CN103571024B - The antifog drop films masterbatch of a kind of long-acting polyolefine - Google Patents
The antifog drop films masterbatch of a kind of long-acting polyolefine Download PDFInfo
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- CN103571024B CN103571024B CN201210250277.0A CN201210250277A CN103571024B CN 103571024 B CN103571024 B CN 103571024B CN 201210250277 A CN201210250277 A CN 201210250277A CN 103571024 B CN103571024 B CN 103571024B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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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
- 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
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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
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
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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
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides antifog drop films masterbatch of a kind of polyolefine and preparation method thereof, in the weight of EVA for a hundred per cent, comprising: the EVA of (1) 100%, the modified aluminas of (2) 1% ~ 2.5%, the antifogging agent of (3) 4% ~ 8%, the EVA-g-BMA grafts of (4) 1% ~ 4%; The activated alumina contained in this masterbatch, after polyol ester compounds surface modification, is conducive to the dispersion of activated alumina in antifogging agent, obviously strengthens drip agent adsorption efficiency.Modified aluminas and EVA-g-BMA grafts interact and create slow release effect significantly to polyvalent alcohol laurate class antifogging agent simultaneously, effectively solve the problem of antifogging agent in PE resin internal migration and precipitation, improve film wettability of the surface energy significantly, by the Anti-fogging Shed Film that this antifog drop films masterbatch of interior addition manner introducing can be prepared in polyethylene film, its anti-droplet lasting period reaches more than 65 months.
Description
Technical field
The present invention relates to a kind of polyolefine resin composition, be specifically related to a kind of antifog drop films masterbatch of ethylene and vinyl acetate copolymer (EVA) that can significantly improve polyethylene green house film anti-droplet persistence and initial stage anti-droplet effect.
Background technology
At present, the plastic greenhouse film mainly polyethylene film of China, polyethylene has the characteristics such as excellent cold-resistant, dust-proof, easy processing, but it is a kind of hydrophobic resin, and the surface tension of its film differs larger with the surface tension of water.When early spring or season in late fall, temperature and humidity inside and outside plastic greenhouse differs greatly, adopt general thin to cover behind canopy room, when Plastic film surface temperature reaches below dew point, the steam in air reach capacity or supersaturation time will condense into a large amount of droplet at canopy film inwall.The existence of droplet can cause scattering of light or reflection, reduces as light transmission that is agricultural or gardening awning film, affects the photosynthesis of crop.Droplet is dropped in canopy implants simultaneously, also can cause the withered of the leaf of plant, stem, bud or rot, directly reducing the seed output and quality of crop.China carries out the development of polyethylene antifogging film in phase late 1980s, tensio-active agent is utilized to improve poly critical surface tension, thus make the tiny drops of water condensing 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, improve the wettability of frosting and the method for giving its anti-fogging property mainly contains two kinds: outer coating dripless agent type and interior interpolation dripless agent type.One is that outer cladding process adopts high-pressure spray gun to carry out surface spraying process in booth.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 there is the problem of solvent evaporates contaminate environment, so additive process in domestic many employings.Two are interior additive processs is exactly in the production process of plastic greenhouse film, is added to by dripless agent in material resin and together carries out mixing, plasticizing, then Blown Film.As: ZL03119742.6 provides a kind of nothing be jointly made up of maleic anhydride alcohol ether ester mixture and higher alcohols ether mixture and drips a polyethylene green house film composition.CN1225929A disclose a kind of with the antifogging agent of fluorine-containing, silicon-containing surfactant be mixed with demisting high-effective dripless agent in proportion with the dripless agent of polyol ester and alkylphenol polyoxyethylene, produce with it and there is excellent fog dispersal function and without the agriculture greenhouse film dripping efficiency.JP11310648 adopts ethene and hexene copolymer and LDPE and appropriate stearate class antifogging agent, fluorochemical surfactant to be jointly blow molded into film, and its anti-droplet validity period reaches 10 months.JP11322965 provides a kind of antifogging agent be jointly made up of fluorochemical surfactant and sorbitan monostearate, two Stearic diglycerides, methylene radical distearyl acid amides, hydrolysis stone, adds in LLDPE canopy film and can show good long-term antifogging property.ZL200810238307.X provides a kind of inner additive type agricultural long-acting non drip defogging film containing EVA resin, and the anti-drop defogging phase of this film was increased to more than 160 days from about 100 days, added transmittance and the heat-insulating property of film simultaneously.CN1225929A provides one and jointly forms a kind of anti-aging and dropless agricultural film by polyethylene, ethylene-vinyl acetate copolymer (EVA), processing modifying agent (as: diatomite, silicon-dioxide, magnesiumcarbonate etc.), dripping inhibitor.The no-wait flow shop problem of this film reaches more than 9 months.
