CN102746563B - Preparation method for special-purpose material of LLDPE transparent shed film - Google Patents

Preparation method for special-purpose material of LLDPE transparent shed film Download PDF

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CN102746563B
CN102746563B CN201110102225.4A CN201110102225A CN102746563B CN 102746563 B CN102746563 B CN 102746563B CN 201110102225 A CN201110102225 A CN 201110102225A CN 102746563 B CN102746563 B CN 102746563B
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nucleator
lldpe
weight percent
proportioning
film
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CN102746563A (en
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张明强
邹恩广
邱丽萍
马建英
姜进宪
王熺
王登飞
郭桂悦
张德英
安彦杰
王文燕
葛滕杰
刘龙
梁忠越
闫兵
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China Petroleum and Natural Gas Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to a preparation method for a special-purpose material of an LLDPE transparent shed film. The special-purpose material of the LLDPE transparent shed film is prepared by adding 0.01-0.2% of a nucleating agent, 0.01-0.1% of an antistatic agent, and 0.01-0.2% of zinc stearate based on the 100% of LLDPE resin by weight, mixing the mixture evenly in a mixing roll, carrying out fusion and extrusion in an extruder, and carrying out grinding. The preparation method can effectively improve transparent performance and mechanical properties of the film, and does not increase the cost for adding auxiliary agents at the same time. Thus, the haze of the special-purpose material of LLDPE transparent shed film is decreased to less than 13%, both the tensile strength and the fracture elongation of the film are both improved, and the light transmittance reaches more than 92%.

Description

The preparation method of the transparent canopy film special material of a kind of LLDPE
Technical field:
The present invention relates to the preparation method of the transparent canopy film special material of a kind of LLDPE.
Background technology:
The advantages such as linear low density polyethylene (LLDPE) film has good toughness, and tearing toughness is high, and puncture resistance is good, are widely used in farm-oriented mulch and awning film etc.In recent years, along with increase and the plastic sheeting for farm use market of packaging industry to transparent material demand is more and more higher to the properties of transparency requirement of canopy film and mulch film, transparent LLDPE film relies on its excellent mechanical property to be rapidly developed, and market demand rises year by year.
The transparent modified approach of LLDPE mainly contains three kinds: (1) improves the properties of transparency of LLDPE film by changing comonomer, the LLDPE film properties of transparency excellence of producing with this technological method, mist degree is below 10%, the at present domestic problem existing at this technical elements is comonomer dependence on import, and raw materials cost is too high; (2) change catalyst system, the catalyzer of dynamics model is changed into the catalyzer of single active center, the main metallocene catalyst that adopts is produced high transparent LLDPE material, the mist degree of the LLDPE film of producing with this technological method is below 5%, the limitation of this technology is that the molecular weight distribution of resin is too narrow, poor processability; (3) improve auxiliary formula, improve the properties of transparency of LLDPE resin, the advantage of this technological method is simple to operate, flexible, need not undergo technological transformation to device.
LLDPE resin is by Qi-Na catalyzer, is formed by ethene, butene-1 copolymerization by polycoordination mechanism.Because the copolymerized ability of catalyst system is poor, butene-1 be radom insertion to PE macromole, cause LLDPE resin branching wider distribution, some macromole is highly branched, and some macromole is linear random coil structure, this just causes the defect of LLDPE resin crystalline texture.According to Flory crystal formation theory, linear random coil molecule is pressed folded-chain structure and is generated platelet, and then grows up to nucleus, and LLDPE macromole, centered by these nucleus, is produced large-sized spherocrystal.Because the generation of nucleus is random, so cause the inhomogeneous of LLDPE resin crystalline region dispersion.
In blown film production process, when resin from molten state to glassy transition process, in a certain temperature range lower than fusing point, start crystallization, because nucleus is random generation, growing under field conditions (factors) of spherocrystal, causes spherulite size large, and skewness.There is luminous reflectance in large-sized spherocrystal, makes the transparent variation of film on LLDPE film surface, in addition, because crystalline region and non-crystalline region refractive index there are differences, cause interface that irregular scattering of light and reflection occur, thereby make the properties of transparency of LLDPE resin poor.Therefore, by controlling the crystal property of LLDPE resin, reduce the difference in crystalline phase district and amorphous phase interval, can improve the transparency of LLDPE film.
Nucleator is as the core of heterogeneous nucleation, can effectively increase the density of nucleus, improve Tc and cleanliness factor, in the time that the abundant nucleator of quantity is dispersed, nucleus reaches and is uniformly distributed, and the growing space of spherocrystal diminishes, and reduces spherulite size, can weaken scattering of light and the luminous reflectance on film surface, the properties of transparency of LLDPE film is improved.
Common PE canopy film does not add the ageing-resistant tunica albuginea that waits auxiliary agent directly to produce with raw material blowing, and booth and middle hut application quantity are very large at present, generally detain canopy in spring, autumn, only 4～6 months usage period, can only plant one season crop, waste energy, increase recruitment, in production, be eliminated gradually.PE anti-aging film (long-lived grid film) ties up in PE resin and adds antiager, through Blown Film.This canopy film thickness 0.08～0.12mm, the usage period can reach 12～18 months, can carry out the arable farming of 2～3 seasons, not only the usage period extends, cost, energy-conservation, and output and the output value are increased considerably, it is the plastic sheeting for farm use kind that in current facility cultivation, emphasis is promoted.PE has anti-drop property, weathering resistance, light transmission and good heat preservation performance without dripping anti-aging film (two anti-plastic sheeting for farm use) simultaneously, anti-droplet effect can keep 2～4 months, the ageing-resistant life-span can reach 12～18 months, that current performance is more complete, use plastic sheeting for farm use kind widely, not only can be used for greenhouse and big or middle hut, and also comparatively applicable to the cultivation of energy-saving heliogreenhouse stubble in early spring.This covering material of PE thermal insulation greenhouse film can stop infrared rays to radiation in atmosphere, can improve 1～2 DEG C of greenhouse temperature, and in cold district, effect is better.PE multifunctional composite film has without dripping, insulation, the several functions such as weather-proof, long-lived, and what have has a ultraviolet function of obstruct, makes in canopy ultraviolet ray see through and reduces.What have can suppress sclerotium disease apothecium and formation that botrytis cinerea divides spore.Usage period can reach 12～18 months.
To all kinds of PE canopy films, the selection of base resin should meet: (1) relative molecular mass is higher, and Mw/Mn is narrower, side chain number, carbon-carbon double bond number are few, chromophoric group (carbonyl) content is low, and catalyst residue amount is few, ensures that product has good mechanical property and ageing resistance; (2) crystalline size of resin is less, ensures that product has good visible light transmissivity; (3) be conducive to drip agent, antifogging agent, heat preserving agent performance usefulness; (4) resin of same kind has lower degree of crystallinity.
The mechanical property of film is relevant with the relative molecular mass of resin and distribution, the degree of branching, degree of crystallinity, fabrication process condition and additive etc.Generally, compared with ldpe film, the tensile strength of LLDPE film, elongation at break and angle tear strength improve respectively 60%～70%, 60%～80% and 50%～70%.But LLDPE melt viscosity is larger, and melt strength is lower, processing characteristics when extrusion-blown modling wide cut canopy film is not as good as LDPE.For improving mechanical property, improve processing characteristics, reduce raw materials cost, China generally adopts LDPE and LLDPE blend production wide cut canopy film.Generally believe, the relative molecular mass of PE is high, Mw/Mn is narrow, and the ageing-resistant performance of canopy mould is all right.And oxidation and light stability depend on the short-chain branch number of PE to a great extent.The base resin that short-chain branch number is higher, less stable.The degree of branching is higher, shows the weakness of chain structure the more, and superpolymer stability is poorer.Its reason is that tertiary carbon atom and hydrogen bond increase, and these weak bonds are subject to O 2attack, further generate hydroperoxide, start Auto-oxidation reaction by general mechanism.Analyze from molecular structure aspect, the ageing-resistant performance of LLDPE is better than LDPE.In addition, in LLDPE, transition metal ion content (catalyst residue amount) has a significant effect to the ageing-resistant performance of film.As less in the MFR of certain trade mark LLDPE, relative molecular mass is higher, and side chain number is less, but catalyst residue amount is more, and with the film of its blowing, in natural climate exposure test, mechanical property retention rate obviously reduces.
The influence factor of LDPE/LLDPE canopy film transmittance and mist degree is more.LDPE/LLDPE canopy film optical property not only has direct relation with molecular structure, crystal habit, crystal size and the degree of crystallinity of LDPE and LLDPE, and processing condition also have relation with extruder temperature, mouthful mould and mouthful of in-molded section runner degree of cleaning, blowing film bubble be cooling etc.Generally, the transmittance of ldpe film is higher than LLDPE film, and mist degree is lower than LLDPE film.The crystallization of LDPE/LLDPE blending resin melt in process of cooling is very complicated.Suitably improving extruder temperature and strengthening under blowing film bubble cooling conditions, can improve the transmittance of film, reduce mist degree.
The degree of crystallinity of the inner additive type drip agent mechanism of action and base resin is closely related.Drip agent is distributed in the noncrystalline domain of resin, and thus to film surface transport.In crystallizing field, can not contain drip agent, can not make its migration as passage.So distribution, travelling speed, the drip effect of the crystalline state of canopy film on drip agent has impact.Degree of crystallinity is high, except affecting canopy film transparency, also anti-drop property is produced to negative effect.The defects such as the canopy film that degree of crystallinity is high exists drip agent at face skewness, and the drip lasting period is short.
The molecular structure difference of LLDPE and LDPE shows: LLDPE does not have or seldom has long-chain branch, and the conventional film polymkeric substance (Mw/Mn is 3～4) that is narrow Mw/Mn with LLDPE.The chain length of LLDPE short-chain branch depends on the type of comonomer.Side chain number depends on the co-monomer content of institute's combination.Only have carbonatoms to be more than or equal to 4 alpha-olefinic copolymerization and could effectively upset closely piling up of chain molecule, obtain LLDPE thereby reduce density, produce the tie molecule that connects different crystalline regions simultaneously, improve toughness and the intensity of polymkeric substance.So film is all the multipolymer of ethene and 1-butylene, 1-hexene, 1-octene or 3-methyl-amylene with LLDPE.LLDPE crystalline state not only depends on the type of comonomer, also depends on the distribution of comonomer in polymkeric substance and the frequency distributing in molecular chain.Under same isodensity, the fusing point of LLDPE is higher 10～15 DEG C than LDPE.Use high power polarized light microscope observing, LLDPE spherocrystal diameter is 10～20 μ m, and only 2～3 μ m of LDPE spherocrystal diameter.
In a word, LLDPE, compared with LDPE, has significantly improved tensile strength, tear strength, puncture resistance, and has heat-resisting and cold tolerance preferably.And aspect processing characteristics, the susceptibility of LLDPE counter stress is poor,, under the shearing force of extruding processing, melt viscosity is much higher, need to be compared with high pulling torque, higher melt temperature and die pressure, and easily there is melt fracture; But do not harden in the time of film bubble drawing-off.Have good drawability, ratio of drawing can reach 25～150.Can be not height-oriented under large tensile deformation, can not produce strong two-way unbalancedness.But LLDPE melt strength is poor, when film bubble is cooling, the cold wind of resistance to high speed does not impact, and poor stability, need to strengthen the design of cooling vane.
CN200910232637.2 relates to a kind of special compound additive of polyethylene film with high tranparency and low density, taking high-pressure polyethylene as carrier, by 25%～30% silicon-dioxide opening agent, 5%～15% organosilicon glidant, 2～8% organosilicon active crosslinker, 1～10% organosilicon oxidation inhibitor and surplus high pressure polyethylene resin are by being uniformly mixed, preheating Ball milling at 75～85 DEG C, finally at 140 DEG C～170 DEG C, the particle obtaining by dual-screw pelletizer extruding pelletization, add the low-density polyethylene film that this composite assistant is made, tasteless, high transparent, there is good physiological security, high opening, smoothness and fabulous resistance to migration.Can be applicable to especially food, medicine, business card, identity card overlay film and advertisement packaging etc. film is had to the field that high transparent, high security and high opening require.
CN200710064958.7 relates to a kind of preparation method of high-transparent linear low density polyethylene, particularly a kind of method of preparing high-transparent linear low density polyethylene taking Acrylate polyethylene glycol monoester as transparent agent.First synthetic transparent agent Acrylate polyethylene glycol monoester, Acrylate polyethylene glycol monoester is to be raw material with vinylformic acid, polyoxyethylene glycol, Resorcinol, tosic acid, β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propylene octadecyl ester, distearyl pentaerythritol phosphite; After synthetic transparent agent, by transparent agent Acrylate polyethylene glycol monoester and linear low density polyethylene by weight 0.1～1.5: 100, extrude at 160 DEG C～210 DEG C melt blendings, make high-transparent linear low density polyethylene resin.
CN01115615.5 relates to a kind of agricultural canopy film, this canopy film contains 50～90% the common Low Density Polyethylene of being prepared by Ziegler one Natta catalyst or high-pressure polymerization process and 10～50% the linear low density polyethylene of being prepared by metallocene catalyst, and film thickness is 0.020～0.045mm.The angle tear strength of this film is high, and has good light transmission.
Summary of the invention:
Object of the present invention is added a kind of composite transparent special assistant, and in the solution LLDPE course of processing, nucleus is few, the key issue that geode size is large.Improve crystalline state by refinement crystalline size, effectively improve properties of transparency, the mechanical property of film, do not increase auxiliary agent simultaneously and add cost, thereby high transparent canopy film special material of a kind of LLDPE and preparation method thereof is provided.
LLDPE of the present invention is high, and transparent canopy film special material is by LLDPE weight resin 100%, in LLDPE resin, add nucleator 0.01～0.2%, static inhibitor 0.01～0.1%, Zinic stearas is 0.01～0.2%, in mixing roll, mix, in forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.
Described nucleator forms by Sorbitol Nucleator, organic phosphate nucleating agent, mineral-type nucleator, rosin based nucleator is composite forms.Sorbitol Nucleator/organic phosphate nucleating agent/mineral-type nucleator/rosin based nucleator is 0～15%/0～15%/50～100%/0～20% by weight percentage, preferably 3～12%/3～15%/60～90%/4～20%, most preferably 0～5/0～5/80～100/0～10;
Sorbitol Nucleator of the present invention is dibenzal sorbitol, DMDBS], one in MDBS three.
Organic phosphate nucleating agent nucleator of the present invention is the one in two kinds of n-butylbenzene al formates, p-tert-butyl benzoic acid oxyaluminum.
Mineral-type nucleator of the present invention is one or more in talcum powder and silicon-dioxide, mica, the proportioning of talcum powder/silicon-dioxide/mica is 0～25/0～25/50～100, preferably 0～15/0～15/70～100, most preferably 0～5/0～5/90～100;
Rosin based nucleator of the present invention is dehydroabietic acid or contains dehydroabietic acid as the one in the rosin resin acid constituents of main ingredient;
Static inhibitor of the present invention is three kinds of static inhibitor amine hydroxybenzenes, behenic acid acid amides, erucicamide is composite forms, when playing antistatic property, also can play smooth effect, the transparency that is conducive to improve film, has antireflective effect to film, and the processing characteristics of resin is made moderate progress.The proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide is 0～10/85～100/0～5 (weight percents), preferably 5～10/80～90/5～10, most preferably 5～8/84～90/5～8;
According to the above ratio raw material is fully mixed in mixing roll, melt extrude at forcing machine, extrusion temperature is 100～200 DEG C, preferably 130～170 DEG C, and most preferably 140～160 DEG C; Screw speed 100～300r/min, preferably 100～260r/min, most preferably 100～200r/min.
Preparation method's cost of the present invention is low, easily processing.The made LLDPE canopy film special material mist degree of product is down to below 13%, and tensile strength and the elongation at break of film also increase.
Embodiment:
Below in all case study on implementation, in LLDPE resin, add nucleator 0.01～0.2% (weight percent), static inhibitor 0.01～0.1% (weight percent), Zinic stearas is 0.01～0.2% (weight percent), in mixing roll, mix, in forcing machine, melt extrude granulation, the high transparent canopy film special material of preparation LLDPE.
Wherein nucleator composition is that 0～15/0～15/50～100/0～20 (weight percent) is composite forms according to the proportioning of Sorbitol Nucleator/nucleator in organic phosphate class/mineral-type nucleator/rosin based nucleator; Mineral-type nucleator is 0～25/0～25/50～100 (weight percents) according to the proportioning of talcum powder/silicon-dioxide/mica.Static inhibitor is 0～10/85～100/0～5 (weight percents) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
Comparative example 1
In LLDPE resin, add slipping agent 0.05% (weight percent), Zinic stearas is 0.05% (weight percent), in mixing roll, mixes, and melt extrudes granulation, the high transparent canopy film special material of preparation LLDPE in forcing machine.Test result is in table 1.
Embodiment 1
Nucleator is that 0/0/100/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 0/0/100 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 2
Nucleator is that 0/0/100/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 20/70/0 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 3
Nucleator is that 0/0/100/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/50/0 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 4
Nucleator is that 0/0/100/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/50/0 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 30/70/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 5
Nucleator is that 50/0/50/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 0/0/100 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 6
Nucleator is that 50/0/50/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/20/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 7
Nucleator is that 50/20/30/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/20/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 20/80/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 8
Nucleator is that 50/0/0/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/20/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 9
Nucleator is that 50/0/0/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 20/50/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/100/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 10
Nucleator is that 10/0/50/40 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/20/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 50/50/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 11
Nucleator is that 0/0/50/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/50/0 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/50/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 12
Nucleator is that 0/0/50/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 0/50/50 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 50/0/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 13
Nucleator is that 0/0/50/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/0/50 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 50/0/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 14
Nucleator is that 0/0/50/50 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 30/40/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 0/50/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 15
Nucleator is that 50/0/50/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/50/0 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 50/0/50 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 16
Nucleator is that 50/0/50/0 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/50/0 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 50/50/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 17
Nucleator is that 0/10/50/40 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/50/0 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 50/50/0 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 18
Nucleator is that 0/10/50/40 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 50/20/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 50/30/20 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 19
Nucleator is that 50/0/40/10 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 30/40/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 30/40/30 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Embodiment 20
Nucleator is that 50/10/0/40 (weight percent) is composite forms according to dibenzal sorbitol/n-butylbenzene al formate/mineral-type nucleator/dehydroabietic acid proportioning; Wherein mineral-type nucleator is 30/40/30 composite forming according to the proportioning of talcum powder/silicon-dioxide/mica.
Static inhibitor is 50/40/10 (weight percent) according to the proportioning of amine hydroxybenzene/behenic acid acid amides/erucicamide, composite forming.
In LLDPE resin, add nucleator 0.01% (weight percent), static inhibitor 0.01% (weight percent), Zinic stearas is 0.01% (weight percent), in mixing roll, mix, in forcing machine, melt extrude, granulation, the high transparent canopy film special material of preparation LLDPE.Test result is in table 1.
Can find out from example 1～20 and comparative example, preparation method's cost of the present invention is low, easily processing, and auxiliary agent blanking is smooth and easy, stable, without taste.The made LLDPE canopy film special material mist degree of product is down to below 13%, and the shock strength that falls to marking of film also increases, and obtains downstream awning film enterprise and highly approves.
Subordinate list 1
Figure BDA0000056948980000131

Claims (1)

1. the preparation method of the transparent canopy film special material of LLDPE, it is characterized in that: by LLDPE weight resin 100%, add nucleator 0.01～0.2%, static inhibitor 0.01～0.1%, Zinic stearas is 0.01～0.2%, in mixing roll, mixes, and in forcing machine, melt extrudes, granulation, the transparent canopy film special material of preparation LLDPE;
Described nucleator is by one, mineral-type nucleator in two kinds of Sorbitol Nucleator, n-butylbenzene al formate or p-tert-butyl benzoic acid oxyaluminum, rosin based nucleator is composite to be formed, by weight percentage in two kinds of Sorbitol Nucleator/n-butylbenzene al formate or p-tert-butyl benzoic acid oxyaluminum a kind of/proportioning of mineral-type nucleator/rosin based nucleator is 3～12%/3～15%/60～90%/4～20%;
Described Sorbitol Nucleator is the one of two kinds of dibenzal sorbitols, MDBS;
Described mineral-type nucleator is one or more in talcum powder and silicon-dioxide, mica, by weight percentage: the proportioning of talcum powder/silicon-dioxide/mica is 0～25/0～25/50～100;
Described rosin based nucleator is dehydroabietic acid or contains dehydroabietic acid as the one in the rosin resin acid constituents of main ingredient;
Described static inhibitor is three kinds of static inhibitor amine hydroxybenzenes, behenic acid acid amides, erucicamide is composite forms, and amine hydroxybenzene by weight percentage/behenic acid acid amides/erucicamide proportioning is 5～8/84～90/5～8;
The extrusion temperature of described forcing machine is 100～200 DEG C; Screw speed 100～300r/min.
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