CN104031185A - Catalyst and polymerization method for preparing polypropylene with high melt index by hydrogen regulating method - Google Patents
Catalyst and polymerization method for preparing polypropylene with high melt index by hydrogen regulating method Download PDFInfo
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Abstract
The invention provides a catalyst and a polymerization method for preparing polypropylene with high melt index by a hydrogen regulating method. The catalytic system comprising a multi-element external electron donor comprises a solid catalytic component (A), aluminum alkyl (B) and the multi-element external electron donor (C), wherein the component (A) is magnesium chloride loaded Ti solid component and comprises a di-phthalate internal electron donor, the component (B) is trialkyl aluminum, the component (C) is a first-type external electron donor and a second-type external electron donor in a molar ratio of (1-70):(30-99); the first-type external electron donor is selected from dialkyl dimethoxy silanes, and the second-type external electron donor is selected from silanes with a structure as shown in the specification, wherein R1 is alkyl with C1-C8, naphthenic base or alkoxy with C1-C3, and R2 is alkyl with C1-C3. In the presence of hydrogen, the melt index of polypropylene can be regulated in a range of 10-250g/10min under high catalytic activity by controlling the proportion of the silane type external electron donors and the hydrogenation rate.
Description
Technical field
The present invention relates to hydrogen adjusts legal system for the polyacrylic catalyzer of high fusion index and polymerization process.Particularly, relate to the catalyst system that contains polynary external electron donor, and under catalyst system, prepare the polyacrylic polymerization process of high fusion index.
Background technology
Polypropylene cost performance is high, is widely used.The production technique such as polypropylene can be used for injection moulding, extrudes, blowing, in injection moulding and expressing technique, in order to improve working (machining) efficiency and the large-scale Injection moulded part of preparation, conventionally need to improve polyacrylic melting index and meet processing request.Generally, propylene polymerization adopts MgCl
2the Ziegler-Natta catalyst preparation of load, when propylene polymerization, add hydrogen as molecular weight regulator, hydrogen can reduce polyacrylic molecular weight, increases polyacrylic melting index, yet, after amounts of hydrogen increases to a certain degree, the degree that melting index increases reduces, and catalytic activity declines, and affects catalytic efficiency, therefore, the add-on of hydrogen is subject to the restriction of polymerization technique.At present, on full scale plant, in order to obtain high fusion index polypropylene, conventionally, after polypropylene is produced, add a certain amount of superoxide to impel degradation of polypropylene to increase polyacrylic melting index.High fusion index polypropylene color prepared by the method is easily turned to be yellow, and with certain smell, affects the outward appearance of polypropylene articles.
At present, the catalyzer that industrial production polypropylene is used is mainly the MgCl that contains diester internal electron donor
2supported Z-N catalyst, such catalyzer need to be equipped with external electron donor when polymerization.The Main Function of external electron donor is to regulate polyacrylic degree of isotacticity and the susceptibility of catalyzer to hydrogen, and the copolymerization performance of catalyst activity, polyacrylic apparent density and propylene and ethene etc. is also had to impact to a certain degree.The external electron donor using is now mainly the silicane electron donor that contains 1 to 4 alkoxyl group, and the most frequently used is dialkyl group dimethoxy silane.The structure of external electron donor is different, and the hydrogen susceptibility of polyacrylic degree of isotacticity, catalyzer and activity are had to different impacts.According to different demands, can select different external electron donors to produce the polypropylene product of the different trades mark.
