CN102924800A - Weather-resistant polyethylene resin composition for agricultural film and preparation method thereof - Google Patents
Weather-resistant polyethylene resin composition for agricultural film and preparation method thereof Download PDFInfo
- Publication number
- CN102924800A CN102924800A CN2011102280412A CN201110228041A CN102924800A CN 102924800 A CN102924800 A CN 102924800A CN 2011102280412 A CN2011102280412 A CN 2011102280412A CN 201110228041 A CN201110228041 A CN 201110228041A CN 102924800 A CN102924800 A CN 102924800A
- Authority
- CN
- China
- Prior art keywords
- uldpe
- weather
- low density
- ultra
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 87
- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 229920013716 polyethylene resin Polymers 0.000 title claims description 47
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims abstract description 113
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 110
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 67
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 66
- 238000002156 mixing Methods 0.000 claims abstract description 58
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims description 79
- 229920005989 resin Polymers 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 69
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 33
- 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
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 229920003023 plastic Polymers 0.000 claims description 18
- 239000004033 plastic Substances 0.000 claims description 18
- 239000004611 light stabiliser Substances 0.000 claims description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 10
- -1 polyethylene Polymers 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229920000573 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
- 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 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 238000007664 blowing Methods 0.000 abstract description 42
- 150000001875 compounds Chemical class 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 3
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 38
- 239000003112 inhibitor Substances 0.000 description 28
- 230000003647 oxidation Effects 0.000 description 28
- 238000007254 oxidation reaction Methods 0.000 description 28
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 25
- 239000004744 fabric Substances 0.000 description 22
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 16
- 235000013539 calcium stearate Nutrition 0.000 description 15
- 239000008116 calcium stearate Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000630 rising effect Effects 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000008096 xylene Substances 0.000 description 6
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- NFZJABPIWWKYPF-UHFFFAOYSA-N [O].C(CCCCCCC)C1=CC=C(C=C1)O Chemical compound [O].C(CCCCCCC)C1=CC=C(C=C1)O NFZJABPIWWKYPF-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical compound C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003381 stabilizer Substances 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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 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 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000004711 α-olefin Substances 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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 Linear Low Density Polyethylene (LLDPE) resin composition for a weather-resistant agricultural film and a preparation method thereof, wherein the LLDPE resin composition comprises the following components in percentage by weight: (1)100 percent of LLDPE, (2)0.05 to 0.3 percent of compound crosslinking assistant agent, (3)10 to 30 percent of ultra-low density polyethylene (ULDPE) weather resistant master batch; the composition can be used for blowing a wide greenhouse film (the width is more than or equal to 8m, the thickness is more than or equal to 80 mu m) without any mixing, the surface of the greenhouse film has few crystal points and excellent weather resistance, 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, and the method has the advantages of short flow, simple process, low development cost, stable product quality and the like.
Description
Technical field
The present invention relates to a kind of polyethylene resin composition and preparation method thereof, be specifically related to the agricultural canopy film resin combination with excellent weather resistance take linear low density polyethylene as base resin.
Background technology
Agricultural plastic film is extremely important to agricultural modernization, and is closely bound up with national economy, effectively alleviates the contradiction of agriculture production and development, brought material benefit to the peasant.At present, China is one of maximum country of agricultural plastic film production and consumption, wherein the polyvinyl resin consumption of agricultural canopy film surpasses more than 1,200,000 tons, particularly agricultural canopy film annual polyvinyl resin consumption in west area has reached 500,000 tons, and agricultural canopy film has become one of important applied field of polyethylene (PE) resin.
At present, first of the output of China's agricultural canopy film and the area coverage Jun Ju world.But the developmental level of the present agricultural canopy film of China is compared with advanced international standard, still has very large gap, not only shows on quantity, the kind, and shows on the performance index such as weathering resistance, the transparency, anti-droplet.Abroad, agricultural canopy film be the long lifetime plastic sheeting for farm use absolutely almost, can detain the canopy use and reach 18 months the nature breakage does not occur, and the common agricultural canopy film of China can't reach this requirement.This generally adopts hp-ldpe/linear low density polyethylene (LDPE/LLDPE) blending resin mainly due to domestic agricultural canopy film covering material, and wherein the LDPE molecular weight is low, molecular weight distribution is wide; LLDPE is comprised of ethene and 1-butylene copolymerization, side chain is short, branch is many, the catalyst residue amount is high, under the impact that is subject to the factors such as sunlight, temperature, wind-force, chain rupture easily occurs in the molecular chain of LDPE and LLDPE, " backboard effect " (phenomenon that the canopy film easily ftractures at the skeleton place) easily occur.The difference of the resin grade of blending, mixing proportion makes its agricultural canopy film quality uneven in addition, has greatly shortened the work-ing life of agricultural canopy film.Therefore, in the Application and Development of agripast canopy film, improve the work-ing life of agricultural canopy film for save energy, saving manpower, environmental contamination reduction, reduce farmer's burdens all very favourable.
