CN102924798B - Weather-resistant metallocene polyethylene agricultural film resin composition and preparation method thereof - Google Patents
Weather-resistant metallocene polyethylene agricultural film resin composition and preparation method thereof Download PDFInfo
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- CN102924798B CN102924798B CN201110228038.0A CN201110228038A CN102924798B CN 102924798 B CN102924798 B CN 102924798B CN 201110228038 A CN201110228038 A CN 201110228038A CN 102924798 B CN102924798 B CN 102924798B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 84
- 239000011342 resin composition Substances 0.000 title claims abstract description 7
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 title claims abstract description 6
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims abstract description 120
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 113
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims description 77
- 229920005989 resin Polymers 0.000 claims description 77
- 229920003023 plastic Polymers 0.000 claims description 56
- 239000004033 plastic Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 50
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 35
- 238000005469 granulation Methods 0.000 claims description 33
- 230000003179 granulation Effects 0.000 claims description 33
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 30
- 238000001125 extrusion Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 19
- 239000004611 light stabiliser Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- SIAIIXKVTSMNBQ-UHFFFAOYSA-N [O].C(C)(C)(CC(C)(C)C)C1=CC=C(C=C1)O Chemical compound [O].C(C)(C)(CC(C)(C)C)C1=CC=C(C=C1)O SIAIIXKVTSMNBQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 229920013716 polyethylene resin Polymers 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
- VCSCKXNPGKIQRY-UHFFFAOYSA-N [Ni].C(CCCCCCC)N(C(S)=S)CCCCCCCC Chemical compound [Ni].C(CCCCCCC)N(C(S)=S)CCCCCCCC VCSCKXNPGKIQRY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 238000007664 blowing Methods 0.000 abstract description 24
- 239000013078 crystal Substances 0.000 abstract 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 28
- 239000004744 fabric Substances 0.000 description 23
- 239000003963 antioxidant agent Substances 0.000 description 22
- 230000003078 antioxidant effect Effects 0.000 description 22
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 19
- 235000013539 calcium stearate Nutrition 0.000 description 19
- 239000008116 calcium stearate Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- WPRMJBJYCFNTKE-UHFFFAOYSA-L (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinate;nickel(2+) Chemical compound [Ni+2].CCOP([O-])(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCOP([O-])(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WPRMJBJYCFNTKE-UHFFFAOYSA-L 0.000 description 1
- 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
- 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 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
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 230000009471 action Effects 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
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003335 steric effect Effects 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- B29C48/92—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
- B29C2948/92704—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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a metallocene polyethylene agricultural film resin composition and a preparation method thereof, wherein the metallocene polyethylene agricultural film resin composition comprises the following components in percentage by weight of mLLDPE: (1) 100% of mLLDPE, (2) 0.07-0.2% of compound crosslinking assistant, and (3) 10-30% of POE weather resistant master batch; the composition can be used for blowing a wide greenhouse film with the width of more than or equal to 8m and the thickness of more than or equal to 60 mu m without any mixing, the surface of the greenhouse film has few 'crystal points', and the greenhouse film can be continuously buckled for more than 40 months without natural damage. The invention further provides a preparation method of the resin composition.
Description
Technical field
The present invention relates to a kind of metallocene PE plastic sheeting for farm use resin combination, be specifically related to the weathering resistance agricultural wide cut canopy film resin composition and method of making the same of resin based on metallocene linear low density polyethylene (mLLDPE).
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 weathering resistance is bad, work-ing life is short, cannot resist the weather feature that the NORTHWEST CHINA area sunshine duration is long, uitraviolet intensity is high, this weather easily causes warmhouse booth to occur large-area breakage.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 factor such as sunlight, temperature, 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), cause canopy film short for work-ing life.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% ~ 0.35% (wt) di-tert-butyl hydrogen peroxide and 0.005% ~ 0.041% (wt) in CN201010114242.5 in mLLDPE.
Above-mentioned patent and document are only improving the melt strength of mLLDPE resin and are improving its blown film processing characteristics.Secondly, add in the blending resin of mLLDPE anti-aging system exist unreasonable, auxiliary agent kind is many, bad dispersibility, the persistence that auxiliary agent uses is short, easily the problems such as migration and precipitation occurs.
Summary of the invention
The object of the invention is to provide a kind of metallocene PE plastic sheeting for farm use resin combination and preparation method thereof.Said composition any blending just need not can blow out fabric width >=8m, the wide cut canopy film of thickness >=60 μm, and its film surface " brilliant point " is few, can detain canopy more than 40 months continuously and nature breakage does not occur.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) POE weatherable master batch 10% ~ 30%
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.
The blend that described POE weatherable master batch is made up of grafts (POE-g-VA grafts) and the dispersion agent of polymer P OE, composite light stabilizer, POE and vinyl acetate between to for plastic.Polymer P OE is the multipolymer adopting metallocene catalyst to realize ethene and octene in-situ polymerization, and wherein the content of ethene is: 10% ~ 40%; Melt flow rate (MFR) (MFR) is: 2 ~ 20g/10min; Density: 0.850 ~ 0.910g/cm
3.Described melt flow rate (MFR) (MFR) is at 190 DEG C, the measured value under 2.16Kg load.
The compound system that composite light stabilizer is made up of quencher and radical scavenger.Quencher is organo-nickel compounds, as: two (3, 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel (Irgastab 2002), 2, 2-thiobis (4-tertiary octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound (UV-1084), 2, 2-thiobis (4-tertiary octyl phenol oxygen base) nickel (AM-101), N, N-nickel dibutyl dithiocarbamate (NBC), one in dioctyl dithiocarbamic acid nickel (AM-108), organo-nickel compounds is because of the toxicity problem of heavy metal ion, its consumption should be strict controlled in 0.01% ~ 0.04% (weight percent meter by POE).Radical scavenger selects the hindered amine as light stabilizer (HALS) with space steric effect, as: the one in Tinuvin123, Tinuvin622, Tinuvin791, GW-540, GW-480, GW-544, CH944, its consumption is 0.05% ~ 0.25% (weight percent meter by POE).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, reach the work-ing life extending resin.
POE-g-VA grafts is the graft copolymer be grafted to by grafted monomer under the effect of initiator on POE 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 (DTBP), dicumyl peroxide, diisopropylbenzenehydroperoxide (DBHP), benzoyl peroxide or peroxide di-t-butyl; preferred employing 2; 5-dimethyl-2,5-di-t-butyl hexane peroxide (BPDH).Grafted monomer is selected from polymerization-grade vinyl acetate between to for plastic (VA).
Dispersion agent can be the one or composite wherein such as sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax, white oil, preferably adopts white oil.
POE weatherable master batch preparation method provided by the invention comprises:
(1) preparation method of POE-g-VA grafts:
By the weight percent meter of POE, by the POE high-speed mixing 5 ~ 10min of the vinyl acetate between to for plastics of 3 ~ 7 parts (VA) with 100 parts, the material mixed is placed 5 ~ 10h in encloses container; Then getting the initiator of 0.01 ~ 0.1 part and acetone is be mixed with mixing solutions at 1: 10 ~ 1: 20 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 ~ 200 DEG C, reaction times 5 ~ 10min, extrude, cool, granulation, obtain the POE-g-VA grafts that VA percentage of grafting is 1% ~ 4%.
(2) preparation of POE weatherable master batch
By the weight percent meter of POE, put in super mixer together with the POE of 100 parts and the POE-g-VA grafts of 5 ~ 10 parts, the dispersion agent of 0.3 ~ 0.9 part, high-speed mixing 3 ~ 5min; And then add the composite light stabilizer of 0.06 ~ 0.29 part, high-speed mixing 5 ~ 10min; Mixed material is added twin screw extruder, temperature of reaction 165 ~ 210 DEG C, reaction times 3 ~ 5min, extrudes, cools, granulation, obtain POE weatherable master batch.
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 POE weatherable master batch 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 PE plastic sheeting for farm use resin combination.
The present invention also can add a certain amount of thermo-stabilizer and oxidation inhibitor in the preparation process of POE weatherable master batch and resin combination, and its total add-on is 0.1% ~ 0.5% (with the weight of mLLDPE for percentages).
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, POE molecular structure in POE weatherable master batch does not have unsaturated double-bond and contains long side octyl group, and also there is certain crosslinked action in POE and crosslinking coagent, more physical crosslinking point can be formed in the molecular structure, the weathering resistance of base resin can be improved significantly.And along with the consistency adding enhancing POE resin and photostabilizer of POE-g-VA grafts, improve the dispersion effect of photostabilizer in resin, thus improve the high efficiency of photostabilizer; POE-g-VA grafts has certain adsorption to photostabilizer in addition, avoid the migration of photostabilizer in resin and precipitation problem, drastically increase the persistence of photostabilizer, reach and obtain best weather-proof modifying function with minimum add-on, minimum cost.POE resin and photostabilizer can produce certain positive cooperativity simultaneously, and this has very significant effect to the weathering resistance improving agricultural canopy film base resin.Secondly, select the composite cross-linking system of a kind of low activity and highly active organo-peroxide composition, 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, and avoid a kind of organo-peroxide of single use not to be occur excessively being cross-linked, cause consumption excessive exactly, the problem that film surface easily occurs " brilliant point ".Make said composition can without the common blown film unit of any transformation stably can be blown out the wide cut canopy film (fabric width >=8m with excellent weather resistance without the need to any blending like this, thickness >=60 μm), canopy more than 40 months can be detained continuously nature breakage does not occur, be particularly suitable for laying in the west area of inclement condition and sunshine duration length.
