CN103571025A - Lasting anti-fogging polyolefin film master batch - Google Patents
Lasting anti-fogging polyolefin film master batch Download PDFInfo
- Publication number
- CN103571025A CN103571025A CN201210250678.6A CN201210250678A CN103571025A CN 103571025 A CN103571025 A CN 103571025A CN 201210250678 A CN201210250678 A CN 201210250678A CN 103571025 A CN103571025 A CN 103571025A
- Authority
- CN
- China
- Prior art keywords
- mlldpe
- masterbatch
- vam
- grafts
- droplet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 70
- 230000002045 lasting effect Effects 0.000 title abstract description 6
- 229920000098 polyolefin Polymers 0.000 title description 2
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims abstract description 68
- 238000002360 preparation method Methods 0.000 claims abstract description 53
- 239000004698 Polyethylene Substances 0.000 claims abstract description 41
- -1 polyethylene Polymers 0.000 claims abstract description 40
- 229920000573 polyethylene Polymers 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 238000005469 granulation Methods 0.000 claims description 16
- 230000003179 granulation Effects 0.000 claims description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 13
- 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 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000600 sorbitol Substances 0.000 claims description 12
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- 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 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 229940035044 sorbitan monolaurate Drugs 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 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
- 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 claims description 3
- 239000001587 sorbitan monostearate Substances 0.000 claims description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 3
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 239000001593 sorbitan monooleate Substances 0.000 claims description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 2
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000000071 blow moulding Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 229920000092 linear low density polyethylene Polymers 0.000 description 8
- 239000004707 linear low-density polyethylene Substances 0.000 description 8
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 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
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 150000002632 lipids Chemical class 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
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002688 persistence Effects 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
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920005862 polyol Polymers 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
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004448 titration 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- C08L23/06—Polyethene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides an anti-fogging polyethylene film master batch and a preparation method thereof, wherein the master batch comprises the following components in percentage by weight of mLLDPE: (1) 100% of mLLDPE, (2) 6-12% of antifogging drop agent, (3) 5-10% of mLLDPE-g-VAM graft; the master batch obviously improves the compatibility of the anti-fogging agent and the PE resin, prevents the micromolecule anti-fogging agent from rapidly migrating and separating out in the PE resin, and solves the problem of fog drip hazard in the middle and later periods of the use of the polyethylene greenhouse film. The anti-fogging lasting period of the master batch can be prolonged to more than 35 months from about 3-10 months of the common internal addition type blow molding agricultural polyethylene greenhouse film, the anti-fogging performance of the agricultural polyethylene greenhouse film is obviously improved, and the master batch has a good market application prospect.
Description
Technical field
The present invention relates to a kind of polyethylene resin composition, be specifically related to significantly improve anti-droplet effect and persistent polyethylene film masterbatch in polyethylene green house film.
Background technology
At present, the plastic greenhouse film of China is mainly polyethylene green house 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.JP 11310648 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.JP 11322965 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.
Above-mentioned patent is substantially all directly to add antifogging agent, although having obtained obvious effect aspect the anti-droplet of raising polyethylene film, be not very good aspect the long-lasting of the anti-droplet of film.Due to antifogging agent and PE resin compatible poor; hydrophilic small molecules antifogging agent is in the inner problem that has migration and separate out of PE resin; under the continuous effect of water; 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 35 months and the good antifog drop films masterbatch of mLLDPE of anti-droplet effect of initial stage.The present invention further proposes the preparation method of masterbatch.
The anti-droplet polyethylene film of the present invention masterbatch, the weight of metallocene linear-low density polyethylene (mLLDPE) of take is absolutely, mainly to comprise following component:
1) 100% mLLDPE
2) 6%～12% antifogging agent
3) 5%～10% mLLDPE-g-VAM grafts
Described mLLDPE-g-VAM grafts is grafted monomer to be grafted to the graft copolymer on mLLDPE 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), benzoyl peroxide (BPO), preferably BPO.Grafted monomer is vinyl acetate (VAM), purity >=99%.Polymkeric substance mLLDPE to be to adopt single site catalysts---polyethylene prepared by metallocene catalysis system, can be ethene and butene-1, hexene-1, octene-1 copolymerization and obtain, and also can be obtained by ethylene homo.Density (ρ): 0.865～0.941g/cm wherein
3; Melt flow rate (MFR) (MFR): 0.5～10g/10min.