In the prior art, the report of relevant organo-peroxide modification LLDPE is a lot.The cumyl superoxide that adds 100～200ppm such as USA4578431 in LLDPE (MFR 2g/10min) carries out extrusion reaction, and the gained resin can be blow molded into the film of 25 μ m.ZL03137608.8 is at LLDPE (C
4～C
8Alpha olefin copolymer) in add ditertiary butyl peroxide, be to carry out crosslinked extrused reaction under 0.3wt%～0.6wt% at its consumption, make a kind of canopy film resin composition that is suitable for blowing 8000 * 0.08mm specification.React in the n-heptane solution of JP 1113411 (A) proposition tert-butyl peroxide and LLDPE, obtain the good little crosslinked LLDPE of processibility.US4614764 adopts a kind of LLDPE and another kind of through the LLDPE of organo-peroxide modification blend, and preparation is suitable for the resin combination of blown film.JP1113411 adds UV light absorber in LLDPE and ethene-vinyl acetate (EVA) blending resin, prepare weather-proof film.CN1056696A adds by UV light absorber, photostabilizer, oxidation inhibitor, reaches the master batch that other processing aid is made in Low Density Polyethylene (LDPE) and ethene-vinyl acetate (EVA) blending resin, prepares weather-proof film.CN90101638.1 provides a kind of and has added photostabilizer, oxidation inhibitor, visible light conditioning agent and other processing aid at polyethylene or take polyethylene in main polyolefin blends, the warmhouse booth film manufacturing method that extrusion-blown modling becomes to have weathering resistance.
Above-mentioned patent is single resin to be carried out cross-linking modified substantially, and emphasis just improves the melt strength of resin, improves its processing characteristics, yet limited in the amplitude that improves aspect the agricultural canopy film weathering resistance.At present, the LDPE, the LLDPE base resin weather resistance that use during agricultural canopy film is produced at home are low, cause agricultural canopy film short work-ing life, the ageing-resistant system that adds simultaneously exists, and persistence unreasonable, that the auxiliary agent kind is many, production cost is high, auxiliary agent uses are short, and problems such as moving and separate out easily occurs.
Summary of the invention
The object of the invention provides a kind of linear low density polyethylene canopy film resin composition.Said composition is that (thickness 〉=80 μ m, fabric width 〉=8m) have good weathering resistance can be detained continuously canopy the nature breakage did not occur more than 40 months for the wide cut canopy film of raw material production.The present invention further proposes the preparation method of composition.
Take the weight of linear low density polyethylene (LLDPE) as absolutely, resin combination of the present invention comprises:
1) 100% LLDPE;
2) 0.05%～0.3% composite crosslinking coagent;
3) the weather-proof master batch of 10%～30% ultra-low density polyethylene (ULDPE);
Wherein said composite crosslinking coagent is di-tert-butyl hydrogen peroxide (TBHP) and the composite composition of dibenzoyl peroxide (BPO), and the mass ratio of two kinds of crosslinking coagents is TBHP/BPO=30: 1～5: 1.
The blend that the weather-proof master batch of described ULDPE is comprised of grafts (ULDPE-g-VA) and the dispersion agent of ULDPE, composite light stabilizer, ULDPE and vinyl acetate between to for plastic.Polymkeric substance ULDPE makes the multipolymer of optimal ethylene and butylene, wherein density: 0.860～0.915g/cm by ethene and a-alkene (propylene, butylene, hexene and octene) by vapor phase process, solution method or high-pressure process copolymerization
3Melt flow rate (MFR) (MFR) is: 0.1～20g/10min.Described melt flow rate (MFR) (MFR) is at 190 ℃, the measured value under the 2.16Kg load.
The compound system that composite light stabilizer is comprised of quencher and radical scavenger.Quencher is the organic nickel compound, as: two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel (Irgastab 2002), 2,2-thiobis (uncle's 4-octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound (UV-1084), 2,2-thiobis (uncle's 4-octyl phenol oxygen base) nickel (AM-101), dioctyl dithiocarbamic acid nickel (AM-108), N, a kind of in the N-nickel dibutyl dithiocarbamate (NBC), the organic nickel compound is because of the toxicity problem of heavy metal ion, and its consumption should be strict controlled in 0.01%～0.04% (pressing the weight percent meter of ULDPE).
Radical scavenger is selected the hindered amine as light stabilizer (HALS) with space steric effect, as: a kind of among Tinuvin123, Tinuvin622, Tinuvin791, Tinuvin328, Tinuvin326, GW-540, GW-480, GW-544, the CH944, its consumption is 0.1%～0.5% (pressing the weight percent meter of ULDPE).This compound system can reduce the excited state functional group that has reactive behavior in the molecular resin after cross-linking modified effectively, promptly catch free radical R, ROO that linking agent produces, destroy the growth of living chain, improve the stability of base resin molecular structure, reached the work-ing life that prolongs resin.