Above-mentioned patent is substantially all directly add antifogging agent, although obtained obvious effect in raising polyethylene film antifogging performance.But not very good in the long-lasting and initial stage antifogging performance of the anti-droplet of film; the problem that small molecules antifogging agent exists migration in PE resin inside and separates out; often there will be antifogging agent run off gradually and lose its function; its anti-droplet lasting period can only maintain about 3 ~ 10 months, more outstanding in the middle and later periods droplet evil problem that polyethylene green house film uses like this.
Summary of the invention
The object of the invention is to provide a kind of anti-droplet lasting period more than 65 months and the antifog drop films masterbatch of EVA of initial stage anti-droplet excellent effect.The present invention proposes the preparation method of masterbatch further.
The antifog drop films masterbatch of EVA of the present invention, in the weight of EVA for a hundred per cent, mainly comprises following component:
1) EVA of 100%;
2) modified aluminas of 1% ~ 2.5%;
3) antifogging agent of 4% ~ 8%;
4) the EVA-g-BMA grafts of 1% ~ 4%.
Described polymer EVA is the multipolymer by ethene and vinyl acetate between to for plastic (VA) copolymerization, is film-grade.Wherein the content of vinyl acetate between to for plastic (VA) is: < 9%; Melt flow rate (MFR) (MFR) is: 0.1 ~ 5g/10min; Density: 0.910 ~ 0.930g/cm
3.Described melt flow rate (MFR) (MFR) is at 190 DEG C, the measured value under 2.16Kg load.
" part " of the present invention all refers to weight part.
The mixture that described modified aluminas is made up of jointly activated alumina and surface-modifying agent.Activated alumina: AL
2o
3content is greater than 93%, and particle diameter is greater than 200 orders.Surface-modifying agent is polyol ester compounds, can be selected from the one in glycol ester, pentaerythritol ester, propylene glycol ester, glycerine ester, butanediol ester.
The preparation method of modified aluminas is: by weight, is by volume together to join the activated alumina of 100 parts and deionized water in condensing field at 1: 10 ~ 1: 15, and high-speed mixing 10 ~ 30min is mixed with aaerosol solution; Then getting the surface-modifying agent of 5 ~ 10 parts and ethanol is be mixed with mixing solutions at 1: 2 ~ 1: 4 by weight; Again surface-modifying agent mixing solutions is placed in aluminum oxide aaerosol solution, is warming up to 80 ~ 100 DEG C, stirring reaction 60 ~ 120min, obtain modified aluminas finally by suction filtration, grinding, vacuum-drying.
Described EVA-g-BMA grafts is the graft copolymer be grafted to by grafted monomer under the effect of initiator on EVA main chain.Initiator is selected from tertbutyl peroxide, 2; 5-dimethyl-2; one in 5-di-t-butyl hexane peroxide (BPDH), ditertiary butyl peroxide (DTBP), dicumyl peroxide (DCP), diisopropylbenzenehydroperoxide (DBHP), benzoyl peroxide or peroxide di-t-butyl; preferred employing 2; 5-dimethyl-2,5-di-t-butyl hexane peroxide (BPDH).Grafted monomer is butyl methacrylate (BMA), purity >=99%.