Described melt flow rate (MFR) (MFR) is at 190 ℃, the measured value under 2.16Kg load.
The preparation method of described mLLDPE-g-VAM grafts is: by the weight percent meter of mLLDPE, mLLDPE high-speed mixing 5～10min by the vinyl acetate of 5～10 parts (VAM) with 100 parts places 10～20h by the material mixing in encloses container; Then initiator and the acetone of getting 0.05～0.2 part are within 1: 2～1: 4, to be mixed with mixing solutions by weight, again by mixing solutions and the mixture high-speed mixing 5～10min placing, finally by carrying out melting graft reaction in twin screw extruder, 160～210 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain VAM percentage of grafting and be 2%～4% mLLDPE-g-VAM 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=131～134 of general BPO ℃/1min; Transformation period T=179～186 of BPDH ℃/1min.
Described mLLDPE can be powdery or granular resin, but best with powdered resin for reaching better mixed effect.
Antifogging agent of the present invention is polyhydric alcohol fatty acid ester compounds (containing the lipid acid of 10-22 C), can be selected from one or more mixtures in sorbitan mono-laurate (S-20), anhydrous sorbitol monopalmitate (S-40), sorbitan monostearate (S-60), anhydrous sorbitol tristearate (S-65), sorbitan monooleate (S-80), Witconol AL 69-66 (S-85) etc., its consumption is that 6%～12%(is by the weight percent meter of mLLDPE).
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.
Particularly, the preparation method of the anti-droplet masterbatch of mLLDPE provided by the invention is as follows: press the weight percent meter of mLLDPE, the mLLDPE of 100 parts is put in super mixer to high-speed mixing 3～5min with together with the mLLDPE-g-VAM grafts of 5～10 parts; And then add the antifogging agent of 6～12 parts, the stablizer of 0.1～0.2 part, the oxidation inhibitor high-speed mixing 3～5min of 0.1～0.2 part; Finally the material mixing is added to twin screw extruder, 170～220 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, makes the antifog drop films masterbatch of mLLDPE.
The present invention also can add the auxiliary agents such as a certain amount of thermo-stabilizer and oxidation inhibitor in the preparation process of the anti-droplet masterbatch of mLLDPE, and only adding of auxiliary agent stablized the requirement of processing for meeting, and can not exert an influence to the performance of masterbatch.
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.Stablizer is stearates, as Zinic stearas, calcium stearate, Magnesium Stearate etc.
The addition of the anti-droplet masterbatch of mLLDPE of the present invention in polyethylene green house film is that 10%～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 35 months polyethylene green house films.
In masterbatch of the present invention, first, in the anti-droplet masterbatch of mLLDPE, the polarity effect of mLLDPE-g-VAM grafts can obviously improve the consistency of antifogging agent and vector resin mLLDPE, and mLLDPE has similar molecular structure to the base resin of polyethylene green house film, antifogging agent just can be evenly dispersed in polyethylene green house film with the form of master batch, and then give the anti-drip performance that polyethylene green house film is good.
Simultaneously, the mLLDPE-g-VAM grafts of this low percentage of grafting has certain absorption to antifogging agent small molecules, but this being adsorbed on the in the situation that of not affecting droplet agent and disperse in canopy film base resin, can hinder again the fast transferring of antifogging agent small molecules in polyethylene green house film and separate out, play certain slow releasing function, make antifogging agent at leisure to film surface transport, reach the effect of long-term anti-droplet.