ULDPE-g-VA is at the graft copolymer that under the effect of initiator grafted monomer is grafted on the ULDPE main chain; initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate (TBPA), tertbutyl peroxide, 2; 5-dimethyl-2; a kind of in 5-di-t-butyl hexane peroxide (BPDH), ditertiary butyl peroxide (DTBP), dicumyl peroxide (DCP), diisopropylbenzenehydroperoxide (DBHP), benzoyl peroxide or the peroxide di-t-butyl preferably adopts dicumyl peroxide (DCP).Grafted monomer is selected from polymerization-grade vinyl acetate between to for plastic (VA).
Dispersion agent can be wherein a kind of or composite such as sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax, white oil, preferably adopts white oil.
The weather-proof agglomerate preparation method of ULDPE provided by the invention comprises:
(1) preparation method of ULDPE-g-VA grafts:
With the ULDPE high-speed mixing 5～10min of 5～10 parts vinyl acetate between to for plastics (VA) with 100 parts, the material that mixes is placed 5～10h in encloses container; Then get 0.01～0.1 part initiator and acetone and be by weight and be mixed with mixing solutions in 1: 10～1: 20, again with mixing solutions and the mixture high-speed mixing 5～10min that places, at last by carrying out melting graft reaction in the twin screw extruder, 160～200 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain the VA percentage of grafting and be 2%～7% ULDPE-g-VA grafts.
(2) preparation of the weather-proof master batch of ULDPE
100 parts ULDPE and 4～10 parts ULDPE-g-VA grafts, 0.5～1.0 part dispersion agent are put in the super mixer high-speed mixing 3～5min together; And then add 0.11～0.54 part composite light stabilizer, high-speed mixing 5～10min; Mixed material is added twin screw extruder, 165～210 ℃ of temperature of reaction, reaction times 3～5min extrudes, cooling, granulation, obtains the weather-proof master batch of ULDPE.
LLDPE described in the composition is the ethene of the efficient ziegler-natta catalyst systems preparation of employing and the copolymerization product of 1-butylene, MFR:0.7～3.0g/10min; Density: 0.915～0.925g/cm
3LLDPE can be powdery or granular resin among the present invention, but best with powdered resin for reaching better mixed effect.
Composite crosslinking coagent described in the composition is that TBHP and BPO are by the composite composition of different ratios.Wherein the scope of total add-on of composite crosslinking coagent is that the optimum mixture ratio of 0.05%～0.3%, two kinds of crosslinking coagents is TBHP/BPO=25: 1～10: 1.Two kinds of superoxide are the commercially available prod, and its half life temperature is because of manufacturer's difference difference slightly, the transformation period T=246 of general TBHP～267 ℃/1min; The transformation period T=131 of BPO～134 ℃/1min.
The used in amounts of general BPO is strictly controlled, its consumption can not surpass 0.03%, processing temperature can not be above 230 ℃ in the composition preparation process in addition, otherwise degree of crosslinking is uncontrollable, is prone to excessive crosslinked generation gel, and the agricultural canopy film surface is prone to " brilliant point ", its tear strength and weathering resistance not only do not improve, cause on the contrary mechanics mechanical property variation, brittle fracture occurs, the problems such as processing units damage and environmental protection also can occur simultaneously.
The preparation of resin combination of the present invention also can be carried out in Banbury mixer, kneader, forcing machine, but take twin screw extruder as best.
Particularly, the preparation method of polyethylene resin composition provided by the invention comprises: first with two kinds of crosslinking coagents composite rear adding solvent in proportion, adding accounts for the powdery LLDPE that gross weight is 5%～10% (wt) again, then behind high-speed mixing 3～5min, makes the premix masterbatch; Then remaining powdery LLDPE, premix masterbatch and the weather-proof master batch of ULDPE are joined together by charging opening and carry out extrusion reaction in the forcing machine, temperature of reaction is 165～220 ℃, reaction times is 2～5min, extrudes, cooling, granulation, makes polyethylene resin composition.
The present invention also can add a certain amount of thermo-stabilizer and oxidation inhibitor in the preparation process of the weather-proof master batch of ULDPE and polyethylene greenhouse film resin composition, its total add-on is 0.2%～0.5% (take the weight of LLDPE as per-cent).Wherein, oxidation inhibitor can be one or several compounds in phenols, hindered amines, the phosphite ester kind antioxidant, and its consumption is 0.1%～0.2%.Thermo-stabilizer can be stearates, and such as Zinic stearas, calcium stearate etc., consumption is generally 0.1%～0.3%.