The preparation method of described EVA-g-BMA grafts is: by the weight percent meter of EVA, by the EVA high-speed mixing 5 ~ 10min of the butyl methacrylate of 5 ~ 10 parts (BMA) and 100 parts; Then getting the initiator of 0.1 ~ 0.2 part and acetone is be mixed with mixing solutions at 1: 2 ~ 1: 4 by weight, again mixing solutions is placed into mixture high speed mixing 5 ~ 10min, the material mixed is placed 5 ~ 10h in encloses container, melting graft reaction is carried out finally by twin screw extruder, temperature of reaction 150 ~ 190 DEG C, reaction times 3 ~ 6min, extrudes, cools, granulation, obtains the EVA-g-BMA grafts that BMA percentage of grafting is 1.0% ~ 2.0%.
Described initiator is that organo-peroxide is commercially available prod, and its half life temperature is slightly difference because of the difference of manufacturer, transformation period T=182 ~ 185 of general BPDH DEG C/1min.
Described antifogging agent is lauric acid polyol ester compounds, can be selected from one or more in lauric acid glycol ester, lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester.
The preparation of masterbatch of the present invention can be carried out in Banbury mixer, kneader, twin screw extruder, but is the best with twin screw extruder.When selecting twin screw extruder to prepare, raw material can be adopted to be pre-mixed, carry out the preparation technology that extrudes again.Preparation process comprises the steps: particularly
1) EVA, modified aluminas, antifogging agent, EVA-g-BMA grafts, oxidation inhibitor, stablizer are put in super mixer together, high-speed mixing 5 ~ 10min.
2) mixed material is added twin screw extruder, temperature of reaction 160 ~ 200 DEG C, reaction times 3 ~ 5min, extrudes, cools, granulation, the obtained antifog drop films masterbatch of EVA.
According to the requirement of stable resin processing in the present invention, in the preparation process of masterbatch, the auxiliary agents such as a certain amount of thermo-stabilizer and oxidation inhibitor can be added.
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.In the weight of EVA resin for a hundred per cent, the consumption of oxidation inhibitor is: 0.1% ~ 0.3%.
Described stablizer is stearates, as Zinic stearas, calcium stearate, Magnesium Stearate etc.In the weight of EVA resin for a hundred per cent, the consumption of stearate is: 0.1% ~ 0.2%.
The addition of the antifog drop films masterbatch of EVA of the present invention in polyethylene green house film is the parts by weight of 5% ~ 15%(by polyethylene green house film resin), the initial stage that can obtain anti-droplet excellent effect, the anti-polyethylene green house film of droplet lasting period more than 65 months.
In masterbatch of the present invention, first, activated alumina is after polyol ester compounds surface modification, the polar group on activated alumina surface and the effect of ester group generation adsorption by hydrogen bond, diatomaceous polar group is made to be attracted to particle surface, non-polar group is allowed to demonstrate outside, thus the free energy on surface is reduced, be conducive to the dispersion of activated alumina in antifogging agent, obvious enhanced activity aluminum oxide is to drip agent adsorption efficiency, significantly can suppress the rate of migration of antifogging agent in canopy film base resin, reach the effect of long-term anti-droplet.Simultaneously EVA-g-BMA grafts has certain absorption to antifogging agent small molecules, can hinder the fast transferring of antifogging agent small molecules in polyethylene green house film resin and precipitation, play certain slow releasing function, improve the lasting period of anti-droplet.In addition; the hydroxyl on the carboxyl in EVA-g-BMA grafts and modified aluminas surface and acyl group isoreactivity group generation chemisorption or physical adsorption; improve the consistency of activated alumina and polyethylene green house film base resin; modified aluminas and EVA-g-BMA grafts is caused to produce certain synergistic effect in prolongation antifogging agent result of use; this effect can realize effectively adsorbing to antifogging agent and the passage of slowly-releasing, greatly improves the antifogging performance of polyethylene green house film.
Secondly, the feature of poly-hydroxy and many carboxyls is contained in modified aluminas surface and EVA-g-BMA grafts, there is very strong wetting ability, the molecular backbone chain structure of its EVA resin is identical with polyethylene green house film base resin molecular structure, its hydrophilic radical can be made to be distributed to polyethylene green house film surface equably, effectively improve film wettability of the surface energy, reduce the contact angle between water and face, ensure that the initial stage anti-droplet effect that canopy film uses.
Embodiment
(1) raw material
1) resin
2) other auxiliary agent
(2) performance test
The mensuration of film contacts angle θ: the antifogging film getting 8cm × 2cm is fixed on slide glass, measures on contact angle instrument.
Initial stage antifogging performance: Water Tank with Temp.-controlled beaker being placed in 60 DEG C, envrionment temperature is room temperature, observes the water mark situation of 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.
High temperature antifogging performance: get a block length 15cm, wide 15cm, thickness is about the square canopy film of 0.08mm, and cover on the beaker of 500mL, rim of a cup is tightened, and beaker is built with 300mL water.Then beaker is placed in the Water Tank with Temp.-controlled of 60 DEG C, in 15 ° of inclination angles, envrionment temperature is room temperature.When 60 DEG C on film droplet area exceed 1/3 of face be considered as lost efficacy.The timing definition that canopy film is experienced from bringing into use to losing efficacy is the no-wait flow shop problem of canopy film.
Low temperature antifogging performance: get a block length 15cm, wide 15cm, thickness is about the square canopy film of 0.08mm, and cover on the beaker of 500mL, rim of a cup is tightened, and beaker is built with 300mL water.Then beaker is placed in the Water Tank with Temp.-controlled of 18 DEG C, envrionment temperature is-5 DEG C.On film, droplet area is considered as more than 1/4 losing efficacy.
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 the number of days of 50%.●: the distribution area of canopy film internal surface flakey water droplet reaches less than 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 so that invention effect of the present invention to be described, but protection scope of the present invention is not limited in these embodiments, in composition, each component is with the weight parts of EVA resin.
Embodiment 1
(1) preparation of modified aluminas: by the weight percent meter of activated alumina, be together to join in condensing field at 1: 12 by volume by the activated alumina of 100 parts and deionized water, high-speed mixing 30min is mixed with aaerosol solution; Then getting the pentaerythritol ester of 5.5 parts and ethanol is be mixed with mixing solutions at 1: 4 by weight; Again mixing solutions is placed in aluminum oxide aaerosol solution, is warming up to 90 DEG C, open the tachyphylaxis 100min that agitator keeps certain, obtain modified aluminas a finally by suction filtration, grinding, vacuum-drying.
(2) preparation of EVA-g-BMA grafts: by the EVA(LD358 of the butyl methacrylate of 6 parts (BMA) with 100 parts) resin high-speed mixing 5min, then BPDH and the 0.4 part acetone getting 0.12 part is mixed with mixing solutions, then by mixing solutions high-speed mixing 5min together with mixture above; The material mixed is placed on 10h in encloses container; Finally joined in Φ 67 twin screw extruder by the material placed, screw zones temperature of reaction (DEG C) is followed successively by: 150, and 160,165,170,180,190,185,175,170; Carry out melting graft reaction, after reaction 5min, extrude, cool, granulation, obtain the EVA-g-BMA grafts that percentage of grafting is 1.1%.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(LD358) and 1.5 parts of percentage of grafting be the EVA-g-BMA grafts of 1.1%, 1.1 parts of modified aluminas a, 4.3 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 2
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(LD358) and 1.9 parts of percentage of grafting be the EVA-g-BMA grafts of 1.1%, 1.3 parts of modified aluminas a, 4.7 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 3
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(LD358) and 2.3 parts of percentage of grafting be the EVA-g-BMA grafts of 1.1%, 1.5 parts of modified aluminas a, 5.0 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 4
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(LD358) and 2.5 parts of percentage of grafting be the EVA-g-BMA grafts of 1.1%, 1.7 parts of modified aluminas a, 5.6 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 5
(1) preparation of modified aluminas: by the weight percent meter of activated alumina, be together to join in condensing field at 1: 12 by volume by the activated alumina of 100 parts and deionized water, high-speed mixing 30min is mixed with aaerosol solution; Then getting the glycol ester of 8.5 parts and ethanol is be mixed with mixing solutions at 1: 3 by weight; Again mixing solutions is placed in aluminum oxide aaerosol solution, is warming up to 90 DEG C, open the tachyphylaxis 100min that agitator keeps certain, obtain modified aluminas b finally by suction filtration, grinding, vacuum-drying.
(2) preparation of EVA-g-BMA grafts: by the EVA(EF320 of the butyl methacrylate of 9 parts (BMA) with 100 parts) resin high-speed mixing 5min, then BPDH and the 0.5 part acetone getting 0.15 part is mixed with mixing solutions, then by mixing solutions high-speed mixing 5min together with mixture above; The material mixed is placed on 10h in encloses container; Finally joined in Φ 67 twin screw extruder by the material placed, screw zones temperature of reaction (DEG C) is followed successively by: 150, and 160,165,170,180,190,185,175,170; Carry out melting graft reaction, after reaction 5min, extrude, cool, granulation, obtain the EVA-g-BMA grafts that percentage of grafting is 1.7%.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(EF320) and 2.8 parts of percentage of grafting be the EVA-g-BMA grafts of 1.7%, 1.9 parts of modified aluminas b, 6.0 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 6
(1) preparation of modified aluminas: with embodiment 5.
(2) preparation of EVA-g-BMA grafts: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(EF320) and 3.1 parts of percentage of grafting be the EVA-g-BMA grafts of 1.7%, 2.1 parts of modified aluminas b, 6.7 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 7
(1) preparation of modified aluminas: with embodiment 5.
(2) preparation of EVA-g-BMA grafts: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(EF320) and 3.4 parts of percentage of grafting be the EVA-g-BMA grafts of 1.7%, 2.2 parts of modified aluminas b, 7.1 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 8
(1) preparation of modified aluminas: with embodiment 5.
(2) preparation of EVA-g-BMA grafts: with embodiment 5.
(3) preparation of the antifog drop films masterbatch of EVA: by 100 parts of EVA(EF320) and 3.9 parts of percentage of grafting be the EVA-g-BMA grafts of 1.7%, 2.4 parts of modified aluminas b, 7.5 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 1
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of EVA antifog drop films masterbatch: other condition is identical with embodiment 1, difference is that EVA-g-BMA grafts in the preparation process of masterbatch (percentage of grafting: add-on 1.1%) is 0.5 part, that is: by 100 parts of EVA(LD358) and 0.5 part of percentage of grafting are the EVA-g-BMA grafts of 1.1%, 10 liters of high-speed mixer high speeds mixing 10min put into together by 1.1 parts of modified aluminas a, 4.3 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 2
(1) preparation of modified aluminas: with embodiment 1.
(2) preparation of EVA-g-BMA grafts: with embodiment 1.
(3) preparation of EVA antifog drop films masterbatch: other condition is identical with embodiment 2, difference is not add lauric acid glycol ester dripping inhibitor in the preparation process of masterbatch, that is: by 100 parts of EVA(LD358) and 1.9 parts of percentage of grafting be the EVA-g-BMA grafts of 1.1%, 1.3 parts of modified aluminas a, 0.2 part of antioxidant 1010,0.15 part of calcium stearate put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 3
(1) preparation of EVA-g-BMA grafts: with embodiment 1.
(2) preparation of EVA antifog drop films masterbatch: other condition is identical with embodiment 3, difference is not add modified aluminas a in the preparation process of masterbatch, that is: by 100 parts of EVA(LD358) and 2.3 parts of percentage of grafting be the EVA-g-BMA grafts of 1.1%, 5.0 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 4
(1) preparation of EVA-g-BMA grafts: with embodiment 1.
(2) preparation of EVA antifog drop films masterbatch: other condition is identical with embodiment 4, difference is not add modified aluminas a in the preparation process of masterbatch, but directly add activated alumina, its add-on is 1.7 parts, that is: by 100 parts of EVA(LD358) and 2.5 parts of percentage of grafting be the EVA-g-BMA grafts of 1.1%, 1.7 parts of activated aluminas, 5.6 parts of lauric acid glycol esters, 0.2 part of antioxidant 1010,0.15 part of calcium stearate put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 5
(1) preparation of modified aluminas: with embodiment 5.
(2) preparation of EVA antifog drop films masterbatch: other condition is identical with embodiment 5, difference is not add EVA-g-BMA grafts in the preparation process of masterbatch, that is: by 100 parts of EVA(EF320) and 1.9 parts of modified aluminas b, 6.0 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 6
(1) preparation of EVA-g-BMA grafts: with embodiment 5.
(2) preparation of EVA antifog drop films masterbatch: other condition is identical with embodiment 6, difference is not add modified aluminas b in the preparation process of masterbatch, but directly add activated alumina, its add-on is 2.1 parts, that is: by 100 parts of EVA(EF320) and 3.1 parts of percentage of grafting be the EVA-g-BMA grafts of 1.7%, 2.1 parts of activated aluminas, 6.7 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 7
(1) preparation of EVA-g-BMA grafts: with embodiment 5.
(2) preparation of EVA antifog drop films masterbatch: other condition is identical with embodiment 7, difference is that the add-on of modified aluminas b in the preparation process of masterbatch is 0.5 part, that is: by 100 parts of EVA(EF320) and 3.4 parts of percentage of grafting be the EVA-g-BMA grafts of 1.7%, 0.5 part of modified aluminas b, 7.1 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Comparative example 8
(1) preparation of EVA antifog drop films masterbatch: other condition is identical with embodiment 8, difference is not add modified aluminas b and EVA-g-BMA grafts in the preparation process of masterbatch, that is: by 100 parts of EVA(EF320) and 7.5 parts of lauric acid butanediol esters, 0.25 part of irgasfos 168,0.2 part of Zinic stearas put into 10 liters of high-speed mixer high speeds mixing 10min together; Then joined by the material mixed in Φ 67 twin screw extruder, barrel each section of temperature of reaction (DEG C) is followed successively by: 160,170,180,190,195,200,190,185,180; After reaction 4min, extrude, cool, granulation, obtain the antifog drop films masterbatch of EVA.
Embodiment 1 ~ 8 and the Comparison study of anti-droplet masterbatch in canopy film obtained by comparative example 1 ~ 8: by linear low density polyethylene speciality for green house film LLDPE(LL106AA) respectively with the anti-droplet masterbatch obtained by embodiment 1 ~ 8 and comparative example 1 ~ 8 with 10% addition (by LLDPE parts by weight) mix, the masterbatch that wherein prepared by comparative example 2 also needs to carry out giving first mixing with 0.47 part of lauric acid glycol ester, the masterbatch that comparative example 3 obtains also needs to be pre-mixed with 0.15 part of modified aluminas a, the EVA-g-BMA grafts that it is 1.7% that the masterbatch that comparative example 8 obtains also needs with 0.24 part of modified aluminas b and 0.39 part percentage of grafting gives and first mixing, then at Φ 120 3 layers of compound blown film unit blowing up wide cut canopy film (fabric width 8m, thickness is 0.08mm), be labeled as respectively: implement film 1 ~ 8 and comparative film 1 ~ 8, the test result of its canopy film antifogging property is in table 1.
Table 1 contains the canopy film antifogging property of 10% embodiment and comparative example masterbatch
Claims (6)
1. an antifog drop films masterbatch, in the weight of EVA for a hundred per cent, mainly comprises following component:
1) EVA of 100%;
2) modified aluminas of 1% ~ 2.5%;
3) antifogging agent of 4% ~ 8%;
4) the EVA-g-BMA grafts of 1% ~ 4%;
Described polymer EVA is the multipolymer by ethene and vinyl acetate between to for plastic copolymerization, and described EVA-g-BMA grafts is the graft copolymer be grafted to by butylmethacrylate monomer under the effect of initiator on EVA main chain; The mixture that described modified aluminas is made up of jointly activated alumina and polyol ester compounds surface-modifying agent;
Described antifogging agent be selected from lauric acid glycol ester, lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester one or more.
2. film masterbatch as claimed in claim 1, is characterized in that described surface-modifying agent is selected from the one in glycol ester, pentaerythritol ester, propylene glycol ester, glycerine ester, butanediol ester.
3. film masterbatch as claimed in claim 1, it is characterized in that the preparation method of described modified aluminas is: by weight, be together to join in condensing field at 1: 10 ~ 1: 15 by volume by the activated alumina of 100 parts and deionized water, high-speed mixing 10 ~ 30min is mixed with aaerosol solution; Then getting the surface-modifying agent of 5 ~ 10 parts and ethanol is be mixed with mixing solutions at 1: 2 ~ 1: 4 by weight; Again surface-modifying agent mixing solutions is placed in aluminum oxide aaerosol solution, is warming up to 80 ~ 100 DEG C, stirring reaction 60 ~ 120min, obtain modified aluminas finally by suction filtration, grinding, vacuum-drying.
4. film masterbatch as claimed in claim 1, is characterized in that the preparation method of described EVA-g-BMA grafts is: by the weight percent meter of EVA, by the EVA high-speed mixing 5 ~ 10min of the butyl methacrylate of 5 ~ 10 parts and 100 parts; Then getting the initiator of 0.1 ~ 0.2 part and acetone is be mixed with mixing solutions at 1: 2 ~ 1: 4 by weight, again mixing solutions is placed into mixture high speed mixing 5 ~ 10min, the material mixed is placed 5 ~ 10h in encloses container, melting graft reaction is carried out finally by twin screw extruder, temperature of reaction 150 ~ 190 DEG C, reaction times 3 ~ 6min, extrudes, cools, granulation, obtains EVA-g-BMA grafts.
5. film masterbatch as claimed in claim 1, it is characterized in that described initiator is selected from tertbutyl peroxide, 2, one in 5-dimethyl-2,5-di-t-butyl hexane peroxide, ditertiary butyl peroxide, dicumyl peroxide, diisopropylbenzenehydroperoxide, benzoyl peroxide.
6. a preparation method for film masterbatch as claimed in claim 1, is characterized in that comprising the steps:
1) EVA, modified aluminas, antifogging agent, EVA-g-BMA grafts are put in super mixer together, high-speed mixing 5 ~ 10min;
2) mixed material is added twin screw extruder, temperature of reaction 160 ~ 200 DEG C, reaction times 3 ~ 5min, extrudes, cools, granulation, the obtained antifog drop films masterbatch of EVA.
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| CN108485162A (en) * | 2018-03-30 | 2018-09-04 | 吕莉 | A kind of preparation method of automobile-used ageing-resistant antifog film |
| US20200064520A1 (en) * | 2018-08-22 | 2020-02-27 | GM Global Technology Operations LLC | Smart multifunctional lens coatings |
| CN111320804A (en) * | 2020-03-24 | 2020-06-23 | 张露 | Aluminum oxide multifunctional greenhouse film master batch and preparation method and application thereof |
| CN113136065B (en) * | 2021-04-20 | 2022-04-12 | 福州大学 | Polyethylene anti-fogging film and preparation method thereof |
| CN114133651B (en) * | 2021-11-17 | 2024-06-04 | 安徽国风新材料股份有限公司 | Durable anti-fog drip-free polyethylene film master batch and preparation method thereof |
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| JP2003182007A (en) * | 2001-12-19 | 2003-07-03 | Sumitomo Chem Co Ltd | Anti-fogging film |
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