US5652303 and US5844046 report, can the polyacrylic molecular weight distribution of moderate adjusting and melting index by dialkoxy silicane and trialkoxy silane combination.Diether and siloxanes combination also can reach the object (US5869418) of regulation and control polypropylene degree of isotacticity, molecular weight distribution and MFR, but its effect is not so good as the obvious of two kinds of silane combinations.US6087459, by dicyclo amyl group dimethoxy silane and propyl-triethoxysilicane combination, can regulate and control polyacrylic melting index (MFR) in very wide scope, particularly can obtain the polypropylene of high MFR.The polypropylene degree of isotacticity that tetraethoxysilane produces is low, but there is high melting index, PP prepared by dicyclo amyl group dimethoxy silane has high degree of isotacticity and low melting index, Exxson company (US6111039) is in two sections of polymerizations, first paragraph is used tetraethoxysilane as electron donor, second segment is used tetraethoxysilane/dicyclo amyl group dimethoxy silane mixture electron donor, has obtained that rigidity is high, the PP of medium molecular weight distributions and medium melting index.US71832342006 report, by the combination of two Decahydroisoquinolinpreparation dimethoxy silane/propyl-triethoxysilicane, can regulate and control polyacrylic MFR and molecular weight distribution in wider scope.Chinese patent CN99805994.3 has reported that the combination of use dicyclo amyl group dimethoxy silane and propyl-triethoxysilicane prepares impact polypropylene.
In CN102225975A patent, disclosing a kind of same use hydrogen adjusts legal system for the polyacrylic catalyst system of high Rong Rong index, wherein first kind external electron donor is selected from dialkyl group dimethoxy silicon, 9,9-bis-(methoxyl methyl) fluorenes or 2,2-diisobutyl-1,3-Propanal dimethyl acetal and composition thereof, Equations of The Second Kind external electron donor is selected from 3-halogen propyl trimethoxy silicon or 3-halogen propyl triethoxy alkane and composition thereof, and the molar ratio of first kind external electron donor and Equations of The Second Kind external electron donor is 2.5-15: 85-97.5.The first kind tyre electron of this disclosure of the invention and Equations of The Second Kind tyre electron can be prepared the polypropylene of high fusion index, and the alignment degree in prepared result is also high than conventional art.But exist, electron composition is comparatively complicated in addition, and the shortcomings such as the more difficult control of chemical reaction, although its regularity is higher than conventional catalyst system, also do not reach more excellent effect.
Utilize combination external electron donor to coordinate with the Ziegler-Natta catalyst that contains diester, can prepare the polypropylene of high fusion index.
Summary of the invention
This patent is to provide the combination of better external electron donor, with the efficiency system of higher catalytic activity and Geng Gao for high fusion index polypropylene.
The invention provides and use MgCl
2the TiCl of load
4type Ziegler-Natta catalyst solid ingredient, and the catalyst system of aluminum alkyls and multielement silicon alkanes external electron donor composition, and the hydrogen carrying out under this catalyst system is adjusted method polymerization process.It is achieved through the following technical solutions:
A catalyst system that contains polynary external electron donor, comprises solid catalytic component (A), aluminum alkyls (B) and polynary external electron donor (C), wherein
The Ti solid ingredient that component (A) is magnesium chloride load, and contain Bisphthalate internal electron donor;
Component (B) is trialkylaluminium;
Component (C) comprises first kind external electron donor and Equations of The Second Kind external electron donor, and the molar ratio of first kind external electron donor and Equations of The Second Kind external electron donor is 1-70 30-99; Wherein said first kind external electron donor is selected from dialkyl group dimethoxy silicon; Equations of The Second Kind external electron donor is selected from the silane of structure as follows:
R wherein
1for C1-C8 alkyl, the alkoxyl group of cycloalkyl or C1-C3, the alkyl that R2 is C1-C3.
Component (A), (B) and (C) in, Al/Ti mol ratio is 10-1000, preferably 40-800, more selects 60-600; C/Ti mol ratio is 2-50, preferably 5-30.
Wherein the molar ratio of the first kind external electron donor in component (C) and Equations of The Second Kind external electron donor is 2.5-50:50-97.5.First kind external electron donor in preferred ingredient (C) and the molar ratio of Equations of The Second Kind external electron donor are 2.5-15 85-97.5.
Wherein the Bisphthalate internal electron donor in component (A) is selected from diisobutyl phthalate, n-butyl phthalate or n-propyl phthalate and composition thereof.
Wherein in component (B), trialkylaluminium is selected from triethyl aluminum or triisobutyl aluminium.
Wherein the dialkyl group dimethoxy silicon in component (C) is selected from cyclohexyl methyl dimethoxy silicon, diisopropyl dimethoxy silane, diisobutyl dimethoxy silicon, dicyclopentyl dimethoxyl silicon, isopropyl butyl dimethoxy silicon, one or more in isobutyl-cyclohexyl dimethoxy silicon.
R wherein
1be selected in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, cyclopentyl, cyclohexyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy; R
2be selected from methoxyl group, oxyethyl group, positive propoxy, isopropoxy.
According to technical scheme of the present invention, also comprise the polyacrylic method of preparation, it is specifically achieved by the following scheme:
Prepare the polyacrylic method of high fusion index, it is characterized in that adopting above-mentioned catalyst system.
According to technical scheme of the present invention, this preparation method comprises that use is as the catalyst system of claim 1-9 any one, and under hydrogen exists, the polypropylene of high fusion index is prepared in catalyzing propone polymerization.Preferably propylene polymerization in propylene body, carry out or gas-phase propene in carry out.
The polyacrylic melting index of described high fusion index is between 10-250 g/10min.
According to technical scheme of the present invention, use said components (A) and (B) any in two kinds of catalyzer, under hydrogen existence, catalyzing propone polymerization can be prepared the polypropylene of high fusion index.With preparation the polyacrylic melting index of high fusion index between 10-250 g/10min.Propylene polymerization in propylene body, carry out or gas-phase propene in carry out.
The component of above-mentioned catalyst system (A) comprises MgCl
2, TiCl
4with a kind of diester internal electron donor.This solid ingredient can be taked several different methods preparation, and as Chinese patent CN 00109216.2, CN 02122750.0, CN 02136543.1, CN 200310101833.9, CN 200380106197.X, and CN 200410017269.7, CN 87101423, CN 90104123.8, and CN 93102795.0, and CN 94102813.5, CN 94103454, the method described in CN 97112005.6.
The first kind in catalyst component (C) is during separately as external electron donor, there is high isotactic directional property and low hydrogen response, Equations of The Second Kind in catalyst component (C) during separately as external electron donor, generally has low isotactic directional property and high hydrogen response.The effect of an external electron donor part is and aluminum alkyls complexing, reduce the reducing power of aluminum alkyls, another part is and the complexing of Ziegler-Natta catalyst active centre that the inhibition poor active centre of isotactic directional property, further improves the isotactic directional property in the active centre that isotactic directional property is high.Different electron donors are different with the action intensity in Ziegler-Natta catalyst active centre.The first kind of component (C) can alternative compositions (C) Equations of The Second Kind in the complexing in active centre.During by the first kind in component (C) and Equations of The Second Kind mixing use, when the content of the first kind is less than 2.5 % by mole, the isotactic directional property of catalyzer is poor, during the too high levels of the first kind, identical when mixing the hydrogen regulation performance of electron donor and using the first kind separately, can not obtain height and melt finger polypropylene.The first kind of component (C) and Equations of The Second Kind, under suitable ratio, can effectively strengthen the hydrogen regulation performance of catalyzer, prepare high isotactic, height melts finger polypropylene.
Testing method
Polyacrylic degree of isotacticity is used heptane extracting to send out mensuration, and 2g left and right polypropylene, as in Soxhlet extractor, with boiling heptane extracting 6 hours, is dried to constant weight by residual polymer, take residual polymer and add for the first time polymer ratio as degree of isotacticity.
Polyacrylic melting index is measured according to testing standard ASTM D1238, and experiment condition is 2.16Kg, 230 ℃.
Embodiment
Below in conjunction with embodiment, the present invention is described further.It should be noted that, following embodiment can not be as limiting the scope of the invention, and any improvement of making on basis of the present invention is all without prejudice to spirit of the present invention.
Embodiment 1:
The heating of 5L autoclave is vacuumized, and excluding air and water, with nitrogen replacement, three times repeatedly, then add MgCl
2the TiCl of load
4catalyst solid constituent 20 mg, in solid ingredient, the content of Ti is 2.36 wt%, triethyl aluminum add-on is Al/Ti(mole)=600, isobutyl-sec.-propyl dimethoxy silane (IBIPDMS), trimethyl silicon based triethoxyl silane, the mol ratio of the two is 5:95, two kinds of total add-ons of silane are calculated as Si/Ti(mole by silicon)=20, then add 94 mmol hydrogen and 1.2 kilograms of propylene, hydrogen and propylene mol ratio are 2.94 mmol/mol.Off-response still, by still temperature rise to 70 ℃, starts polymerization, after reaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES 820g, and catalytic activity is 41 KgPP/g catalyzer, and polyacrylic melting index is 12 gPP/10min, and degree of isotacticity is 98.5%.
Embodiment 2:
The heating of 5L autoclave is vacuumized, and excluding air and water, with nitrogen replacement, three times repeatedly, then add MgCl
2the TiCl of load
4catalyst solid constituent 20 mg, in solid ingredient, the content of Ti is 2.36 wt%, triethyl aluminum add-on is Al/Ti(mole)=300, isobutyl-cyclohexyl dimethoxy silane (IBCHDMS), trimethyl silicon based triethoxyl silane, the mol ratio of the two is 5:95, two kinds of total add-ons of silane are calculated as Si/Ti(mole by silicon)=20, then add 94 mmol hydrogen and 1.2 kilograms of propylene, hydrogen and propylene mol ratio are 2.94 mmol/mol.Off-response still, by still temperature rise to 70 ℃, starts polymerization, after reaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES 810g, and catalytic activity is 40.5 KgPP/g catalyzer, and polyacrylic melting index is 16 gPP/10min, and degree of isotacticity is 98.2%.
Embodiment 3:
The heating of 5L autoclave is vacuumized, and excluding air and water, with nitrogen replacement, three times repeatedly, then add MgCl
2the TiCl of load
4catalyst solid constituent 20 mg, in solid ingredient, the content of Ti is 2.36 wt%, triethyl aluminum add-on is Al/Ti(mole)=600, dicyclopentyl dimethoxyl silane, trimethyl silicon based triethoxyl silane, the mol ratio of the two is 2.5:97.5, two kinds of total add-ons of silane are calculated as Si/Ti(mole by silicon)=15, then add 94 mmol hydrogen and 1.2 kilograms of propylene, hydrogen and propylene mol ratio are 2.94 mmol/mol.Off-response still, by still temperature rise to 70 ℃, starts polymerization, after reaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES 840g, and catalytic activity is 42 KgPP/g catalyzer, and polyacrylic melting index is 19 gPP/10min, and degree of isotacticity is 98.3%.
Embodiment 4:
The heating of 5L autoclave is vacuumized, and excluding air and water, with nitrogen replacement, three times repeatedly, then add MgCl
2the TiCl of load
4catalyst solid constituent 20 mg, in solid ingredient, the content of Ti is 2.36 wt%, triethyl aluminum add-on is Al/Ti(mole)=600, diisobutyl dimethoxy silicon, trimethyl silicon based triethoxyl silane, the mol ratio of the two is 2.5:97.5, two kinds of total add-ons of silane are calculated as Si/Ti(mole by silicon)=20, then add 94 mmol hydrogen and 1.2 kilograms of propylene, hydrogen and propylene mol ratio are 2.94 mmol/mol.Off-response still, by still temperature rise to 70 ℃, starts polymerization, after reaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES 830g, and catalytic activity is 41.5 KgPP/g catalyzer, and polyacrylic melting index is 25 gPP/10min, and degree of isotacticity is 97.9%.
Comparative example 1:
The heating of 5L autoclave is vacuumized, and excluding air and water, with nitrogen replacement, three times repeatedly, then add MgCl
2the TiCl of load
4catalyst solid constituent 20 mg, in solid ingredient, the content of Ti is 2.36 wt%, triethyl aluminum add-on is Al/Ti(mole)=600, diisobutyl dimethoxy silicon, add-on is calculated as Si/Ti(mole by silicon)=20, then add 94 mmol hydrogen and 1.2 kilograms of propylene, hydrogen and propylene mol ratio are 2.94 mmol/mol.Off-response still, by still temperature rise to 70 ℃, starts polymerization, after reaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES 840g, and catalytic activity is 42 KgPP/g catalyzer, and polyacrylic melting index is 3.1 gPP/10min, and degree of isotacticity is 98.9%.
Embodiment 5
The heating of 5L autoclave is vacuumized, and excluding air and water, with nitrogen replacement, three times repeatedly, then add MgCl
2the TiCl of load
4catalyst solid constituent 20 mg, in solid ingredient, the content of Ti is 2.36 wt%, triethyl aluminum add-on is Al/Ti(mole)=600, diisopropyl dimethoxy silane, trimethyl silicon based Trimethoxy silane, the mol ratio of the two is 5:95, two kinds of total add-ons of silane are calculated as Si/Ti(mole by silicon)=20, then add 205 mmol hydrogen and 1.2 kilograms of propylene, hydrogen and propylene mol ratio are 6.83 mmol/mol.Off-response still, by still temperature rise to 70 ℃, starts polymerization, after reaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES 810g, and catalytic activity is 40.5 KgPP/g catalyzer, and polyacrylic melting index is 60.4 gPP/10min, and degree of isotacticity is 98.4%.
Embodiment 6:
The heating of 5L autoclave is vacuumized, and excluding air and water, with nitrogen replacement, three times repeatedly, then add MgCl
2the TiCl of load
4catalyst solid constituent 20 mg, in solid ingredient, the content of Ti is 2.36 wt%, triethyl aluminum add-on is Al/Ti(mole)=400, diisopropyl dimethoxy silane, trimethyl silicon based methyl dimethoxysilane, the mol ratio of the two is 5:95, two kinds of total add-ons of silane are calculated as Si/Ti(mole by silicon)=20, then add 205 mmol hydrogen and 1.2 kilograms of propylene, hydrogen and propylene mol ratio are 6.83 mmol/mol.Off-response still, by still temperature rise to 70 ℃, starts polymerization, after reaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES 840g, and catalytic activity is 42 KgPP/g catalyzer, and polyacrylic melting index is 13 gPP/10min, and degree of isotacticity is 99.0%.
Comparative example 2:
The heating of 5L autoclave is vacuumized, and excluding air and water, with nitrogen replacement, three times repeatedly, then add MgCl
2the TiCl of load
4catalyst solid constituent 20 mg, in solid ingredient, the content of Ti is 2.36 wt%, triethyl aluminum add-on is Al/Ti(mole)=600, trimethyl silicon based triethoxyl silane, add-on is calculated as Si/Ti(mole by silicon)=20, then add 205mmol hydrogen and 1.2 kilograms of propylene, hydrogen and propylene mol ratio are 6.83 mmol/mol.Off-response still, by still temperature rise to 70 ℃, starts polymerization, after reaction 2h, discharges unreacting propylene, obtains polypropylene GRANULES 540g, and catalytic activity is 27 KgPP/g catalyzer, and polyacrylic melting index is 260 gPP/10min, and degree of isotacticity is 93.5%.
Claims (9)
1. a catalyst system that contains polynary external electron donor, comprises solid catalytic component (A), and aluminum alkyls (B) and polynary external electron donor (C), is characterized in that, wherein:
The Ti solid ingredient that component (A) is magnesium chloride load, and contain Bisphthalate internal electron donor;
Component (B) is trialkylaluminium;
Component (C) comprises first kind external electron donor and Equations of The Second Kind external electron donor, and the molar ratio of first kind external electron donor and Equations of The Second Kind external electron donor is 1-70 30-99; Wherein said first kind external electron donor is selected from dialkyl group dimethoxy silicon; Equations of The Second Kind external electron donor is selected from the silane of structure as follows:
R wherein
1for C1-C8 alkyl, the alkoxyl group of cycloalkyl or C1-C3, the alkyl that R2 is C1-C3.
2. according to the catalyst system of claim 1, it is characterized in that, wherein the molar ratio of the first kind external electron donor in component (C) and Equations of The Second Kind external electron donor is 2.5-50:50-97.5; First kind external electron donor in preferred ingredient (C) and the molar ratio of Equations of The Second Kind external electron donor are 2.5-15 85-97.5.
3. according to the catalyst system of claim 1-3 any one, it is characterized in that, wherein the Bisphthalate internal electron donor in component (A) is selected from diisobutyl phthalate, n-butyl phthalate or n-propyl phthalate and composition thereof.
4. according to the catalyst system of claim 1-3 any one, it is characterized in that, wherein in component (B), trialkylaluminium is selected from triethyl aluminum or triisobutyl aluminium.
5. according to the catalyst system of claim 1-4 any one, it is characterized in that, wherein the dialkyl group dimethoxy silicon in component (C) is selected from cyclohexyl methyl dimethoxy silicon, diisopropyl dimethoxy silane, diisobutyl dimethoxy silicon, dicyclopentyl dimethoxyl silicon, isopropyl butyl dimethoxy silicon, one or more in isobutyl-cyclohexyl dimethoxy silicon.
6. according to the catalyst system of claim 1-5 any one, it is characterized in that the R in wherein said Equations of The Second Kind tyre electron silane structure
1be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, cyclopentyl, cyclohexyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy; R
2be selected from methoxyl group, oxyethyl group, positive propoxy, isopropoxy.
7. prepare a polyacrylic method, it is characterized in that adopting the catalyst system described in claim 1-6 any one.
8. according to claim 7 a kind of, prepare polyacrylic method, it is characterized in that, use as the catalyst system of claim 1-7 any one, under hydrogen existence, the polypropylene of high fusion index is prepared in catalyzing propone polymerization.
9. according to Claim 8 a kind of prepares polyacrylic method, it is characterized in that the described polyacrylic melting index of high fusion index is between 10-250 g/10min; Preferably propylene polymerization in propylene body, carry out or gas-phase propene in carry out.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574340A (en) * | 2019-09-29 | 2021-03-30 | 中国石油天然气股份有限公司 | Preparation method of polyethylene with high melt index |
| CN112625157A (en) * | 2020-12-17 | 2021-04-09 | 黄河三角洲京博化工研究院有限公司 | Catalyst for preparing ultrapure polypropylene and preparation method for preparing ultrapure polypropylene by batch bulk method |
| CN116003656A (en) * | 2022-12-29 | 2023-04-25 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
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| JPH06136029A (en) * | 1991-09-11 | 1994-05-17 | Tonen Corp | Production of propylene-ethylene block copolymer |
| CN102225975A (en) * | 2011-04-19 | 2011-10-26 | 中国科学院化学研究所 | Catalyst and polymerization method for preparing high MFR polypropylene with hydrogen regulation method |
| CN103819599A (en) * | 2012-11-16 | 2014-05-28 | 中国石油天然气股份有限公司 | Polypropylene resin for high-performance film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH06136029A (en) * | 1991-09-11 | 1994-05-17 | Tonen Corp | Production of propylene-ethylene block copolymer |
| CN102225975A (en) * | 2011-04-19 | 2011-10-26 | 中国科学院化学研究所 | Catalyst and polymerization method for preparing high MFR polypropylene with hydrogen regulation method |
| CN103819599A (en) * | 2012-11-16 | 2014-05-28 | 中国石油天然气股份有限公司 | Polypropylene resin for high-performance film and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574340A (en) * | 2019-09-29 | 2021-03-30 | 中国石油天然气股份有限公司 | Preparation method of polyethylene with high melt index |
| CN112625157A (en) * | 2020-12-17 | 2021-04-09 | 黄河三角洲京博化工研究院有限公司 | Catalyst for preparing ultrapure polypropylene and preparation method for preparing ultrapure polypropylene by batch bulk method |
| CN116003656A (en) * | 2022-12-29 | 2023-04-25 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
| CN116003656B (en) * | 2022-12-29 | 2024-04-26 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
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Application publication date: 20140910 |