In the resin combination preparation process of the present invention, add solvent in composite crosslinking coagent, described solvent is a kind of in toluene, dimethylbenzene, the acetone, and its add-on is 2～4 times of composite crosslinking coagent weight.
In the composition of the present invention, on the one hand, low, the intermolecular freeboard of the ULDPE density in the weather-proof master batch of ULDPE is large, degree of crystallinity is low, it is larger to have and more complete spherocrystal, will reduce refraction and the range of light in resin; Simultaneously again owing to short-chain branch in the molecular structure is many, and with crosslinking coagent certain crosslinked action occuring, can form more physical crosslinking point in molecular structure, can greatly improve the weathering resistance of base resin.Secondly, the ULDPE-g-VA grafts has improved the consistency of resin and photostabilizer, has improved the dispersion effect of photostabilizer in resin; The ULDPE-g-VA grafts has certain adsorption to photostabilizer in addition, avoided photostabilizer in resin migration and separate out problem, greatly improved persistence and the high efficiency of photostabilizer.ULDPE and photostabilizer can produce certain positive cooperativity like this, and this has fairly obvious effect to the weathering resistance of improving the agricultural canopy film base resin, and the add-on, the minimum cost that have reached with minimum obtain best weathering resistance.
On the other hand, the composite cross-linking system that the superoxide of selecting two kinds of transformation period to differ larger forms, can effectively control cross-linked speed and the crosslinking degree of base resin, realized the little crosslinked of molecular structure, under the prerequisite that guarantees the base resin basic physical properties, linking agent just can reach blowing wide cut canopy film (thickness 〉=80um, the desired melt strength of fabric width 〉=8m) when few additive.Simultaneously avoided to greatest extent being used alone superoxide and crosslinked excessive or crosslinked deficiency occurred, easily caused film surface " brilliant point " to occur or can't blow separately the problem of wide cut canopy film.So that can need not at the common blown film unit without any transformation any blending, said composition can stably blow out the wide cut canopy film (thickness 〉=80 μ m with excellent weather resistance like this, fabric width 〉=8m), can detain continuously canopy the nature breakage did not occur more than 40 months, be particularly suitable for west area long in the sunshine duration, awful weather and lay.
Embodiment
1, raw material
1) resin
2) superoxide
3) auxiliary agent
2, performance test standard
3, equipment and instrument
The German Lestreiz of Φ 67 twin-screw extrusion captains/directly=34/1 company
The fast mixing machine of 10 risings Fuxin plastics machinery factory
120 3 layers of compound inflation film manufacturing machine of Φ Dalian rubber and plastics machine factory
Embodiment and Comparative Examples
Enumerate following examples invention effect of the present invention is described, but protection scope of the present invention is not limited in these embodiment, each component is in the parts by weight of base resin LLDPE in the composition.
Embodiment 1
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, with the ULDPE high-speed mixing 6min of 6 parts vinyl acetate between to for plastics (VA) with 100 parts, the material that mixes is placed 10hr in encloses container; Then the acetone of getting 0.02 part of DCP and 0.3 part is put into beaker and is mixed, and again the solution that mixes and mixture, 0.15 part of antioxidant 1010,0.15 part of calcium stearate of placing is put into 10L high-speed mixer, high-speed mixing 5min together; At last the material that mixes is joined in Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, behind the reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 2.8%).
2.8%), 0.6 part white oil 5# puts in the high-speed mixer high-speed mixing 5min together (two) preparation of the weather-proof master batch of ULDPE: press the weight percent meter of ULDPE, with the ULDPE-g-VA grafts of 100 parts ULDPE and 5 parts (percentage of grafting:; And then add 0.2 part hindered amine as light stabilizer CH944 and 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.01 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; Behind the reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch a of ULDPE.
(3) preparation of polyethylene resin composition: 0.002 part of BPO and 0.05 part of TBHP with after 0.2 part of acetone solvent mixes, are then added 5 parts of LLDPE (101AA) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 11 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.15 part of oxidation inhibitor B561,0.15 part of calcium stearate, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 2
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene resin composition: 0.005 part of BPO and 0.12 part of TBHP with after 0.3 part of acetone solvent mixes, are then added 5 parts of LLDPE (101AA) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 13 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.15 part of oxidation inhibitor B561,0.2 part of calcium stearate, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 3
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene resin composition: 0.008 part of BPO and 0.17 part of TBHP with after 0.4 part of acetone solvent mixes, are then added 5 parts of LLDPE (101AA) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 15 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 4
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene resin composition: 0.009 part of BPO and 0.18 part of TBHP with after 0.4 part of acetone solvent mixes, are then added 5 parts of LLDPE (101AA) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 17 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 5
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene resin composition: 0.012 part of BPO and 0.22 part of TBHP with after 0.5 part of acetone solvent mixes, are then added 5 parts of LLDPE (101AA) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 19 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 6
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, with the ULDPE high-speed mixing 6min of 8 parts vinyl acetate between to for plastics (VA) with 100 parts, the material that mixes is placed 10hr in encloses container; Then the acetone of getting 0.03 part of DCP and 0.4 part is put into beaker and is mixed, and again the solution that mixes and mixture, 0.15 part of antioxidant 1010,0.15 part of calcium stearate of placing is put into 10L high-speed mixer, high-speed mixing 5min together; At last the material that mixes is joined in Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, behind the reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 3.9%).
