CN103571024A - Long-acting polyolefin anti-fogging film master batch - Google Patents
Long-acting polyolefin anti-fogging film master batch Download PDFInfo
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- CN103571024A CN103571024A CN201210250277.0A CN201210250277A CN103571024A CN 103571024 A CN103571024 A CN 103571024A CN 201210250277 A CN201210250277 A CN 201210250277A CN 103571024 A CN103571024 A CN 103571024A
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- eva
- film
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 69
- 229920000098 polyolefin Polymers 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 61
- -1 polyol ester compound Chemical class 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000000694 effects Effects 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 25
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- 238000005469 granulation Methods 0.000 claims description 22
- 230000003179 granulation Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- 239000005639 Lauric acid Substances 0.000 claims description 12
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims 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 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 19
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- 229920000573 polyethylene Polymers 0.000 abstract description 17
- 230000002045 lasting effect Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- 229940070765 laurate Drugs 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 9
- 235000013539 calcium stearate Nutrition 0.000 description 9
- 239000008116 calcium stearate Substances 0.000 description 9
- OYYFSKLLXXTKNM-UHFFFAOYSA-N butane-1,1-diol dodecanoic acid Chemical class C(CCC)(O)O.C(CCCCCCCCCCC)(=O)O OYYFSKLLXXTKNM-UHFFFAOYSA-N 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 206010043087 Tachyphylaxis Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a polyolefin anti-fogging film master batch and a preparation method thereof, wherein the master batch comprises the following components in percentage by weight of EVA: (1) 100% of EVA, (2) 1% -2.5% of modified alumina, (3) 4% -8% of anti-fogging agent, and (4) 1% -4% of EVA-g-BMA graft; after the surface of the active alumina contained in the master batch is modified by the polyol ester compound, the dispersion of the active alumina in the anti-fogging agent is facilitated, and the adsorption efficiency of the convection agent is obviously enhanced. Meanwhile, the interaction of the modified alumina and the EVA-g-BMA graft produces an obvious slow-release effect on the polyol laurate anti-fogging agent, the problems of migration and precipitation of the anti-fogging agent in PE resin are effectively solved, the wettability of the film surface is obviously improved, the anti-fogging film master batch can be introduced into a polyethylene film in an internal addition mode to prepare the anti-fogging greenhouse film, and the anti-fogging lasting period of the anti-fogging greenhouse film is as long as more than 65 months.
Description
Technical field
The present invention relates to a kind of polyolefine resin composition, be specifically related to a kind of antifog drop films masterbatch of ethylene and vinyl acetate copolymer (EVA) that can significantly improve the anti-droplet persistence of polyethylene green house film and anti-droplet effect of initial stage.
Background technology
At present, the plastic greenhouse film of China is mainly polyethylene film, and polyethylene has good cold-resistant, dustproof, the easy characteristic such as processing, but it is a kind of hydrophobic resin, and the surface tension of its film and the surface tension of water differ larger.When early spring or season in late fall, the inside and outside temperature and humidity of plastic greenhouse differs greatly, adopt general thin to cover behind canopy chamber, when plastics film surface temperature reaches dew point when following, airborne steam reaches capacity or will condense into a large amount of droplets at canopy film inwall during supersaturation.The existence of droplet can cause scattering of light or reflection, reduces the light transmission of using awning film as agricultural or gardening, affects the photosynthesis of crop.Simultaneously droplet is dropped in canopy implants, also can cause leaf, stem, bud withered of plant or rot, and directly reduces output and the quality of crop.China carries out the development of polyethylene antifogging film in phase late 1980s, utilize tensio-active agent to improve poly critical surface tension, thereby make the tiny drops of water that condenses upon polyethylene film inwall sprawl into layer of transparent moisture film, and along the downward inflow surface of membranous wall, reach the effect of anti-droplet.