Embodiment
(1) raw material
1) resin
2) organo-peroxide
BPO transformation period T=133 DEG C/1min, Lanzhou auxiliary reagent factory
BPDH transformation period T=186 DEG C/1min, Lanzhou auxiliary reagent factory
DTBP transformation period T=192 DEG C/1min, Lanzhou auxiliary reagent factory
3) other auxiliary agent
(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 POE-g-VA grafts: by the weight percent meter of POE, by the POE high-speed mixing 6min of the vinyl acetate between to for plastics of 4 parts (VA) with 100 parts, places 10h by the material mixed in encloses container; Then the acetone getting 0.03 part of BPDH and 0.3 part is put into beaker and is mixed, then the solution mixed is put into 10L high-speed mixer, high-speed mixing 5min 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 170,180,190,200,190,180,175,170; Carry out melting graft reaction, after reaction 7min, extrude, cool, granulation, obtain POE-g-VA grafts (percentage of grafting: 2.1%).
(2) preparation of POE weatherable master batch: by the weight percent meter of POE, by the POE of 100 parts and the POE-g-VA grafts of 6 parts (percentage of grafting: 2.1%), put in high-speed mixer together with the white oil 5# of 0.4 part, high-speed mixing 5min; And then add the quencher of hindered amine as light stabilizer CH944 and 0.02 part 2002,0.15 part of oxidation inhibitor B561 of 0.1 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruder, screw zones temperature of reaction (DEG C) is followed successively by: 165, and 170,180,190,200,210,190,180,170; After reaction 4min, extrude, cool, granulation, obtain POE weatherable master batch a.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 12 parts of POE weatherable master batch a 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of POE weatherable master batch is completely identical with embodiment 1.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 14 parts of POE weatherable master batch a 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of POE weatherable master batch is completely identical with embodiment 1.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 16 parts of POE weatherable master batch a 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of POE weatherable master batch is completely identical with embodiment 1.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 18 parts of POE weatherable master batch a 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of POE weatherable master batch is completely identical with embodiment 1.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 20 parts of POE weatherable master batch a 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts: by the weight percent meter of POE, by the POE high-speed mixing 7min of the vinyl acetate between to for plastics of 5 parts (VA) with 100 parts, places 8h by the material mixed in encloses container; Then the acetone getting 0.04 part of BPDH and 0.5 part is put into beaker and is mixed, then the solution mixed is put into 10L high-speed mixer, high-speed mixing 9min 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 170,180,190,200,190,180,175,170; Carry out melting graft reaction, after reaction 6min, extrude, cool, granulation, obtain POE-g-VA grafts (percentage of grafting: 2.9%).
(2) preparation of POE weatherable master batch: by the weight percent meter of POE, by the POE of 100 parts and the POE-g-VA grafts of 7 parts (percentage of grafting: 2.9%), put in high-speed mixer together with the white oil 5# of 0.6 part, high-speed mixing 5min; And then add the quencher AM-101 of hindered amine as light stabilizer CH944 and 0.03 part of 0.2 part, 0.2 part of oxidation inhibitor B561,0.2 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruder, screw zones temperature of reaction (DEG C) is followed successively by: 165, and 170,180,190,200,210,190,180,170; After reaction 4min, extrude, cool, granulation, obtain POE weatherable master batch b.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 21 parts of POE weatherable master batch b 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of POE weatherable master batch is completely identical with embodiment 6.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 23 parts of POE weatherable master batch b 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of POE weatherable master batch is completely identical with embodiment 6.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 25 parts of POE weatherable master batch b 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of POE weatherable master batch is completely identical with embodiment 6.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 27 parts of POE weatherable master batch b 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts: by the weight percent meter of POE, by the POE high-speed mixing 6min of the vinyl acetate between to for plastics of 6 parts (VA) with 100 parts, places 7h by the material mixed in encloses container; Then the acetone getting 0.08 part of DTBP and 0.8 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, 0.2 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 170,180,190,200,190,180,175,170; Carry out melting graft reaction, after reaction 9min, extrude, cool, granulation, obtain POE-g-VA grafts (percentage of grafting: 3.7%).
(2) preparation of POE weatherable master batch: by the weight percent meter of POE, by the POE of 100 parts and the POE-g-VA grafts of 8 parts (percentage of grafting: 3.7%), put in high-speed mixer together with the whiteruss 3# of 0.9 part, high-speed mixing 3min; And then add the quencher of hindered amine as light stabilizer GW-540 and 0.04 part 2002,0.2 part of oxidation inhibitor B561 of 0.24 part, 0.2 part of calcium stearate, high-speed mixing 6min; Mixed material is joined Φ 67 twin screw extruder, screw zones temperature of reaction (DEG C) is followed successively by: 165, and 170,180,190,200,210,190,180,170; After reaction 4min, extrude, cool, granulation, obtain POE weatherable master batch c.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 29 parts of POE weatherable master batch c 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of POE weatherable master batch is completely identical with embodiment 1.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 12 parts of POE weatherable master batch a 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of POE weatherable master batch is completely identical with embodiment 1.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: 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 take out 14 parts of POE weatherable master batch a 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 1.
(2) preparation of POE weatherable master batch is completely identical with embodiment 1.
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: other condition is identical with embodiment 3, difference is that the add-on of POE weatherable master batch a in composition preparation process is 6 parts, that is: after 0.09 part of BPDH and 0.005 part BPO being 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 take out 6 parts of POE weatherable master batch a 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 PE plastic sheeting for farm use resin combination.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 4
The preparation of mLLDPE plastic sheeting for farm use resin combination: difference is not add POE weatherable master batch a in resin combination preparation process, and other condition is identical with embodiment 4.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
(1) preparation of POE weatherable master batch: difference is not add POE-g-VA grafts (percentage of grafting: 2.1%) in POE weatherable master batch preparation process, other processes are identical with embodiment 1, obtained POE weatherable master batch (a-1).
(2) preparation of mLLDPE plastic sheeting for farm use resin combination: other condition is identical with embodiment 5, difference is that the POE weatherable master batch added in composition preparation process is not containing POE-g-VA grafts, the add-on of POE weatherable master batch (a-1) 20 parts, that is: after 0.12 part of BPDH and 0.008 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 take out 20 parts of POE weatherable master batch (a-1) 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 PE plastic sheeting for farm use resin combination.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 6
The preparation of mLLDPE plastic sheeting for farm use resin combination: other condition is identical with embodiment 6, difference is not add POE weatherable master batch b in composition preparation process but adds POE (8203), the add-on of POE (8203) 21 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 21 parts of POE (8203) 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of POE weatherable master batch: difference is not add quencher 2002 in POE weatherable master batch preparation process, the add-on of hindered amine as light stabilizer 944 is 0.23 part, that is: by the POE of 100 parts and the POE-g-VA grafts of 7 parts (percentage of grafting: 2.9%), put in high-speed mixer together with the white oil 5# of 0.6 part, high-speed mixing 3min; And then add hindered amine as light stabilizer 944,0.2 part of oxidation inhibitor B561 of 0.23 part, 0.2 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruder, screw zones temperature of reaction (DEG C) is followed successively by: 165, and 170,180,190,200,210,190,180,170; After reaction 4min, extrude, cool, granulation, obtain POE weatherable master batch (b-1).
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: other condition is identical with embodiment 7, difference is that the POE weatherable master batch added in composition preparation process is not containing quencher 2002, the add-on of POE weatherable master batch (b-1) 23 parts, that is: after 0.14 part of BPDH and 0.01 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 23 parts of POE weatherable master batch (b-1) 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 PE plastic sheeting for farm use resin combination.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 POE-g-VA grafts is completely identical with embodiment 6.
(2) preparation of POE weatherable master batch: difference is not add hindered amine as light stabilizer 944 in POE weatherable master batch preparation process, the add-on of quencher 2002 is 0.23 part, that is: by the POE of 100 parts and the POE-g-VA grafts of 7 parts (percentage of grafting: 2.9%), put in high-speed mixer together with the white oil 5# of 0.6 part, high-speed mixing 3min; And then add quencher 2002,0.2 part of oxidation inhibitor B561 of 0.23 part, 0.2 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruder, screw zones temperature of reaction (DEG C) is followed successively by: 165, and 170,180,190,200,210,190,180,170; After reaction 4min, extrude, cool, granulation, obtain POE weatherable master batch (b-2).
(3) preparation of mLLDPE plastic sheeting for farm use resin combination: other condition is identical with embodiment 8, difference is that the POE weatherable master batch added in composition preparation process is not containing hindered amine as light stabilizer 944, the add-on of POE weatherable master batch (b-2) 25 parts, 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 take out 25 parts of POE weatherable master batch (b-2) 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 PE plastic sheeting for farm use resin combination.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
(1) preparation of POE weatherable master batch: difference is not add POE-g-VA grafts in POE weatherable master batch preparation process, and other processes are identical with embodiment 6, obtained POE weatherable master batch (b-3).
(2) preparation of mLLDPE plastic sheeting for farm use resin combination: other condition is identical with embodiment 9, difference is that the POE weatherable master batch added in composition preparation process is not containing POE-g-VA grafts, the add-on of POE weatherable master batch (b-3) 27 parts, that is: after 0.16 part of BPDH and 0.02 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 27 parts of POE weatherable master batch (b-3) 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 PE plastic sheeting for farm use resin combination.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 10
The preparation of mLLDPE plastic sheeting for farm use resin combination: difference is not add POE weatherable master batch c in resin combination preparation process, but add POE (8203), the add-on of POE (8203) 29 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 29 parts of POE (8203) 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 PE plastic sheeting for farm use resin combination.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 1mLLDPE canopy film
*heavy natural sunning place: Gansu Wuwei.
Claims (7)
1. a Metallocene polyethylene resin composition, in the weight of mLLDPE for a hundred per cent, is characterized in that comprising:
(1)mLLDPE 100％
(2) composite crosslinking coagent 0.07 ~ 0.2%
(3) POE weatherable master batch 10 ~ 30%
The blend that described POE weatherable master batch is made up of polymer P OE, composite light stabilizer, POE-g-VA grafts and dispersion agent; Described composite crosslinking coagent is 2,5-dimethyl-2,5-di-t-butyl hexane peroxide and the composite composition of dibenzoyl peroxide, and the mass ratio of the two is 25: 1 ~ 5: 1; The preparation method of described POE-g-VA grafts comprises: by the weight percent meter of POE, by the POE high-speed mixing 5 ~ 10min of the vinyl acetate between to for plastic of 3 ~ 7 parts and 100 parts, the material mixed is placed 5 ~ 10h in encloses container; Then getting the initiator of 0.01 ~ 0.1 part and acetone is be mixed with mixing solutions at 1: 10 ~ 1: 20 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 ~ 200 DEG C, reaction times 5 ~ 10min, extrude, cool, granulation, obtain the POE-g-VA grafts that vinyl acetate between to for plastic percentage of grafting is 1% ~ 4%.
2. resin combination as claimed in claim 1, is characterized in that described composite light stabilizer is made up of quencher and radical scavenger.
3. resin combination as claimed in claim 2, it is characterized in that described quencher is for two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel, 2,2-thiobis (4-tertiary octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound, 2,2-thiobis (4-tertiary octyl phenol oxygen base) nickel, N, one in N-nickel dibutyl dithiocarbamate, dioctyl dithiocarbamic acid nickel, in the weight of POE for a hundred per cent, consumption is 0.01% ~ 0.04%.
4. resin combination as claimed in claim 2, is characterized in that described radical scavenger is hindered amine as light stabilizer, and in the weight of POE for a hundred per cent, consumption is 0.05% ~ 0.25%.
5. resin combination as claimed in claim 1, is characterized in that described dispersion agent is the one in sherwood oil, paraffin, naphthenic oil, polyethylene wax.
6. resin combination as claimed in claim 1, it is characterized in that the preparation method of described POE weatherable master batch comprises: by the weight percent meter of POE, put in super mixer together with the POE of 100 parts and the POE-g-VA grafts of 5 ~ 10 parts, the dispersion agent of 0.3 ~ 0.9 part, high-speed mixing 3 ~ 5min; And then add the composite light stabilizer of 0.06 ~ 0.29 part, high-speed mixing 5 ~ 10min; Mixed material is added twin screw extruder, temperature of reaction 165 ~ 210 DEG C, reaction times 3 ~ 5min, extrudes, cools, granulation, obtain POE weatherable master batch.
7. 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 total amount 5% ~ 10% (wt) again, then after high-speed mixing 3 ~ 5min, make premix masterbatch; Then residue mLLDPE, premix masterbatch and POE weatherable master batch 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 PE plastic sheeting for farm use resin combination.
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