(2) preparation of the weather-proof master batch of ULDPE: the weight percent meter of pressing ULDPE, 3.9%), 0.8 part whiteruss puts in the high-speed mixer high-speed mixing 5min together with the ULDPE-g-VA grafts of 100 parts ULDPE and 7 parts (percentage of grafting:; And then add 0.4 part hindered amine as light stabilizer Tinuvin 791 and 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.02 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; Behind the reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch b of ULDPE.
(3) preparation of polyethylene resin composition: 0.014 part of BPO and 0.15 part of TBHP with after 0.4 part of xylene solvent mixes, are then added 7 parts of LLDPE (7042) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 21 parts of weather-proof master batch b of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 7
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 6.
(3) preparation of polyethylene resin composition: 0.017 part of BPO and 0.14 part of TBHP with after 0.4 part of xylene solvent mixes, are then added 7 parts of LLDPE (7042) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 23 parts of weather-proof master batch b of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 8
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 6.
(3) preparation of polyethylene resin composition: 0.02 part of BPO and 0.26 part of TBHP with after 0.6 part of acetone solvent mixes, are then added 7 parts of LLDPE (7042) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 25 parts of weather-proof master batch b of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 9
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 6.
(3) preparation of polyethylene resin composition: 0.022 part of BPO and 0.23 part of TBHP with after 0.6 part of acetone solvent mixes, are then added 7 parts of LLDPE (7042) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 27 parts of weather-proof master batch b of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Embodiment 10
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, with the ULDPE high-speed mixing 6min of 9 parts vinyl acetate between to for plastics (VA) with 100 parts, the material that mixes is placed 10hr in encloses container; Then the acetone of getting 0.04 part of TBPA and 0.6 part is put into beaker and is mixed, and again the solution that mixes and mixture, 0.15 part of antioxidant 1010,0.15 part of calcium stearate of placing is put into 10L high-speed mixer, high-speed mixing 5min together; At last the material that mixes is joined in Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, behind the reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 4.2%).
4.2%), 0.9 part white oil 5# puts in the high-speed mixer high-speed mixing 5min together (two) preparation of the weather-proof master batch of ULDPE: press the weight percent meter of ULDPE, with the ULDPE-g-VA grafts of 100 parts ULDPE and 8 parts (percentage of grafting:; And then add 0.5 part hindered amine as light stabilizer CH944 and 0.03 part quencher AM-101,0.15 part of oxidation inhibitor B561,0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; Behind the reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch c of ULDPE.
(3) preparation of polyethylene resin composition: 0.007 part of BPO and 0.2 part of TBHP with after 0.4 part of xylene solvent mixes, are then added 5 parts of LLDPE (101AA) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 29 parts of weather-proof master batch c of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of calcium stearate, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 1
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 1, difference is not add in the composition preparation process BPO, the add-on of TBHP is 0.052 part, that is: with 0.052 part of TBHP with after 0.2 part of acetone solvent mixes, then add 5 parts of LLDPE (101AA) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 11 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.15 part of oxidation inhibitor B561,0.15 part of calcium stearate, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 2
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 2, difference is not add in the composition preparation process TBHP, the add-on of BPO is 0.125 part, that is: with 0.125 part of BPO with after 0.3 part of acetone solvent mixes, then add 5 parts of LLDPE (101AA) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 13 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.15 part of oxidation inhibitor B561,0.2 part of calcium stearate, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 3
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 3, difference is that the add-on of the weather-proof master batch a of ULDPE in the composition preparation process is 6 parts, that is: with 0.008 part of BPO and 0.17 part of TBHP with after 0.4 part of acetone solvent mixes, then add 5 parts of LLDPE (101AA) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 6 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 4
(1) preparation of the weather-proof master batch of ULDPE: difference is not add the ULDPE-g-VA grafts in the weather-proof master batch preparation process of ULDPE, and other processes and embodiment 1 are identical, make the weather-proof master batch of ULDPE (a-1).
