CN102746563A - Preparation method of special material for LLDPE transparent greenhouse film - Google Patents
Preparation method of special material for LLDPE transparent greenhouse film Download PDFInfo
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- CN102746563A CN102746563A CN2011101022254A CN201110102225A CN102746563A CN 102746563 A CN102746563 A CN 102746563A CN 2011101022254 A CN2011101022254 A CN 2011101022254A CN 201110102225 A CN201110102225 A CN 201110102225A CN 102746563 A CN102746563 A CN 102746563A
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- 229920000092 linear low density polyethylene Polymers 0.000 title claims abstract description 109
- 239000004707 linear low-density polyethylene Substances 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- 239000003112 inhibitor Substances 0.000 claims description 49
- 230000003068 static effect Effects 0.000 claims description 48
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 46
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 44
- -1 methyl benzal Chemical class 0.000 claims description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 229960001866 silicon dioxide Drugs 0.000 claims description 26
- UKMSUNONTOPOIO-UHFFFAOYSA-N Behenic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 25
- 235000021357 Behenic acid Nutrition 0.000 claims description 25
- 229940116226 behenic acid Drugs 0.000 claims description 25
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 25
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 25
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 claims description 24
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 claims description 24
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical group OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 claims description 24
- 229940118781 dehydroabietic acid Drugs 0.000 claims description 24
- 238000005469 granulation Methods 0.000 claims description 24
- 230000003179 granulation Effects 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 23
- 229960003742 phenol Drugs 0.000 claims description 23
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 22
- 239000000600 sorbitol Substances 0.000 claims description 22
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 11
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 9
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 4
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- 239000002075 main ingredient Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 10
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 239000002667 nucleating agent Substances 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract description 4
- 239000002216 antistatic agent Substances 0.000 abstract 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229920001684 low density polyethylene Polymers 0.000 description 13
- 239000004702 low-density polyethylene Substances 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 7
- 239000003595 mist Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000009967 tasteless effect Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000123650 Botrytis cinerea Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- RLIPARRCKPWOIA-UHFFFAOYSA-N P(O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC Chemical compound P(O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC RLIPARRCKPWOIA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 241001558929 Sclerotium <basidiomycota> Species 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009305 arable farming Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000007115 recruitment Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a preparation method of a special material for LLDPE transparent greenhouse film; adding 0.01-0.2% of nucleating agent, 0.01-0.1% of antistatic agent and 0.01-0.2% of zinc stearate into LLDPE resin according to 100% of weight of the LLDPE resin, uniformly mixing in a mixing roll, carrying out melt extrusion in an extruder, and granulating to prepare the special material for the LLDPE transparent greenhouse film; the method effectively improves the transparency and mechanical property of the film, does not increase the addition cost of the auxiliary agent, can reduce the haze of the special material for the LLDPE greenhouse film to be below 13 percent, improves the tensile strength and the elongation at break of the film and ensures that the light transmittance reaches more than 92 percent.
Description
Technical field:
The present invention relates to the preparation method of the transparent canopy film special material of a kind of LLDPE.
Background technology:
Advantages such as linear low density polyethylene (LLDPE) film has good toughness, and tearing toughness is high, and puncture resistance is good are widely used in farmland film and awning film etc.In recent years, along with packaging industry is increasingly high to the properties of transparency requirement of canopy film and mulch film to the increase and the plastic sheeting for farm use market of transparent material demand, transparent LLDPE film relies on its excellent mechanical property to obtain fast development, and market demand rises year by year.
The transparent modified approach of LLDPE mainly contains three kinds: (1) is through changing the properties of transparency that comonomer improves the LLDPE film; LLDPE film properties of transparency with this technological method is produced is excellent; Mist degree is below 10%; The at present domestic problem that exists at this technical elements is the comonomer dependence on import, and raw materials cost is too high; (2) change catalyst system; Change the catalyzer in many active site into the catalyzer of single active center; The main metallocene catalyst that adopts is produced high transparent LLDPE material; The mist degree of the LLDPE film that this technological method of usefulness is produced is below 5%, and the MWD that this technological limitation is a resin is too narrow, poor processability; (3) improve auxiliary formula, improve the properties of transparency of LLDPE resin, the advantage of this technological method is simple to operate, flexible, need not undergo technological transformation to device.
The LLDPE resin is by Qi-Na catalyzer, is formed by ethene, butene-1 copolymerization by polycoordination mechanism.Because the copolymerized ability of catalyst system is relatively poor; Butene-1 is to be inserted at random on the PE macromole, causes LLDPE resin branching wider distribution, and promptly some macromole is highly branched; And some macromole is linear random coil structure, and this just causes the defective of LLDPE resin crystalline texture.Theoretical according to the Flory crystal formation, linear random coil molecule is pressed folded-chain structure and is generated platelet, and then grows up to nucleus, and the LLDPE macromole is the center with these nucleus, produces large-sized spherocrystal.Because the generation of nucleus is at random, so cause LLDPE resin crystalline region dispersive inhomogeneous.
In the blown film production process, when resin from molten state to the glassy transition process, in being lower than a certain TR of fusing point, begin crystallization; Because nucleus is to produce at random; Growing under field conditions (factors) of spherocrystal causes spherulite size big, and skewness.Luminous reflectance takes place on LLDPE film surface in large-sized spherocrystal, makes the transparent variation of film, in addition, because crystalline region and non-crystalline region refractive index there are differences, causes irregular scattering of light and reflection take place at the interface, thereby makes the properties of transparency of LLDPE resin relatively poor.Therefore,, reduce the interval difference of crystalline phase district and amorphous phase, can improve the transparency of LLDPE film through the crystal property of control LLDPE resin.
Nucleator can effectively increase the density of nucleus as the core of heterogeneous nucleation, improves Tc and cleanliness factor; When the abundant nucleator homodisperse of quantity; Nucleus reaches uniform distribution, and the growing space of spherocrystal diminishes, and reduces spherulite size; Can weaken the scattering of light and the luminous reflectance on film surface, the properties of transparency of LLDPE film is improved.
Common PE canopy film does not add the ageing-resistant tunica albuginea that waits auxiliary agent directly to produce with raw material blowing, and booth and middle hut application quantity are very big at present, generally detain canopy in spring, autumn; Only 4～6 months usage period, can only plant one season crop, waste energy; Increase recruitment, be eliminated gradually in the production.PE anti-aging film (long-lived grid film) ties up to and adds ageing-resistant auxiliary agent in the PE resin, through the blowing film forming.This canopy film thickness 0.08～0.12mm, the usage period can reach 12～18 months, can carry out the arable farming of 2～3 seasons; Not only the usage period prolongs; Cost reduction, energy-conservation, and the output and the output value are increased considerably, it is the plastic sheeting for farm use kind that emphasis is promoted in the present facility cultivation.PE does not have the anti-aging film (two anti-plastic sheeting for farm use) of dripping and has anti-drop property, weathering resistance, light transmission and good heat preservation performance simultaneously; Anti-droplet effect can keep 2～4 months; The ageing-resistant life-span can reach 12～18 months, is that present performance is more complete, uses plastic sheeting for farm use kind widely; Not only can be used for greenhouse and big or middle hut, and also comparatively suitable to the cultivation of energy-saving heliogreenhouse stubble in early spring.This covering material of PE thermal insulation greenhouse film can stop infrared rays radiation in atmosphere, can improve 1～2 ℃ of greenhouse temperature, and is better at the cold district effect.The PE multifunctional composite film have do not have to drip, multiple functions such as insulation, weather-proof, longevity, what have has a ultraviolet function of obstruct, ultraviolet ray is seen through reduce.What have can suppress the sclerotium disease apothecium and formation that botrytis cinerea divides spore.Usage period can reach 12～18 months.
To all kinds of PE canopy films, the selection of base resin should be satisfied: (1) relative molecular mass is higher, and Mw/Mn is narrower, and side chain number, carbon-carbon double bond number are few, and chromophoric group (carbonyl) content is low, and the catalyst residue amount is few, guarantees that product has excellent mechanical property and stability to aging; (2) crystalline size of resin is less, guarantees that product has good visible light transmissivity; (3) help drip agent, antifogging agent, heat preserving agent performance usefulness; (4) resin of same kind has lower percent crystallinity.
Mechanical properties in films is relevant with relative molecular mass and distribution, the degree of branching, percent crystallinity, fabrication process condition and the additive etc. of resin.Generally speaking, compare with ldpe film, the tensile strength of LLDPE film, elongation at break and angle tear strength improve 60%～70%, 60%～80% and 50%～70% respectively.But the LLDPE melt viscosity is bigger, and melt strength is lower, and the processing characteristics during extrusion-blown modling wide cut canopy film is not as good as LDPE.For improving mechanical property, improve processing characteristics, reduce raw materials cost, China generally adopts LDPE and LLDPE blend production wide cut canopy film.Generally believe that the relative molecular mass of PE is high, Mw/Mn is narrow, then the ageing-resistant performance of canopy mould is all right.And oxidation and light stability depend on the short-chain branch number of PE to a great extent.The base resin that the short-chain branch number is higher, less stable.The degree of branching is higher, the weakness that shows chain structure the more, superpolymer stability is poorer.Its reason is that tertiary carbon atom and hydrogen bond increase, and these weak bonds are subject to O
2Attack, further generate hydroperoxide, begin autoxidation reaction by general mechanism.Analyze from the molecular structure aspect, the ageing-resistant performance of LLDPE is superior to LDPE.In addition, transition metal ion content (catalyst residue amount) has a significant effect to the ageing-resistant performance of film among the LLDPE.MFR like certain trade mark LLDPE is less, and relative molecular mass is higher, and the side chain number is less, but the catalyst residue amount is more, and the film of using its blowing is in the natural climate exposure test, and the mechanical property retention rate obviously reduces.
The influence factor of LDPE/LLDPE canopy film transmittance and mist degree is more.LDPE/LLDPE canopy film optical property not only has direct relation with molecular structure, crystal habit, crystal size and the percent crystallinity of LDPE and LLDPE, and with extruder temperature, mouthful mould and processing condition such as mouthful of in-molded section runner degree of cleaning, the cooling of blown film bubble relation is arranged also.Generally speaking, the transmittance of ldpe film is higher than the LLDPE film, and mist degree is lower than the LLDPE film.The crystallization of LDPE/LLDPE blending resin melt in process of cooling is very complicated.Suitably improving extruder temperature and strengthening under the blown film bubble cooling conditions, can improve the transmittance of film, reduce mist degree.
The percent crystallinity of the inner additive type drip agent mechanism of action and base resin is closely related.Drip agent is distributed in the noncrystalline domain of resin, and thus to the film surface transport.Can not contain drip agent in the crystallizing field, can not make its migration as passage.So the crystalline state of canopy film is all influential to distribution, travelling speed, the drip effect of drip agent.Percent crystallinity is high, except that influencing canopy film transparency, also anti-drop property is produced negative effect.Defectives such as the canopy film that percent crystallinity is high exists drip agent at the face skewness, and the drip lasting period is short.
The molecular structure difference of LLDPE and LDPE shows: LLDPE does not have or long-chain branch is seldom arranged, and conventional film use LLDPE is the polymkeric substance (Mw/Mn is 3～4) of narrow Mw/Mn.The chain length of LLDPE short-chain branch depends on the type of comonomer.The side chain number depends on institute's bonded co-monomer content.Have only carbonatoms could upset closely piling up of chain molecule effectively, obtain LLDPE, produce the tie molecule that connects different crystalline regions simultaneously, improve the toughness and the intensity of polymkeric substance thereby reduce density more than or equal to 4 alpha-olefinic copolymerization.So film all is the multipolymer of ethene and 1-butylene, 1-hexene, 1-octene or 3-methyl-amylene with LLDPE.The LLDPE crystalline state not only depends on the type of comonomer, also depends on the distribution of comonomer in polymkeric substance and the frequency that in molecular chain, distributes.With under the isodensity, the fusing point of LLDPE is higher 10～15 ℃ than LDPE.Use the high power polarized light microscope observing, LLDPE spherocrystal diameter is 10～20 μ m, and LDPE spherocrystal diameter 2～3 μ m only.
In a word, LLDPE compares with LDPE, has significantly improved tensile strength, tear strength, puncture resistance, and has better heat-resisting and cold tolerance.And aspect processing characteristics, the susceptibility of LLDPE counter stress is poor, is promptly extruding under the shearing force of processing, and melt viscosity is much higher, need be than high pulling torque, higher melt temperature and die pressure, and be prone to take place melt fracture; But when the drawing-off of film bubble, do not harden.But good drawdown is arranged, and ratio of drawing can reach 25～150.Can be not height-oriented under big tensile deformation, can not produce the two-way unbalancedness of intensive.But the LLDPE melt strength is poor, the not cold wind of anti-high speed impact during cooling of film bubble, and poor stability needs to strengthen the design of cooling vane.
CN200910232637.2 relates to a kind of special compound additive of polyethylene film with high tranparency and low density; With the high-pressure polyethylene is carrier; By 25%～30% silicon-dioxide opening agent, 5%～15% organosilicon glidant, 2～8% organosilicon active crosslinker, 1～10% organosilicon oxidation inhibitor and surplus high pressure polyethylene resin through mix, 75～85 ℃ of following preheating Ball milling; Under 140 ℃～170 ℃,, add the low-density polyethylene film that this composite assistant is processed at last through the particle that the dual-screw pelletizer extruding pelletization gets; Tasteless, high transparent, have good physiological safety property, high opening property, smooth property and fabulous resistance to migration.Can be applicable to food, medicine, business card, identity card overlay film and advertisement packing etc. especially and film is had the field of high transparent, high security and high opening property requirement.
CN200710064958.7 relates to a kind of preparation method of high-transparent linear low density polyethylene, and particularly a kind of is the method that transparent agent prepares high-transparent linear low density polyethylene with the polyalkylene glycol acrylate monoesters.At first synthetic transparent agent polyalkylene glycol acrylate monoesters; The polyalkylene glycol acrylate monoesters be with vinylformic acid, polyoxyethylene glycol, Resorcinol, tosic acid, β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propylene octadecyl ester, distearyl pentaerythritol phosphite be raw material; Behind the synthetic transparent agent, with transparent agent polyalkylene glycol acrylate monoesters and linear low density polyethylene by weight 0.1～1.5: 100, extrude at 160 ℃～210 ℃ melt blendings, make the high-transparent linear low density polyethylene resin.
CN01115615.5 relates to a kind of agricultural canopy film; This canopy film contain 50～90% by the common new LDPE (film grade) of Ziegler one Natta catalyst or high-pressure polymerization process preparation and 10～50% linear low density polyethylene by metallocene catalysts, film thickness is 0.020～0.045mm.The angle tear strength of this film is high, and has good light transmission.
Summary of the invention:
The object of the invention adds a kind of composite transparent special assistant, and nucleus is few in the solution LLDPE course of processing, the key issue that the geode size is big.Improve crystalline state through the refinement crystalline size, effectively improve properties of transparency, the mechanical property of film, do not increase auxiliary agent simultaneously and add cost, thereby high transparent canopy film special material of a kind of LLDPE and preparation method thereof is provided.
LLDPE of the present invention is high, and transparent canopy film special material is by LLDPE weight resin 100%; In the LLDPE resin, add nucleator 0.01～0.2%, static inhibitor 0.01～0.1%, Zinic stearas are 0.01～0.2%; In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.
Described nucleator is made up of glucitols nucleator, organic phosphate nucleating agent, mineral-type nucleator, the rosin based nucleator is composite forms.Glucitols nucleator/organic phosphate nucleating agent/mineral-type nucleator/rosin based nucleator is 0～15%/0～15%/50～100%/0～20% by weight percentage; Preferred 3～12%/3～15%/60～90%/4～20%, most preferably 0～5/0～5/80～100/0～10;
Glucitols nucleator of the present invention is dibenzal sorbitol, two (3, a 4-dimethyl-benzal) sorbyl alcohol], a kind of in two (to the methyl benzal) sorbyl alcohol three.
Organic phosphate nucleating agent nucleator of the present invention is a kind of in two kinds of the n-butylbenzene al formates, p-tert-butyl benzoic acid oxyaluminum.
Mineral-type nucleator of the present invention is one or more in talcum powder and silicon-dioxide, the mica; Talcum powder/silicon-dioxide/micaceous proportioning is 0～25/0～25/50～100; Preferred 0～15/0～15/70～100, most preferably 0～5/0～5/90～100;
Rosin based nucleator of the present invention is dehydroabietic acid or contains a kind of as in the rosin resin acid constituents of main ingredient of dehydroabietic acid;
Static inhibitor of the present invention is three kinds of static inhibitor amine hydroxybenzenes, behenic acid acid amides, erucicamide is composite forms; Also can play smooth effect when playing antistatic property; Help improving the transparency of film, film is had antireflective effect, the processing characteristics of resin is made moderate progress.The proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide is 0～10/85～100/0～5 (weight percents), and is preferred 5～10/80～90/5～10, most preferably 5～8/84～90/5～8;
With raw material thorough mixing in mixing roll, melt extrude at forcing machine according to the above ratio, extrusion temperature is 100～200 ℃, preferred 130～170 ℃, and most preferably 140～160 ℃; Screw speed 100～300r/min, preferred 100～260r/min, most preferably 100～200r/min.
Preparing method's cost of the present invention is low, is prone to processing.The made LLDPE canopy film special material mist degree of product is reduced to below 13%, and the tensile strength and the elongation at break of film also increase.
Embodiment:
Below in all case study on implementation; In the LLDPE resin, add nucleator 0.01～0.2% (weight percent), static inhibitor 0.01～0.1% (weight percent), Zinic stearas are 0.01～0.2% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.
Wherein to form the proportioning according to glucitols nucleator/nucleator in organic phosphate class/mineral-type nucleator/rosin based nucleator be that 0～15/0～15/50～100/0～20 (weight percent) is composite forms to nucleator; The mineral-type nucleator is 0～25/0～25/50～100 (weight percents) according to talcum powder/silicon-dioxide/micaceous proportioning.Static inhibitor is 0～10/85～100/0～5 (weight percents) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
Comparative Examples 1
In the LLDPE resin, add slipping agent 0.05% (weight percent), Zinic stearas is 0.05% (weight percent), in mixing roll, mixes, and in forcing machine, melt extrudes granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 1
Nucleator is that 0/0/100/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 0/0/100 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 2
Nucleator is that 0/0/100/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 20/70/0 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 3
Nucleator is that 0/0/100/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/50/0 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 4
Nucleator is that 0/0/100/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/50/0 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 30/70/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 5
Nucleator is that 50/0/50/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 0/0/100 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 6
Nucleator is that 50/0/50/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/20/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 7
Nucleator is that 50/20/30/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/20/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 20/80/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 8
Nucleator is that 50/0/0/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/20/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 9
Nucleator is that 50/0/0/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 20/50/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 10
Nucleator is that 10/0/50/40 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/20/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 50/50/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 11
Nucleator is that 0/0/50/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/50/0 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/50/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 12
Nucleator is that 0/0/50/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 0/50/50 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 50/0/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 13
Nucleator is that 0/0/50/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/0/50 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 50/0/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 14
Nucleator is that 0/0/50/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 30/40/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 0/50/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 15
Nucleator is that 50/0/50/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/50/0 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 50/0/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 16
Nucleator is that 50/0/50/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/50/0 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 50/50/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 17
Nucleator is that 0/10/50/40 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/50/0 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 50/50/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 18
Nucleator is that 0/10/50/40 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 50/20/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 50/30/20 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 19
Nucleator is that 50/0/40/10 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 30/40/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 30/40/30 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Embodiment 20
Nucleator is that 50/10/0/40 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein the mineral-type nucleator is 30/40/30 composite forming according to talcum powder/silicon-dioxide/micaceous proportioning.
Static inhibitor is 50/40/10 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In the LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas are 0.01% (weight percent); In mixing roll, mix; In forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.Test result is seen table 1.
Can find out that from instance 1～20 and Comparative Examples preparing method's cost of the present invention is low, be prone to processing, the auxiliary agent blanking is smooth and easy, stable, tasteless.The made LLDPE canopy film special material mist degree of product is reduced to below 13%, and the shock strength that falls to marking of film also increases, and obtains downstream awning film enterprise and highly approves.
Subordinate list 1
Claims (1)
1. the preparation method of the transparent canopy film special material of LLDPE is characterized in that: by LLDPE weight resin 100%, add nucleator 0.01～0.2%; Static inhibitor 0.01～0.1%; Zinic stearas is 0.01～0.2%, in mixing roll, mixes, and in forcing machine, melt extrudes; Granulation, the transparent canopy film special material of preparation LLDPE;
Described nucleator is by glucitols nucleator, nucleator in organic phosphate class, mineral-type nucleator; The rosin based nucleator is composite to form, and the proportioning of glucitols nucleator/nucleator in organic phosphate class/mineral-type nucleator/rosin based nucleator is 0～15/0～15/50～100/0～20 by weight percentage;
Described glucitols nucleator is dibenzal sorbitol, two (3, a 4-dimethyl-benzal) sorbyl alcohol], a kind of in two (to the methyl benzal) sorbyl alcohol three;
Described nucleator in organic phosphate class is a kind of in two kinds of the n-butylbenzene al formates, p-tert-butyl benzoic acid oxyaluminum;
Described mineral-type nucleator is one or more in talcum powder and silicon-dioxide, the mica, and by weight percentage: talcum powder/silicon-dioxide/micaceous proportioning is 0～25/0～25/50～100;
Described rosin based nucleator is dehydroabietic acid or contains a kind of as in the rosin resin acid constituents of main ingredient of dehydroabietic acid;
Described static inhibitor is three kinds of static inhibitor amine hydroxybenzenes, behenic acid acid amides, erucicamide is composite forms, and amine hydroxybenzene/behenic acid acid amides/erucicamide proportioning is 0～10/85～100/0～5 by weight percentage;
The extrusion temperature of described forcing machine is 100～200 ℃; Screw speed 100～300r/min.
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| CN114763023A (en) * | 2021-05-19 | 2022-07-19 | 上海骊塑商贸有限公司 | Energy-saving and environment-friendly bubble structure film and preparation process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696185A (en) * | 2004-05-11 | 2005-11-16 | 中国科学院化学研究所 | Polyethylene in super molecular weight modified by Nano silicon rubber its prepn. provess and usage |
| CN101701084A (en) * | 2009-11-22 | 2010-05-05 | 李庆民 | Improved high-pressure polyethylene transparency complex additive and preparation method thereof |
| CN101942126A (en) * | 2009-07-08 | 2011-01-12 | 中国石油天然气股份有限公司 | Transparent antistatic polyethylene film master batch |
-
2011
- 2011-04-22 CN CN201110102225.4A patent/CN102746563B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696185A (en) * | 2004-05-11 | 2005-11-16 | 中国科学院化学研究所 | Polyethylene in super molecular weight modified by Nano silicon rubber its prepn. provess and usage |
| CN101942126A (en) * | 2009-07-08 | 2011-01-12 | 中国石油天然气股份有限公司 | Transparent antistatic polyethylene film master batch |
| CN101701084A (en) * | 2009-11-22 | 2010-05-05 | 李庆民 | Improved high-pressure polyethylene transparency complex additive and preparation method thereof |
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| CN102807684B (en) * | 2012-08-31 | 2014-05-21 | 南京工程学院 | High concentration sericite master batch and preparation method and application thereof |
| CN104231400A (en) * | 2014-09-24 | 2014-12-24 | 句容市给力包装制品厂 | Plastic packaging film and preparation method thereof |
| CN105254986A (en) * | 2015-11-23 | 2016-01-20 | 常熟市天娇塑业有限公司 | High-transparency polyethylene film |
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| CN106750730A (en) * | 2016-11-21 | 2017-05-31 | 中山火炬职业技术学院 | A kind of oxidation-type Biodegradable polyethylene film |
| CN107540924A (en) * | 2017-08-30 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of high glaze puncture-resistant linear polyethylene construct blow-molded |
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| CN108410057A (en) * | 2017-08-30 | 2018-08-17 | 中国石油化工集团公司 | A kind of polyolefin compound anti-reflection agent and preparation method thereof |
| CN108410057B (en) * | 2017-08-30 | 2021-04-02 | 中国石油化工股份有限公司 | Nano EVA composite nucleating agent and preparation method thereof |
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| CN109385006A (en) * | 2018-11-12 | 2019-02-26 | 金陵科技学院 | A kind of high transparency water-proof sheet material PP Pipe Compound and preparation method thereof |
| CN114763023A (en) * | 2021-05-19 | 2022-07-19 | 上海骊塑商贸有限公司 | Energy-saving and environment-friendly bubble structure film and preparation process thereof |
| CN114230897A (en) * | 2021-12-31 | 2022-03-25 | 杭州欧信包装科技有限公司 | High-permeability material applied to air column bag |
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