CN102408601A - Ultra-wide metallocene polyethylene greenhouse film resin composition and preparation method thereof - Google Patents
Ultra-wide metallocene polyethylene greenhouse film resin composition and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011342 resin composition Substances 0.000 title abstract description 4
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 title abstract description 3
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 25
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims description 65
- 229920005989 resin Polymers 0.000 claims description 65
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 235000013539 calcium stearate Nutrition 0.000 claims description 10
- 239000008116 calcium stearate Substances 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- -1 YLENE Natural products 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000000155 melt Substances 0.000 abstract description 4
- 241000251468 Actinopterygii Species 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract 1
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 20
- 238000012545 processing Methods 0.000 description 20
- 239000004744 fabric Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010096 film blowing Methods 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000003595 mist 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
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 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
- 235000013311 vegetables Nutrition 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
- B29C48/03—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
- B29C2948/92561—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)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a metallocene polyethylene greenhouse film resin composition, which comprises the following components in percentage by weight of metallocene linear low density polyethylene (mLLDPE): 1) the flow rate of mLLDPE melt is 0.5-10 g/10 min; 2)0.11 to 0.37 percent of compound crosslinking auxiliary agent consisting of 1, 1-dimethyl ethyl-hydrogen peroxide and tert-butyl peroxyacetate; 3) 0.011% -0.027% of dibenzoyl peroxide; the melt strength of the shed film resin composition is improved by more than 2 times compared with mLLDPE, and an ultra-wide shed film (the width is more than or equal to 14m, and the thickness is more than or equal to 60 mu m) with high strength and few fish eyes can be stably blown without any blending. The invention further discloses a preparation method of the composition.
Description
Technical field
The present invention relates to a kind of metallocene PE canopy film resin compsn; Being specifically related to the metallocene linear-low density polyethylene is base resin, through little cross-linking modified resin combination that improves its melt strength blowing excess of export wide cut canopy film significantly and preparation method thereof.
Background technology
Metallocene linear-low density polyethylene (mLLDPE) has been able to develop rapidly since the suitability for industrialized production that is realized first by american exxon (Exxon) company the nineties in 20th century.According to statistics, the metallocene linear-low density polyethylene YO is about more than 1,500 ten thousand tons in the world at present, accounts for 15% of linear low density polyethylene aggregate consumption, expects this ratio in 2012 and will reach about 22%.This has benefited from mainly that mLLDPE adopts be have the single-activity center, catalytic activity is high, shows outstanding catalysis in a homogeneous system, can freely design the metallocene catalyst of micmstructure of polymer.Therefore, the molecular structure of mLLDPE has than narrow molecular weight distributions, and the composition of comonomer distributes very evenly and uniform content between molecular chain, and molecular chain is examined brilliant formation speed and equated the equal first-class characteristics of crystal formation.These constructional features just make mLLDPE compare with conventional linear polyethylene resin (LLDPE): have high physical mechanical strength, good anti tear and anti-ly pierce through performance, optical transparence is good.Thereby, mLLDPE in agricultural canopy film by number of applications.
At present; The developmental level of China's agricultural canopy film is compared with advanced international standard; Still have bigger gap, these gaps show that mainly to lack high performance canopy film resin dedicated, cause that state's lambing shed film toughness is low, the life-span short; Mist degree is high, light transmission is poor, the quality product fluctuation is big etc., can't satisfy the needs of booth cultivation technical development.Current agricultural requires increasingly highly to canopy film functions of use, no longer is simple growing vegetables, but uses and extend to fruit, flowers, nursery, numerous production fields such as breed fish.So just make that (fabric width 4～8m) can't satisfy this demand for development to the common film of canopy in a narrow margin, and in order to adapt to this requirement, the development of canopy film is being tending towards wide cutization and functionalization.Because its melt strength of mLLDPE molecular structure characteristics decision is low; Insensitive to shearing, cause in the extrusion-blown modling complete processing, showing: mouthful mould place " stick-slip phenomenon " is obvious, is prone to the heap film; The swing of film bubble; Bubble stability is relatively poor, can't produce the ultra wide cut awning film of excellent performance separately, has greatly limited its application development space in the agricultural canopy film field.
In the prior art, the relevant method of improving processing capability of metallocene polyethylene has: 1). the processing characteristics of through polymer blending, select that structure is close for use, the general Vilaterm of good processability or other polymkeric substance improving metallocene PE.Like: CN101323674A with 90% Vilaterm and 9% glyceryl monooleate and 1%2.5-methyl-2.5 bishexane at 200 ℃ of following blend grafts, in three layers of compound blowing unit, blow out longevity polar shed film then 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, prepare the angle tear strength height, and thickness is 0.02～0.045mm canopy film.CN1252417A prepares the unilateral stretching film with the mixture of metallocene PE and new LDPE (film grade) and processing aid.Document " research of metallocene PE wide cut blowing moulding greenhouse film " (Chinese plastics; 2002 16 1 phases of volume; The 45-50 page or leaf) mLLDPE and LDPE blend have been introduced; Solve processing problems such as the mLLDPE melt viscosity is big, melt strength is low, blowing goes out thickness 0.06mm～0.08mm, the wide cut canopy film of folding footpath 4000mm～5000mm.2). through optimizing the processing characteristics that polymerization technique improves the metallocene PE resin.As: CN1927897A adds the oxidation inhibitor of 0.1～3 weight part in mLLDPE (100 weight part); Put into force chemical reactor after mixing; Under 15～35 ℃ of conditions, carry out chemical reaction and handle, preparing can be at the general general mLLDPE resin of extruding, inject smooth forming process on the processing units.3). utilize reactive extruding technology, through the processing characteristics of little cross-linking modified metallocene PE resin.As: the wide cut canopy film that in mLLDPE, adds the peroxidized t-butyl perbenzoate preparation folding footpath 8000mm of 0.05～0.35wt% di-tert-butyl hydrogen peroxide and 0.005～0.041wt% among the CN201010114242.5.
Above-mentioned document is limited at the melt strength that improves resin and the amplitude of improving aspect its blown film processing characteristics; Can only blow ultrathin membrane and common wide cut canopy film; Can not solve well when resin melt intensity significantly improves; Be prone to produce too much gel, cause film " flake " many, the problem that causes it to blow and to use.Do not see relevant report at the few ultra wide cut canopy of the mLLDPE film of blown film " flake " (fabric width >=14m, thickness >=60 μ m) aspect.
Summary of the invention
The object of the invention provides a kind of metallocene PE canopy film resin compsn.This canopy film resin compsn melt strength improves more than 2 times than mLLDPE, need not any blending just can blow out intensity height, ultra wide cut canopy film (fabric width >=14m, thickness >=60 μ m) that " flake " is few.The present invention further proposes the preparation of compositions method.
A kind of metallocene PE resin combination is a hundred per cent in the weight of mLLDPE, comprising:
(1)mLLDPE 100％
(2) composite crosslinking coagent 0.11%～0.37%
(3) BPO (BPO) 0.011%～0.027%
Composite crosslinking coagent described in the compsn is 1,1-dimethyl ethyl-hydrogen peroxide (TB) and the composite composition of tert-butyl peroxy acetate (TBPA), and TB is 20: 1～3: 2 with the mixed weight ratio of TBPA, preferred 10: 1～7: 4.
Can also add other auxiliary agent in the resin combination of the present invention, like thermo-stabilizer and oxidation inhibitor, its total add-on is 0.1～0.5% (wt) (weight in mLLDPE is per-cent).Wherein thermo-stabilizer is a kind of in the stearates, and like Zinic stearas, calcium stearate etc., consumption is 0.05%～0.25%.Oxidation inhibitor is a kind of in phenols, hindered amines, the phosphite ester kind antioxidant, and consumption is 0.05%～0.25%.
The preparing method's of metallocene PE resin combination of the present invention concrete steps are:
1) at first with adding solvent behind two kinds of crosslinking coagent proportional mixing, again with the mLLDPE that accounts for total amount 5%～10% (wt) and thermo-stabilizer and oxidation inhibitor mixed at high speed 3～5min after, process the premix masterbatch and add forcing machine by charging opening;
2) will remain mLLDPE and add forcing machine by charging opening, the reaction times is 1～3min, and temperature of reaction is 155～210 ℃;
3) with BPO and solvent solution-forming, be added drop-wise in the forcing machine fluxing zone, control is no more than 20 seconds the residence time of BPO in forcing machine, and temperature of reaction is no more than 225 ℃, extrudes, cooling, granulation.
Metallocene linear-low density polyethylene described in the compsn (mLLDPE) is to adopt single site catalysts---and the Vilaterm of metallocene catalysis system preparation can be ethene and butene-1, hexene-1 copolymerization and get, and also can be got by ethylene homo.Weight-average molecular weight Mw:6～15 * 104, MWD MWD :≤2.2, density: 0.865～0.941g/cm
3, melt flow rate(MFR): 0.5～10g/10min.Described melt flow rate(MFR) (MFR) is at 190 ℃, the measured value under the 2.16Kg load.
Resin combination of the present invention prepares in the process, in composite crosslinking coagent and BPO, adds solvent, and said solvent is toluene, YLENE, acetone etc., and its add-on is composite crosslinking coagent or BPO weight 2～5 times.
The preparation of resin combination of the present invention can be carried out in Banbury mixer, kneader, screw extrusion press, but is the best with the twin screw extruder.
Described in the compsn 1,1-dimethyl ethyl-hydrogen peroxide (TB) and tert-butyl peroxy acetate (TBPA) are the commercially available prod, and the half life temperature of superoxide is because of manufacturer's difference difference slightly, transformation period T=256～267 of general TB ℃/1min; Transformation period T=159～161 of TBPA ℃/1min.
General BPO (BPO) is the commercially available prod, its transformation period T=131～134 ℃/1min; Amount ranges: 0.011%～0.027%, to the strict control of its used in amounts, consumption can not surpass 0.027%; Processing temperature can not surpass 225 ℃ in the preparation of compositions process in addition, and the reaction times can not surpass 20 seconds, otherwise degree of crosslinking is uncontrollable; Be prone to gel; Produce more " brilliant point ", make ultra wide cut canopy film to process and to use, serious point can cause the screw rod locking to damage processing units.But its add-on can not be less than 0.011%, otherwise the increase rate of compsn melt strength is not enough, do not reach the requirement of the ultra wide cut canopy film of blowing.
MLLDPE described in the compsn can be powdery or granular resin, but best with powdered resin for reaching the better mixing effect.
In the compsn of the present invention, on the one hand, select the composite cross-linking system of the superoxide composition of a kind of low activity and greater activity; Base resin is given crosslinking reaction, can control the cross-linked speed and the crosslinking degree of resin effectively, realize little crosslinking structure; Can appropriateness improve the melt strength of resin, improve its processing characteristics, avoid a kind of superoxide of single use be not occur excessively crosslinked; Cause consumption excessive exactly, be unfavorable for problems such as safety, environmental protection, modification cost.On the other hand; According to of the requirement of the ultra wide cut canopy film of blowing to the base resin melt strength; On basis with precrosslink structural resin, add a small amount of highly active organo-peroxide once more, extrude under the strictness control in temperature of reaction and reaction times through reactivity; Little crosslinking reaction takes place once more, makes the increase rate of melt strength of base resin significantly increase.This synergy, the crosslinking structure of compsn is appeared, and " staged " amplifies step by step, realizes a large amount of little crosslinking structures but not the build crosslinking structure, avoids being prone to the problem of gel because of the melt strength increase rate of resin is big.Can make the said composition melt strength improve more than 2 times like this than mLLDPE; Can on common three layers of compound blown film unit, stably blow excess of export wide cut canopy film (fabric width >=14m, thickness >=60 μ m) without any transformation; Reached the requirement of producing ultra wide cut canopy film; Solved the problem that mLLDPE can't blow ultra wide cut canopy film, and the film product outward appearance do not have " flake " basically, make the excellent rerum natura of mLLDPE be able to give full play to aspect the use of canopy film.
The inventive method makes the crosslinking structure of base resin mLLDPE amplify step by step; Realized the controlled of degree of crosslinking; Prevent that gel from occurring, melt strength can improve significantly, can prepare the metallocene PE canopy film resin compsn of a kind of " flake " few ultra wide cut.This method has advantages such as flow process is short, technology is simple, cost of development is low, the construction cycle is short, the quality product fluctuation is little.
Embodiment
(1) raw material
1) resin
2) superoxide
TB transformation period T=264 ℃/1min, the auxiliary reagent factory, Lanzhou
TBPA transformation period T=160 ℃/1min, the auxiliary reagent factory, Lanzhou
BPO transformation period T=133 ℃/1min, the auxiliary reagent factory, Lanzhou
(2) performance test standard
Melt flow rate(MFR) MFR (g/10min) GB/T3682-2000
Density (g/cm
3) GB/T1033-1986
Film stretching intensity GB/T1040-1992
Film elongation at break GB/T1040-1992
Film tear strength GB/T16578
(3) equipment and instrument
Φ 67 twin screw extruders are long/directly=34/1 German Lestreiz company
The fast mixing machine of 10 risings Fuxin plastics machinery factory
Plunger type metering pump range: 0～100 liter of/hour U.S. Paasche Fei De company
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 mLLDPE in the compsn.
Embodiment 1
0.33 part of TB and 0.025 part of TBPA with after 0.8 part of acetone solvent mixes, are added 5 parts of mLLDPE (HPR18H10AX) powder resins and 0.05 part of antioxidant 1010,0.15 part of calcium stearate then, 10 raise mix 3min in the fast mixing machine after; Processing the premix masterbatch, with premix masterbatch and 95 parts of mLLDPE (HPR18H10AX) powder resin and joined in the forcing machine by charging opening, is under 155～210 ℃ of conditions behind the reaction 2min at barrel temperature; Again 0.012 part of BPO and 0.04 part of acetone solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～225 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Embodiment 2
0.29 part of TB and 0.03 part of TBPA with after 0.7 part of xylene solvent mixes, are added 5 parts of mLLDPE (ECD350) pellet resin and 168,0.2 part of Zinic stearas of 0.1 part of oxidation inhibitor then, 10 raise mix 3min in the fast mixing machine after; Processing the premix masterbatch, with premix masterbatch and 95 parts of mLLDPE (ECD350) powder resin and joined in the forcing machine by charging opening, is under 155～210 ℃ of conditions behind the reaction 2min at barrel temperature; Again 0.015 part of BPO and 0.05 part of xylene solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～225 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Embodiment 3
0.26 part of TB and 0.08 part of TBPA with after 0.9 part of acetone solvent mixes, are added 8 parts of mLLDPE (HPR18H10AX) powder resins and 0.1 part of antioxidant 1010,0.2 part of Zinic stearas then, 10 raise mix 3min in the fast mixing machine after; Processing the premix masterbatch, with premix masterbatch and 92 parts of mLLDPE (HPR18H10AX) powder resin and joined in the forcing machine by charging opening, is under 155～210 ℃ of conditions behind the reaction 2min at barrel temperature; Again 0.02 part of BPO and 0.05 part of acetone solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～225 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Embodiment 4
0.27 part of TB and 0.05 part of TBPA with after 0.7 part of acetone solvent mixes, are added 8 parts of mLLDPE (HPR18H10AX) powder resins and 0.15 part of antioxidant 1010,0.2 part of calcium stearate then, 10 raise mix 3min in the fast mixing machine after; Processing the premix masterbatch, with premix masterbatch and 92 parts of mLLDPE (HPR18H10AX) powder resin and joined in the forcing machine by charging opening, is under 155～210 ℃ of conditions behind the reaction 2min at barrel temperature; Again 0.022 part of BPO and 0.06 part of acetone solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～225 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Embodiment 5
0.25 part of TB and 0.09 part of TBPA with after 0.9 part of xylene solvent mixes, are added 8 parts of mLLDPE (ECD350) pellet resin and 168,0.2 part of calcium stearate of 0.15 part of oxidation inhibitor then, 10 raise mix 3min in the fast mixing machine after; Processing the premix masterbatch, with premix masterbatch and 92 parts of mLLDPE (ECD350) powder resin and joined in the forcing machine by charging opening, is under 155～210 ℃ of conditions behind the reaction 2min at barrel temperature; Again 0.024 part of BPO and 0.06 part of xylene solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～225 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Embodiment 6
0.23 part of TB and 0.11 part of TBPA with after 0.9 part of acetone solvent mixes, are added 8 parts of mLLDPE (HPR18H10AX) powder resins and 0.15 part of antioxidant 1010,0.2 part of calcium stearate then, 10 raise mix 3min in the fast mixing machine after; Processing the premix masterbatch, with premix masterbatch and 92 parts of mLLDPE (HPR18H10AX) powder resin and joined in the forcing machine by charging opening, is under 155～210 ℃ of conditions behind the reaction 2min at barrel temperature; Again 0.027 part of BPO and 0.07 part of acetone solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～225 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Comparative Examples 1
Other condition is identical with embodiment 1, and difference is not add in the preparation of compositions process TBPA, and the add-on of TB is 0.355 part; That is: with 0.355 part of TB with after 0.8 part of acetone solvent mixes, add 5 parts of mLLDPE (HPR18H10AX) powder resins and 0.05 part of antioxidant 1010,0.15 part of calcium stearate then, 10 raise mix 3min in the fast mixing machine after; Processing the premix masterbatch, with premix masterbatch and 95 parts of mLLDPE (HPR18H10AX) powder resin and joined in the forcing machine by charging opening, is under 155～210 ℃ of conditions behind the reaction 2min at barrel temperature; Again 0.012 part of BPO and 0.04 part of acetone solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～225 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Comparative Examples 2
Other condition is identical with embodiment 2, and difference is not add in the preparation of compositions process TB, and the add-on of TBPA is 0.32 part; That is: with 0.32 part of TBPA with after 0.7 part of xylene solvent mixes, add 5 parts of mLLDPE (ECD350) pellet resin and 168,0.2 part of Zinic stearas of 0.1 part of oxidation inhibitor then, 10 raise mix 3min in the fast mixing machine after; Processing the premix masterbatch, with premix masterbatch and 95 parts of mLLDPE (ECD350) powder resin and joined in the forcing machine by charging opening, is under 155～210 ℃ of conditions behind the reaction 2min at barrel temperature; Again 0.015 part of BPO and 0.05 part of xylene solvent are mixed with solution; Dripping in the forcing machine fluxing zone, is under 200～225 ℃ at barrel temperature, and extrusion reaction is after 17 seconds; Cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Comparative Examples 3
Other condition is identical with embodiment 3, and difference is in the preparation of compositions process BPO and TB and TBPA to be added simultaneously, that is: with 0.26 part of TB and 0.08 part of TBPA, 0.02 part of BPO and after 0.9 part of acetone solvent mixes; Add 8 parts of mLLDPE (HPR18H10AX) powder resins and 0.1 part of antioxidant 1010,0.2 part of Zinic stearas then; 10 raise mix 3min in the fast mixing machine after, process the premix masterbatch, with premix masterbatch and 92 parts of mLLDPE (HPR18H10AX) powder resin and join in the forcing machine by charging opening; At barrel temperature is under 155～210 ℃ of conditions; Behind the extrusion reaction 2min, cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Comparative Examples 4
Other condition is identical with embodiment 4, and difference is not add in the preparation of compositions process BPO, that is: with 0.27 part of TB and 0.05 part of TBPA with after 0.7 part of acetone solvent mixes; Add 8 parts of mLLDPE (HPR18H10AX) powder resins and 0.15 part of antioxidant 1010,0.2 part of calcium stearate then; 10 raise mix 3min in the fast mixing machine after, process the premix masterbatch, with premix masterbatch and 92 parts of mLLDPE (HPR18H10AX) powder resin and join in the forcing machine by charging opening; At barrel temperature is under 155～210 ℃ of conditions; Behind the extrusion reaction 2min, cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Comparative Examples 5
Other condition is identical with embodiment 5, and difference is that the add-on of BPO is 0.029 part, that is: with 0.25 part of TB and 0.09 part of TBPA with after 0.9 part of xylene solvent mixes; Add 8 parts of mLLDPE (ECD350) pellet resin and 168,0.2 part of calcium stearate of 0.15 part of oxidation inhibitor then, in the fast mixing machine of 10 risings, behind the mixing 3min, process the premix masterbatch; With premix masterbatch and 92 parts of mLLDPE (ECD350) powder resin and join in the forcing machine by charging opening; After barrel temperature is to react 2min under 155～210 ℃ of conditions, again 0.029 part of BPO and 0.06 part of xylene solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～225 ℃; After the extrusion reaction 17 seconds, cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
Comparative Examples 6
Other condition is identical with embodiment 6, and difference is in the preparation of compositions process to add that the extrusion reaction time is 27 seconds behind the BPO, that is: with 0.23 part of TB and 0.11 part of TBPA with after 0.9 part of acetone solvent mixes; Add 8 parts of mLLDPE (HPR18H10AX) powder resins and 0.15 part of antioxidant 1010,0.2 part of calcium stearate then, in the fast mixing machine of 10 risings, behind the mixing 3min, process the premix masterbatch; With premix masterbatch and 92 parts of mLLDPE (HPR18H10AX) powder resin and join in the forcing machine by charging opening; After barrel temperature is to react 2min under 155～210 ℃ of conditions, again 0.027 part of BPO and 0.07 part of acetone solvent are mixed with solution, drip in the forcing machine fluxing zone; At barrel temperature is under 200～225 ℃; After the extrusion reaction 27 seconds, cooling, compsn is prepared in granulation.Said composition is blown ultra wide cut canopy film (fabric width 14m, thickness are 60 μ m) on 120 3 layers of compound blown film unit of Φ, its composition properties, and film-blowing process condition and canopy film properties are seen table 1, table 2, table 3 respectively.
The physicals * of table 1 resin combination
| Numbering | MFR(g/10min) | Density (g/cm 3) | Melt strength cN |
| Embodiment 1 | 0.41 | 0.921 | 5.9 |
| Embodiment 2 | 0.35 | 0.918 | 6.8 |
| Embodiment 3 | 0.37 | 0.921 | 6.3 |
| Embodiment 4 | 0.28 | 0.922 | 6.7 |
| Embodiment 5 | 0.27 | 0.918 | 7.4 |
| Embodiment 6 | 0.11 | 0.923 | 6.9 |
| Comparative Examples 1 | 0.57 | 0.920 | 4.7 |
| Comparative Examples 2 | 0.39 | 0.918 | 5.3 |
| Comparative Examples 3 | 0.07 | 0.923 | 2.5 |
| Comparative Examples 4 | 0.43 | 0.921 | 4.3 |
| Comparative Examples 5 | 0.04 | 0.919 | 1.9 |
| Comparative Examples 6 | 0.01 | 0.923 | 1.8 |
Remarks
*: mLLDPE (HPR18H10AX) melt strength is 2.9cN, and mLLDPE (ECD350) melt strength is 3.2cN
The processing condition of the ultra wide cut canopy film of table 2 resin combination blowing
*
*120 3 layers of compound blown film unit of the Φ that Dalian rubber and plastics machine factory provides
The physicals of table 3 canopy film and outward appearance situation
*Reference appearance: the commercially available orchidization production LDPE/LLDPE (8: 2) of film factory of HTC blending material shed film (14000 * 0.06mm)
Claims (9)
1. metallocene PE resin combination is a hundred per cent in the weight of mLLDPE, comprising:
(1)mLLDPE 100％
(2) composite crosslinking coagent 0.11%～0.37%
(3)BPO 0.011％～0.027％
Composite crosslinking coagent described in the compsn is 1, the composite composition of 1-dimethyl ethyl-hydrogen peroxide and tert-butyl peroxy acetate, and the mixed weight ratio of the two is 20: 1～3: 2.
2. resin combination as claimed in claim 1 is characterized in that 1, and 1-dimethyl ethyl-hydrogen peroxide is 10: 1～7: 4 with the mixing quality ratio of tert-butyl peroxy acetate.
3. resin combination as claimed in claim 1 is characterized in that described mLLDPE is the Vilaterm with the metallocene catalysis system preparation, and this Vilaterm is that ethene and butene-1, hexene-1 copolymerization get, and is perhaps got by ethylene homo.
4. resin combination as claimed in claim 1 is characterized in that described resin combination can add thermo-stabilizer and oxidation inhibitor, is per-cent in the weight of mLLDPE, and its total add-on is 0.1～0.5wt%.
5. resin combination as claimed in claim 1 is characterized in that thermo-stabilizer is Zinic stearas, calcium stearate, and consumption is 0.05%～0.25%.
6. resin combination as claimed in claim 1 is characterized in that oxidation inhibitor is a kind of in phenols, hindered amines, the phosphite ester kind antioxidant, and consumption is 0.05%～0.25%.
7. the preparation method of a resin combination as claimed in claim 1 is characterized in that step is:
1) at first with adding solvent behind two kinds of crosslinking coagent proportional mixing, again with the mLLDPE that accounts for total amount 5%～10% (wt) and thermo-stabilizer and oxidation inhibitor mixed at high speed 3～5min after, process the premix masterbatch and add forcing machine by charging opening;
2) will remain mLLDPE and add forcing machine by charging opening, the reaction times is 1～3min, and temperature of reaction is 155～210 ℃;
3) with BPO and solvent solution-forming, be added drop-wise in the forcing machine fluxing zone, control is no more than 20 seconds the residence time of BPO in forcing machine, and temperature of reaction is no more than 225 ℃, extrudes, cooling, granulation.
8. preparation method as claimed in claim 7; It is characterized in that preparing in the process at resin combination; In composite crosslinking coagent and BPO, add solvent, said solvent is toluene, YLENE, acetone, and its add-on is composite crosslinking coagent or BPO weight 2～5 times.
9. preparation method as claimed in claim 7 is characterized in that the preparation of resin combination can be carried out in Banbury mixer, kneader, screw extrusion press.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103571025A (en) * | 2012-07-19 | 2014-02-12 | 中国石油天然气股份有限公司 | Lasting anti-fogging polyolefin film master batch |
| CN114441740A (en) * | 2020-11-04 | 2022-05-06 | 中国石油天然气股份有限公司 | Evaluation method of polyethylene raw material for electronic protective film |
| CN117021722A (en) * | 2023-08-21 | 2023-11-10 | 江阴市彩虹塑业有限公司 | Flexible substrate film for flexible electronic device and preparation method thereof |
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| JPH09265841A (en) * | 1996-03-28 | 1997-10-07 | Fujikura Ltd | Crosslinked polyethylene insulation cable |
| US20070048472A1 (en) * | 2005-08-30 | 2007-03-01 | Krishnaswamy Rajendra K | Polymeric pipe and method of making a polymeric pipe |
| CN101538386A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Agricultural polyethylene resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09265841A (en) * | 1996-03-28 | 1997-10-07 | Fujikura Ltd | Crosslinked polyethylene insulation cable |
| US20070048472A1 (en) * | 2005-08-30 | 2007-03-01 | Krishnaswamy Rajendra K | Polymeric pipe and method of making a polymeric pipe |
| CN101538386A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Agricultural polyethylene resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103571025A (en) * | 2012-07-19 | 2014-02-12 | 中国石油天然气股份有限公司 | Lasting anti-fogging polyolefin film master batch |
| CN103571025B (en) * | 2012-07-19 | 2015-12-02 | 中国石油天然气股份有限公司 | Lasting anti-fogging polyolefin film master batch |
| CN114441740A (en) * | 2020-11-04 | 2022-05-06 | 中国石油天然气股份有限公司 | Evaluation method of polyethylene raw material for electronic protective film |
| CN114441740B (en) * | 2020-11-04 | 2024-03-08 | 中国石油天然气股份有限公司 | Evaluation method of polyethylene raw material for electronic protective film |
| CN117021722A (en) * | 2023-08-21 | 2023-11-10 | 江阴市彩虹塑业有限公司 | Flexible substrate film for flexible electronic device and preparation method thereof |
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