CN102134290B - Polypropylene with high melt strength and product thereof - Google Patents
Polypropylene with high melt strength and product thereof Download PDFInfo
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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 with high fondant-strength, be particularly useful for making foaming product, articles thermoformed therefrom, biaxially oriented film, blown film and blow-molded article.
Technical background
The cutting out property of alfon structure make its in injection moulding, extrude, obtain a wide range of applications in the manufacture field such as curtain coating, two-way stretch.But common polypropylene molecular chain is linear structure, there is the elastic zone of rubber like in wide temperature range unlike the polymkeric substance (as PS) of amorphous, therefore, polypropylene can not carry out thermoforming in wide temperature range.Simultaneously, polyacrylic softening temperature and fusing point approach, after temperature is higher than fusing point, the viscosity of its melt strength and melt sharply descends, product wall thickness inequality while causing thermoforming, extrude, be coated with, easily occur edge curl, contraction while rolling, the abscess problem such as subside during extrusion foaming, this has limited its application in fields such as thermoforming, foaming and blowings.Therefore, development has the polypropylene of high fondant-strength and good ductility, is the interested problems of people always.So-called high melt strength, propylene (HMSPP) just refers to that melt, under pulled out condition, can bear higher power during fracture.Usually, existing melting index MI is about the alfon of 2g/min left and right, and its higher melt strength can reach 0.8-1N (newton).
The principal element that affects melt strength of polypropylene is the structure of polymer molecule, comprises the size of molecular weight, whether contains the length of long-chain branch and long-chain branch on molecular weight distribution and molecular chain and distributes etc.Usually, the molecular weight of propene polymer is larger, and its melt strength is larger, but molecular weight is larger, more unfavorable for polyacrylic post-treatment processability.Therefore, for the practical application of considering material, making polypropylene have wider molecular weight distribution needs, and in addition, it is also very important making in polymkeric substance to contain very high molecular weight block, can improve significantly polyacrylic melt strength like this.In order to obtain the performance of best propene polymer, desirable polymer product should contain the fraction of the fraction of a small amount 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 published 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 the method for comparatively commonly using, and normally by a plurality of reactors, prepares broad molecular weight distribution polypropylene or adopts the metallocene catalyst in-situ polymerization to obtain the long-chain branch polypropylene, thereby improve the melt strength of final polymkeric substance.Wherein, adopting the reactor of a plurality of series connection to prepare broad molecular weight distribution polypropylene commonly uses the most, it is normally selecting different amounts of hydrogen, different comonomers, be conducive to produce 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 is conducive to produce the polymkeric substance of higher molecular weight, and another kind of reactor is conducive to produce the polymkeric substance of lower molecular weight.
A kind of method for preparing the propene polymer with high fondant-strength and wide molecular weight distribution is for example disclosed in U.S. Pat 6875826 and US7365136, it is in the endless tube-gas-phase polymerization reactor of series connection, select a kind of Ziegler-Natta catalyst of adjusting susceptibility than low hydrogen that has, the maximum characteristics of this Ziegler-Natta catalyst are exactly to 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 first stage production high molecular weight block, the polypropylene of subordinate phase production low molecular weight fraction, finally obtain 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 is 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 impact significantly to taxis and the molecular weight distribution of polymkeric substance usually.Above-mentioned when passing through a plurality of reactors and preparing the method for wide molecular weight distribution homo-polypropylene when adopting, perfect condition is to make to determine that molecular weight and the degree of isotacticity of high molecular weight block of mechanical properties of polymer is more high better, especially the fraction that possesses a certain amount of very high molecular, and the molecular weight of fraction that determines polymer-extruded performance (processing characteristics) is more low better, and possesses more content, but because component and the characteristic of catalyzer in above-mentioned patent do not change in two reactors, therefore in the polyreaction in two stages, catalyzer is consistent for the reaction sensibility of molecular weight regulator (hydrogen), control or 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, due to the limitation of described polymerization technique, make its polymkeric substance be difficult to obtain 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 simultaneously.Therefore, the performance of final polymkeric substance produced to certain impact.
Summary of the invention
The problem existed in order to solve above-mentioned prior art, the invention provides a kind of alfon with high vertical structure isotactic and high fondant-strength, and it has feature:
(1) melting index (190 ℃/2.16kg) is 1.0-10g/min;
(2) molecular weight distribution mw/mn=6-20;
(3) content that molecular weight is greater than 5,000,000 fractions is more than or equal to 0.8wt%;
(4) M
Z+1/ M
nBe more 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 characteristics, 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 to there is a certain amount of very high-molecular weight polymer fraction on the one hand, and on the other hand, need again to there is relatively large low-molecular weight polymer fraction, be i.e. a kind of molecular weight distribution of relative broad range.
As everyone knows, polymer is not comprised of the compound of unimodal molecular weight, even the polymer of a kind of " purely ", also mixture identical by chemical constitution, molecular weight does not wait, structure is different polymeric homologue is formed.The characteristic of this high molecular molecular weight heterogeneity (be molecular size range differ, uneven), just be called the polymolecularity of molecular weight.The high molecular molecular weight generally recorded is all 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 increased successively, i.e. Mn<Mw
w<Mz<Mz
+ 1.Usually, people adopt Mw/Mn to mean the molecular weight distribution of polymkeric substance, and Mn is near low-molecular-weight part in polymkeric substance, and low molecular weight part is larger on the Mn impact; Mw
WwNear the part of high molecular in polymkeric substance, the high molecular part is to Mw
WwAffect larger.In order to make polypropylene there is over-all properties/processing characteristics preferably, within generally the molecular weight distribution mw/mn of propene polymer being controlled to 6-20, but the inventor finds by repetition test, only control these data, can not meet 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 the fraction Mw due to a small amount of ultra high molecular weight, but can affect significantly M
Z+1And relatively large low-molecular weight polymer fraction is larger on the Mn impact, therefore, in propene polymer of the present invention, guarantees M
Z+1It is very important that/Mn is more than or equal to 70.
In the alfon of the invention described above, preferably, molecular weight is greater than 5,000,000 fraction content and is more than or equal to 1.0wt%, more preferably, is more than or equal to 1.5wt%.M
Z+1/ Mn is preferably more than or equals 80.Preferably, the content that molecular weight is less than 50,000 fraction is more than or equal to 15.0wt%, is less than or equal to 40%, is preferably more than or equals 17.5wt%, is less than or equal to 30%.
In addition, the present invention, by the control to each molecular weight fraction, can obtain the polymkeric substance that dispersion index is 6.0-20.0, 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 controlling in the Ziegler-Natta catalyst system external electron donor component in kind and the ratio in differential responses stage, the preferably control of binding molecule amount conditioning agent consumption, can prepare the propene polymer that there is 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, be 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:
First stage: under Ziegler-Natta catalyst exists, under polymerization temperature, lower hydrogen content (being less than 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) a kind of take a kind of organoaluminum component in ingredient of solid catalyst, (2), (3) the first external electron donor components that magnesium, titanium, halogen and internal electron donor be main ingredient; Wherein the ratio between component (1) and component (2) is counted with aluminium/titanium ratio: 10～500 (weight ratios); Ratio between organoaluminum (2) and the first external electron donor component is 10～150 (weight ratios).
Subordinate phase: on the basis of first stage resultant of reaction, under hydrogen exists, add the second external electron donor component to carry out the equal polymerization reaction of propylene, the MFR of final polymkeric substance is 0.1-10g/min; The amount that fills into the second external electron donor component determines by the amount of the organoaluminum component that the first stage adds, and the ratio between organoaluminum component and the second external electron donor component is 1～50 (weight ratio).
Wherein the first external electron donor component is as R
1 nSi (OR
2)
4-nShown in, in formula, R is identical or different, is C
3-C
6Aliphatic group branching or ring-type; R
2For C
1-C
3Linear aliphatic group, for example methyl, ethyl or propyl group; N is 1 or 2.
Wherein the second external electron donor component is as general formula R
3 nSi (OR
4)
4-nShown in, in formula, n is 0 or 1 or 2, R
3And R
4For identical or different C
1-C
3The linear aliphatic group; Or as general formula be R
5R
6Si (OR
7)
2Shown in, R in general formula
7For C
1-C
3The linear aliphatic group, R
5For C
1-C
3The linear aliphatic group, R
6For C
3-C
6Aliphatic group branching or ring-type.
The hydrogen add-on of first stage and subordinate phase is controlled with the requirement of final melting index.
Wherein the productivity ratio of first stage 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 includes but are not limited to Ziegler-Natta catalyst.The Ziegler-Natta catalyst used is by open in a large number, the catalyzer that preferably has high stereoselective, " Ziegler-Natta catalyst of high stereoselective " described herein refers to and can prepare the alfon that isotactic index is greater than 95%.This type of catalyzer contains (1) ingredient of solid catalyst usually, is preferably the solid catalyst active ingredient of titaniferous; (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 be used, and also can after pre-complexing and/or prepolymerization, add.Catalyzer described in Chinese patent CN85100997, CN93102795.0, CN98111780.5 and CN02100900.7, have advantage especially for high melt strength, propylene preparation method of the present invention.
Cocatalyst component of the present invention (2) is 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, take the Ti/Al molar ratio computing as 1: 25～1: 100.
According to the requirement to the different molecular weight fraction, add the external electron donor with different qualities in different reactor.Particularly, in the first stage, be that in the first reactor, the present invention need to prepare the propene polymer of high molecular weight block, in order to make this fraction, has the taxis of higher molecular weight and Geng Gao, selected a kind of have than low hydrogen adjust the susceptibility external electron donor, it is as R
1 nSi (OR
2)
4-nShown in, in formula, R is identical or different, is C
3-C
6Aliphatic group branching or ring-type, preferably R
1For cyclopentyl, sec.-propyl or cyclohexyl; R
2For 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 first stage resulting polymers is controlled at 0.01-0.3g/10min, according to actual needs, usually be chosen in the molecular weight regulator that the first reactor does not add molecular weight regulator or adds minute quantity (being less than or equal to 300ppmV), as hydrogen, in order to obtain the fraction of higher molecular weight.
On the basis of first stage polyreaction resultant, add the second external electron donor component and molecular weight regulator (hydrogen) to carry out the polyreaction of subordinate phase, and the MFR value of controlling final polymkeric substance is controlled as 0.1-10g/min.
The general formula of the second external electron donor component is R
3 nSi (OR
4)
4-n, in formula, n is 0 or 1 or 2.R in general formula
3And R
4For 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 general formula
7For C
1-C
3The linear aliphatic group, R
5For C
1-C
3The linear aliphatic group, R
6For C
3-C
6Aliphatic group branching or ring-type, for example methylcyclohexyl dimethoxy silane.
The polyreaction of the different steps described in polymerization process of the present invention can be carried out respectively in different reactors.A concrete embodiment is: the polyreaction of first stage is carried out in the first reactor, and the polyreaction of subordinate phase is carried out in the second reactor.In the first reactor, add: (1) a kind of take a kind of organoaluminum component in ingredient of solid catalyst, (2), (3) the first external electron donor components that magnesium, titanium, halogen and internal electron donor be main ingredient, under the condition of no hydrogen, carry out the equal polymerization reaction of propylene, the gained polymerisate is introduced the second reactor, add the second external electron donor component, carry out the equal polymerization reaction of further propylene under certain hydrogen exists.
In the first reactor, described three kinds of catalyst components can directly join in the first reactor, after the pre-complexing and/or prepolymerization that also can know altogether through industry, then join in the first reactor.Wherein the form of the reactor of pre-complex reaction can be various, its objective is that catalyst components can be obtained fully effectively to be mixed, can be continuous stirred tank reactor, annular-pipe reactor, containing one section pipeline of static mixer, can be even also the pipeline of one section material in turbulence state.
The temperature control 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 optionally prepolymerization without the catalyzer of pre-complexing and process.Prepolymerization can be carried out continuously under the liquid phase bulk conditions, also can the inert solvent discontinuous carry out.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized temperature control 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 propylene the saturated vapour pressure under corresponding polymerization temperature.When vapour phase polymerization, polymerization temperature is 0～150 ℃, with 40～100 ℃ for well; Polymerization pressure can be normal pressure or higher, and preferred pressure is 1.0～3.0MPa (gauge pressure, lower same).
Polymerization can be to carry out continuously, also may be carried out batchwise.Successive polymerization can be Liquid-phase reactor or the Gas-phase reactor of two or more series connection, Liquid-phase reactor can be annular-pipe reactor or stirred-tank reactor, Gas-phase reactor can be horizontal type agitated bed reactor or vertical mixing bed bioreactor 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, usually adds the additive that this technical field is used during granulation, 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 while by adjustment, adding two reactors of series connection or periodical operation, do not need to use special catalyst, also need not add in addition any multi-functional comonomer, compare to the conventional method that only by difference, adds hydrogen concentration adjustment molecular weight distribution, 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
Below will describe the present invention by specific embodiment, but it is only to explain rather than limit the present invention.
In embodiment, the polymkeric substance relevant data obtains by following testing method:
1. polymer tacticity index.The method of describing by GB GB 2412 is measured.
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 contrary, polymkeric substance is after the single screw extrusion machine fusion plastification, through 90 ° of circular hole die heads that turn to, extrude again, being clamped in the acceleration accelerated manner such as employing between two rollers is stretched by single shaft, drawing force can be measured by the measure force element, the so-called melt strength of maximal force recorded when stretching starts to melt fracture.
3. melt flow rate (MFR) (MFR) is pressed ISO1133,230 ℃, under 2.16kg load, measures.
4. molecular weight polydispersity index PI: the rheometer that the model of selling with U.S. Rheometric Scientific Inc is ARES (senior rheometer expanding system) is at 190 ℃, viscosity and the modulus value of certain frequency scope working sample, the pattern of sample clamp is flat.Molecular weight polydispersity index PI=10
5/ G, the modulus value that G is storage modulus (G ')-frequency curve and out-of-phase modulus (G ")-frequency curve intersection point place.The test before by 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 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 is (containing 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 measurement.
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, adopt the Y501C intrinsic viscosity analyser of U.S. VISCOTEK company, press the measurement of ASTM D 5225-1998 method.Solvent is perhydronaphthalene, 135 ℃ of probe temperatures.
10. solubles content, adopt the CRYSTEX instrument of Spain PolyChar company to record, and solvent is trichlorobenzene.Its result cold xylene solvend Data correction of the polymkeric substance recorded according to ASTM D 5492-2006 standard.
Embodiment 1:
Polyreaction is carried out on a set of polypropylene pilot plant.Its major equipment comprises prepolymerization reactor, first ring pipe reactor and the second annular-pipe reactor.Polymerization process and step are as follows:
(1) prepolymerization:
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%.
Primary Catalysts, promotor (triethyl aluminum), the first external electron donor (dicyclopentyl dimethoxyl silane, DCPMS) after the pre-contact of 10 ℃, 20min, add continuously prepolymerization reactor to 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 under this condition, the pre-polymerization multiple of catalyzer is about 120-150 times.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 the annular-pipe reactor of two series connection, completes the equal polymerization reaction of propylene in annular-pipe reactor.Two 70 ℃ of 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 approximately 45: 55.
Do not add hydrogen in the charging of first ring pipe reactor, density of hydrogen<10ppmV that on-line chromatograph detects, add a certain amount of hydrogen in the second annular-pipe reactor charging, and the density of hydrogen that on-line chromatograph detects is 4500ppmV.
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, therefore, in the first ring pipe reactor, triethyl aluminum/dicyclopentyl dimethoxyl silane (Al/Si-I) is 19.0 (weight ratios) than the ratio be in catalyst prepolymer.
Add the tetraethoxysilane (TEOS) into 0.67g/hr in the second annular-pipe reactor, therefore, triethyl aluminum/tetraethoxysilane in the second annular-pipe reactor (Al/Si-II) is than being 9.4 (weight ratios).The concrete technology condition is in Table 1.
From the second endless tube, polymkeric substance out is after flash separation goes out propylene, then removes the active and heat drying of the catalyzer of unreacted device through wet nitrogen, obtains polymer powders.
Add IRGAFOS 168 additives of 0.1wt%, IRGANOX 1010 additives of 0.2wt% and the calcium stearate of 0.05wt% in the powder that polymerization is obtained, use the twin screw extruder granulation.The gained pellet is carried out to performance test by existing relevant ASTM standard.
Embodiment 2:
With embodiment 1, just in the supplementary propylene feed of first ring pipe reactor, add a small amount of hydrogen, the density of hydrogen that on-line chromatograph detects is 230ppmV.In the supplementary propylene feed of the second annular-pipe reactor, the hydrogen feed amount is adjusted into 8500ppmV.By adjusting the external electron donor inlet amount, Al/Si-I is adjusted into to 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, by adjusting the external electron donor inlet amount, Al/Si-I is adjusted into to 85 (weight ratios).The add-on of promotor triethyl aluminum is constant.。
Embodiment 4:
With embodiment 3, just hydrogen feed amount in the supplementary propylene feed of the second annular-pipe reactor is adjusted into to 12000ppmV.
Embodiment 5:
With embodiment 2, the tetraethoxysilane that just will advance the second annular-pipe reactor changes Cyclohexylmethyldimethoxysilane (CHMMS) into, and add-on is 1.51g/hr, and the Al/Si-II ratio is 4.2 (weight ratios).
The concrete technology parameter of each embodiment, resulting polymers analytical results and polymer physics performance are listed in table 1～4.
Claims (14)
1. the alfon with high fondant-strength, it has following characteristics:
(1) melting index is 1.0-10g/10min, 230 ° of C/2.16kg;
(2) molecular weight distribution mw/mn=6-20;
(3) content that molecular weight is greater than 5,000,000 fractions is more than or equal to 0.8wt%;
(4) M
Z+1/ M
nBe more than or equal to 70.
2. the alfon with high fondant-strength according to claim 1, the content that wherein molecular weight is greater than 5,000,000 fractions is more than or equal to 1.0wt%.
3. the alfon with high fondant-strength according to claim 1, the content that wherein molecular weight is greater than 5,000,000 fractions is more than or equal to 1.5wt%.
4. the alfon with high fondant-strength according to claim 1, wherein M
Z+1/ M
nBe more than or equal to 80.
5. the alfon with high fondant-strength according to claim 1, wherein melting index is 1.6-6g/10min, 230 ° of C/2.16kg.
6. the alfon with high fondant-strength according to claim 1, wherein melting index is 2.5-6g/10min,, 230 ° of C/2.16kg.
7. the alfon with high fondant-strength according to claim 1, the content that wherein molecular weight is less than 50,000 fractions is more than or equal to 15.0wt%, is less than or equal to 40%.
8. the alfon with high fondant-strength according to claim 1, the content that wherein molecular weight is less than 50,000 fractions is more than or equal to 17.5wt%, is less than or equal to 30%.
9. according to the described alfon with alfon of high fondant-strength of one of claim 1-8, it is characterized in that, the dispersion index of polymkeric substance is 6.0-20.0.
10. according to the described alfon with alfon of high fondant-strength of one of claim 1-8, it is characterized in that, the dispersion index of polymkeric substance is 9.0-16.0.
11. the alfon with high fondant-strength, it has following characteristics:
(1) melting index is 1.6-6g/10min, 230 ° of C/2.16kg;
(2) molecular weight distribution mw/mn=6-20;
(3) content that molecular weight is greater than 5,000,000 fractions is more than or equal to 1.0wt%;
(4) M
Z+1/ M
nBe more than or equal to 80;
(5) content that molecular weight is less than 50,000 fractions is more than or equal to 17.5wt%, is less than or equal to 30%;
(6) dispersion index of polymkeric substance is 9.0-16.0.
12. according to the described alfon with alfon of high fondant-strength in one of claim 1-8 or 11, it is characterized in that, described polymkeric substance, by the reactor of two serial operations, carries out the equal polymerization of two stage propylene and reacts to prepare, wherein:
First stage: under Ziegler-Natta catalyst exists, under the polymerization temperature of 50～100 ℃, 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 controls as 0.01-0.3g/10min, ISO1133,230 ° of C/2.16kg, described Ziegler-Natta catalyst is the reaction product of following component: (1) a kind of take the ingredient of solid catalyst that magnesium, titanium, halogen and internal electron donor be main ingredient, (2) a kind of organoaluminum component, (3) first external electron donor components; Wherein the ratio between component (1) and component (2) is counted with aluminium/titanium weight ratio: 10:1～500:1; Part by weight between organoaluminum and the first external electron donor component is 10:1～150:1;
Subordinate phase: on the basis of first stage resultant of reaction, under hydrogen exists, add the second external electron donor component to proceed the equal polymerization reaction of propylene, the MFR of final polymkeric substance controls as 0.1-10g/10min, ISO1133,230 ° of C/2.16kg; The amount that fills into the second external electron donor component determines by the amount of the organoaluminum component that the first stage adds, and the part by weight between organoaluminum component and the second external electron donor component is 1:1～50:1.
The alfon that there is high fondant-strength 13. according to claim 12, wherein the first external electron donor is dicyclopentyl dimethoxyl silane and/or diisopropyl dimethoxy silane, and the second external electron donor is tetraethoxysilane and/or Cyclohexylmethyldimethoxysilane.
14. the described alfon in one of claim 1-8 or 11 can be used for preparing foaming product, articles thermoformed therefrom, biaxially oriented film, reaches blow-molded article.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100009741A CN102134290B (en) | 2010-01-22 | 2010-01-22 | Polypropylene with high melt strength and product thereof |
| KR1020127021847A KR101798500B1 (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 |
| CN201180010274.3A CN102884093B (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 |
| SG10201500468RA SG10201500468RA (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 |
| EP11734336.8A EP2527376B1 (en) | 2010-01-22 | 2011-01-21 | Preparation method for propylene homopolymer having high melt strength |
| US13/574,435 US9068030B2 (en) | 2010-01-22 | 2011-01-21 | Propylene homopolymer having high melt strength and preparation method thereof |
| 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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| CN106317608B (en) * | 2015-06-25 | 2018-10-16 | 中国石油化工股份有限公司 | It is used to prepare the composition of PP foam material and its expanded moldings of preparation |
| CN106317612B (en) * | 2015-06-25 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of high fondant-strength impact polypropylene foamed material and preparation method |
| CN106317611B (en) * | 2015-06-25 | 2019-02-19 | 中国石油化工股份有限公司 | It is used to prepare the composition of PP foam material and its expanded moldings of preparation |
| 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 |
| CN106674719B (en) * | 2015-11-06 | 2020-04-07 | 中国石油化工股份有限公司 | Polypropylene blown film and preparation method thereof |
| CN107325324B (en) | 2016-04-28 | 2019-08-20 | 中国石油化工股份有限公司 | Fire retardant, fire-resistant antistatic composition and fire-resistant antistatic polypropylene foaming beads |
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