDH and 0.031 part BPO being mixed with 0.3 part of xylene solvent, then 7 parts of mLLDPE (ECD350) and 0.2 part of antioxidant 1010,0.2 part of Zinic stearas is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 21 parts of ULDPE-g-St grafts (percentage of grafting: 7.1%) join in Φ 67 twin screw extruder together with charging opening with 93 parts of mLLDPE (ECD350) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Comparative example 8
(1) preparation of ULDPE-g-St grafts is completely identical with embodiment 6.
(2) preparation of mLLDPE canopy film resin composition: other condition is identical with embodiment 8, difference is the (percentage of grafting: 7.1%) add-on 7 parts of ULDPE-g-St grafts in composition preparation process, that is: after 0.16 part of BPDH and 0.015 part BPO being mixed with 0.3 part of xylene solvent, then 7 parts of mLLDPE (ECD350) and 0.2 part of antioxidant 1010,0.2 part of Zinic stearas is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then 7 parts of ULDPE-g-St grafts (percentage of grafting: 7.4%) join in Φ 67 twin screw extruder together with charging opening with 93 parts of mLLDPE (ECD350) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180 are taken out, 190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
Comparative example 9
The preparation of mLLDPE canopy film resin composition: difference is not add ULDPE-g-St grafts in resin combination preparation process, and other processes are identical with embodiment 9.Its composition blowing wide cut canopy film properties is in table 1.
Comparative example 10
The preparation of mLLDPE canopy film resin composition: other condition is identical with embodiment 10, difference is not add ULDPE-g-St grafts in resin combination preparation process, but add ULDPE (4201G), ULDPE (4201G) add-on 25 parts, that is: after 0.17 part of BPDH and 0.022 part BPO being mixed with 0.4 part of acetone solvent, then 5 parts of mLLDPE (HPR18H10AX) and 0.2 part of antioxidant 1010,0.2 part of calcium stearate is added, mix 3min in 10 liters of high-speed mixers after, make premix masterbatch; Then take out 25 parts of ULDPE (4201G) to join in Φ 67 twin screw extruder together with charging opening with 95 parts of mLLDPE (HPR18H10AX) with premix masterbatch, be followed successively by barrel temperature (DEG C): 155,180,190,195,200,210,200,190,180, after extrusion reaction 3min, extrude, cool, granulation, prepare metallocene polyethylene greenhouse film resin composition.Said composition is Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 60 μm), and its canopy film properties is in table 1.
The properties and application situation of table 1 metallocene PE canopy film
* heavy natural sunning place: Gansu Wuwei
Claims (5)
1. a Metallocene polyethylene resin composition, in the weight of mLLDPE for a hundred per cent, comprising:
(1)mLLDPE 100％
(2) composite crosslinking coagent 0.07 ~ 0.2%
(3) ULDPE-g-St grafts 10% ~ 25%
Described composite crosslinking coagent is 2,5-dimethyl-2,5-di-t-butyl hexane peroxide and dibenzoyl peroxide is 25: 1 ~ 5: 1 composite composition according to mass ratio; The preparation method of described ULDPE-g-St grafts is: by the ULDPE high-speed mixing 5 ~ 10min of the vinylbenzene of 10 ~ 20 weight parts and 100 weight parts, the material mixed is placed 12 ~ 24h in encloses container; Then getting the initiator of 0.3 ~ 1.0 weight part and acetone is be mixed with mixing solutions at 1: 2 ~ 1: 4 by weight, again by mixing solutions and the mixture high-speed mixing 5 ~ 10min placed, melting graft reaction is carried out finally by twin screw extruder, temperature of reaction 160 ~ 210 DEG C, reaction times 5 ~ 10min, extrude, cool, granulation, obtain the ULDPE-g-St grafts that styrene-grafted rate is 6% ~ 9%.
2. resin combination as claimed in claim 1, is characterized in that the mixing quality ratio of 2,5-described dimethyl-2,5-di-t-butyl hexane peroxides and dibenzoyl peroxide is 20: 1 ~ 8: 1.
3. resin combination as claimed in claim 1; it is characterized in that described initiator was selected from octanoic acid ter-butyl ester, t-butyl peroxy-acetate, tertbutyl peroxide, 2; one in 5-dimethyl-2,5-di-t-butyl hexane peroxide, dicumyl peroxide, diisopropylbenzenehydroperoxide, benzoyl peroxide or peroxide di-t-butyl.
4. resin combination as claimed in claim 1, it is characterized in that adding thermo-stabilizer and oxidation inhibitor in the preparation process of described resin combination and ULDPE-g-St grafts, in the weight of mLLDPE for a hundred per cent, the add-on of the two is 0.1% ~ 0.5%.
5. the preparation method of a resin combination as claimed in claim 1, it is characterized in that comprising: after being first mixed in proportion by two kinds of crosslinking coagents, add solvent, add the mLLDPE accounting for gross weight 5% ~ 10% again, then after high-speed mixing 3 ~ 5min, make premix masterbatch; Then residue mLLDPE, premix masterbatch and ULDPE-g-St grafts are joined in forcing machine together by charging opening and carry out extrusion reaction, temperature of reaction is 155 ~ 210 DEG C, reaction times is 1 ~ 3min, extrudes, cools, granulation, obtained Metallocene polyethylene resin composition.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827658A (en) * | 2006-03-28 | 2006-09-06 | 广州市合诚化学有限公司 | Materials dedicated for antibacterial and permeable polyolefin film and preparation method thereof |
| CN101979431A (en) * | 2010-10-14 | 2011-02-23 | 苏州康斯坦普工程塑料有限公司 | Organosilane crosslinked polyethylene film special material, preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827658A (en) * | 2006-03-28 | 2006-09-06 | 广州市合诚化学有限公司 | Materials dedicated for antibacterial and permeable polyolefin film and preparation method thereof |
| CN101979431A (en) * | 2010-10-14 | 2011-02-23 | 苏州康斯坦普工程塑料有限公司 | Organosilane crosslinked polyethylene film special material, preparation and application thereof |
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