Secondly, the molecular backbone chain structure of mLLDPE-g-VAM grafts is identical with sub polyethylene minor structure, make it have hydrophilic ethyl ester side group and can be distributed to equably polyethylene green house film surface, again because it has poly-hydroxy strong hydrogen bonding feature, can effectively improve the surface tension of face, greatly reduce the contact angle between water and face, on film surface, be easy to adsorb the micro-moisture in surrounding environment, thereby the fine mist that makes to condense on film surface diffuses to form rapidly continuous moisture film, so just greatly improved the anti-droplet of initial stage of polyethylene green house film.
Embodiment
(1) raw material
1) resin
2) organo-peroxide
BPO transformation period T=133 ℃/1min, auxiliary reagent factory, Lanzhou
BPDH transformation period T=186 ℃/1min, auxiliary reagent factory, Lanzhou
3) 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
Ф 67 twin-screw extrusion captain/footpath=34/1 German Lestreiz companies
10 liters of high-speed mixer Fuxin plastics machinery factories
120 3 layers of compound inflation film manufacturing machine Dalian rubber and plastics machine factory of Ф
Contact angle instrument J2150 Chengde experimental machine company
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 base resin mLLDPE.
Embodiment 1
(1) preparation of mLLDPE-g-VAM grafts: the mLLDPE high-speed mixing 5min by the vinyl acetate of 6 parts (VAM) with 100 parts places 12h by the material mixing in encloses container; Then BPO and the 0.2 part of acetone of getting 0.08 part are mixed with mixing solutions, then mixing solutions is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing; Finally the material mixing is joined in Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,165,170,180,195,210,190,180,170; Carry out melting graft reaction, after reaction 6min, extrude, cooling, granulation, obtain mLLDPE-g-VAM grafts (percentage of grafting: 2.3%).
(2) preparation of the anti-droplet masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 5.5 parts of percentage of grafting be 2.3% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 7 parts of sorbitan mono-laurates (S-20), 0.1 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Embodiment 2
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 1.
(2) preparation of the anti-droplet masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 7 parts of percentage of grafting be 2.3% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 9 parts of sorbitan mono-laurates (S-20), 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Embodiment 3
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 1.
(2) preparation of the anti-droplet masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 8 parts of percentage of grafting be 2.3% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 10 parts of sorbitan mono-laurates (S-20), 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Embodiment 4
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 1.
(2) preparation of the anti-droplet masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 9 parts of percentage of grafting be 2.3% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 11 parts of sorbitan mono-laurates (S-20), 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Embodiment 5
(1) preparation of mLLDPE-g-VAM grafts: the mLLDPE high-speed mixing 5min by the vinyl acetate of 9 parts (VAM) with 100 parts places 12h by the material mixing in encloses container; Then BPO and the 0.4 part of acetone of getting 0.12 part are mixed with mixing solutions, then mixing solutions is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing; Finally the material mixing is joined in Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,165,170,180,195,210,190,180,170; Carry out melting graft reaction, after reaction 6min, extrude, cooling, granulation, obtain mLLDPE-g-VAM grafts (percentage of grafting: 3.4%).
(2) preparation of the anti-droplet masterbatch of mLLDPE: by 100 parts of mLLDPE(ECD350) and 5.5 parts of percentage of grafting be 3.4% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 7 parts of anhydrous sorbitol monopalmitates (S-40), 0.1 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Embodiment 6
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 5.
(2) preparation of the anti-droplet masterbatch of mLLDPE: by 100 parts of mLLDPE(ECD350) and 7 parts of percentage of grafting be 3.4% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 9 parts of anhydrous sorbitol monopalmitates (S-40), 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Embodiment 7
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 5.
(2) preparation of the anti-droplet masterbatch of mLLDPE: by 100 parts of mLLDPE(ECD350) and 8 parts of percentage of grafting be 3.4% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 10 parts of anhydrous sorbitol monopalmitates (S-40), 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Embodiment 8
(1) preparation of mLLDPE-g-VAM grafts: the mLLDPE high-speed mixing 5min by the vinyl acetate of 8 parts (VAM) with 100 parts places 12h by the material mixing in encloses container; Then BPDH and the 0.5 part of acetone of getting 0.15 part are mixed with mixing solutions, then mixing solutions is put into 10L high-speed mixer, high-speed mixing 5min together with the mixture placing; Finally the material mixing is joined in Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,165,170,180,195,210,190,180,170; Carry out melting graft reaction, after reaction 6min, extrude, cooling, granulation, obtain mLLDPE-g-VAM grafts (percentage of grafting: 3.1%).
(2) preparation of the anti-droplet masterbatch of mLLDPE: by 100 parts of mLLDPE(ECD350) and 9 parts of percentage of grafting be 3.1% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 6 parts of sorbitan mono-laurates (S-20), 5 parts of anhydrous sorbitol monopalmitates (S-40), 0.15 part of irgasfos 168,0.2 part of Zinic stearas, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Comparative example 1
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 1.
(2) preparation of the anti-droplet masterbatch of mLLDPE: other condition is identical with embodiment 1, difference is mLLDPE-g-VAM grafts (percentage of grafting: add-on 2.3%) is 4 parts in the preparation process of masterbatch, that is: by 100 parts of mLLDPE(HPR18H10AX) and 4 parts of percentage of grafting be 2.3% mLLDPE-g-VAM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 7 parts of sorbitan mono-laurates (S-20), 0.1 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Ф 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 170,180,190,200,210,220,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the anti-droplet masterbatch of mLLDPE.
Comparative example 2
The preparation of the anti-droplet masterbatch of mLLDPE: other condition is identical with embodiment 2, difference is not add mLLDPE-g-VAM grafts (percentage of grafting: 2.3%) in the preparation process of masterbatch.
Comparative example 3
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 1.
(2) preparation of the anti-droplet masterbatch of mLLDPE: other condition is identical with embodiment 3, difference is not add sorbitan mono-laurate (S-20) in the preparation process of masterbatch.
Comparative example 4
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 1.
(2) preparation of the anti-droplet masterbatch of mLLDPE: other condition is identical with embodiment 4, difference is not add sorbitan mono-laurate (S-20) in the preparation process of masterbatch.
Comparative example 5
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 5.
(2) preparation of the anti-droplet masterbatch of mLLDPE: other condition is identical with embodiment 5, difference is not add mLLDPE-g-VAM grafts (percentage of grafting: 3.4%) in the preparation process of masterbatch.
Comparative example 6
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 5.
(2) preparation of the anti-droplet masterbatch of mLLDPE: other condition is identical with embodiment 6, difference is not add anhydrous sorbitol monopalmitate (S-40) in the preparation process of masterbatch.
Comparative example 7
The preparation of the anti-droplet masterbatch of mLLDPE: other condition is identical with embodiment 7, difference is not add mLLDPE-g-VAM grafts (percentage of grafting: 3.4%) in the preparation process of masterbatch.
Comparative example 8
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 8.
(2) preparation of the antifog drop films masterbatch of mLLDPE: other condition is identical with embodiment 8, difference is not add anhydrous sorbitol monopalmitate (S-40) and sorbitan mono-laurate (S-20) in the preparation process of masterbatch.
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 3 preparations also needs to be pre-mixed with 1.0 parts of sorbitan mono-laurates (S-20); The masterbatch that comparative example 6 makes also needs to be pre-mixed with 0.9 part of anhydrous sorbitol monopalmitate (S-40); The masterbatch of comparative example 8 preparations also needs to be pre-mixed with 0.6 part of sorbitan mono-laurate (S-20) and 0.5 part of anhydrous sorbitol monopalmitate (S-40), then at 120 3 layers of compound blown film unit blowing up wide cut canopy processed film (fabric width 8m of Ф, 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.
Comparative film 9
(1) preparation of mLLDPE-g-VAM grafts: with embodiment 1.
(2) preparation of polyethylene green house film: mLLDPE-g-VAM grafts in the preparation process of canopy film (percentage of grafting: 2.3%) and sorbitan mono-laurate (S-20) be not that form with masterbatch adds, but directly join the resin dedicated LLDPE(LL106AA of polyethylene green house film) in, and add-on is 10% identical with embodiment 1 consumption, that is: by LLDPE weight part, by 100 parts of resin dedicated LLDPE(LL106AA of linear low density polyethylene canopy film) and 0.55 part of mLLDPE-g-VAM that percentage of grafting is 2.3%, 0.7 part of sorbitan mono-laurate (S-20) directly mixes, then at 120 3 layers of compound blown film unit blowing up wide cut canopy processed film (fabric width 8m of Ф, thickness is 0.08mm), 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 anti-droplet polyethylene film masterbatch, the weight of mLLDPE of take is absolutely, it is characterized in that comprising following component:
1) 100% mLLDPE
2) 6%～12% antifogging agent
3) 5%～10% mLLDPE-g-VAM grafts
Described mLLDPE-g-VAM grafts is Vinyl Acetate Monomer to be grafted to the graft copolymer on mLLDPE main chain under the effect of initiator.
2. polyethylene 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, benzoyl peroxide.
3. polyethylene film masterbatch as claimed in claim 1, the preparation method who it is characterized in that described mLLDPE-g-VAM grafts is: by the weight percent meter of mLLDPE, mLLDPE high-speed mixing 5～10min by the vinyl acetate of 5～10 parts and 100 parts places 10～20h by the material mixing in encloses container; Then initiator and the acetone of getting 0.05～0.2 part are within 1: 2～1: 4, to be mixed with mixing solutions by weight, again by mixing solutions and the mixture high-speed mixing 5～10min placing, finally by carrying out melting graft reaction in twin screw extruder, 160～210 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain mLLDPE-g-VAM grafts.
4. polyethylene film masterbatch as claimed in claim 1, it is characterized in that described antifogging agent is selected from one or more mixtures in sorbitan mono-laurate, anhydrous sorbitol monopalmitate, sorbitan monostearate, anhydrous sorbitol tristearate, sorbitan monooleate, Witconol AL 69-66 etc., press the weight percent meter of mLLDPE, its consumption is 6%～12%.
5. polyethylene film masterbatch as claimed in claim 1, is characterized in that adding oxidation inhibitor and thermo-stabilizer in film masterbatch preparation process.
6. polyethylene film masterbatch as claimed in claim 1, is characterized in that by the weight part of polyethylene green house film resin, and the addition of the anti-droplet masterbatch of described mLLDPE in polyethylene green house film is 10%～15%.
7. the preparation method of the polyethylene film masterbatch as described in one of claim 1-5, it is characterized in that comprising: by the weight percent meter of mLLDPE, the mLLDPE of 100 parts is put in super mixer to high-speed mixing 3～5min with together with the mLLDPE-g-VAM grafts of 5～10 parts; And then add the antifogging agent high-speed mixing 3～5min of 6～12 parts; Finally the material mixing is added to twin screw extruder, 170～220 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, makes anti-droplet polyethylene film masterbatch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210250678.6A CN103571025B (en) | 2012-07-19 | 2012-07-19 | Lasting anti-fogging polyolefin film master batch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210250678.6A CN103571025B (en) | 2012-07-19 | 2012-07-19 | Lasting anti-fogging polyolefin film master batch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103571025A true CN103571025A (en) | 2014-02-12 |
| CN103571025B CN103571025B (en) | 2015-12-02 |
Family
ID=50043783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210250678.6A Active CN103571025B (en) | 2012-07-19 | 2012-07-19 | Lasting anti-fogging polyolefin film master batch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103571025B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110978689A (en) * | 2019-10-31 | 2020-04-10 | 福建师范大学福清分校 | High-temperature antifogging breathable polyolefin heat-sealing film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101469086A (en) * | 2007-12-29 | 2009-07-01 | 上海润龙包装用品有限公司 | Polyethylene membrane |
| CN101469087A (en) * | 2007-12-29 | 2009-07-01 | 上海润龙包装用品有限公司 | Polyethylene membrane composite master batch |
| CN102167855A (en) * | 2010-02-25 | 2011-08-31 | 中国石油天然气股份有限公司 | Metallocene polyethylene greenhouse film resin composition |
| CN102408601A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Ultra-wide metallocene polyethylene greenhouse film resin composition and preparation method thereof |
-
2012
- 2012-07-19 CN CN201210250678.6A patent/CN103571025B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101469086A (en) * | 2007-12-29 | 2009-07-01 | 上海润龙包装用品有限公司 | Polyethylene membrane |
| CN101469087A (en) * | 2007-12-29 | 2009-07-01 | 上海润龙包装用品有限公司 | Polyethylene membrane composite master batch |
| CN102167855A (en) * | 2010-02-25 | 2011-08-31 | 中国石油天然气股份有限公司 | Metallocene polyethylene greenhouse film resin composition |
| CN102408601A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Ultra-wide metallocene polyethylene greenhouse film resin composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 庞明娟等: "LDPE-g-MAA 作为基体树脂的防雾膜的研制", 《中国塑料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110978689A (en) * | 2019-10-31 | 2020-04-10 | 福建师范大学福清分校 | High-temperature antifogging breathable polyolefin heat-sealing film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103571025B (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103571000B (en) | Lasting anti-fogging polyethylene film master batch | |
| CN103571023B (en) | Polyethylene anti-fogging film master batch | |
| CN103571021B (en) | Polyolefin long-acting anti-fogging film master batch | |
| CN103571022B (en) | Polyethylene anti-fogging film master batch | |
| US10738184B2 (en) | Saponified ethylene-vinyl ester copolymer pellet and method for producing same | |
| CN102369854B (en) | High-performance PE/EVA (Polyurethane/Ethylene Vinyl Acetate) composite multifunctional greenhouse film | |
| CN109673334A (en) | It is a kind of to keep the temperature ageing-resistant fog dispersal agricultural canopy film and preparation method thereof | |
| CN103571024B (en) | Long-acting polyolefin anti-fogging film master batch | |
| CN108314805A (en) | Degradable gas phase fruit-vegetable plastic wrap and preparation method thereof | |
| CN103571001B (en) | Lasting anti-fogging polyolefin film master batch | |
| HU211763B (en) | Nonextruded concentrates of additives, fillers, pigments or combinations thereof | |
| CN102922839B (en) | High-performance EVA multifunctional composite shed plastic film | |
| CN110922663A (en) | Antibacterial PE water supply pipe and processing technology | |
| CN103571025B (en) | Lasting anti-fogging polyolefin film master batch | |
| CN104530546A (en) | Special anti-reflection reinforced master batch for agricultural greenhouse film and preparation method of anti-reflection reinforced master batch | |
| EP2216362A1 (en) | Polyolefin film compositions with permanent antifog properties, in particular for agro film applications and for packaging moist products | |
| RU2418014C1 (en) | Biodegradable thermoplastic composition using natural filler | |
| RU2738477C1 (en) | Antimicrobial polymer composition | |
| ITMI940015A1 (en) | FILM EQUIPPED WITH HIGH ANTI-CONDENSATION PROPERTIES METHOD FOR PACKAGING PRODUCTS WITH HIGH HUMIDITY CONTENT AND PRODUCTS SO PACKAGED | |
| CN103627071B (en) | Low-haze polyolefin film resin composition | |
| CN101905554A (en) | Method for preparing polyethylene four-layer extruding composite multifunctional greenhouse film | |
| CN101480843A (en) | Method for preparing nano composite material long-acting anti-dropping film | |
| CN102838802A (en) | Polypropylene resin sheet for heating molding process and preparation method thereof | |
| CN103627070B (en) | Low-haze polyethylene film resin composition | |
| JPH1045944A (en) | Anticlouding and antifogging agent for synthetic resin and synthetic resin composition and agricultural film containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |