CN102134290A - Polypropylene with high melt strength and product thereof - Google Patents
Polypropylene with high melt strength and product thereof Download PDFInfo
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- CN102134290A CN102134290A CN2010100009741A CN201010000974A CN102134290A CN 102134290 A CN102134290 A CN 102134290A CN 2010100009741 A CN2010100009741 A CN 2010100009741A CN 201010000974 A CN201010000974 A CN 201010000974A CN 102134290 A CN102134290 A CN 102134290A
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Abstract
The invention provides homo-polypropylene with high isotacticity and high melt strength, which is characterized in that: (1) the melt index is (190 DEG C/2.16kg)1.0-10g/min; (2) the molecular weight distribution Mw/Mn=6-20; (3) the content of molecules with the molecular weight of greater than 5 million fractions is greater than or equal to 0.8wt%; and (4) Mz+1/Mn is greater than or equal to 70. The polymer can be used for producing foamed products, hot forming products, biaxially oriented films, blown films and blow molding products.
Description
Technical field
The present invention relates to a kind of propene polymer, more particularly, relate to a kind of alfon, be particularly useful for making foaming product, articles thermoformed therefrom, biaxially oriented film, blown film and blow-molded article with high fondant-strength.
Technical background
The cutting out property of alfon structure make its in injection moulding, extrude, obtained to use widely in the manufacture fields such as curtain coating, two-way stretch.But common polypropylene molecular chain is a linear structure, has the elastic zone of rubber like unlike the polymkeric substance (as PS) of amorphous in wide temperature range, and therefore, polypropylene can not carry out thermoforming in wide temperature range.Simultaneously, polyacrylic softening temperature and fusing point are approaching, after temperature is higher than fusing point, the viscosity of its melt strength and melt sharply descends, product wall thickness inequality when causing thermoforming, extrude, be coated with, occur edge curl, contraction when rolling easily, abscess problem such as subside during extrusion foaming, this has limited its application in fields such as thermoforming, foaming and blowings.Therefore, the polypropylene that development has high fondant-strength and good ductility is the interested problems of people always.So-called high melt strength, propylene (HMSPP) just is meant that melt under pulled out condition, can bear higher power during fracture.Usually, existing melting index MI is about the alfon about 2g/min, and its higher melt strength can reach 0.8-1N (newton).
The principal element of impact polypropylene melt strength is the structure of polymer molecule, comprises the size of molecular weight, whether contains the length and distribution or the like of long-chain branch and long-chain branch on molecular weight distribution and the molecular chain.Usually, the molecular weight of propene polymer is big more, and its melt strength is big more, but molecular weight is big more, and is unfavorable more for polyacrylic post-treatment processability.Therefore, for the practical application of considering material, making polypropylene have wider molecular weight distribution needs, and in addition, makes and contains in the polymkeric substance very that high molecular weight block also is very important, can improve polyacrylic melt strength significantly like this.In order to obtain the performance of best propene polymer, the ideal polymer product should contain the fraction of the fraction of a spot of very high-molecular weight polymer, a certain amount of higher molecular weight polymer and relatively large low-molecular weight polymer fraction simultaneously.
The method of disclosed raising melt strength of polypropylene generally comprises: improve polypropylene molecule amount and distribution thereof or introduce the way of branched structure by the polymerization technique technology, or take when the polymer processing moulding and other amorphous or low crystalline resins, elastomerics carry out blend.
Wherein polymerization technique is a method comparatively commonly used, normally obtains the long-chain branch polypropylene by a plurality of reactor made broad molecular weight distribution polypropylenes or employing metallocene catalyst in-situ polymerization, thereby improves the melt strength of final polymkeric substance.Wherein, it is the most commonly used adopting a plurality of placed in-line reactor made broad molecular weight distribution polypropylenes, it is normally selecting different amounts of hydrogen, different comonomers, promptly help producing the polypropylene that obtains wide molecular weight distribution (MWD) in the different reactor of differing molecular weight polymers by the series connection polymerization, for example: wherein a kind of reactor helps producing the polymkeric substance of higher molecular weight, and another kind of reactor then helps producing the polymkeric substance of lower molecular weight.