(2) preparation of polyethylene resin composition: other condition is identical with embodiment 4, difference is that the weather-proof master batch of the ULDPE that adds in the composition preparation process does not contain the ULDPE-g-VA grafts, 17 parts of the add-ons of the weather-proof master batch of ULDPE (a-1), that is: with 0.009 part of BPO and 0.18 part of TBHP with after 0.4 part of acetone solvent mixes, then add 5 parts of LLDPE (101AA) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 17 parts of weather-proof master batches of ULDPE (a-1) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 5
The preparation of polyethylene resin composition: difference is not add in the resin combination preparation process the weather-proof master batch a of ULDPE, and other processes and embodiment 5 are identical.The canopy film properties of its composition blowing sees Table 1.
Comparative Examples 6
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 6.
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 6, difference is not add in the composition preparation process the weather-proof master batch b of ULDPE, but add ULDPE (4404G), 21 parts of the add-ons of ULDPE (4404G), that is: with 0.014 part of BPO and 0.15 part of TBHP with after 0.4 part of xylene solvent mixes, then add 7 parts of LLDPE (7042) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 21 parts of ULDPE (4404G) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 7
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE: other condition is identical with embodiment 6, difference is not add quencher 2002 in the weather-proof master batch preparation process of ULDPE, the add-on of hindered amine as light stabilizer Tinuvin 791 is 0.42 part, 3.9%), 0.8 part whiteruss puts in the high-speed mixer high-speed mixing 5min together that is: with 100 parts ULDPE and 7 parts ULDPE-g-VA grafts (percentage of grafting:; And then add 791,0.15 parts of oxidation inhibitor B561 of hindered amine as light stabilizer Tinuvin of 0.42 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; Behind the reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch of ULDPE (b-1).
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 7, difference is that the weather-proof master batch of the ULDPE that adds in the composition preparation process does not contain quencher 2002,23 parts of the add-ons of the weather-proof master batch of ULDPE (b-1), that is: with 0.017 part of BPO and 0.14 part of TBHP with after 0.4 part of xylene solvent mixes, then add 7 parts of LLDPE (7042) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 23 parts of weather-proof master batches of ULDPE (b-1) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 8
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 6.
(2) preparation of the weather-proof master batch of ULDPE: other condition is identical with embodiment 6, difference is not add hindered amine as light stabilizer Tinuvin 791 in the weather-proof master batch preparation process of ULDPE, the add-on of quencher 2002 is 0.42 part, 3.9%), 0.8 part whiteruss puts in the high-speed mixer high-speed mixing 5min together that is: with 100 parts ULDPE and 7 parts ULDPE-g-VA grafts (percentage of grafting:; And then add 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.42 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; Behind the reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch of ULDPE (b-2).
(3) preparation of polyethylene resin composition: other condition is identical with embodiment 8, difference is that the weather-proof master batch of the ULDPE that adds in the composition preparation process does not contain hindered amine as light stabilizer Tinuvin 791,25 parts of the add-ons of the weather-proof master batch of ULDPE (b-2), that is: with 0.02 part of BPO and 0.26 part of TBHP with after 0.6 part of acetone solvent mixes, then add 7 parts of LLDPE (7042) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 25 parts of weather-proof master batches of ULDPE (b-2) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 9
(1) preparation of the weather-proof master batch of ULDPE: difference is not add the ULDPE-g-VA grafts in the weather-proof master batch preparation process of ULDPE, and other processes and embodiment 6 are identical, make the weather-proof master batch of ULDPE (b-3).
(2) preparation of polyethylene resin composition: other condition is identical with embodiment 9, difference is that the weather-proof master batch of the ULDPE that adds in the composition preparation process does not contain the ULDPE-g-VA grafts, 27 parts of the add-ons of the weather-proof master batch of ULDPE (b-3), that is: with 0.022 part of BPO and 0.23 part of TBHP with after 0.6 part of acetone solvent mixes, then add 7 parts of LLDPE (7042) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 27 parts of weather-proof master batches of ULDPE (b-3) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 93 parts of LLDPE (7042) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
Comparative Examples 10
The preparation of polyethylene resin composition: difference is not add in the resin combination preparation process the weather-proof master batch c of ULDPE, but add ULDPE (4404G), 29 parts of the add-ons of ULDPE (4404G), that is: with 0.007 part of BPO and 0.2 part of TBHP with after 0.4 part of xylene solvent mixes, then add 5 parts of LLDPE (101AA) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 29 parts of ULDPE (4404G) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of LLDPE (101AA) powder resins and 0.2 part of oxidation inhibitor B561,0.2 part of calcium stearate, the screw zones temperature of reaction (℃) be followed successively by: 165,180,190,195,210,220,210,200,190; Behind the reaction 3min, extrude, cooling, granulation, prepare polyethylene resin composition.Said composition is at 120 3 layers of compound blown film unit blowing up wide cut canopy processed of Φ film (fabric width 8m, thickness are 80 μ m), and the canopy film properties of its composition blowing sees Table 1.
The performance of table 1 polyethylene green house film and applicable cases
*Heavy natural sunning place: Gansu Wuwei
*Reference sample: the commercially available orchidization production LDPE/LLDPE (7: 3) of film factory of HTC blending material shed film (8000 * 0.08mm).
Claims (11)
1. polyethylene resin composition is characterized in that comprising take the weight of LLDPE as absolutely:
1) 100% LLDPE
2) 0.05%～0.3% composite crosslinking coagent
3) the weather-proof master batch of 10%～30% ultra-low density polyethylene
The blend that the weather-proof master batch of described ultra-low density polyethylene is comprised of grafts and the dispersion agent of ultra-low density polyethylene, composite light stabilizer, ultra-low density polyethylene and vinyl acetate between to for plastic.
2. resin combination as claimed in claim 1 is characterized in that composite light stabilizer is comprised of quencher and radical scavenger.
3. resin combination as claimed in claim 2 is characterized in that quencher is the organic nickel compound.
4. resin combination as claimed in claim 2 is characterized in that radical scavenger is hindered amine as light stabilizer.
5. resin combination as claimed in claim 1 is characterized in that described dispersion agent is a kind of in sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax, the white oil.
6. resin combination as claimed in claim 1, the grafts that it is characterized in that described ultra-low density polyethylene and vinyl acetate between to for plastic are at the graft copolymer that under the effect of initiator vinyl acetate between to for plastic is grafted on the ultra-low density polyethylene main chain.
7. resin combination as claimed in claim 6; it is characterized in that described initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate, tertbutyl peroxide, 2; 5-dimethyl-2, a kind of in 5-di-t-butyl hexane peroxide, ditertiary butyl peroxide, dicumyl peroxide, diisopropylbenzenehydroperoxide, benzoyl peroxide or the peroxide di-t-butyl.
8. resin combination as claimed in claim 1, the preparation method who it is characterized in that the grafts of described ultra-low density polyethylene and vinyl acetate between to for plastic comprises: with 5～10 parts of vinyl acetate between to for plastics and 100 parts of ultra-low density polyethylene high-speed mixing 5～10min, the material that mixes is placed 5～10h in encloses container; Then get 0.01～0.1 part of initiator and acetone and be by weight and be mixed with mixing solutions in 1: 10～1: 20, again with mixing solutions and the mixture high-speed mixing 5～10min that places, at last by carrying out melting graft reaction in the twin screw extruder, 160～200 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain the vinyl acetate between to for plastic percentage of grafting and be 2%～7% ultra-low density polyethylene and the grafts of vinyl acetate between to for plastic.
9. resin combination as claimed in claim 1, the preparation method who it is characterized in that the weather-proof master batch of ultra-low density polyethylene comprises: 100 parts of ultra-low density polyethylenes, 4～10 parts of ultra-low density polyethylenes and the grafts of vinyl acetate between to for plastic, 0.5～1.0 part of dispersion agent are put in the super mixer high-speed mixing 3～5min together; And then add 0.11～0.54 part composite light stabilizer, high-speed mixing 5～10min; Mixed material is added twin screw extruder, 165～210 ℃ of temperature of reaction, reaction times 3～5min extrudes, cooling, granulation, obtains the weather-proof master batch of ultra-low density polyethylene.
10. resin combination as claimed in claim 1 is characterized in that described composite crosslinking coagent is di-tert-butyl hydrogen peroxide and the composite composition of dibenzoyl peroxide, and the mass ratio of two kinds of crosslinking coagents is 30: 1～5: 1.
11. the preparation method of a resin combination as claimed in claim 1, it is characterized in that comprising: first with two kinds of crosslinking coagents composite rear adding solvent in proportion, add again that to account for gross weight be 5%～10% powdery LLDPE, then behind high-speed mixing 3～5min, make the premix masterbatch; Then remaining powdery LLDPE, premix masterbatch and the weather-proof master batch of ultra-low density polyethylene are joined together by charging opening and carry out extrusion reaction in the forcing machine, temperature of reaction is 165～220 ℃, reaction times is 2～5min, extrudes, cooling, granulation, makes polyethylene resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110228041.2A CN102924800B (en) | 2011-08-10 | 2011-08-10 | Weather-resistant polyethylene resin composition for agricultural film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110228041.2A CN102924800B (en) | 2011-08-10 | 2011-08-10 | Weather-resistant polyethylene resin composition for agricultural film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102924800A true CN102924800A (en) | 2013-02-13 |
| CN102924800B CN102924800B (en) | 2014-06-04 |
Family
ID=47639740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110228041.2A Active CN102924800B (en) | 2011-08-10 | 2011-08-10 | Weather-resistant polyethylene resin composition for agricultural film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102924800B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724486A (en) * | 2020-12-22 | 2021-04-30 | 金发科技股份有限公司 | Polyolefin material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578431A (en) * | 1983-08-31 | 1986-03-25 | Mobil Oil Corporation | Process for improving melt strength of ethylene polymers by treatment with organic peroxide |
| US4614764A (en) * | 1985-03-06 | 1986-09-30 | Mobil Oil Corporation | Linear low density ethylene polymers blended with modified linear low density ethylene polymers |
| CN1056696A (en) * | 1990-03-23 | 1991-12-04 | 中国科学院长春应用化学研究所 | Weather-resistant polyethylene film |
| CN1135496A (en) * | 1995-05-11 | 1996-11-13 | 成都市柯力化工研究所 | Starch/polyethylene modified masterbatch |
| CN1844220A (en) * | 2006-05-13 | 2006-10-11 | 兰州定元塑料制品有限责任公司 | Dedicated modified materials for agricultural polyethylene film |
| CN101143945A (en) * | 2007-09-04 | 2008-03-19 | 上海新上化高分子材料有限公司 | Color weatherable silane crosslinked polyethylene plastic and application thereof |
-
2011
- 2011-08-10 CN CN201110228041.2A patent/CN102924800B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578431A (en) * | 1983-08-31 | 1986-03-25 | Mobil Oil Corporation | Process for improving melt strength of ethylene polymers by treatment with organic peroxide |
| US4614764A (en) * | 1985-03-06 | 1986-09-30 | Mobil Oil Corporation | Linear low density ethylene polymers blended with modified linear low density ethylene polymers |
| CN1056696A (en) * | 1990-03-23 | 1991-12-04 | 中国科学院长春应用化学研究所 | Weather-resistant polyethylene film |
| CN1135496A (en) * | 1995-05-11 | 1996-11-13 | 成都市柯力化工研究所 | Starch/polyethylene modified masterbatch |
| CN1844220A (en) * | 2006-05-13 | 2006-10-11 | 兰州定元塑料制品有限责任公司 | Dedicated modified materials for agricultural polyethylene film |
| CN101143945A (en) * | 2007-09-04 | 2008-03-19 | 上海新上化高分子材料有限公司 | Color weatherable silane crosslinked polyethylene plastic and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724486A (en) * | 2020-12-22 | 2021-04-30 | 金发科技股份有限公司 | Polyolefin material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102924800B (en) | 2014-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102993535B (en) | Polyethylene resin composition for pipes | |
| CN101967288A (en) | Wood flour filled polypropylene composite material and preparation method thereof | |
| CN103374171B (en) | metallocene polyethylene resin composition with high melt strength and preparation method thereof | |
| CN102924797B (en) | Weather-resistant polyethylene agricultural film resin composition and preparation method thereof | |
| CN107541004B (en) | Load-resistant and fatigue-resistant TPE (thermoplastic elastomer) and preparation method thereof | |
| CN101962453A (en) | Polyethylene greenhouse film resin composition and preparation method thereof | |
| CN102924775B (en) | Polyethylene pipe resin composition | |
| WO2019150907A1 (en) | Cellulose fiber master batch, cellulose fiber-containing resin composition, method for producing cellulose fiber master batch, method for producing cellulose fiber-containing resin composition, and molded body of cellulose fiber-containing resin composition | |
| CN102924799A (en) | Metallocene polyethylene resin composition for weather-resistant agricultural film and preparation method thereof | |
| CN102924800B (en) | Weather-resistant polyethylene resin composition for agricultural film and preparation method thereof | |
| CN102408600B (en) | High-strength ultra-wide metallocene polyethylene greenhouse film resin composition and preparation method thereof | |
| CN102816369B (en) | Polyethylene resin composition for agricultural film and preparation method thereof | |
| CN102295797B (en) | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof | |
| CN102408601B (en) | Ultra-wide metallocene polyethylene greenhouse film resin composition and preparation method thereof | |
| CN103160015B (en) | Polyethylene resin composition for greenhouse film and preparation method thereof | |
| CN102924798B (en) | Weather-resistant metallocene polyethylene agricultural film resin composition and preparation method thereof | |
| CN102924774B (en) | Polyethylene resin composition for pipes | |
| CN102952319B (en) | Polyethylene agricultural film resin composition and preparation method thereof | |
| CN102993536B (en) | Polyethylene pipe resin composition | |
| CN102408614B (en) | High-strength and ultra-wide polyethylene greenhouse film resin composition and preparation method thereof | |
| CN103627070B (en) | Low-haze polyethylene film resin composition | |
| CN102816364B (en) | Metallocene polyethylene resin composition for agricultural film and preparation method thereof | |
| CN110804216A (en) | Film-grade starch-based composite material and preparation method thereof | |
| CN102408615B (en) | Polyethylene geomembrane resin composition and preparation method thereof | |
| CN102952310B (en) | Metallocene polyethylene agricultural film resin composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |