CN103087403A - Polypropylene composition and preparation method thereof, and stretched film prepared from polypropylene composition - Google Patents
Polypropylene composition and preparation method thereof, and stretched film prepared from polypropylene composition Download PDFInfo
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Abstract
The present invention provides a polypropylene composition for preparing a stretched film, and the stretched film. The polypropylene composition comprises, by weight, (A) 100 parts of a propylene polymer composition, and (B) 0.01-1 part of a nucleating agent, wherein the component (A) is a polypropylene homopolymer composition prepared through an asymmetric external electron donor addition polymerization method, the whole stereoregularity [mm] is 94-95%, a melt flow rate is 2-4 g/10 min, molecular weight distribution Mw/Mn is 6-8, and the component (B) is at least one selected from a sorbitol nucleating agent or an aryl phosphate nucleating agent. The obtained film of the polypropylene composition has characteristics of excellent high temperature tension property, good rigidity, low haze and high gloss, and shows strong competitiveness when the film is used for preparing thinning BOPP films.
Description
Technical field
The present invention relates to a kind of polypropene composition, say further, relate to a kind of polypropene composition for the preparation of oriented film and its preparation method and oriented film prepared therefrom.
Background technology
As everyone knows, polypropylene film is because it has excellent optical property, mechanical property and packing adaptability, is widely used in the wrapping material fields.Particularly BiOriented Polypropylene Films (BOPP) is especially because it has that matter is soft, transparency is high, nontoxic, good waterproof performance and physical strength high, be widely used in the last few years the packing of the products such as food, medicine, daily necessities, cigarette, and can be used as the base material of the compound film of high strength.
BiOriented Polypropylene Films (BOPP, Biaxial Oriented Polypropylene) normally take acrylic resin as raw material, after film extrusion, then forms through a series of course of processing manufacturings such as two-way stretch, thermal treatment, cooling process.Produce in order to adapt to large-scale high speed film forming, not only require the acrylic resin raw material to have tensile strength preferably, but also require it to have drawing by high temperature characteristic preferably.Generally believe for polypropylene, the degree of isotacticity of its polymkeric substance is lower, and the melt temperature of polymkeric substance is lower, and is more favourable for the machine-shaping of BOPP film, but can reduce the mechanical property of final film, as performances such as the tensile strength of film and deflections.
In described polypropylene double-way stretched film (BOPP) is used, the BOPP packing film that is used for packing cigarette is a kind of product of top grade, compare with common BOPP packing film, it has lower heat-sealing temperature, better barrier property, high transparent, high rigidity and the good characteristics such as glossiness.In the prior art, the PP Pipe Compound of making the BOPP cigarette packaging film generally adopts polypropylene resin composite, and said composition comprises isotatic polypropylene base-material and some applicable additives usually, for example: nucleator, thermo-stabilizer and oxidation inhibitor etc.For example Chinese patent CN101597400A discloses a kind of polypropylene resin composite, it is take isotatic polypropylene as base-material, selected 2,2-methylene radical-two-(4,6-di-t-butyl phenoxy group) sodium phosphate to improve the method for BOPP film transparency and glossiness as nucleator.But it is limited that it improves the modulus of film and mist degree, be more or less the same with commercially available other products, so this polypropylene resin composite is during for the preparation of oriented film, and the over-all properties of gained film can't be satisfactory.
Generally believe in the industry, nucleator plays the effect that improves rigidity of material usually in polypropylene modification, and its addition must be lower; But some nucleator addition improves the transparency that can also increase material.These two performances must consider, the content of disclosed nucleator is to add 0.01 to 0.02 part in every 100 parts of polypropylene in Chinese patent CN101597400A, but the nucleator of this utmost point low levels is very limited for the castering action of polypropylene transparent and glossiness.
Summary of the invention
For solving problems of the prior art, the inventor is through repetition test, the polypropylene base-material that has improved by use, and be equipped with suitable nucleator, the oriented film of resulting polypropene composition preparation has excellent drawing by high temperature characteristic, good rigidity, lower mist degree and higher glossiness, has shown very strong competitive power.
One of purpose of the present invention is to provide a kind of polypropene composition that can be used for preparing oriented film.
A kind of polypropene composition for the preparation of oriented film includes the component of following parts by weight:
(A) prolylene polymer composition is 100 parts;
(B) nucleator is 0.01～1 part, is preferably 0.05～0.5 part.
Wherein said component (A) is a kind of prolylene polymer composition, and the overall degree of isotacticity [mm] of the prolylene polymer composition of described component (A) is 94～95% (use
13C-NMR records), melt flow rate (MFR) is 2～4g/10min, molecular weight distribution mw/mn is 6～8.
Described prolylene polymer composition adopts a kind of prolylene polymer composition that makes according to Chinese patent CN 100491458C.The described prolylene polymer composition that this preparation method and this preparation method obtain is all quoted CN100491458C.The method is a kind of asymmetric polymerization process that adds external electron donor.It is included in the annular-pipe reactor of two series connection, carry out continuously homopolymerization or the copolyreaction of propylene, reaction is carried out under the Ziegler-Natta catalyst with stereoselective exists, and described Ziegler-Natta catalyst with stereoselective comprises active solid catalyst component, organo-aluminium compound and the silicoorganic compound of titaniferous.Wherein add the molecular weight regulator of inequality in the first and second polymerized loop reactors, so that the ratio of the MRR value of final gained propene polymer and the MFR value of the first step gained propene polymer is greater than 1, in the first ring pipe reactor, organo-aluminium compound and silicoorganic compound ratio is both counted 10-300 with the weight ratio of aluminium/silicon, in the second annular-pipe reactor supplemented with organic silicon compound, thereby the weight ratio that makes aluminium/silicon is less than the value in the first endless tube; Aluminium in the first endless tube/silicon weight ratio be in the second annular-pipe reactor supplemented with the 2-20 of the aluminium after organic silicon compound/silicon weight ratio doubly.The productivity ratio of first, second annular-pipe reactor is 65: 35～55: 45, and the temperature of two endless tube polyreactions is controlled at 60～80 ℃, and polyreaction is liquid phase noumenal method.
Concrete grammar is as follows:
the polyacrylic polymer method that the present invention prepares wide molecular weight distribution comprises following multistep polymerization reaction: the first step is under Ziegler-Natta catalyst exists, carry out the equal polymerization of propylene or the copolymerization of propylene and alpha-olefin, then under the polymkeric substance that generates and the existence of the first step used catalyst, carry out the equal polymerization of second step propylene or the copolymerization of propylene and alpha-olefin alkene, the molecular weight regulator that wherein adds inequality in the first and second polyreactions is nitrogen for example, so that the ratio of the MFR value of final gained propene polymer and the MFR value of the first step gained propene polymer is greater than 1, preferred scope is 5-15, increase the external electron donor component or/and improve the consumption of external electron donor component in second step, so that the isotacticity index of final gained propene polymer is greater than the isotacticity index of the first step gained propene polymer, namely both ratio is greater than 1, is preferably greater than 1 and be less than or equal to 1.2, wherein the productivity ratio of the first step and second step is 30: 70～70: 30, is preferably 65: 35～55: 45.
In preparation method of the present invention, the Ziegler-Natta catalyst that uses is by open in a large number, the catalyzer that preferably has high stereoselective, " Ziegler-Natta catalyst of high stereoselective " described herein refer to prepare isotactic index greater than 95% alfon.This type of catalyzer contains (1) active solid catalyst component usually, is preferably the solid catalyst active ingredient of titaniferous; (2) organo-aluminium compound cocatalyst component; (3) and randomly add the external electron donor component.
The specific examples of operational this class catalyzer is disclosed in Chinese patent CN85100997A, CN1258680A, CN1258683A, CN1258684A, CN1091748A, CN1330086A, CN1298887A, CN1298888A, CN1436796A.Described catalyzer can directly use, and also can add through after prepolymerization.Catalyzer described in Chinese patent CN1330086A, CN85100997 and CN1258683A is used for catalyzer of the present invention and has especially advantage.
Organo-aluminium compound preferred alkyl aluminum compound as the catalyzer cocatalyst component, more preferably comprise trialkylaluminium, as triethyl aluminum, triisobutyl aluminium, three n-butylaluminum etc., wherein the active solid catalyst component with the ratio of organo-aluminium compound cocatalyst component take the Ti/Al molar ratio computing as 1: 25-1: 100.
Randomly add the external electron donor component in the first step polyreaction.Described external electron donor component is preferably silicoorganic compound.Its general formula is R
nSi (OR ')
4-n, 0＜n in formula＜3, in general formula, R and R ' they are alkyl of the same race or not of the same race, cycloalkyl, aryl, haloalkyl etc., R also can be halogen or nitrogen-atoms.
specifically can comprise the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, isopropyl methyl dimethoxy silane, two phenoxy group dimethoxy silane, the phenylbenzene diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, 2-ethyl piperidine base-2 tertiary butyl dimethoxy silane, (1, 1, the 1-trichlorine, the 2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1, 1, 1-three chloro-2-propyl group)-methyl dimethoxysilane etc.
When not adding the external electron donor component in the first step polyreaction, the second step polyreaction need to be added the external electron donor component.When having added the external electron donor component in the first step polyreaction, the second step polyreaction needs to add the external electron donor component or adds the external electron donor component of orientation property in other improved active centre.Generally, the second step polyreaction does not need to add active solid catalyst component and organo-aluminium compound.
Usually, the ratio between cocatalyst component organo-aluminium compound and external electron donor component silicoorganic compound can be controlled the isotacticity index (degree of isotacticity) of propene polymer effectively.Preferably, add the external electron donor component in the first step polyreaction, and make organo-aluminium compound and silicoorganic compound ratio both count 10-300 with the weight ratio of aluminium/silicon, more preferably 30-150.Add the external electron donor component in the second step polyreaction, the value of the weight ratio that makes aluminium/silicon during than the first step decreases, namely the aluminium in the first endless tube/silicon weight ratio greater than in the second annular-pipe reactor supplemented with the aluminium after organic silicon compound/silicon weight ratio, preferably both ratio be 2-20 doubly.
Preferably, the prolylene polymer composition powder of said components (A) is carried out extruding pelletization, obtain the prolylene polymer composition pellet of said components (A).Can add the general additive of this technical field during granulation, as oxidation inhibitor, anti-halogen agent, photostabilizer, thermo-stabilizer, tinting material and filler etc.Concrete as adding the oxidation inhibitor such as phenolic antioxidant, phosphorous acid esters; The anti-halogen agent of fat metallic salt etc.Consumption is also conventional amount used of the prior art.
The prolylene polymer composition of being produced by patent CN100491458C has the commercially available prod, as the polypropylene (product grade F280Z) of Zhenghai petrochemical complex limited-liability company production or the polypropylene (product grade F280Q) of Qingdao refinery company production, its melt flow rate (MFR) is 3.0g/10min, and overall isotacticity index (is used
13[mm] that C-NMR records) be 94.6%, molecular weight distribution mw/mn is 7.3, dissolves in the fraction content 2.5wt% of dimethylbenzene.
Component described in polypropene composition of the present invention (B) is selected from least a in Sorbitol Nucleator or aryl orthophosphate nucleator.
particularly, described aryl orthophosphate nucleator generally is selected from least a in following material: sodium-2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, sodium-2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, lithium-2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, lithium-2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, sodium-2,2 '-ethidine-two (4-sec.-propyl-6-di-tert-butyl-phenyl) phosphoric acid salt, lithium-2,2 '-methylene radical-two (4-methyl-6-di-tert-butyl-phenyl) phosphoric acid salt, lithium-2,2 '-methylene radical-two (4-ethyl-6-di-tert-butyl-phenyl) phosphoric acid salt, calcium-two [2,2 '-thiobis (4-methyl-6-di-tert-butyl-phenyl) phosphoric acid salt], calcium-two [2,2 '-thiobis (4-ethyl-6-di-tert-butyl-phenyl) phosphoric acid salt], calcium-two [2,2 '-thiobis (4,6-di-tert-butyl-phenyl) phosphoric acid salt], magnesium-two [2,2 '-thiobis (4,6-di-tert-butyl-phenyl) phosphoric acid salt], magnesium-two [2,2 '-thiobis (4,6-, two uncle's octyl phenyls) phosphoric acid salt], sodium-2,2 '-Ding pitches base-two (4,6-3,5-dimethylphenyl) phosphoric acid salt, sodium-2,2 '-uncle octyl group methylene radical-two (4,6-3,5-dimethylphenyl) phosphoric acid salt, sodium-2,2 '-uncle octyl group methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, calcium-two [2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], magnesium-two [2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], barium-two [2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], sodium-2,2 '-methylene radical-two (4-methyl-6-tert butyl phenyl) phosphoric acid salt, sodium-2,2 '-methylene radical-two (4-ethyl-6-tert-butyl-phenyl) phosphoric acid salt, calcium-two [4,4 '-dimethyl-6,6 '-di-t-butyl-2,2 '-xenyl) phosphoric acid salt], sodium-2,2 '-ethidine-two (the meta-butyl of 4--6-tert-butyl-phenyl) phosphoric acid salt, sodium-2,2 '-methylene radical-two (4,6-3,5-dimethylphenyl) phosphoric acid salt, sodium-2,2 '-methylene radical-two (4,6-diethyl phenyl) phosphoric acid salt, potassium-2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, calcium-two [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], magnesium-two [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], barium-two [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], aluminium-hydroxyl-two [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], aluminium-three couple [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], hydroxyl-two [2,4,8,10-four (1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] closes aluminium.
When at least a below the aryl orthophosphate nucleator of component (B) is preferred: sodium-2,2 '-methylene radical-two (4, ADK NA-11), aluminium-hydroxyl-two [2 the 6-di-tert-butyl-phenyl) (company produces phosphoric acid salt as Japanese rising sun electrification:, 2 '-ethidine-two (4, the 6-di-tert-butyl-phenyl) phosphoric acid salt], hydroxyl-two [2,4,8,10-four (1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] (Japanese rising sun electrification company produces: ADK NA-21) to close aluminium.
at least a in the preferred following material of described Sorbitol Nucleator: 1, 3-2, 4-two (α-tolylene)-D-glucitol, 1, 3-2, 4-two (4-methylbenzene subunit)-D-glucitol, 1, 3-2, 4-two (3, 4-dimethyl benzene methylene radical)-D-glucitol, 1, 3-2, 4-two (4-ethylbenzene methylene radical)-D-glucitol, two-1, 3-2, 4-(4 '-propyl group benzylidene)-1-allyl group sorbyl alcohol, two-1, 3-2, 4-(4 '-ethyl benzylidene)-1-allyl group sorbyl alcohol, two-1, 3-2, 4-(4 '-propoxy-benzylidene)-1-allyl group sorbyl alcohol, two-1, 3-2, 4-(4 '-propyl group benzylidene)-1-propyl group sorbyl alcohol, two-1, 3-2, 4-(4 '-propoxy-benzylidene)-1-propyl group sorbyl alcohol.
In described Sorbitol Nucleator 1,3-2,4-two (3,4-dimethyl benzene methylene radical)-D-glucitol (Millad 3988 that agree company's production as beautiful in the U.S.), two-1,3-2,4-(4 '-propyl group benzylidene)-1-propyl group sorbyl alcohol (NX8000 that agree company's production as beautiful in the U.S.) or its mixture are preferred.
In addition, in the polypropene composition for the preparation of oriented film of the present invention, can also include other auxiliary agents that usually contain in the resin combination that in prior art, the preparation oriented film is used, as oxidation inhibitor, static inhibitor, slipping agent, opening agent etc.The consumption of these conventional auxiliary agents is also conventional amount used of the prior art.
Two of purpose of the present invention is to provide a kind of preparation method of the polypropene composition for the preparation of oriented film.The method comprises that after mixing by weight, melt blending makes described polypropene composition for the preparation of oriented film with described component (A) prolylene polymer composition pellet and (B) component of nucleator.
In the preparation method of described polypropene composition of the present invention, the mixing of material mixing equipment used is mixing equipment commonly used in plastic working, as homogenizer, and dough mixing machine etc.The melt blending that carries out after mixing of materials is even is melt blending technique commonly used in the polypropylene processing industry.Its equipment is also common melt blending equipment, as twin screw extruder or twin-roll plasticator etc.Related processing parameter such as melt temperature, rate of extrusion etc. also are general temperature and the rate of extrusion of melt blending in polypropylene processing.
Three of purpose of the present invention is to provide a kind of oriented film by the polypropene composition preparation for the preparation of oriented film of the present invention.Can adopt method well-known in the art to prepare oriented film by polypropene composition of the present invention, such as flat embrane method or periosteum method etc.The most often adopt flat embrane method, its technical process is: raw material mixes, extrudes, curtain coating, stretching (longitudinal stretching and/or cross directional stretch), trimming, corona treatment, rolling, ageing, cut, the step such as finished product packing.
Polypropene composition for the preparation of oriented film of the present invention can be used for preparing single or multiple lift, unidirectional or biaxially oriented film.Have at least one deck to be prepared by described prolylene polymer composition in described multilayer stretched film.
Preferably, the biaxially oriented film that uses polypropene composition of the present invention to make, its film thickness be less than or equal to 25 μ m, preferably less than or equal to 15 μ m, is more preferably less than and equals 12 μ m, most preferably less than or equal to 10 μ m.The lower limit of film thickness is without particular requirement.
Utilize the BiOriented Polypropylene Films of polypropene composition manufacturing of the present invention to show excellent physicals, not only have very high deflection, and have mist degree and the luster performance of good light transmission and improvement.
All documents that this paper quotes are all introduced the present invention as a reference for all purposes at this in full.
Herein each related ratio, per-cent, content etc. all by weight, except as otherwise noted.
Embodiment
The below will describe the present invention by specific embodiment, but it is only to explain rather than limit the present invention.
In the embodiment of the present invention, relevant experimental data obtains by following testing method:
1, overall tacticity index is measured by the method that GB GB 2412-89 describes.
2, overall degree of isotacticity [mm] adopts
13C-NMR measures.[mm] is the molar content of triad structure.(NMR) measure.The instrument that adopts is the AVANCE 400 type nuclear magnetic resonance spectrometers of German Bruker company.Solvent be deuterium for orthodichlorobenzene, 140 ℃ of dissolved samples, 125 ℃ of probe temperatures, 10 millimeters of detecting head specifications, 2 seconds time of lag (D1), in 4 seconds sampling times (AT), scanning times is more than 5000 times.Experimental implementation, the identification of composing the peak and data processing method secundum legem
13The C-NMR standard is carried out.
3, melt flow rate (MFR) (MFR) is pressed ISO1133-05,230 ℃, measures under 2.16kg load.
4, molecular weight distribution (M
w/ M
n) adopt Britain Polymer Laboratories company to produce molecular weight and the molecular weight distribution of the IR5 detector coupling working sample of PL-GPC 220 gel permeation chromatographs and Spain Polymer Char company product, chromatographic column is 3 series connection Plgel 10 μ m MIXED-B posts, solvent and moving phase are 1,2,4-trichlorobenzene (containing 0.3g/1000ml oxidation inhibitor 2, the 6-dibutyl paracresol), 150 ℃ of column temperatures, flow velocity 1.0ml/min.
5, xylene soluble part is pressed ASTM D5492-98 mensuration.
6, resin stretched intensity is pressed ASTM D638-00 measurement.
7, the resin modulus in flexure is pressed ASTM D790-97 measurement.
8, the Izod shock strength is pressed ASTM D256-00 measurement.
9, the transmittance of film, mist degree are pressed the GB/T2410 measurement.
10, the surface gloss of film is pressed ASTM D2457-08 measurement.
11, film stretching modulus, tensile break strength are pressed GB/T 13022-1991 measurement.
Above each test is all carried out under envrionment conditions, except as otherwise noted.
Component in the embodiment of the present invention (A) adopts following methods to make:
Primary Catalysts (the solid catalyst active ingredient of titaniferous) adopts the method that in Chinese patent CN93102795, embodiment 1 describes to obtain, its Ti content: 2.4wt%, Mg content 18.0wt%, n-butyl phthalate content: 13wt%.
Polyreaction is carried out on a collar plumber skill polypropylene pilot plant.Primary Catalysts, promotor (triethyl aluminum), part external electron donor (Cyclohexylmethyldimethoxysilane) are after 10 ℃, the pre-contact of 1min, add continuously prepolymerization reactor to carry out pre-polymerization reactor, the pre-polymerization rear catalyst enters in the annular-pipe reactor of two series connection, completes the equal polymerization reaction of propylene in annular-pipe reactor.15 ℃ of prepolymerization temperature, two 70 ℃ of endless tube polymeric reaction temperatures.The processing condition of gate ring pipe reactor, the productivity ratio that makes first, second endless tube is 45: 55.
Add hydrogen in the charging of first ring pipe reactor, concentration is controlled to be 180ppmV, adds a part of hydrogen in the second annular-pipe reactor charging, makes into the raw hydrogen total concn of the second endless tube and is controlled to be 2600ppmV.The triethyl aluminum flow that advances prepolymerization reactor is 5.29g/hr, and methylcyclohexyl dimethoxy silane flow is 0.13g/hr, and the Primary Catalysts flow is 0.01g/hr.Directly enter the first ring pipe reactor after prepolymerization due to these catalyst components, the first ring pipe reactor no longer includes any other charging except propylene, hydrogen, and therefore, in the first ring pipe reactor, the Al/Si ratio is 40 (weight ratios).Add the Cyclohexylmethyldimethoxysilane into 0.4g/hr in the second annular-pipe reactor.Making the Al/Si ratio in the second endless tube is 10 (weight ratios).
Add IRGAFOS 168 additives of 0.1wt%, IRGANOX 1010 additives of 0.2wt% and the calcium stearate of 0.05wt% in component (A) powder that polymerization is obtained, obtain the pellet of component (A) with the twin screw extruder granulation.The pellet of obtained component (A) is carried out performance test by existing relevant ASTM standard.The results are shown in Table 1.Above raw materials used all can be through commercially available and get.
Table 1
Comparative Examples component (A): adopt commercially available polypropylene, trade names: T36F (Shandong petrochemical complex limited-liability company).These trade names are to adopt single loop reactors to produce, and its melt flow rate (MFR) is 3.0g/10min, and overall degree of isotacticity (is used
13[mm] that C-NMR records) be 93.7%, molecular weight distribution mw/mn is 5.6, dissolves in the fraction content 3.5wt% of dimethylbenzene.
Embodiment 1:
1, polypropene composition preparation: following component is stirred well in homogenizer according to parts by weight mixes:
100 parts of component (A) pellets
0.05 part of nucleator ADK NA-21 (Japanese rising sun electrochemical production)
0.1 part of oxidation inhibitor Irgafos168 (Switzerland's Ciba-Geigy is produced)
0.2 part of anti-oxidant Irganox 1010 (Switzerland's Ciba-Geigy is produced)
Said mixture utilizes 20 millimeters twin screw extruders, carries out granulation under 220 ℃.
2, BOPP thin film technology: with pellet obtained above utilize diameter be the sheet extruder of 30 millimeters 230 ℃ of meltings, be squeezed into cast film, this film is cooling on the cooling roller of 50 ℃, forms the casting films of 0.7mm.Utilize German Bruckner company
Koro4Two-way stretch device with 5.5 times of the sheet material longitudinal stretchings that obtain, subsequently 7 times of 165 ℃ of cross directional stretchs, obtains thickness and is the A-B-A biaxially oriented film of 19 microns at 155 ℃, and its top layer and sandwich layer are identical polypropene composition of the present invention.Measure the correlated performance of film, see Table 2.A-B-A biaxially oriented film described herein refers to three layers of compound biaxially oriented film.Two A are the top layer, and middle B is sandwich layer, adopts 3 forcing machine co-extrusions to obtain.
Embodiment 2:
1, polypropene composition preparation: with following component according to the parts by weight extruding pelletization:
100 parts of component (A) pellets
0.1 part of nucleator ADK NA-21 (Japanese rising sun electrochemical production)
0.1 part of oxidation inhibitor Irgafos168 (Switzerland's Ciba-Geigy is produced)
0.2 part of anti-oxidant Irganox 1010 (Switzerland's Ciba-Geigy is produced)
Said mixture utilizes 20 millimeters twin screw extruders, carries out granulation under 220 ℃.
2, BOPP thin film technology: method is with embodiment 1.Measure the correlated performance of film, see Table 2.
Embodiment 3:
1, polypropene composition preparation: with following component according to the parts by weight extruding pelletization:
100 parts of component (A) pellets
0.25 part of nucleator ADK NA-21 (Japanese rising sun electrochemical production mainly contains)
0.1 part of oxidation inhibitor Irgafos168 (Switzerland's Ciba-Geigy is produced)
0.2 part of anti-oxidant Irganox 1010 (Switzerland's Ciba-Geigy is produced)
Said mixture utilizes 20 millimeters twin screw extruders, carries out granulation under 220 ℃.
2, BOPP thin film technology: method is with embodiment 1.Measure the correlated performance of film, see Table 2.
Embodiment 4:
1, polypropene composition preparation: with following component according to the parts by weight extruding pelletization:
100 parts of component (A) pellets
0.3 part of nucleator Millad3988 (glucitols transparent nucleater, U.S. Milliken company produces)
0.1 part of oxidation inhibitor Irgafos168 (Switzerland's Ciba-Geigy is produced)
0.2 part of anti-oxidant Irganox 1010 (Switzerland's Ciba-Geigy is produced)
Said mixture utilizes 20 millimeters twin screw extruders, carries out granulation under 220 ℃.
2, BOPP thin film technology: method is with embodiment 1.Measure the correlated performance of film, see Table 2.
Embodiment 5:
1, polypropene composition preparation: with following component according to the parts by weight extruding pelletization:
100 parts of component (A) pellets
0.5 part of nucleant agent N X8000 (glucitols transparent nucleater, U.S. Mei Liken produces)
0.1 part of oxidation inhibitor Irgafos168 (Switzerland's Ciba-Geigy is produced)
0.2 part of anti-oxidant Irganox 1010 (Switzerland's Ciba-Geigy is produced)
Said mixture utilizes 20 millimeters twin screw extruders, carries out granulation under 220 ℃.
2, BOPP thin film technology: method is with embodiment 1.Measure the correlated performance of film, see Table 2.
Comparative Examples 1:(blank test, not Added Nucleating Agents)
1, polypropene composition preparation: with following component according to the parts by weight extruding pelletization:
100 parts of component (A) pellets
0.1 part of oxidation inhibitor Irgafos168 (Switzerland's Ciba-Geigy is produced)
0.2 part of anti-oxidant Irganox 1010 (Switzerland's Ciba-Geigy is produced)
Said mixture utilizes 20 millimeters twin screw extruders, carries out granulation under 220 ℃.
2, BOPP thin film technology: method is with embodiment 1.Obtain comparative sample film 1, measure the correlated performance of film, see Table 2.
Comparative Examples 2:
1, polypropene composition preparation: with embodiment 3, only component (A) is replaced with commercially available trade names T36F (Shandong petrochemical complex limited-liability company).
2, BOPP thin film technology: method is with embodiment 1.Obtain comparative sample film 2, measure the correlated performance of film, see Table 2.
Comparative Examples 3:
1, polypropene composition preparation: with embodiment 5, only component (A) is replaced with commercially available trade names T36F (Shandong petrochemical complex limited-liability company).
2, BOPP thin film technology: method is with embodiment 1.Obtain comparative sample film 3, measure the correlated performance of film, see Table 2.
Table 2
Annotate: MD is along machine direction; TD is perpendicular to machine direction
As can be seen from Table 1, the BOPP film that adopts polypropene composition of the present invention to make has identical with the comparative sample film or slightly good transmittance, and the mist degree performance is improved, and the surface is also more level and smooth.
Claims (10)
1. polypropene composition for the preparation of oriented film includes following component:
(A) prolylene polymer composition 100 parts by weight;
(B) nucleator 0.01～1 parts by weight;
above-described component (A) is the alfon composition, the prolylene polymer composition of described component (A) is made by following multistep polymerization reaction: the first step is under Ziegler-Natta catalyst exists, carry out the equal polymerization of propylene or the copolymerization of propylene and the alpha-olefin except propylene, then under the polymkeric substance that generates and the existence of the first step used catalyst, carry out the equal polymerization of second step propylene or the copolymerization of propylene and the alpha-olefin except propylene, wherein add the molecular weight regulator of inequality in the first and second polyreactions, so that the ratio of the MFR value of final gained propene polymer and the MFR value of the first step gained propene polymer is 1-15, increase the external electron donor component or improve the consumption of external electron donor component in second step, so that the ratio of the degree of isotacticity of final polymkeric substance and the degree of isotacticity of the first step gained propene polymer is greater than 1, and be less than or equal to 1.2, wherein the productivity ratio of the first step and second step is 30: 70～70: 30, the overall degree of isotacticity of described prolylene polymer composition [mm] is 94～95%, and melt flow rate (MFR) is 2～4g/10min, and molecular weight distribution mw/mn is 6～8,
The nucleator of wherein said component (B) is selected from least a in Sorbitol Nucleator or aryl orthophosphate nucleator.
2. the polypropene composition for the preparation of oriented film according to claim 1, the nucleator parts by weight of wherein said component (B) are 0.05～0.5 part.
3. the polypropene composition for the preparation of oriented film according to claim 1, the Sorbitol Nucleator of wherein said component (B) is selected from least a in following material: 1, 3-2, 4-two (α-tolylene)-D-glucitol, 1, 3-2, 4-two (4-methylbenzene subunit)-D-glucitol, 1, 3-2, 4-two (3, 4-dimethyl benzene methylene radical)-D-glucitol, 1, 3-2, 4-two (4-ethylbenzene methylene radical)-D-glucitol, two-1, 3-2, 4-(4 '-propyl group benzylidene)-1-allyl group sorbyl alcohol, two-1, 3-2, 4-(4 '-ethyl benzylidene)-1-allyl group sorbyl alcohol, two-1, 3-2, 4-(4 '-propoxy-benzylidene)-1-allyl group sorbyl alcohol, two-1, 3-2, 4-(4 '-propyl group benzylidene)-1-propyl group sorbyl alcohol, two-1, 3-2, 4-(4 '-propoxy-benzylidene)-1-propyl group sorbyl alcohol.
4. the polypropene composition for the preparation of oriented film according to claim 3, the Sorbitol Nucleator of wherein said component (B) is selected from 1,3-2,4-two (3,4-dimethyl benzene methylene radical)-D-glucitol, two-1,3-2,4-(4 '-propyl group benzylidene)-1-propyl group sorbyl alcohol or its mixture.
5. the polypropene composition for the preparation of oriented film according to claim 1, the aryl orthophosphate nucleator of wherein said component (B) is selected from least a in following material: sodium-2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, sodium-2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, lithium-2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, lithium-2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, sodium-2,2 '-ethidine-two (4-sec.-propyl-6-di-tert-butyl-phenyl) phosphoric acid salt, lithium-2,2 '-methylene radical-two (4-methyl-6-di-tert-butyl-phenyl) phosphoric acid salt, lithium-2,2 '-methylene radical-two (4-ethyl-6-di-tert-butyl-phenyl) phosphoric acid salt, calcium-two [2,2 '-thiobis (4-methyl-6-di-tert-butyl-phenyl) phosphoric acid salt], calcium-two [2,2 '-thiobis (4-ethyl-6-di-tert-butyl-phenyl) phosphoric acid salt], calcium-two [2,2 '-thiobis (4,6-di-tert-butyl-phenyl) phosphoric acid salt], magnesium-two [2,2 '-thiobis (4,6-di-tert-butyl-phenyl) phosphoric acid salt], magnesium-two [2,2 '-thiobis (4,6-, two uncle's octyl phenyls) phosphoric acid salt], sodium-2,2 '-Ding pitches base-two (4,6-3,5-dimethylphenyl) phosphoric acid salt, sodium-2,2 '-uncle octyl group methylene radical-two (4,6-3,5-dimethylphenyl) phosphoric acid salt, sodium-2,2 '-uncle octyl group methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, calcium-two [2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], magnesium-two [2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], barium-two [2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], sodium-2,2 '-methylene radical-two (4-methyl-6-tert butyl phenyl) phosphoric acid salt, sodium-2,2 '-methylene radical-two (4-ethyl-6-tert-butyl-phenyl) phosphoric acid salt, calcium-two [4,4 '-dimethyl-6,6 '-di-t-butyl-2,2 '-xenyl) phosphoric acid salt], sodium-2,2 '-ethidine-two (the meta-butyl of 4--6-tert-butyl-phenyl) phosphoric acid salt, sodium-2,2 '-methylene radical-two (4,6-3,5-dimethylphenyl) phosphoric acid salt, sodium-2,2 '-methylene radical-two (4,6-diethyl phenyl) phosphoric acid salt, potassium-2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt, calcium-two [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], magnesium-two [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], barium-two [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], aluminium-hydroxyl-two [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], aluminium-three couple [2,2 '-ethidine-two (4,6-di-tert-butyl-phenyl) phosphoric acid salt], hydroxyl-two [2,4,8,10-four (1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] closes aluminium.
6. the polypropene composition for the preparation of oriented film according to claim 5, the nucleator of wherein said component (B) is selected from least a in following material: sodium-2,2 '-methylene radical-two (4, the 6-di-tert-butyl-phenyl) phosphoric acid salt, aluminium-hydroxyl-two [2,2 '-ethidine-two (4, the 6-di-tert-butyl-phenyl) phosphoric acid salt], hydroxyl-two [2,4,8,10-four (1,1 '-dimethyl ethyl)-6-hydroxyl-12H-dibenzo [d, g] dioxy phospha eight ring-6-oxygen] close aluminium.
7. the preparation method of one of one kind according to claim 1～6 described polypropene composition for the preparation of oriented film, the method comprises and will include described component (A) prolylene polymer composition and (B) component of nucleator, after mixing by described parts by weight, melt blending makes described polypropene composition for the preparation of oriented film.
8. one of one kind according to claim 1～6 oriented film that described polypropene composition is made, comprise single or multiple lift, unidirectional or biaxially oriented film, and having one deck in wherein said multilayer stretched film at least is described polypropene composition preparation.
9. the biaxially oriented film made of polypropene composition according to claim 8, is characterized in that described film thickness is less than or equal to 25 μ m.
10. the biaxially oriented film made of polypropene composition according to claim 9, is characterized in that described film thickness less than or equal to 15 μ m, preferably less than or equal to 12 μ m.
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| CN106317276A (en) * | 2015-06-29 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method of highly crystallized polypropylene |
| CN109503937A (en) * | 2018-10-25 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of preparation method of high fluidity high-modulus high heat resistance thin-walled injection moulding acrylic resin |
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| CN106317276A (en) * | 2015-06-29 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method of highly crystallized polypropylene |
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| CN109503937A (en) * | 2018-10-25 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of preparation method of high fluidity high-modulus high heat resistance thin-walled injection moulding acrylic resin |
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