Among U.S. Pat 6875826 and the US7365136 method that a kind of preparation has the propene polymer of high fondant-strength and wide molecular weight distribution is disclosed for example, it is in placed in-line endless tube-gas-phase polymerization reactor, select a kind of Ziegler-Natta catalyst of transferring susceptibility than low hydrogen that has, the maximum characteristics of this Ziegler-Natta catalyst are exactly need to adopt for example dicyclopentyl dimethoxyl silane of a kind of siloxanes that contains cycloalkyl, as external electron donor, carry out the equal polymerization of propylene or the copolymerization of multistage (two reactors), by controlling the density of hydrogen of each reactor, the polypropylene of fs production high molecular weight block, the polypropylene of subordinate phase production low molecular weight fraction finally obtains having wide molecular weight distribution, linear high fondant-strength alfon.The high molecular weight block that contains MFR＜0.1g/min in this polymkeric substance, weight content are 10-35%, and MFR＞0.5g/min in or the low molecular weight fraction weight content be 65-90%; The MFR=0.1-20g/min of final polymkeric substance, molecular weight distribution mw/mn＞6.
As everyone knows, for propylene polymerization, the kind of external electron donor produces influence significantly to the taxis and the molecular weight distribution of polymkeric substance usually.Above-mentioned when passing through the method for a plurality of reactor made wide molecular weight distribution homo-polypropylene when adopting, perfect condition is to make the molecular weight and the degree of isotacticity of the high molecular weight block that determines the polymkeric substance mechanical property high more good more, especially possesses a certain amount of very high-molecular weight fraction, and determine that the molecular weight of fraction of polymer-extruded performance (processing characteristics) is low more good more, and possesses more content, but because the component of catalyzer and characteristic not variation in two reactors in the above-mentioned patent, therefore in the polyreaction in two stages, catalyzer is consistent for the reaction sensibility of molecular weight regulator (hydrogen), and control or the adjusting for the polymer chain characteristic has certain limitation like this.For some polyacrylic concrete application, foaming product for example, the requirement of its melting index is about 2-3g/min, because the limitation of described polymerization technique makes its polymkeric substance be difficult to obtain simultaneously very fraction, the fraction of a certain amount of higher molecular weight polymer and the relatively large low-molecular weight polymer fraction of high-molecular weight polymer.Therefore, final polymer properties is produced certain influence.
Summary of the invention
In order to solve the problem that above-mentioned prior art exists, the invention provides a kind of alfon with high upright structure isotactic and high fondant-strength, it has feature:
(1) melting index (190 ℃/2.16kg) be 1.0-10g/min;
(2) molecular weight distribution mw/mn=6-20;
(3) molecular weight greater than the content of 5,000,000 fractions more than or equal to 0.8wt%;
(4) M
Z+1/ M
nMore than or equal to 70.
In order to improve the melt strength of polymkeric substance, the molecular weight that improves polymkeric substance is necessary, but in order to guarantee that product has good processing properties, in certain molecular-weight average (being certain melting index) scope, the distribution of controlling its molecular weight is very crucial.In this polymkeric substance, need have a certain amount of very high-molecular weight polymer fraction on the one hand, and on the other hand, need to have relatively large low-molecular weight polymer fraction again, be i.e. a kind of molecular weight distribution of relative broad range.
As everyone knows, polymer is not made up of the compound of unimodal molecular weight, even the polymer of a kind of " purely ", the mixture of the polymeric homologue also identical by chemical constitution, that molecular weight does not wait, structure is different is formed.The characteristic of this high molecular molecular weight heterogeneity (being that molecular weight is not of uniform size, uneven) just is called the polymolecularity of molecular weight.The high molecular molecular weight that generally records all is a molecular-weight average.The molecular-weight average of polymkeric substance is identical, but dispersiveness is not necessarily identical.Usually, people use gel permeation chromatograph to measure the molecular weight distribution of polymkeric substance, by molecular weight distribution curve, can obtain number-average molecular weight, weight-average molecular weight, Z-average molecular weight or (Z+1)-average molecular weight.High molecular weight block is different to the weight of these molar mass average values, is the trend that increases successively, i.e. Mn＜Mw
w＜Mz＜Mz
+ 1Usually, people adopt Mw/Mn to represent the molecular weight distribution of polymkeric substance, and Mn is near low-molecular-weight part in the polymkeric substance, and promptly low molecular weight part is bigger to the Mn influence; Mw
WwNear high-molecular weight part in the polymkeric substance, promptly the high molecular part is to Mw
WwInfluence bigger.In order to make polypropylene have better comprehensive performance/processing characteristics, generally the molecular weight distribution mw/mn with propene polymer is controlled within the 6-20, but the inventor finds by repetition test, only control these data, can not satisfy the demand that this problem prepares high fondant-strength, also very high molecular weight polymer present fraction and very low molecular weight polymers fraction must be controlled in certain scope quantitatively, particularly the content of very high molecular weight polymer present fraction just can reach purpose of the present invention.Consider not remarkably influenced of fraction Mw, but can influence M significantly owing to a spot of ultra high molecular weight
Z+1And relatively large low-molecular weight polymer fraction is bigger to the Mn influence, therefore, guarantees M in propene polymer of the present invention
Z+1/ Mn is very important more than or equal to 70.
In the alfon of the invention described above, preferably, molecular weight greater than 5,000,000 fraction content more than or equal to 1.0wt%, more preferably, more than or equal to 1.5wt%.M
Z+1/ Mn is preferably more than or equals 80.Preferably, molecular weight more than or equal to 15.0wt%, is less than or equal to 40% less than the content of 50,000 fraction, is preferably more than or equals 17.5wt%, is less than or equal to 30%.
In addition, the present invention can obtain the polymkeric substance that dispersion index is 6.0-20.0 by the control to each molecular weight fraction, is preferably 9.0-16.0.
The Tm of alfon feature of the present invention is more than or equal to 163 ℃, and Tpeak-atref is more than or equal to 122 ℃.Xylene soluble part content is less than or equal to 4wt%.
Alfon with high fondant-strength of the present invention is realized by the following method:
At the different propylene polymerization of serial operation in the stage, requirement according to the different molecular weight fraction, by external electron donor component in the control Ziegler-Natta catalyst system in the kind and the ratio in differential responses stage, the preferably control of binding molecule amount conditioning agent consumption, can prepare the propene polymer that has wide molecular weight distribution and contain the ultra high molecular weight fraction, this polymkeric substance has good mechanical property, particularly has very high melt strength.
Propene polymerizing method of the present invention is included in the reactor of two or more serial operations, carries out the equal polymerization reaction of two stages or above propylene of two stages:
Fs: Ziegler-Natta catalyst exists down, under the polymerization temperature, lower hydrogen content (smaller or equal to 300ppmV) or no hydrogen, carry out the equal polymerization reaction of propylene, obtaining MFR is 0.01-0.3g/10min, described Ziegler-Natta catalyst is the reaction product of following component basically, and (1) is a kind of to be a kind of organoaluminum component in ingredient of solid catalyst, (2), (3) the first external electron donor components of main ingredient with magnesium, titanium, halogen and internal electron donor; Wherein the ratio between component (1) and the component (2) is counted with aluminium/titanium ratio: 10～500 (weight ratios); Ratio between the organoaluminum (2) and the first external electron donor component is 10～150 (weight ratios).
Subordinate phase: on the basis of fs resultant of reaction, hydrogen exists down, adds the equal polymerization reaction that the second external electron donor component is carried out propylene, and the MFR of final polymkeric substance is 0.1-10g/min; Mend the amount of the second external electron donor component and determine that by the amount of the organoaluminum component of fs adding the ratio between the organoaluminum component and the second external electron donor component is 1～50 (weight ratio).
First external electron donor component such as the R wherein
1 nSi (OR
2)
4-nShown in, R is identical or different in the formula, is C
3-C
6Branching or the cyclic aliphatic group; R
2Be C
1-C
3Linear aliphatic group, for example methyl, ethyl or propyl group; N is 1 or 2.
Second external electron donor component such as the general formula R wherein
3 nSi (OR
4)
4-nShown in, n is 0 or 1 or 2 in the formula, R
3And R
4Be identical or different C
1-C
3The linear aliphatic group; Or be R as general formula
5R
6Si (OR
7)
2Shown in, R in the general formula
7Be C
1-C
3The linear aliphatic group, R
5Be C
1-C
3The linear aliphatic group, R
6Be C
3-C
6Branching or the cyclic aliphatic group.
The hydrogen add-on of fs and subordinate phase is controlled with the requirement of final melting index.
Wherein the productivity ratio of fs and subordinate phase is 30: 70～70: 30, is preferably 65: 35～55: 45.
In polymerisation process of the present invention, the catalyzer of propylene polymerization comprises but is not limited only to Ziegler-Natta catalyst.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 are meant and can prepare isotactic index greater than 95% alfon.This type of catalyzer contains (1) ingredient of solid catalyst usually, is preferably titaniferous solid catalyst active ingredient; (2) organo-aluminium compound cocatalyst component; (3) external electron donor component.
The specific examples that operational this class contains active solid catalyst component (1) is disclosed in Chinese patent CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4, CN02100900.7.Described catalyzer can directly use, also can be through adding after pre-complexing and/or the prepolymerization.Catalyzer described in Chinese patent CN85100997, CN93102795.0, CN98111780.5 and the CN02100900.7 is used for high melt strength, propylene preparation method of the present invention and has advantage especially.
Cocatalyst component of the present invention (2) is an organo-aluminium compound, the preferred alkyl aluminum compound, more preferably trialkylaluminium, as: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum etc., wherein the ratio of solids containing titanium catalyst component and organo-aluminium compound cocatalyst component is 1: 25～1: 100 with the Ti/Al molar ratio computing.
According to requirement, in different reactor, add external electron donor with different qualities to the different molecular weight fraction.Particularly, in the fs is that the present invention need prepare the propene polymer of high molecular weight block, has the taxis of higher molecular weight and Geng Gao in order to make this fraction in first reactor, selected a kind of have than low hydrogen transfer the susceptibility external electron donor, it is as R
1 nSi (OR
2)
4-nShown in, R is identical or different in the formula, is C
3-C
6Branching or the cyclic aliphatic group, preferred R
1Be cyclopentyl, sec.-propyl or cyclohexyl; R
2Be C
1-C
3Linear aliphatic group, for example methyl, ethyl or propyl group; N is 1 or 2, is preferably 2.Particular compound is as dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane etc.
The MFR value of fs resulting polymers is controlled at 0.01-0.3g/10min, according to actual needs, usually be chosen in the molecular weight regulator that first reactor does not add molecular weight regulator or adds minute quantity (smaller or equal to 300ppmV), as hydrogen, so that obtain the fraction of higher molecular weight.
On the basis of fs polyreaction resultant, add the second external electron donor component and molecular weight regulator (hydrogen) carries out the polyreaction of subordinate phase, and the MFR value of controlling final polymkeric substance is controlled to be 0.1-10g/min.
The general formula of the second external electron donor component is R
3 nSi (OR
4)
4-n, n is 0 or 1 or 2 in the formula.R in the general formula
3And R
4Be identical or different C
1-C
3Linear aliphatic group, for example methyl, ethyl or propyl group.Specifically can include but are not limited to tetramethoxy-silicane, tetraethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane etc.The general formula of the second external electron donor component is R
5R
6Si (OR
7)
2, R in the general formula
7Be C
1-C
3The linear aliphatic group, R
5Be C
1-C
3The linear aliphatic group, R
6Be C
3-C
6Branching or cyclic aliphatic group, for example methylcyclohexyl dimethoxy silane.
The polyreaction of the different steps described in the polymerization process of the present invention can be carried out in different reactors respectively.A concrete embodiment is: the polyreaction of fs is carried out in first reactor, and the polyreaction of subordinate phase is carried out in second reactor.Add in first reactor: (1) is a kind of to be a kind of organoaluminum component in ingredient of solid catalyst, (2), (3) the first external electron donor components of main ingredient with magnesium, titanium, halogen and internal electron donor, under the condition of no hydrogen, carry out the equal polymerization reaction of propylene, the gained polymerisate is introduced second reactor, add the second external electron donor component, in the presence of certain hydrogen, carry out the equal polymerization reaction of further propylene.
In first reactor, described three kinds of catalyst components can directly join in first reactor, also after the pre-complexing and/or prepolymerization that can know altogether through industry, join in first reactor again.Wherein the form of the reactor of pre-complex reaction can be various, its objective is and make each component of catalyzer can obtain fully effectively to mix, can be continuous stirred tank reactor, annular-pipe reactor, contain one section pipeline of static mixer, even also can be the pipeline that one section material is in turbulence state.
The Controllable Temperature of pre-complexing is between-10～60 ℃, and preferred temperature is 0～30 ℃.The time of pre-complexing is controlled at 0.1～180min, and the preferred time is 5～30min.
Through or can also carry out randomly prepolymerization without the catalyzer of pre-complexing and handle.Prepolymerization can be carried out under the liquid phase bulk conditions continuously, also can the inert solvent discontinuous carry out.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized Controllable Temperature is between-10～60 ℃, and preferred temperature is 0～40 ℃.Prepolymerized multiple is controlled at 0.5～1000 times, and preferred multiple is 1.0～500 times.
Described polyreaction can be in the propylene liquid phase, or carries out in gas phase, or adopts liquid-gas combination technique to carry out.When carrying out liquid polymerization, polymerization temperature is 0～150 ℃, with 40～100 ℃ for well; Polymerization pressure should be higher than the saturated vapour pressure of propylene under corresponding polymerization temperature.Polymerization temperature is 0～150 ℃ when vapour phase polymerization, with 40～100 ℃ for well; Polymerization pressure can be a normal pressure or higher, and preferred pressure is 1.0～3.0MPa (gauge pressure, down together).
Polymerization can be to carry out continuously, also may be carried out batchwise.Successive polymerization can be two or more placed in-line Liquid-phase reactor or Gas-phase reactor, Liquid-phase reactor can be annular-pipe reactor or stirred-tank reactor, Gas-phase reactor can be horizontal type agitated bed reactor or vertical agitated bed reactor or fluidized-bed reactor etc., and above Liquid-phase reactor and Gas-phase reactor be matched combined at random also.
Polymkeric substance of the present invention can carry out extruding pelletization by use equipment, adds the additive that this technical field is used during granulation usually, as oxidation inhibitor, photostabilizer, thermo-stabilizer, tinting material and filler etc.
In the preparation method of polymkeric substance of the present invention, external electron donor consumption, kind and the hydrogen add-on of different steps when adding placed in-line two reactors or periodical operation by adjusting, need not use special catalyst, also need not add any multi-functional comonomer in addition, compare to the conventional method that only adds hydrogen concentration adjustment molecular weight distribution by difference, the present invention can obtain more high molecular weight fraction present, can use the hydrogen of less amount.Thereby can be with the more economical more high performance product of means preparation.
Polymkeric substance of the present invention compared with prior art has higher melt strength, mainly can be used for preparing foaming product, biaxially oriented film, articles thermoformed therefrom and blow-molded article.
Embodiment
To describe the present invention by specific embodiment below, but it only is to explain rather than limit the present invention.
The polymkeric substance relevant data obtains by following testing method among the embodiment:
1. polymer tacticity index.Measure by the method that GB GB 2412 describes.
2. melt strength: the Rheoten melt strength instrument that adopts German Geottfert Werkstoff Pruefmaschinen company to produce.This instrument comprises the roller that a pair of sense of rotation is opposite, polymkeric substance is behind the single screw extrusion machine fusion plastification, extrude through 90 ° of circular hole die heads that turn to again, be clamped in that acceleration accelerated manner such as employing is stretched by single shaft between two rollers, drawing force can be measured the so-called melt strength of maximum, force value that records when stretching begins to melt fracture by the measure force element.
3. melt flow rate (MFR) (MFR) is pressed ISO1133,230 ℃, measures under the 2.16kg load.
4. molecular weight polydispersity index PI: the model of selling with U.S. Rheometric Scientific Inc is that the rheometer of ARES (senior rheometer expanding system) is at 190 ℃, the viscosity and the modulus value of certain frequency scope working sample, the pattern of sample clamp are flat.Molecular weight polydispersity index PI=10
5/ G, G are the modulus value at storage modulus (G ')-frequency curve and out-of-phase modulus (G ")-frequency curve intersection point place.The test before with resin sample at 200 ℃ of thin slices that are molded into 2mm.
5. molecular weight distribution (M
w/ M
n, M
Z+1/ M
n): adopt Britain PolymerLaboratories company to produce the 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, the 4-trichlorobenzene (contains 0.3g/1000ml oxidation inhibitor 2, the 6-dibutyl paracresol), 150 ℃ of column temperatures, flow velocity 1.0ml/min.
6. resin stretched intensity is pressed ASTM D638-00 and is measured.
7. the resin modulus in flexure is pressed ASTM D790-97 measurement.
8. the IZOD notched Izod impact strength is pressed ASTM D256-00 measurement.
9. intrinsic viscosity adopts the Y501C intrinsic viscosity analyser of U.S. VISCOTEK company, presses ASTM D 5225-1998 method and measures.Solvent is a perhydronaphthalene, 135 ℃ of probe temperatures.
10. solubles content adopts the CRYSTEX instrument of Spain PolyChar company to record, and solvent is a trichlorobenzene.Its result uses the cold xylene solvend data of the polymkeric substance that records according to ASTM D 5492-2006 standard to proofread and correct.
Embodiment 1:
Polyreaction is carried out on a cover polypropylene pilot plant.Its major equipment comprises prepolymerization reactor, first annular-pipe reactor and second annular-pipe reactor.Polymerization process and step are as follows:
(1) prepolymerization reaction:
Primary Catalysts (titaniferous solid catalyst active ingredient) adopts the method that embodiment 1 describes among the Chinese patent CN93102795 to obtain its Ti content: 2.4wt%, Mg content 18.0wt%, n-butyl phthalate content: 13wt%.
Primary Catalysts, promotor (triethyl aluminum), first kind of external electron donor (dicyclopentyl dimethoxyl silane, DCPMS) after the pre-contact of 10 ℃, 20min, add prepolymerization reactor continuously and carry out pre-polymerization reactor, prepolymerization is carried out under propylene liquid phase bulk environment, temperature is 15 ℃, the residence time is about 4min, and the pre-polymerization multiple of catalyzer is about 120-150 times under this condition.The triethyl aluminum flow that advances prepolymerization reactor is 6.33g/hr, and two cyclopentyl dimethoxy silane flows are 0.33g/hr, and the Primary Catalysts flow is about 0.01g/hr.
(2) the equal polymerization of propylene:
The pre-polymerization rear catalyst enters in two placed in-line annular-pipe reactors, finishes the equal polymerization reaction of propylene in annular-pipe reactor.70 ℃ of two endless tube polymeric reaction temperatures, reaction pressure 4.0MPa.The processing condition of gate ring pipe reactor, the productivity ratio that makes first, second endless tube is about 45: 55.
Do not add hydrogen in the charging of first annular-pipe reactor, density of hydrogen＜10ppmV that on-line chromatograph detects adds a certain amount of hydrogen in the second annular-pipe reactor charging, and the density of hydrogen that on-line chromatograph detects is 4500ppmV.
Because these catalyst components directly enter first annular-pipe reactor after prepolymerization, first annular-pipe reactor no longer includes any other charging except that propylene, therefore, triethyl aluminum/dicyclopentyl dimethoxyl silane (Al/Si-I) is 19.0 (weight ratios) than the ratio that is in the catalyzer prepolymer in first annular-pipe reactor.
Add the into tetraethoxysilane of 0.67g/hr (TEOS) in second annular-pipe reactor, therefore, triethyl aluminum/tetraethoxysilane in second annular-pipe reactor (Al/Si-II) is than being 9.4 (weight ratios).Concrete processing condition see Table 1.
After the polymkeric substance that comes out from second endless tube goes out propylene through flash separation, remove the activity of such catalysts and the heat drying of unreacted device again through wet nitrogen, obtain polymer powders.
Add IRGAFOS 168 additives, IRGANOX 1010 additives of 0.2wt% and the calcium stearate of 0.05wt% of 0.1wt% in the powder that polymerization is obtained, use the twin screw extruder granulation.The gained pellet is carried out performance test by existing relevant ASTM standard.
Embodiment 2:
With embodiment 1, just in the additional propylene feed of first annular-pipe reactor, add a spot of hydrogen, the density of hydrogen that on-line chromatograph detects is 230ppmV.The hydrogen feed amount is adjusted into 8500ppmV in the additional propylene feed of second annular-pipe reactor.By adjusting the external electron donor inlet amount, Al/Si-I is adjusted into 45 (weight ratios), Al/Si-II is adjusted into 4.2 (weight ratios).The add-on of promotor triethyl aluminum is constant.
Embodiment 3:
With embodiment 2, just, Al/Si-I is adjusted into 85 (weight ratios) by adjusting the external electron donor inlet amount.The add-on of promotor triethyl aluminum is constant.。
Embodiment 4:
With embodiment 3, just hydrogen feed amount in the additional propylene feed of second annular-pipe reactor is adjusted into 12000ppmV.
Embodiment 5:
With embodiment 2, the tetraethoxysilane that just will advance second annular-pipe reactor changes methylcyclohexyl dimethoxy silane (CHMMS) into, and add-on is 1.51g/hr, and the Al/Si-II ratio is 4.2 (weight ratios).
The concrete processing parameter of each embodiment, resulting polymers analytical results and polymer physics performance are listed in table 1～4.
Claims (14)
1. alfon with high fondant-strength, it has following feature:
(1) melting index (190 ℃/2.16kg) be 1.0-10g/min;
(2) molecular weight distribution mw/mn=6-20;
(3) molecular weight greater than the content of 5,000,000 fractions more than or equal to 0.8wt%;
(4) M
Z+1/ M
nMore than or equal to 70.
2. the alfon with high fondant-strength according to claim 1, wherein molecular weight greater than the content of 5,000,000 fractions more than or equal to 1.0wt%.
3. the alfon with high fondant-strength according to claim 1, wherein molecular weight greater than the content of 5,000,000 fractions more than or equal to 1.5wt%.
4. the alfon with high fondant-strength according to claim 1, wherein M
Z+1/ M
nMore than or equal to 80.
5. the alfon with high fondant-strength according to claim 1, wherein melting index (190 ℃/2.16kg) be 1.6-6g/min.
6. the alfon with high fondant-strength according to claim 1, wherein melting index (190 ℃/2.16kg) be 2.5-6g/min.
7. the alfon with high fondant-strength according to claim 1, wherein molecular weight more than or equal to 15.0wt%, is less than or equal to 40% less than the content of 50,000 fractions.
8. the alfon with high fondant-strength according to claim 1, wherein molecular weight more than or equal to 17.5wt%, is less than or equal to 30% less than the content of 50,000 fractions.
9. according to the described alfon of one of claim 1-8, it is characterized in that the dispersion index of polymkeric substance is 6.0-20.0 with alfon of high fondant-strength.
10. according to the described alfon of one of claim 1-8, it is characterized in that the dispersion index of polymkeric substance is 9.0-16.0 with alfon of high fondant-strength.
11. the alfon with high fondant-strength, it has following feature:
(1) melting index (190 ℃/2.16kg) be 1.6-6g/min;
(2) molecular weight distribution mw/mn=6-20;
(3) molecular weight greater than the content of 5,000,000 fractions more than or equal to 1.0wt%;
(4) M
Z+1/ M
nMore than or equal to 80;
(5) molecular weight more than or equal to 17.5wt%, is less than or equal to 30% less than the content of 50,000 fractions;
(6) dispersion index of polymkeric substance is 9.0-16.0.
12., it is characterized in that described polymkeric substance is by in the reactor of two serial operations according to the described alfon of one of claim 1-11 with alfon of high fondant-strength, carry out the equal polymerization of two stage propylene and react and prepare, wherein:
Fs: Ziegler-Natta catalyst exists down, under 50～100 ℃ the polymerization temperature, hydrogen content is less than or equal to 300ppmV, or under the no hydrogen condition, carry out the equal polymerization reaction of propylene, the MFR of resulting polymers is controlled to be 0.01-0.3g/10min, described Ziegler-Natta catalyst is the reaction product of following component: (1) is a kind of to be the ingredient of solid catalyst of main ingredient with magnesium, titanium, halogen and internal electron donor, (2) a kind of organoaluminum component, (3) first external electron donor components; Wherein the ratio between component (1) and the component (2) is counted with aluminium/titanium ratio: 10: 1～500: 1 (weight ratio); Ratio between the organoaluminum and the first external electron donor component is 10: 1～150: 1 (weight ratio);
Subordinate phase: on the basis of fs resultant of reaction, hydrogen exists down, adds the equal polymerization reaction that the second external electron donor component is proceeded propylene, and the MFR of final polymkeric substance is controlled to be 0.1-10g/min; Mend the amount of the second external electron donor component and determine that by the amount of the organoaluminum component of fs adding the ratio between the organoaluminum component and the second external electron donor component is 1: 1～50: 1 (weight ratio).
13. the alfon with high fondant-strength according to claim 12, wherein first external electron donor is dicyclopentyl dimethoxyl silane and/or diisopropyl dimethoxy silane, and second external electron donor is tetraethoxysilane and/or methylcyclohexyl dimethoxy silane.
14. the described alfon of one of claim 1-11 can be used for preparing foaming product, articles thermoformed therefrom, biaxially oriented film, blown film and blow-molded article.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100009741A CN102134290B (en) | 2010-01-22 | 2010-01-22 | Polypropylene with high melt strength and product thereof |
| EP11734336.8A EP2527376B1 (en) | 2010-01-22 | 2011-01-21 | Preparation method for propylene homopolymer having high melt strength |
| CN201180010274.3A CN102884093B (en) | 2010-01-22 | 2011-01-21 | Propylene homopolymer having high melt strength and preparation method thereof |
| KR1020127021847A KR101798500B1 (en) | 2010-01-22 | 2011-01-21 | Propylene homopolymer having high melt strength and preparation method thereof |
| US13/574,435 US9068030B2 (en) | 2010-01-22 | 2011-01-21 | Propylene homopolymer having high melt strength and preparation method thereof |
| PCT/CN2011/000107 WO2011088754A1 (en) | 2010-01-22 | 2011-01-21 | Propylene homopolymer having high melt strength and preparation method thereof |
| MYPI2012003300A MY158286A (en) | 2010-01-22 | 2011-01-21 | Propylene homopolymer having high melt strength and preparation method thereof |
| SG10201500468RA SG10201500468RA (en) | 2010-01-22 | 2011-01-21 | Propylene homopolymer having high melt strength and preparation method thereof |
| BR112012018282A BR112012018282B1 (en) | 2010-01-22 | 2011-01-21 | propylene homopolymer with high resistance to fusion, its use and its preparation process |
| SG2012054078A SG182655A1 (en) | 2010-01-22 | 2011-01-21 | Propylene homopolymer having high melt strength and preparation method thereof |
| ZA2012/06323A ZA201206323B (en) | 2010-01-22 | 2012-08-22 | Propylene homopolymer having high melt strength and preparation method thereof |
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