CN101724111B - Preparation method of polypropylene with wide molecular weight distribution and polymer thereof - Google Patents
Preparation method of polypropylene with wide molecular weight distribution and polymer thereof Download PDFInfo
- Publication number
- CN101724111B CN101724111B CN2008102248684A CN200810224868A CN101724111B CN 101724111 B CN101724111 B CN 101724111B CN 2008102248684 A CN2008102248684 A CN 2008102248684A CN 200810224868 A CN200810224868 A CN 200810224868A CN 101724111 B CN101724111 B CN 101724111B
- Authority
- CN
- China
- Prior art keywords
- electron donor
- molecular weight
- weight distribution
- preparation
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a preparation method of molecular weight distribution polypropylene and a polymer thereof. By using the method, polymerization reaction is carried out in a single reactor or a plurality of series reactors in the presence of catalysts, wherein the catalysts are reactants containing the following components: (1) at least one solid catalyst component comprising magnesium, titanium, halogen and at least two electron donors of a and b, wherein the electron donor a is selected from a diol ester compound; the electron donor b is selected from unitary or multi-element aliphatic carboxylic ester, aromatic aliphatic carboxylic ester or diether compounds; and the weight ratio of the electron donor a to the electron donor b is 2-80; (2) an alkyl aluminum compound; and (3) optimally, an external electron donor component. The acrylic polymer has the advantages of wide molecular weight distribution, high isotacticity and the like; meanwhile, the preparation method has simple operation.
Description
Technical field
The present invention relates to a kind of polyacrylic preparation method and polymkeric substance thereof, more specifically to a kind of polyacrylic preparation method and polymkeric substance thereof with wide molecular weight distribution.
Technical background
Usually; The acrylic resin of wide molecular weight distribution has more excellent performance usually; This is because high molecular weight block wherein provides resin high-modulus, high impact and high fondant-strength; Low molecular weight fraction provides high fluidity of molten, and the broad molecular weight distribution polypropylene melt has shear-thinning effect in addition, so the Vestolen PP 7052 of wide molecular weight distribution has stronger competitive power than the propene polymer of narrow distribution.
In the industrial production of broad molecular weight distribution polypropylene is synthetic, adopt the method for step-by-step polymerization mostly.
For example U.S. Pat 7365136 discloses the synthetic polyacrylic method of a kind of employing annular-pipe reactor-Gas-phase reactor tandem process.The broad molecular weight distribution polypropylene that obtains through two reactor drum asymmetric hydrogenations has higher melt strength and shear-thinning index.Two step (or multistep) polymerizations at asymmetric hydrogenation prepare in the broad molecular weight distribution polypropylene; Synthetic low molecular weight fraction its isotactic index lower (ultra-low molecular amount Vestolen PP 7052) often under high hydrogen concentration; Synthetic macromolecule magnitude branch tends to produce a small amount of (high isotactic) ultra-high molecular weight component under low hydrogen (or not hydrogenation) concentration, influences the processing and the use of resin.In order to overcome this defective; Chinese patent CN101058654 discloses a kind of asymmetric hydrogenation and asymmetric and has added the method that external electron donor (endless tube+endless tube) step-by-step polymerization prepares broad molecular weight distribution polypropylene, and the Vestolen PP 7052 that obtains has the characteristics of the high isotactic of low molecular weight fraction, the low isotactic of high molecular weight block.Asymmetric hydrogenation step-by-step polymerization complicated operation, product performance index fluctuate bigger in addition.
For example Chinese patent ZL95191937.7 discloses the method for a kind of employing different external electron donors (tetraethoxysilane and dicyclopentyl dimethoxyl silane) step-by-step polymerization, the Vestolen PP 7052 that obtains have higher melt flow rate(MFR) with in wide MWD.