In prior art, the method that improves the wettability of frosting and give its anti-fogging property mainly contains two kinds: apply dripless agent type and interior interpolation dripless agent type outward.The one, outer cladding process adopts high-pressure spray gun in booth, to carry out surface spraying processing.The relevant report of the method is more, as: JP2001211760, JP03-244907, JP2003013038 (A), EP0732387, ZL200510025184.8, ZL200610064906.5 etc.Because this method not only needs spraying equipment, complex operation, cost is higher, and has the problem of solvent evaporates contaminate environment, so additive process in domestic adopt more.The 2nd, interior additive process is exactly in the production process of plastic greenhouse film, and dripless agent is added to and in material resin, together carries out mixing, plasticizing, then Blown Film.As: ZL03119742.6 provide a kind of by maleic anhydride alcohol ether ester mixture and higher alcohols ether mixture, is jointly formed without a polyethylene green house film composition.CN1225929A discloses a kind of antifogging agent with fluorine-containing, silicon-containing surfactant and has been mixed with in proportion demisting high-effective dripless agent with the dripless agent with polyol ester and alkylphenol polyoxyethylene, with it, produces and has good fog dispersal function and without the agriculture greenhouse film that drips efficiency.JP11310648 employing ethene and hexene copolymer and LDPE and appropriate stearate class antifogging agent, fluorochemical surfactant are blow molded into film jointly, and its anti-droplet validity period reaches 10 months.JP11322965 provides a kind of antifogging agent being jointly comprised of fluorochemical surfactant and sorbitan monostearate, two Stearic diglycerides, methylene radical distearyl acid amides, hydrolysis stone, adds in LLDPE canopy film and can show good long-term antifogging property.ZL200810238307.X provides a kind of inner additive type agricultural long-acting non drip defogging film containing EVA resin, about the anti-drop defogging phase from 100 days of this film, is increased to more than 160 days, has increased transmittance and the heat-insulating property of film simultaneously.CN1225929A provides a kind of and has jointly formed a kind of anti-aging and dropless agricultural film by polyethylene, ethylene-vinyl acetate copolymer (EVA), processing modifying agent (as: diatomite, silicon-dioxide, magnesiumcarbonate etc.), dripping inhibitor.Reaching more than 9 months without dripping the lasting period of this film.
Above-mentioned patent is substantially all directly to add antifogging agent, although obtaining obvious effect aspect the anti-droplet of raising polyethylene film.But not very good aspect the long-lasting of the anti-droplet of film and anti-droplet of initial stage; small molecules antifogging agent is in the inner problem that has migration and separate out of PE resin; often there will be antifogging agent to run off gradually and lose its function; its anti-droplet lasting period can only maintain about 3～10 months, and the middle and later periods droplet evil problem of using at polyethylene green house film is like this more outstanding.
Summary of the invention
The object of the invention is to provide a kind of anti-droplet lasting period more than 65 months and the good antifog drop films masterbatch of EVA of anti-droplet effect of initial stage.The present invention further proposes the preparation method of masterbatch.
The antifog drop films masterbatch of EVA of the present invention, the weight of EVA of take is absolutely, mainly to comprise following component:
1) 100% EVA;
2) 1%～2.5% modified aluminas;
3) 4%～8% antifogging agent;
4) 1%～4% EVA-g-BMA grafts.
Described polymer EVA is the multipolymer by ethene and vinyl acetate between to for plastic (VA) copolymerization, is film-grade.Wherein the content of vinyl acetate between to for plastic (VA) is: < 9%; Melt flow rate (MFR) (MFR) is: 0.1～5g/10min; Density: 0.910～0.930g/cm
3.Described melt flow rate (MFR) (MFR) is at 190 ℃, the measured value under 2.16Kg load.
" part " of the present invention all refers to weight part.
The mixture that described modified aluminas consists of jointly activated alumina and surface-modifying agent.Activated alumina: AL
2o
3content is greater than 93%, and particle diameter is greater than 200 orders.Surface-modifying agent is polyol ester compounds, can be selected from a kind of in glycol ester, pentaerythritol ester, propylene glycol ester, glycerine ester, butanediol ester.
The preparation method of modified aluminas is: by weight, by the activated alumina of 100 parts and deionized water, be within 1: 10～1: 15, together to join in cohesion still by volume, high-speed mixing 10～30min is mixed with aaerosol solution; Then surface-modifying agent and the ethanol of getting 5～10 parts are within 1: 2～1: 4, to be mixed with mixing solutions by weight; Surface-modifying agent mixing solutions is placed in aluminum oxide aaerosol solution again, is warming up to 80～100 ℃, stirring reaction 60～120min, makes modified aluminas finally by suction filtration, grinding, vacuum-drying.
Described EVA-g-BMA grafts is grafted monomer to be grafted to the graft copolymer on EVA main chain under the effect of initiator.Initiator is selected from tertbutyl peroxide, 2; 5-dimethyl-2; a kind of in 5-di-t-butyl hexane peroxide (BPDH), ditertiary butyl peroxide (DTBP), dicumyl peroxide (DCP), diisopropylbenzenehydroperoxide (DBHP), benzoyl peroxide or peroxide di-t-butyl; preferably adopt 2; 5-dimethyl-2,5-di-t-butyl hexane peroxide (BPDH).Grafted monomer is butyl methacrylate (BMA), purity >=99%.
The preparation method of described EVA-g-BMA grafts is: by the weight percent meter of EVA, by the EVA high-speed mixing 5～10min of the butyl methacrylate of 5～10 parts (BMA) and 100 parts; Then initiator and the acetone of getting 0.1～0.2 part are within 1: 2～1: 4, to be mixed with mixing solutions by weight, again mixing solutions is placed into mixture high speed and mixes 5～10min, the material mixing is placed to 5～10h in encloses container, finally by carrying out melting graft reaction in twin screw extruder, 150～190 ℃ of temperature of reaction, reaction times 3～6min, extrudes, cooling, granulation, obtains BMA percentage of grafting and be 1.0%～2.0% EVA-g-BMA grafts.
Described initiator is that organo-peroxide is commercially available prod, and its half life temperature is because of manufacturer's difference difference slightly, transformation period T=182～185 of general BPDH ℃/1min.
Described antifogging agent is lauric acid polyol ester compounds, can be selected from one or more in lauric acid glycol ester, lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester.
The preparation of masterbatch of the present invention can be carried out in Banbury mixer, kneader, twin screw extruder, but take twin screw extruder as best.While selecting twin screw extruder to prepare, the preparation technology that can adopt raw material to be pre-mixed, to extrude again.Preparation process comprises the steps: particularly
1) EVA, modified aluminas, antifogging agent, EVA-g-BMA grafts, oxidation inhibitor, stablizer are put in super mixer together to high-speed mixing 5～10min.
2) mixed material is added to twin screw extruder, 160～200 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, makes the antifog drop films masterbatch of EVA.
In the present invention, according to the requirement of stable resin processing, in the preparation process of masterbatch, can add the auxiliary agents such as a certain amount of thermo-stabilizer and oxidation inhibitor.
Described oxidation inhibitor can be one or several compounds in phenols, hindered amines, phosphite ester kind antioxidant, as 1010,1076,168,2246,1010 and 168 composite etc.The weight of EVA resin of take is that absolutely the consumption of oxidation inhibitor is: 0.1%～0.3%.
Described stablizer is stearates, as Zinic stearas, calcium stearate, Magnesium Stearate etc.The weight of EVA resin of take is that absolutely the consumption of stearate is: 0.1%～0.2%.
The addition of the antifog drop films masterbatch of EVA of the present invention in polyethylene green house film is that 5%～15%(is by the weight part of polyethylene green house film resin), the initial stage that can make, anti-droplet effect was good, and the anti-droplet lasting period is at more than 65 months polyethylene green house films.
In masterbatch of the present invention, first, activated alumina is after polyol ester compounds surface modification, the polar group on activated alumina surface and the effect of ester group generation adsorption by hydrogen bond, make diatomaceous polar group be attracted to particle surface, allow non-polar group demonstration outside, thereby surperficial free energy is reduced, be conducive to the dispersion of activated alumina in antifogging agent, obviously enhanced activity aluminum oxide is to drip agent adsorption efficiency, can significantly suppress the rate of migration of antifogging agent in canopy film base resin, reach the effect of long-term anti-droplet.EVA-g-BMA grafts has certain absorption to antifogging agent small molecules simultaneously, can hinder the fast transferring of antifogging agent small molecules in polyethylene green house film resin and separate out, and plays certain slow releasing function, has improved the lasting period of anti-droplet.In addition; the hydroxyl on the carboxyl in EVA-g-BMA grafts and modified aluminas surface and acyl group isoreactivity group generation chemisorption or physical adsorption; improved the consistency of activated alumina and polyethylene green house film base resin; cause modified aluminas and EVA-g-BMA grafts producing certain synergistic effect aspect prolongation antifogging agent result of use; this effect can realize the passage of absorption effectively and slowly-releasing to antifogging agent, greatly improves the anti-droplet of polyethylene green house film.
Secondly, the feature that contains poly-hydroxy and many carboxyls in modified aluminas surface and EVA-g-BMA grafts, there is very strong wetting ability, the molecular backbone chain structure of its EVA resin is identical with polyethylene green house film base resin molecular structure, can make its hydrophilic radical be distributed to equably polyethylene green house film surface, effectively improve film wettability of the surface energy, reduce the contact angle between water and face, guaranteed the anti-droplet effect of initial stage that canopy film is used.
Embodiment
(1) raw material
1) resin
2) other auxiliary agent
(2) performance test
The mensuration of film contact angle θ: the antifogging film of getting 8cm * 2cm is fixed on slide glass, measures on contact angle instrument.
Anti-droplet of initial stage: beaker is placed in to the Water Tank with Temp.-controlled of 60 ℃, envrionment temperature is room temperature, the water mark situation of observing film surface in 15min.A: face is unchanged; B: face produces water mark, but disappears in 3min; C: face produces water mark, but disappears in 15min; After D:15min, face still has water mark, but transparent.
The anti-droplet of high temperature: get a block length 15cm, wide 15cm, thickness is about the square canopy film of 0.08mm, covers on the beaker of 500mL, and rim of a cup is tightened, and 300mL water is housed in beaker.Then beaker is placed in to the Water Tank with Temp.-controlled of 60 ℃, is 15 ° of inclination angles, envrionment temperature is room temperature.In the time of 60 ℃, on film, droplet area is considered as losing efficacy over 1/3 of face.Canopy film experienced timing definition from bringing into use to losing efficacy be canopy film without dripping a lasting period.
The anti-droplet of low temperature: get a block length 15cm, wide 15cm, thickness is about the square canopy film of 0.08mm, covers on the beaker of 500mL, and rim of a cup is tightened, and 300mL water is housed in beaker.Then beaker is placed in to the Water Tank with Temp.-controlled of 18 ℃, envrionment temperature is-5 ℃.On film, droplet area is considered as losing efficacy over 1/4.
The antidrip persistence evaluation of canopy film: farmland plastic house carries out actual observation, the distribution area of canopy film internal surface flakey water droplet reaches 50% number of days.●: the distribution area of canopy film internal surface flakey water droplet reaches below 50%, and the film transparency is good.Zero: the distribution area of canopy film internal surface flakey water droplet reaches more than 50%, the film transparency is poor.
Percentage of grafting: chemical titration.
(3) equipment and instrument
Embodiment and comparative example
Enumerate following examples invention effect of the present invention is described, but protection scope of the present invention is not limited in these embodiment, in composition, each component is in the parts by weight of EVA resin.
Embodiment 1
(1) preparation of modified aluminas: pressing the weight percent meter of activated alumina, is together to join at 1: 12 in cohesion still by the activated alumina of 100 parts and deionized water by volume, and high-speed mixing 30min is mixed with aaerosol solution; Then pentaerythritol ester and the ethanol of getting 5.5 parts are to be mixed with mixing solutions at 1: 4 by weight; Again mixing solutions is placed in aluminum oxide aaerosol solution, is warming up to 90 ℃, open agitator and keep certain tachyphylaxis 100min, finally by suction filtration, grinding, vacuum-drying, make modified aluminas a.
(2) preparation of EVA-g-BMA grafts: the EVA(LD358 by the butyl methacrylate of 6 parts (BMA) with 100 parts) resin high-speed mixing 5min, then BPDH and the 0.4 part of acetone of getting 0.12 part are mixed with mixing solutions, then by mixing solutions and high-speed mixing 5min together with mixture above; The material mixing is placed on to 10h in encloses container; Finally the material placing is joined in Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 150,160,165,170,180,190,185,175,170; Carry out melting graft reaction, after reaction 5min, extrude, cooling, granulation, obtain percentage of grafting and be 1.1% EVA-g-BMA grafts.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(LD358) and 1.5 parts of percentage of grafting be 1.1% EVA-g-BMA grafts, 1.1 parts of modified aluminas a, 4.3 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 2
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(LD358) and 1.9 parts of percentage of grafting be 1.1% EVA-g-BMA grafts, 1.3 parts of modified aluminas a, 4.7 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 3
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(LD358) and 2.3 parts of percentage of grafting be 1.1% EVA-g-BMA grafts, 1.5 parts of modified aluminas a, 5.0 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 4
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(LD358) and 2.5 parts of percentage of grafting be 1.1% EVA-g-BMA grafts, 1.7 parts of modified aluminas a, 5.6 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 5
(1) preparation of modified aluminas: pressing the weight percent meter of activated alumina, is together to join at 1: 12 in cohesion still by the activated alumina of 100 parts and deionized water by volume, and high-speed mixing 30min is mixed with aaerosol solution; Then glycol ester and the ethanol of getting 8.5 parts are to be mixed with mixing solutions at 1: 3 by weight; Again mixing solutions is placed in aluminum oxide aaerosol solution, is warming up to 90 ℃, open agitator and keep certain tachyphylaxis 100min, finally by suction filtration, grinding, vacuum-drying, make modified aluminas b.
(2) preparation of EVA-g-BMA grafts: the EVA(EF320 by the butyl methacrylate of 9 parts (BMA) with 100 parts) resin high-speed mixing 5min, then BPDH and the 0.5 part of acetone of getting 0.15 part are mixed with mixing solutions, then by mixing solutions and high-speed mixing 5min together with mixture above; The material mixing is placed on to 10h in encloses container; Finally the material placing is joined in Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 150,160,165,170,180,190,185,175,170; Carry out melting graft reaction, after reaction 5min, extrude, cooling, granulation, obtain percentage of grafting and be 1.7% EVA-g-BMA grafts.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(EF320) and 2.8 parts of percentage of grafting be 1.7% EVA-g-BMA grafts, 1.9 parts of modified aluminas b, 6.0 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 6
(1) preparation of modified aluminas: with embodiment 5.
(2) preparation of EVA-g-BMA grafts: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(EF320) and 3.1 parts of percentage of grafting be 1.7% EVA-g-BMA grafts, 2.1 parts of modified aluminas b, 6.7 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 7
(1) preparation of modified aluminas: with embodiment 5.
(2) preparation of EVA-g-BMA grafts: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(EF320) and 3.4 parts of percentage of grafting be 1.7% EVA-g-BMA grafts, 2.2 parts of modified aluminas b, 7.1 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 8
(1) preparation of modified aluminas: with embodiment 5.
(2) preparation of EVA-g-BMA grafts: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(EF320) and 3.9 parts of percentage of grafting be 1.7% EVA-g-BMA grafts, 2.4 parts of modified aluminas b, 7.5 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 1
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of EVA: other condition is identical with embodiment 1, difference is that EVA-g-BMA grafts, 1.1 parts of modified aluminas a, 4.3 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate that EVA-g-BMA grafts (percentage of grafting: add-on 1.1%) is 0.5 part, that is: by 100 parts of EVA(LD358) in the preparation process of masterbatch and 0.5 part of percentage of grafting are 1.1% put into together 10 liters of high-speed mixer high speeds and mix 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 2
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of EVA: other condition is identical with embodiment 2, difference is not add lauric acid glycol ester dripping inhibitor in the preparation process of masterbatch, that is: by 100 parts of EVA(LD358) and 1.9 parts of percentage of grafting be 1.1% EVA-g-BMA grafts, 1.3 parts of modified aluminas a, 0.2 part of antioxidant 1010,0.15 part of calcium stearate are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 3
(1) preparation of EVA-g-BMA grafts: with embodiment 1.
(2) preparation of the antifog drop films masterbatch of EVA: other condition is identical with embodiment 3, difference is not add modified aluminas a in the preparation process of masterbatch, that is: by 100 parts of EVA(LD358) and 2.3 parts of percentage of grafting be 1.1% EVA-g-BMA grafts, 5.0 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 4
(1) preparation of EVA-g-BMA grafts: with embodiment 1.
(2) preparation of the antifog drop films masterbatch of EVA: other condition is identical with embodiment 4, difference is not add modified aluminas a in the preparation process of masterbatch, but directly add activated alumina, its add-on is 1.7 parts, that is: by 100 parts of EVA(LD358) and 2.5 parts of percentage of grafting be 1.1% EVA-g-BMA grafts, 1.7 parts of activated aluminas, 5.6 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 5
(1) preparation of modified aluminas: with embodiment 5.
(2) preparation of the antifog drop films masterbatch of EVA: other condition is identical with embodiment 5, difference is not add EVA-g-BMA grafts in the preparation process of masterbatch, that is: by 100 parts of EVA(EF320) and 1.9 parts of modified aluminas b, 6.0 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into together 10 liters of high-speed mixer high speeds and mix 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 6
(1) preparation of EVA-g-BMA grafts: with embodiment 5.
(2) preparation of the antifog drop films masterbatch of EVA: other condition is identical with embodiment 6, difference is not add modified aluminas b in the preparation process of masterbatch, but directly add activated alumina, its add-on is 2.1 parts, that is: by 100 parts of EVA(EF320) and 3.1 parts of percentage of grafting be 1.7% EVA-g-BMA grafts, 2.1 parts of activated aluminas, 6.7 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 7
(1) preparation of EVA-g-BMA grafts: with embodiment 5.
(2) preparation of the antifog drop films masterbatch of EVA: other condition is identical with embodiment 7, difference is that the add-on of modified aluminas b in the preparation process of masterbatch is 0.5 part, that is: by 100 parts of EVA(EF320) and 3.4 parts of percentage of grafting be 1.7% EVA-g-BMA grafts, 0.5 part of modified aluminas b, 7.1 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas are put into together 10 liters of high-speed mixer high speeds and mixed 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 8
(1) preparation of the antifog drop films masterbatch of EVA: other condition is identical with embodiment 8, difference is not add modified aluminas b and EVA-g-BMA grafts in the preparation process of masterbatch, that is: by 100 parts of EVA(EF320) and 7.5 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into together 10 liters of high-speed mixer high speeds and mix 10min; Then the material mixing is joined in Φ 67 twin screw extruders, each section of temperature of reaction of barrel (℃) be followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of EVA.
The application of the prepared anti-droplet masterbatch of embodiment 1 ~ 8 and comparative example 1 ~ 8 in canopy film contrast: by the resin dedicated LLDPE(LL106AA of linear low density polyethylene canopy film) mix in 10% addition (by LLDPE weight part) with embodiment 1 ~ 8 and the prepared anti-droplet masterbatch of comparative example 1 ~ 8 respectively, wherein the masterbatch of comparative example 2 preparations also needs to give first and mixing with 0.47 part of lauric acid glycol ester, the masterbatch that comparative example 3 makes also needs to be pre-mixed with 0.15 part of modified aluminas a, the EVA-g-BMA grafts that it is 1.7% that the masterbatch that comparative example 8 makes also needs with 0.24 part of modified aluminas b and 0.39 part of percentage of grafting gives first and mixing, then at 120 3 layers of compound blown film unit blowing up wide cut canopy processed film (fabric width 8m of Φ, thickness is 0.08mm), be labeled as respectively: implement film 1 ~ 8 and comparative film 1 ~ 8, the test result of its canopy film antifogging property is in Table 1.
Table 1 is containing the canopy film antifogging property of 10% embodiment and comparative example masterbatch
Claims (7)
1. an antifog drop films masterbatch, the weight of EVA of take is absolutely, mainly comprises following component:
1) 100% EVA;
2) 1%～2.5% modified aluminas;
3) 4%～8% antifogging agent;
4) 1%～4% EVA-g-BMA grafts;
Described polymer EVA is the multipolymer by ethene and vinyl acetate between to for plastic copolymerization, and described EVA-g-BMA grafts is by the monomer-grafted graft copolymer to EVA main chain of butyl methacrylate under the effect of initiator; The mixture that described modified aluminas consists of jointly activated alumina and polyol ester compounds surface-modifying agent.
2. film masterbatch as claimed in claim 1, is characterized in that described surface-modifying agent is selected from a kind of in glycol ester, pentaerythritol ester, propylene glycol ester, glycerine ester, butanediol ester.
3. film masterbatch as claimed in claim 1, the preparation method who it is characterized in that described modified aluminas is: by weight, by the activated alumina of 100 parts and deionized water, be within 1: 10～1: 15, together to join in cohesion still by volume, high-speed mixing 10～30min is mixed with aaerosol solution; Then surface-modifying agent and the ethanol of getting 5～10 parts are within 1: 2～1: 4, to be mixed with mixing solutions by weight; Surface-modifying agent mixing solutions is placed in aluminum oxide aaerosol solution again, is warming up to 80～100 ℃, stirring reaction 60～120min, makes modified aluminas finally by suction filtration, grinding, vacuum-drying.
4. film masterbatch as claimed in claim 1, is characterized in that the preparation method of described EVA-g-BMA grafts is: by the weight percent meter of EVA, by the EVA high-speed mixing 5～10min of the butyl methacrylate of 5～10 parts and 100 parts; Then initiator and the acetone of getting 0.1～0.2 part are within 1: 2～1: 4, to be mixed with mixing solutions by weight, again mixing solutions is placed into mixture high speed and mixes 5～10min, the material mixing is placed to 5～10h in encloses container, finally by carrying out melting graft reaction in twin screw extruder, 150～190 ℃ of temperature of reaction, reaction times 3～6min, extrudes, cooling, granulation, obtains EVA-g-BMA grafts.
5. film masterbatch as claimed in claim 1; it is characterized in that described initiator is selected from tertbutyl peroxide, 2; 5-dimethyl-2, a kind of in 5-di-t-butyl hexane peroxide, ditertiary butyl peroxide, dicumyl peroxide, diisopropylbenzenehydroperoxide, benzoyl peroxide or peroxide di-t-butyl.
6. film masterbatch as claimed in claim 1, is characterized in that described antifogging agent is selected from one or more in lauric acid glycol ester, lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester.
7. a preparation method for film masterbatch as claimed in claim 1, is characterized in that comprising the steps:
1) EVA, modified aluminas, antifogging agent, EVA-g-BMA grafts are put in super mixer together to high-speed mixing 5～10min;
2) mixed material is added to twin screw extruder, 160～200 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, makes the antifog drop films masterbatch of EVA.
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| CN110895355A (en) * | 2018-08-22 | 2020-03-20 | 通用汽车环球科技运作有限责任公司 | Intelligent multifunctional lens coating |
| CN111320804A (en) * | 2020-03-24 | 2020-06-23 | 张露 | Aluminum oxide multifunctional greenhouse film master batch and preparation method and application thereof |
| CN113136065A (en) * | 2021-04-20 | 2021-07-20 | 福州大学 | Polyethylene anti-fogging film and preparation method thereof |
| CN114133651A (en) * | 2021-11-17 | 2022-03-04 | 安徽国风塑业股份有限公司 | Lasting anti-fog and non-drip polyethylene film master batch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108485162A (en) * | 2018-03-30 | 2018-09-04 | 吕莉 | A kind of preparation method of automobile-used ageing-resistant antifog film |
| CN110895355A (en) * | 2018-08-22 | 2020-03-20 | 通用汽车环球科技运作有限责任公司 | Intelligent multifunctional lens coating |
| CN111320804A (en) * | 2020-03-24 | 2020-06-23 | 张露 | Aluminum oxide multifunctional greenhouse film master batch and preparation method and application thereof |
| CN113136065A (en) * | 2021-04-20 | 2021-07-20 | 福州大学 | Polyethylene anti-fogging film and preparation method thereof |
| CN113136065B (en) * | 2021-04-20 | 2022-04-12 | 福州大学 | Polyethylene anti-fogging film and preparation method thereof |
| CN114133651A (en) * | 2021-11-17 | 2022-03-04 | 安徽国风塑业股份有限公司 | Lasting anti-fog and non-drip polyethylene film master batch and preparation method thereof |
| CN114133651B (en) * | 2021-11-17 | 2024-06-04 | 安徽国风新材料股份有限公司 | Durable anti-fog drip-free polyethylene film master batch and preparation method thereof |
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