CN103571001A - Lasting type anti-fogging polyolefin film master batch - Google Patents
Lasting type anti-fogging polyolefin film master batch Download PDFInfo
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- CN103571001A CN103571001A CN201210250392.8A CN201210250392A CN103571001A CN 103571001 A CN103571001 A CN 103571001A CN 201210250392 A CN201210250392 A CN 201210250392A CN 103571001 A CN103571001 A CN 103571001A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
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Abstract
The present invention provides a polyethylene anti-fogging film master batch and a preparation method thereof. The polyethylene anti-fogging film master batch comprises, by weight of mLLDPE, (1) 100% of mLLDPE, (2) 5-15% of a diatomite/anti-fogging agent complex, and (3) 3-7% of an mLLDPE-g-AM graft. According to the present invention, with the diatomite and the mLLDPE-g-AM graft in the master batch, absorption, migration and slow-release channels for the dripping agent are easily formed so as to solve rapid migration and precipitation of the small molecule anti-fogging agent in the polyethylene greenhouse film and significantly increase utilization efficiency of the dripping agent; and the anti-fogging lasting period of the master batch can be prolonged to more than 50 months from about 3-10 months of the general inner addition type blow molding agricultural polyethylene greenhouse film, the anti-fogging performance of the agricultural polyethylene greenhouse film is significantly increased, and good market application prospects are provided.
Description
Technical field
The present invention relates to a kind of polyethylene resin composition, be specifically related to a kind of anti-droplet effect and persistent polyethylene film masterbatch that can significantly improve 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.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.
Above-mentioned patent is substantially all directly to add antifogging agent, although obtaining obvious effect improving aspect the anti-droplet of polyethylene film, aspect the long-lasting of the anti-droplet of film and anti-droplet of initial stage, be not very good.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 50 months and the good anti-droplet polyethylene film masterbatch 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) diatomite/antifogging agent mixture of 5%～15%;
3) 3%～7% mLLDPE-g-AM grafts.
Described mLLDPE-g-AM grafts is grafted monomer to be grafted to the graft copolymer on mLLDPE main chain under the effect of initiator.Initiator is selected from di-tert-butyl hydrogen peroxide (TBHP), 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 DTBP.Grafted monomer is acrylamide (AM), purity >=95%.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-AM grafts is: by the weight percent meter of mLLDPE, by the acrylamide of 6～11 parts (AM) and dimethylbenzene, be within 1: 0.5～1: 1, to be mixed with mixing solutions by weight, by the mLLDPE high-speed mixing 5～10min of mixing solutions and 100 parts, the material mixing is placed to 10～20h in encloses container again; Then initiator and the acetone of getting 0.01～0.1 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, 150～190 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain AM percentage of grafting and be 1%～3% mLLDPE-g-AM 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=191～194 of general DTBP ℃/1min; Transformation period T=170～173 of DCP ℃/1min.
Described mLLDPE can be powdery or granular resin, but best with powdered resin for reaching better mixed effect.
In described diatomite/antifogging agent mixture, antifogging agent is polyhydric alcohol fatty acid ester compounds (containing the lipid acid of 10 1 22 C), can be selected from sorbitan mono-laurate (S-20), anhydrous sorbitol monopalmitate (S-40), sorbitan monostearate (S-60), Tween-20 (T-20), polyoxyethylene sorbitol acid anhydride monopalmitate (T-40), polyoxyethylene sorbitan monostearate (T-60), etc. in one or more mixtures.Diatomite, SiO
2content is greater than 80%, and particle diameter is greater than 300 orders.
The preparation method of described diatomite/antifogging agent mixture is: by the weight percent meter of antifogging agent, by 10～40 parts, preferably the diatomite of 20～35 parts is put in 10 liters of high-speed mixers with together with the antifogging agent of 100 parts, high-speed mixing 10～20min, after taking-up, be encased in encloses container stand-byly, obtain diatomite/antifogging agent mixture.
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-AM grafts of 3～7 parts; And then add diatomite/antifogging agent mixture of 5～15 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, 160～210 ℃ 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 50 months polyethylene green house films.
In masterbatch of the present invention, first, in the anti-droplet masterbatch of mLLDPE, the mLLDPE-g-AM grafts of 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 the fast transferring of antifogging agent small molecules in polyethylene green house film and separate out, playing certain slow releasing function.
Meanwhile, along with adding of diatomite/antifogging agent mixture, diatomite has vesicular structure, drip agent is easy to form to the passage of absorption, migration, slowly-releasing, has improved the utilization ratio of drip agent.Like this, mLLDPE-g-AM grafts and diatomite/antifogging agent mixture produce certain synergistic effect on the anti-droplet of polyethylene green house film, this effect has greatly improved the long-term anti-droplet effect that canopy film is used, and its anti-droplet lasting period reaches more than 50 months.
Secondly, the molecular backbone chain structure of mLLDPE-g-AM grafts is identical with sub polyethylene minor structure, because of its polarity effect, can obviously improve again the consistency of the base resin of antifogging agent and polyethylene green house film, make antifogging agent can be evenly dispersed in polyethylene green house film with the form of master batch, thereby give the anti-drip performance that polyethylene green house film is good, guaranteed the anti-droplet of initial stage that canopy film is used.
Embodiment
(1) raw material
1) resin
2) organo-peroxide
Transformation period T=192 ℃/1min of ditertiary butyl peroxide (DTBP), auxiliary reagent factory, Lanzhou
Transformation period T=170 ℃/1min of dicumyl peroxide (DCP), 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
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-AM grafts: the dimethylbenzene of the acrylamide of 7 parts (AM) and 5 parts is mixed with to mixing solutions, then by the mLLDPE high-speed mixing 5min of mixing solutions and 100 parts, the material mixing is placed to 12h in encloses container; Then DTBP and the 0.1 part of acetone of getting 0.03 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 Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 150,155,160,170,185,190,190,180,170; Carry out melting graft reaction, after reaction 7min, extrude, cooling, granulation, obtain mLLDPE-g-AM grafts (percentage of grafting: 1.4%).
(2) preparation of diatomite/antifogging agent mixture: the weight percent meter of pressing polyoxyethylene sorbitan monostearate (T-60), by the diatomite of 25 parts (TP750) with together with the polyoxyethylene sorbitan monostearate (T-60) of 100 parts, put into 10 liters of high-speed mixer high speeds and mix 10min, after taking-up, be encased in encloses container, obtain diatomite/polyoxyethylene sorbitan monostearate mixture.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 3.5 parts of percentage of grafting be 1.4% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 5.5 parts of diatomite/polyoxyethylene sorbitan monostearate mixtures, 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Embodiment 2
(1) preparation of mLLDPE-g-AM grafts: with embodiment 1.
(2) preparation of diatomite/antifogging agent mixture: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 4 parts of percentage of grafting be 1.4% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 7 parts of diatomite/polyoxyethylene sorbitan monostearate mixtures, 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Embodiment 3
(1) preparation of mLLDPE-g-AM grafts: with embodiment 1.
(2) preparation of diatomite/antifogging agent mixture: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 5 parts of percentage of grafting be 1.4% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 9.0 parts of diatomite/polyoxyethylene sorbitan monostearate mixtures, 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Embodiment 4
(1) preparation of mLLDPE-g-AM grafts: with embodiment 1.
(2) preparation of diatomite/antifogging agent mixture: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 6.5 parts of percentage of grafting be 1.4% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 10 parts of diatomite/polyoxyethylene sorbitan monostearate mixtures, 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Embodiment 5
(1) preparation of mLLDPE-g-AM grafts: the dimethylbenzene of the acrylamide of 9 parts (AM) and 5 parts is mixed with to mixing solutions, then by the mLLDPE high-speed mixing 5min of mixing solutions and 100 parts, the material mixing is placed to 12h in encloses container; Then DTBP and the 0.2 part of acetone of getting 0.07 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 Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 150,155,160,170,185,190,190,180,170; Carry out melting graft reaction, after reaction 7min, extrude, cooling, granulation, obtain mLLDPE-g-AM grafts (percentage of grafting: 2.1%).
(2) preparation of diatomite/antifogging agent mixture: the weight percent meter of pressing anhydrous sorbitol monopalmitate (S-40), by the diatomite of 30 parts (TP750) with together with the anhydrous sorbitol monopalmitate (S-40) of 100 parts, put into 10 liters of high-speed mixer high speeds and mix 10min, after taking-up, be encased in encloses container, obtain diatomite/anhydrous sorbitol monopalmitate mixture.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(ECD350) and 3.5 parts of percentage of grafting be 2.1% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 11 parts of diatomite/anhydrous sorbitol monopalmitate mixtures, 0.1 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Embodiment 6
(1) preparation of mLLDPE-g-AM grafts: with embodiment 5.
(2) preparation of diatomite/antifogging agent mixture: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(ECD350) and 4 parts of percentage of grafting be 2.1% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 12 parts of diatomite/anhydrous sorbitol monopalmitate mixtures, 0.1 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Embodiment 7
(1) preparation of mLLDPE-g-AM grafts: with embodiment 5.
(2) preparation of diatomite/antifogging agent mixture: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(ECD350) and 5 parts of percentage of grafting be 2.1% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 13 parts of diatomite/anhydrous sorbitol monopalmitate mixtures, 0.1 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Embodiment 8
(1) preparation of mLLDPE-g-AM grafts: the dimethylbenzene of the acrylamide of 10 parts (AM) and 5 parts is mixed with to mixing solutions, then by the mLLDPE high-speed mixing 5min of mixing solutions and 100 parts, the material mixing is placed to 12h in encloses container; Then DCP and the 0.2 part of acetone of getting 0.09 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 Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 150,155,160,170,185,190,190,180,170; Carry out melting graft reaction, after reaction 7min, extrude, cooling, granulation, obtain mLLDPE-g-AM grafts (percentage of grafting: 2.7%).
(2) preparation of diatomite/antifogging agent mixture: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(ECD350) and 6.5 parts of percentage of grafting be 2.7% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 14 parts of diatomite/anhydrous sorbitol monopalmitate mixtures, 0.15 part of irgasfos 168,0.15 part of Zinic stearas, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Comparative example 1
(1) preparation of mLLDPE-g-AM grafts: with embodiment 1.
(2) preparation of diatomite/antifogging agent mixture: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of mLLDPE: other condition is identical with embodiment 1, difference is mLLDPE-g-AM grafts (percentage of grafting: add-on 1.4%) is 1.0 parts in the preparation process of masterbatch, that is: by 100 parts of mLLDPE(HPR18H10AX) and 1.0 parts of percentage of grafting be 1.4% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 5.5 parts of diatomite/polyoxyethylene sorbitan monostearate mixtures, 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Comparative example 2
(1) preparation of mLLDPE-g-AM grafts: with embodiment 1.
(2) preparation of the antifog drop films masterbatch of mLLDPE: other condition is identical with embodiment 2, difference is not add diatomite/polyoxyethylene sorbitan monostearate mixture in the preparation process of masterbatch, but directly add diatomite, its add-on is 7.0 parts, that is: by 100 parts of mLLDPE(HPR18H10AX) and 4 parts of percentage of grafting be 1.4% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 7.0 parts of diatomite, 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Comparative example 3
(1) preparation of mLLDPE-g-AM grafts: with embodiment 1.
(2) preparation of diatomite/antifogging agent mixture: other condition is identical with embodiment 1, difference is that in the preparation process of mixture, diatomaceous add-on is 5.0 parts, press the weight percent meter of polyoxyethylene sorbitan monostearate (T-60), by the diatomite of 5.0 parts (TP750) with together with the polyoxyethylene sorbitan monostearate (T-60) of 100 parts, put into 10 liters of high-speed mixer high speeds and mix 10min, after taking-up, be encased in encloses container, obtain diatomite/polyoxyethylene sorbitan monostearate mixture a.
(3) preparation of the antifog drop films masterbatch of mLLDPE: by 100 parts of mLLDPE(HPR18H10AX) and 5 parts of percentage of grafting be 1.4% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 9.0 parts of diatomite/polyoxyethylene sorbitan monostearate mixture a, 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Comparative example 4
(1) preparation of mLLDPE-g-AM grafts: with embodiment 1.
(2) preparation of the anti-droplet masterbatch of mLLDPE: other condition is identical with embodiment 3, difference is not add diatomite/polyoxyethylene sorbitan monostearate mixture in the preparation process of masterbatch, that is: by 100 parts of mLLDPE(HPR18H10AX) and 6.5 parts of percentage of grafting be 1.4% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 0.15 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Comparative example 5
(1) preparation of diatomite/antifogging agent mixture: 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-AM grafts in the preparation process of masterbatch, that is: by 100 parts of mLLDPE(ECD350) and 11 parts of diatomite/anhydrous sorbitol monopalmitate mixtures, 0.1 part of antioxidant 1010,0.15 part of calcium stearate put into together in 10 liters of high-speed mixers, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Comparative example 6
(1) preparation of mLLDPE-g-AM grafts: with embodiment 5.
(2) preparation of the antifog drop films masterbatch of mLLDPE: other condition is identical with embodiment 6, difference is not add diatomite/anhydrous sorbitol monopalmitate mixture in the preparation process of masterbatch, but directly add diatomite, its add-on is 12 parts, that is: by 100 parts of mLLDPE(ECD350) and 4 parts of percentage of grafting be 2.1% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 12 parts of diatomite, 0.1 part of antioxidant 1010,0.15 part of calcium stearate, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
Comparative example 7
(1) preparation of the antifog drop films masterbatch of mLLDPE: other condition is identical with embodiment 7, difference is not add mLLDPE-g-AM grafts and diatomite/anhydrous sorbitol monopalmitate mixture in the preparation process of masterbatch.
Comparative example 8
(1) preparation of mLLDPE-g-AM 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 diatomite/anhydrous sorbitol monopalmitate mixture in the preparation process of masterbatch, but directly add anhydrous sorbitol monopalmitate, its add-on is 14 parts, that is: by 100 parts of mLLDPE(ECD350) and 6.5 parts of percentage of grafting be 2.7% mLLDPE-g-AM grafts is put in 10 liters of high-speed mixers together, high-speed mixing 3min; And then add 14 parts of anhydrous sorbitol monopalmitates, 0.15 part of irgasfos 168,0.15 part of Zinic stearas, high-speed mixing 5min; Mixed material is joined to Φ 67 twin screw extruders, screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,200,190,180; After reaction 4min, extrude, cooling, granulation, obtain the antifog drop films masterbatch of mLLDPE.
The application contrast of the prepared anti-droplet masterbatch of embodiment 1 ~ 8 and comparative example 1 ~ 8 in canopy film:
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 0.7 part of polyoxyethylene sorbitan monostearate; The masterbatch that comparative example 6 makes also needs to give first and mixing with 1.2 parts of anhydrous sorbitol monopalmitates, 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.Comparative film 9
(1) preparation of mLLDPE-g-AM grafts: with embodiment 5.
(2) preparation of diatomite/antifogging agent mixture: with embodiment 5.
(3) preparation of polyethylene green house film: mLLDPE-g-AM grafts in the preparation process of canopy film (percentage of grafting: 2.1%) and diatomite/anhydrous sorbitol monopalmitate mixture 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 5 consumptions, that is: by LLDPE weight part, by 100 parts of resin dedicated LLDPE(LL106AA of linear low density polyethylene canopy film) and 0.35 part of mLLDPE-g-AM grafts that percentage of grafting is 2.1%, 1.1 parts of diatomite/anhydrous sorbitol monopalmitate mixtures directly mix, 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), 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 (9)
1. an anti-droplet polyethylene film masterbatch, the weight of mLLDPE of take is absolutely, comprises following component:
1) 100% mLLDPE;
2) diatomite/antifogging agent mixture of 5%～15%;
3) 3%～7% mLLDPE-g-AM grafts;
Described mLLDPE-g-AM grafts is acrylamide 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 di-tert-butyl hydrogen 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-AM grafts is: by the weight percent meter of mLLDPE, by the acrylamide of 6～11 parts and dimethylbenzene, be within 1: 0.5～1: 1, to be mixed with mixing solutions by weight, by the mLLDPE high-speed mixing 5～10min of mixing solutions and 100 parts, the material mixing is placed to 10～20h in encloses container again; Then initiator and the acetone of getting 0.01～0.1 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, 150～190 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain mLLDPE-g-AM grafts.
4. polyethylene film masterbatch as claimed in claim 1, is characterized in that described antifogging agent is selected from one or more mixtures in sorbitan mono-laurate, anhydrous sorbitol monopalmitate, sorbitan monostearate, Tween-20, polyoxyethylene sorbitol acid anhydride monopalmitate, polyoxyethylene sorbitan monostearate.
5. polyethylene film masterbatch as claimed in claim 1, the preparation method who it is characterized in that described diatomite/antifogging agent mixture is: by the weight percent meter of antifogging agent, 10～40 parts of diatomite are put in high-speed mixer with together with the antifogging agent of 100 parts, high-speed mixing 10～20min, after taking-up, be encased in encloses container stand-byly, obtain diatomite/antifogging agent mixture.
6. polyethylene film masterbatch as claimed in claim 1, is characterized in that in described diatomite/antifogging agent mixture, diatomaceous add-on is 20～35 parts.
7. polyethylene film masterbatch as claimed in claim 1, is characterized in that adding oxidation inhibitor and thermo-stabilizer in described film masterbatch preparation process.
8. 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%.
9. a polyethylene film masterbatch as claimed in claim 1, 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-AM grafts of 3～7 parts; And then add diatomite/antifogging agent mixture high-speed mixing 3～5min of 5～15 parts; Finally the material mixing is added to twin screw extruder, 160～210 ℃ of temperature of reaction, reaction times 3～5min, extrudes, cooling, granulation, makes the antifog drop films masterbatch of mLLDPE.
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| CN111320804A (en) * | 2020-03-24 | 2020-06-23 | 张露 | Aluminum oxide multifunctional greenhouse film master batch and preparation method and application thereof |
| CN115710379A (en) * | 2022-11-22 | 2023-02-24 | 北京联飞翔科技股份有限公司 | Inorganic nonmetallic mineral composite dripping agent and preparation and application thereof |
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| WO2018121657A1 (en) * | 2016-12-31 | 2018-07-05 | 广州鹿山新材料股份有限公司 | Antifogging polyolefin graft and preparation method therefor |
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| CN115710379A (en) * | 2022-11-22 | 2023-02-24 | 北京联飞翔科技股份有限公司 | Inorganic nonmetallic mineral composite dripping agent and preparation and application thereof |
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