And the inventor is surprised to find that in research process; Use a kind of high polymerization activity, high upright structure directional property catalyzer; In a reactor drum (or two and two above tandem reactors, under same polymerizing condition) carry out propylene polymerization, need not multi-stage polymeric; The gained alfon has wider molecular weight distribution and higher isotactic index, and this polymkeric substance has the good physicals and the balance of processing characteristics.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of preparation method of broad molecular weight distribution polypropylene, particularly, this method is in the presence of catalyzer, carries out the polyreaction of propylene, and described catalyzer comprises the reaction product of following component:
(1) at least a ingredient of solid catalyst, this ingredient of solid catalyst comprise magnesium, titanium, halogen and at least two kinds of electron donor a and b,
Wherein said electron donor a is selected from a kind of diol ester compound in the formula (I):
(I) R in the formula
1-R
6Group is hydrogen identical or inequality, the C of straight or branched
1-C
20Alkyl;
Wherein the electron donor compound b is selected from monobasic or polyhydric aliphatic family carboxylicesters, monobasic or polynary aromatic carboxylic acid esters or diether compound;
Wherein the weight ratio of electron donor compound a and electron donor compound b is 2～80, preferred 2.5～8;
(2) alkylaluminium cpd;
(3) randomly, the external electron donor component is selected from general formula (II) R
1 mSi (OR
2)
4-mSilicoorganic compound, 0≤m in the formula≤3, R
1And R
2Be of the same race or different alkyl, naphthenic base, aryl, haloalkyl, R
1Also can be halogen or Wasserstoffatoms.
Wherein in the component (1), the electron donor compound a of general formula (I) is disclosed among Chinese patent CN1436766A, CN1436796A and the CN1453298A, and its associated viscera is incorporated herein the present invention as a reference.
Said diol-lipid electron donor compound specifically can adopt: 1, and ammediol dibenzoate, 2-methyl isophthalic acid, ammediol dibenzoate, 2-ethyl-1, ammediol dibenzoate, 2-propyl group-1; Ammediol dibenzoate, 2-butyl-1, ammediol dibenzoate, 2 dibenzoate, 2-ethyl-2-butyl-1; Ammediol dibenzoate, 2,2-diethylammonium-1, ammediol dibenzoate, 2-methyl-2-propyl group-1, ammediol dibenzoate, 2-sec.-propyl-2-isopentyl-1; Ammediol dibenzoate, 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-propyl group-2; 4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl--2,4-pentanediol dibenzoate, 2-methyl isophthalic acid; 3-pentanediol dibenzoate, 2,2-dimethyl--1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1; 3-pentanediol dibenzoate, 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl group-1; 3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl--1; 3-pentanediol dibenzoate, 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2,2-dimethyl--1; 3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2; 2,4-trimethylammonium-1,3-pentanediol dibenzoate, 3-methyl-3-butyl-2; 4-pentanediol dibenzoate, 2,2-dimethyl--1,5-pentanediol dibenzoate.
Wherein in the component (1), a kind of in addition electron donor compound b is selected from monobasic or polyhydric aliphatic family carboxylicesters, aromatic carboxylic acid esters or diether compound, and preferred phthalate is concrete like n-butyl phthalate, phthalic acid isobutylate.
Wherein in the component (1), except above-mentioned electron donor compound a and b, catalyst component of the present invention also comprises titanium, magnesium and halogen.Particularly preferably; This catalyst component is that load has the titanium compound with at least one Ti-halogen bond and the reaction product of above-mentioned electron donor compound on a kind of halogenide of magnesium; The halogenide of described magnesium preferably has the magnesium dihalide of active state, is more preferably magnesium dichloride.This magnesium dichloride is well-known as the carrier of Ziegler-Natta catalyst in the art.Usual method is at a kind of MgCl
2Load has titanium compound and described two kinds of reaction product of giving electric body compound a and b, the wherein MgCl with at least one Ti-halogen bond on the nROH adducts
2The nROH adducts is magnesium dichloride and pure adducts, preferred particle spherical in shape, and wherein n is generally 1.5～4, and preferred 2.0～3.5; R is the alkyl of charcoal several 1-4, and described alcohol is ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, isooctyl alcohol etc.
Described general formula with titanium compound of at least one Ti-halogen bond is TiX
n(OR)
4-n, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4.For example: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
With above-mentioned Mgcl
2NROH adducts particle and electron donor compound a of the present invention, b and titanium compound react, and finally obtain catalyst component of the present invention.Relevant preparation process can be carried out with reference to disclosed method among Chinese patent CN1036011C, the CN1330086A, and disclosed associated viscera is incorporated herein the present invention as a reference.
MgCl
2The concrete preparation method of nROH adducts: anhydrous magnesium halide and alcohol are mixed; Temperature reaction generates the magnesium halide alcohol adduct melt; Temperature of reaction is 90～140 ℃; In dispersion medium, after high shear forces, put into the refrigerative inert media, form spherical magnesium halide alcohol adduct particle, after washing, drying, obtain ball type carrier.High shear forces can adopt conventional method to obtain, like high-speed mixing method (like CN1330086), spray method (like US6020279) and high-gravity rotating bed (like CN1580136A) and mulser method (CN1463990A) etc.Dispersant system adopts the hydro carbons inert solvent, like kerosene, white oil, silicone oil, Yellow Protopet 2A, Vaseline wet goods.Heat-eliminating medium is selected from pentane, hexane, heptane, sherwood oil, raffinates oil etc.
The compound method of catalyst component catalyzer of the present invention: the above-mentioned magnesium halide alcohol adduct that obtains is suspended in the mixture of titanium compound or titanium compound and inert solvent (like hexane, heptane, octane, decane, toluene etc.) of precooling; Then said mixture is heated to 80 ℃～130 ℃, in temperature-rise period, adds electron donor compound a and electron donor compound b.Add titanium compound then and handle one or many.At last, repeatedly wash with inert solvent and obtain ingredient of solid catalyst.
In the preparation process of catalyst component of the present invention, the adding of electron donor a and b is order in no particular order.
In the preparation process of catalyst component of the present invention, the weight ratio of titanium, magnesium, chlorine, electron donor compound a and electron donor compound b can be 1:5-15:10-20:2-8:0.1-4.
Wherein in the component (2), alkylaluminium cpd is that general formula is AlR
nX
3-nCompound, R is a hydrogen in the formula, carbonatoms is 1～20 alkyl, X is a halogen, n is 1<the number of n≤3; Specifically can be selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium.
Wherein in the component (3), general formula (II) R
1 mSi (OR
2)
4-mSilicoorganic compound, 0≤m in the formula≤3, R
1And R
2Be of the same race or different alkyl, naphthenic base, aryl, haloalkyl, R
1Also can be halogen or Wasserstoffatoms.For example: cyclohexyl methyl dimethoxy silane is arranged, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane; Second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane; Dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane and (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1; 1,1-three fluoro-2-propyl group)-methyl dimethoxysilane.
The ratio between component (1), component (2) and the component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1～1000:1:2～200.
The preparation method of broad molecular weight distribution polypropylene of the present invention is that polypropylene directly obtains broad molecular weight distribution polypropylene in single reactor drum; Perhaps in two and two above tandem reactors, polypropylene obtains the Vestolen PP 7052 of wide molecular weight distribution under same polymerizing condition.Described reactor drum can be a still formula propene polymerization reactor, also endless tube propene polymerization reactor, and can adopt mass polymerization, vapour phase polymerization and inert solvent is the slurry polymerization of medium.
The propylene polymerization condition can adopt the known polymeric reaction condition of the industry, and between 50-85 ℃ of the polymerization temperatures, polymerization pressure may be up to the vp of liquid propene under polymerization temperature.
Catalyst component, aluminum alkyls and external electron donor compound can add polymerization reactor respectively, also can mix the back and add polymerization reactor, join polymerization reactor after also can adopting the prepolymerization of the known prepolymerization method propylene of the industry.
In polymerization process, hydrogen can be used as the molecular weight that the polymericular weight regulator joins telomerized polymer in the polymerization reactor.
Another object of the present invention has provided the propene polymer by above-mentioned preparation method preparation, and the molecular weight distributing index of this propene polymer (Mw/Mn) is greater than 5.5, preferred Mw/Mn:5.8-9.0; Polydispersity index PI is greater than 4.5; Isotactic index (II) is greater than 97% (can regulate according to the purposes of polymkeric substance); Xylene soluble part (X.S) is less than 2.0%; Melting index (MI) is greater than 0.1g/10min, preferred MI:1.0-10g/10min.
Propene polymer of the present invention has higher draw tensile strength (> 35MPa) and flexural strength (> 35MPa).
Propene polymer of the present invention has the advantages that MWD is wide, degree of isotacticity is high, xylene soluble part is low and modulus is high, has comprehensive good physicals and processing characteristics.
The compound method of wide molecular weight distribution propene polymer of the present invention in industrial production is used, have simple to operate, the characteristics that the polymer performance control indexes is stable.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
Testing method:
1, polymericular weight and MWD MWD (MWD=Mw/Mn): adopt the gel permeation chromatography method; Use PL-GPC220 to measure (standard specimen: PS as solvent down at 150 ℃ with trichlorobenzene; Flow velocity: 1.0ml/min, pillar: 3xPlgel10um MlxED-B300x7.5nm).
2, polymkeric substance isotactic index: adopt the heptane extraction process to measure (heptane boiling extracting 6 hours): two gram exsiccant polymer samples; Be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is isotactic index with 2 ratio.
3, the mensuration of melt index: measure according to ASTM D1238-99
4, xylene soluble part (X.S): the polymer samples of 2 grams was dissolved in the YLENE of ebullient 200ml, and solution is cooled to 25 ℃, with constant temperature 60 minutes.Filter out precipitate, then at 250 ℃ of following evaporated filtrates, the residuum that drying obtains is also weighed, the weight percentage of its shared sample.
5, rheology polydispersity index PI testing method: adopt the ARES rheometer of Rheomitric Scientific company, 190 ℃ of temperature, dynamic frequency scanning, range of scanned frequencies 100～0.01 radian per seconds, 5% strain; It is that the inverse of intersection point modulus (modulus of storage modulus and power consumption modulus joining) multiply by the coefficient corresponding to unit.
6, tensile yield strength: according to ASTM D638-99
7, bending elastic modulus: according to ASTM D790-99
8, flexural strength: according to ASTM D790-99
Embodiment 1
The preparation of catalyst component: in the glass reaction bottle of 500ml, add the 100ml titanium tetrachloride, under agitation add the spherical magnesium chloride alcohol adduct of 8g (MgCl
22.6C
2H
5OH), be warming up to 120 ℃, in temperature-rise period, add 2,4-pentanediol dibenzoate 1.5ml, Witcizer 300 0.5ml kept elimination solution 1 hour under 120 ℃.Add the 100ml titanium tetrachloride, stirred elimination solution 0.5 hour down at 120 ℃.With the hexane wash solids thing of 100ml and under vacuum drying obtain ingredient of solid catalyst.In the catalyst component 2, the content of 4-pentanediol dibenzoate is 10.6wt%, and the content of Witcizer 300 is 2.8wt%.
Propylene polymerization: in the autoclave of a 5L; Adopt stream of nitrogen gas to purge, then the hexane solution (the concentration 0.1mmol/ml of CHMMS) of the cyclohexyl methyl dimethoxy silane (CHMMS) of the hexane solution (concentration of triethyl aluminum is 0.05mmol/ml) of introducing 5ml triethyl aluminum, 1ml, anhydrous hexane and the 10mg catalyst component of 10ml in stream of nitrogen gas.Close autoclave, add the liquid propene of 2.3L.Be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Comparative Examples 1
The preparation of catalyst component: remove 2, the content of 4-pentanediol dibenzoate is 3.9wt%, and the content of Witcizer 300 is that 10.6wt% is outer with embodiment 1.
Propylene polymerization: with embodiment 1
Test result such as table 1.
Comparative Examples 2
The preparation of catalyst component: remove 2, the content of 4-pentanediol dibenzoate is 12wt%, and it is outer with embodiment 1 not contain Witcizer 300.
Propylene polymerization: with embodiment 1
Test result such as table 1.
Comparative Examples 3
The preparation of catalyst component: remove 2, the content of 4-pentanediol dibenzoate is 11.0wt%, and the content of Witcizer 300 is that 0.1wt% is outer with embodiment 1.
Propylene polymerization: with embodiment 1
Test result such as table 1.
Comparative Examples 4
The preparation of catalyst component: except that not containing 2,4-pentanediol dibenzoate, the content of Witcizer 300 are that 12wt% is outer with embodiment 1.
Propylene polymerization: with embodiment 1
Test result such as table 1.
Table 1. propylene polymerization result
| Embodiment | Catalyst activity (kgPP/gcat) | Polymkeric substance degree of isotacticity II (%) | Molecular weight distribution (Mw/Mn) |
| Embodiment 1 | 53.4 | 98.8 | 6.5 |
| Comparative Examples 1 | 56.0 | 98.4 | 5.6 |
| Comparative Examples 2 | 58.7 | 97.2 | 7.0 |
| Comparative Examples 3 | 57.0 | 97.5 | 6.8 |
| Comparative Examples 4 | 40.5 | 98.0 | 5.1 |
Can find out from table 1 result, adopt the MWD of the propene polymer that conventional internal electron donor catalyzer (Comparative Examples 4) obtains in single reactor narrower.
With the diol ester is internal electron donor catalyzer (Comparative Examples 2) can obtain wide molecular weight distribution in single reactor propene polymer, but the degree of isotacticity of polymkeric substance is lower.
Compound with diol ester/Witcizer 300 is internal electron donor; The weight ratio of controlling two kinds of electron donor compounds simultaneously within the specific limits; Shown quite high polymerization activity, and resulting polymkeric substance also have wider molecular weight distribution and higher degree of isotacticity.
Embodiment 2
The preparation of catalyst component: at 3m
3Reaction kettle in add 1.5m
3Titanium tetrachloride, under agitation add the spherical magnesium chloride alcohol adduct of 180kg (MgCl
22.6C
2H
5OH), be warming up to 120 ℃, in temperature-rise period, add 2,4-pentanediol dibenzoate 36kg, Witcizer 300 11.3kg kept elimination solution 1 hour under 120 ℃.Add 1.5m
3Titanium tetrachloride stirred 0.5 hour elimination solution down at 120 ℃.With 1.5 meters
3Hexane wash solids thing and under vacuum drying obtain ingredient of solid catalyst.In the catalyst component 2, the content of 4-pentanediol dibenzoate is 9.0wt%, and the content of Witcizer 300 is 4.0wt%.
Propylene polymerization: in one 120,000 tons/year monocycle pipe polymerization reactor, add continuously catalyst component (concentration is the 230g/L paste) and the triethyl aluminum of propylene and hydrogen, above-mentioned preparation and as the methylcyclohexyl dimethoxy silane (Al/Si=16) of external electron donor.The flow velocity of propylene is 17 tons/hr, and rate of catalyst flow is done corresponding adjustment, makes the density polymer in the reactor drum constant in 540g/L.Mean residence time is 1.1hr.
The test result such as the table 2 of polymkeric substance.
Comparative Examples 4
The preparation of catalyst component: except that not containing 2,4-pentanediol dibenzoate, the content of Witcizer 300 are that 12wt% is outer with embodiment 2.
Propylene polymerization: with embodiment 2.
The test result such as the table 2 of polymkeric substance.
Table 2 polymer properties
| Performance | Unit | Embodiment 2 | Comparative Examples 4 |
| Melting index | g/10min | 3.0 | 3.0 |
| Xylene soluble part | ％ | 1.9 | 2.9 |
| MWD polydispersity index (P.I.) | 4.8 | 3.9 |
| Tensile yield strength | MPa | 35.4 | 32.7 |
| Flexural strength | MPa | 49.1 | 42.3 |
| Bending elastic modulus | GPa | 1.7 | 1.4 |
Can find out that from test result the propene polymer of catalyzer of the present invention has wider molecular weight distribution and lower ultra-low molecular magnitude branch (lower xylene soluble part) and has the better physical processing characteristics.
Claims (8)
1. the preparation method of a broad molecular weight distribution polypropylene, this method is in the presence of catalyzer, in single reactor or in a plurality of tandem reactors, carries out the polyreaction of propylene, described catalyzer comprises the reaction product of following component:
(1) a kind of ingredient of solid catalyst, this ingredient of solid catalyst comprise magnesium, titanium, halogen and at least two kinds of electron donor a and b,
Wherein said electron donor a is selected from a kind of diol ester compound in the formula (I):
R in the formula
1-R
6Group is hydrogen identical or inequality, the C of straight or branched
1-C
20Alkyl;
Wherein the electron donor compound b is selected from monobasic or polyhydric aliphatic family carboxylicesters, monobasic or polynary aromatic carboxylic acid esters;
Wherein the weight ratio of electron donor compound a and electron donor compound b is 2～80;
(2) alkylaluminium cpd;
(3) randomly, the external electron donor component is selected from general formula (II) R
1 mSi (OR
2)
4-mSilicoorganic compound, 0≤m in the formula≤3, R
1And R
2Be of the same race or different alkyl, naphthenic base, aryl or haloalkyl, R
1Also can be halogen or Wasserstoffatoms.
2. the preparation method of broad molecular weight distribution polypropylene according to claim 1 is characterized in that, the weight ratio of described electron donor compound a and electron donor compound b is 2.5～8.
3. the preparation method of broad molecular weight distribution polypropylene according to claim 1 is characterized in that, described electron donor compound b is a phthalic ester.
4. the preparation method of broad molecular weight distribution polypropylene according to claim 1 is characterized in that, this catalyst component is at a kind of MgCl
2.nROH load has titanium compound and the described two kinds of reaction product of giving electric body compound a and b with at least one Ti-halogen bond on the adducts particle, and wherein n is 1.5～4; R is the alkyl of carbon number 1-4.
5. the preparation method of broad molecular weight distribution polypropylene according to claim 1; It is characterized in that; Ratio between described ingredient of solid catalyst (1), alkylaluminium cpd component (2) and the external electron donor component (3), with aluminium: titanium: the molar ratio computing between the silicon is 1: 1～1000: 2～200.
6. a kind of broad molecular weight distribution polypropylene that makes according to the said preparation method of arbitrary claim in the claim 1～5.
7. broad molecular weight distribution polypropylene according to claim 6; It is characterized in that its molecular weight distribution mw/mn is greater than 5.5, polydispersity index PI is greater than 4.5; Isotactic index is greater than 97.0%; Xylene soluble part (X.S) is less than 2.0%, and melting index is greater than 0.1g/10min, and melting index is to measure according to ASTMD1238-99.
8. alfon according to claim 7 is characterized in that, its molecular weight distribution mw/mn is 5.8～9.0, and melting index is 1.0g/10min～10g/10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102248684A CN101724111B (en) | 2008-10-24 | 2008-10-24 | Preparation method of polypropylene with wide molecular weight distribution and polymer thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102248684A CN101724111B (en) | 2008-10-24 | 2008-10-24 | Preparation method of polypropylene with wide molecular weight distribution and polymer thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101724111A CN101724111A (en) | 2010-06-09 |
| CN101724111B true CN101724111B (en) | 2012-02-01 |
Family
ID=42445719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102248684A Active CN101724111B (en) | 2008-10-24 | 2008-10-24 | Preparation method of polypropylene with wide molecular weight distribution and polymer thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101724111B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130131290A1 (en) * | 2010-08-05 | 2013-05-23 | Basell Poliolefine Italia, s.r.l. | Catalyst components for the polymerization of olefins |
| CN102399332B (en) * | 2010-09-16 | 2013-06-05 | 中国石油化工股份有限公司 | Propylene polymerization production technology by loop reactor batch liquid bulk method |
| EP2630170B1 (en) * | 2010-10-19 | 2015-04-22 | Basell Poliolefine Italia S.r.l. | Catalyst system for the polymerization of olefins |
| CN102453149B (en) * | 2010-10-21 | 2013-06-05 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method |
| CN102453147B (en) * | 2010-10-21 | 2013-06-05 | 中国石油化工股份有限公司 | Catalyst component, catalyst and method for olefin polymerization |
| CN102453173A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Resin for polypropylene biaxially oriented film and preparation method thereof |
| CN102453162B (en) * | 2010-10-22 | 2013-07-03 | 中国石油化工股份有限公司 | Catalyst component for polypropylene and catalyst |
| CN102464742A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Propylene polymer and preparation method thereof |
| EP2610274A1 (en) * | 2011-12-30 | 2013-07-03 | Borealis AG | Propylene random copolymer |
| CN104558289B (en) * | 2013-10-25 | 2017-09-29 | 中国石油化工股份有限公司 | Olefin polymerization catalysis and its application and polypropylene and its polymerization |
| CN112707979A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof, catalyst and application thereof |
| CN112625157B (en) * | 2020-12-17 | 2023-04-28 | 黄河三角洲京博化工研究院有限公司 | Catalyst for preparing ultra-pure polypropylene and preparation method for preparing ultra-pure polypropylene by batch bulk method |
| CN115785312B (en) * | 2022-11-15 | 2024-05-14 | 国家能源集团宁夏煤业有限责任公司 | Composite internal electron donor, catalyst and application thereof in dual-peak polypropylene synthesis |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0291958A2 (en) * | 1987-05-19 | 1988-11-23 | Union Carbide Corporation | Process for producing stereoregular polymers having a narrow molecular weight distribution |
| CN1266066A (en) * | 1999-03-08 | 2000-09-13 | 中国石油化工集团公司北京化工研究院 | Composite catalyst for preparing polypropylene with wide molecular weight distribution and its prepn |
| CN1597714A (en) * | 2003-09-18 | 2005-03-23 | 中国石油化工股份有限公司 | Method of producing olefine polymer and its polymer |
| CN1834115A (en) * | 2005-03-16 | 2006-09-20 | 中国石油化工股份有限公司 | Catalyst compsns. for olefin polymerization and its catalyst |
| CN101153062A (en) * | 2006-09-29 | 2008-04-02 | 中国石油化工股份有限公司 | Olefins polymerizing solid catalyst component, producing method and application of the same |
| US7388060B2 (en) * | 2006-01-04 | 2008-06-17 | China Petroleum & Chemical Corporation | Catalyst component for olefin (co)polymerization, preparation thereof, a catalyst comprising the same and use thereof |
-
2008
- 2008-10-24 CN CN2008102248684A patent/CN101724111B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0291958A2 (en) * | 1987-05-19 | 1988-11-23 | Union Carbide Corporation | Process for producing stereoregular polymers having a narrow molecular weight distribution |
| CN1266066A (en) * | 1999-03-08 | 2000-09-13 | 中国石油化工集团公司北京化工研究院 | Composite catalyst for preparing polypropylene with wide molecular weight distribution and its prepn |
| CN1597714A (en) * | 2003-09-18 | 2005-03-23 | 中国石油化工股份有限公司 | Method of producing olefine polymer and its polymer |
| CN1834115A (en) * | 2005-03-16 | 2006-09-20 | 中国石油化工股份有限公司 | Catalyst compsns. for olefin polymerization and its catalyst |
| US7388060B2 (en) * | 2006-01-04 | 2008-06-17 | China Petroleum & Chemical Corporation | Catalyst component for olefin (co)polymerization, preparation thereof, a catalyst comprising the same and use thereof |
| CN101153062A (en) * | 2006-09-29 | 2008-04-02 | 中国石油化工股份有限公司 | Olefins polymerizing solid catalyst component, producing method and application of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101724111A (en) | 2010-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101724111B (en) | Preparation method of polypropylene with wide molecular weight distribution and polymer thereof | |
| EP2610273B1 (en) | Catalyst component | |
| US10113021B2 (en) | Propylene random copolymer | |
| CN107629153B (en) | Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and application thereof | |
| CN104558282B (en) | Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application | |
| CN101993506B (en) | Preparation method of catalyst component for olefin polymerization and catalyst | |
| JP5554416B2 (en) | Method for producing solid catalyst for propylene polymerization | |
| US20070093378A1 (en) | Process for forming a Ziegler-Natta catalyst system having a controlled morphology | |
| CN101724102B (en) | Catalyst component for olefin polymerization and catalyst thereof | |
| CN102040690A (en) | Method for preparing polypropylene with low ash content | |
| CN101165073B (en) | Catalyst component used for olefin polymerization reaction and catalyst thereof | |
| CN102234338B (en) | Catalyst component for olefin polymerization and catalyst comprising same | |
| CN102234339B (en) | Catalyst components for olefin polymerization and preparation method thereof | |
| KR20170110077A (en) | Olefin-polymerization solid catalytic component, production method for olefin-polymerization catalyst, and production method for olefin polymer | |
| US20110034651A1 (en) | Mixed donor system for high melt flow and high activity | |
| CN104395354B (en) | Catalyst system for olefin polymerization | |
| CN101759816A (en) | Method for preparing a catalyst component for olefinic polymerization, and a catalyst component thereof | |
| CN102453173A (en) | Resin for polypropylene biaxially oriented film and preparation method thereof | |
| CN101050248B (en) | Process for the preparation of a catalyst component and component thus obtained | |
| WO2001004166A1 (en) | Process for producing polypropylene | |
| JPH03124705A (en) | Ziegler-natta catalyst composition | |
| CN109705241A (en) | The polymerization of spheric catalyst and spherical catalyst components and its preparation method and application and alkene | |
| CN102453162B (en) | Catalyst component for polypropylene and catalyst | |
| CN100491418C (en) | Preparing method of catalyst for slurry polymerization of ethylene | |
| CN105111357B (en) | Acrylic polymers and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Yuexiang Inventor after: Zhao Jin Inventor after: Peng Renqi Inventor after: Xia Xianzhi Inventor after: Wang Xinsheng Inventor after: Zhang Tianyi Inventor after: Gao Ping Inventor after: Qiao Suzhen Inventor after: Yin Maoping Inventor after: Li Weili Inventor after: Zhang Jigui Inventor before: Liu Yuexiang Inventor before: Zhao Jin Inventor before: Peng Renqi Inventor before: Xia Xianzhi Inventor before: Wang Xinsheng Inventor before: Zhang Tianyi Inventor before: Gao Ping Inventor before: Qiao Suzhen Inventor before: Yin Maoping Inventor before: Li Weili Inventor before: Zhang Jigui |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |