CN108409896B - Ziegler-natta catalyst compositions and uses thereof - Google Patents
Ziegler-natta catalyst compositions and uses thereof Download PDFInfo
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- CN108409896B CN108409896B CN201810296059.8A CN201810296059A CN108409896B CN 108409896 B CN108409896 B CN 108409896B CN 201810296059 A CN201810296059 A CN 201810296059A CN 108409896 B CN108409896 B CN 108409896B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
The invention provides a Ziegler-Natta catalyst composition and application thereof. The Ziegler-Natta catalyst composition provided by the invention comprises a main catalyst component, a cocatalyst component and an external electron donor component, wherein the main catalyst component comprises a titanium-containing compound, an ester or ether internal electron donor compound and a magnesium chloride carrier, the cocatalyst component comprises alkyl aluminum, the external electron donor component comprises a first external electron donor and a second external electron donor, the first external electron donor is an alkoxysilane stereo-structure selective control agent, and the second external electron donor is an unsaturated aliphatic ester high-temperature activity inhibitor. The invention also provides the application of the Ziegler-Natta catalyst composition in the homopolymerization polymerization reaction of propylene and the copolymerization polymerization reaction of propylene and at least one copolymerizable monomer. The catalyst composition can effectively reduce the activity of a high-temperature polymerization process and ensure the stable reaction.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a polyolefin catalyst composition with a high-temperature activity inhibiting effect in an olefin polymerization process and an olefin polymerization catalyst composition.
Background
The catalysts used in the polyolefin industry at present are mainly MgCl2 supported Ziegler-Natta (Z-N) catalysts containing diester or diether internal electron donors (Z-N catalysts for short), and the catalysts are used in combination with an alkylaluminum cocatalyst and a stereoselective control agent external electron donor component. Particularly, polymers with higher yield and higher isotacticity can be obtained in the polymerization of alpha-olefin with 3 or more carbon atoms, wherein the internal and external electron donor compounds are one of the essential components in the catalyst components, and the combination of the internal and external electron donors develops different coordination systems as the polyolefin catalyst is continuously updated. At present, a large number of electron donor compounds have been disclosed, such as mono-or polycarboxylic esters of internal electron donors, ketones, mono-or polyethers, amines and the like and their derivatives, and alkoxy siloxane compounds of external electron donors. The independent alkoxy silane external electron donor is matched with the existing solid catalyst, is applied to catalyzing propylene polymerization, can have higher activity and orientation capability, and in a gas phase reaction process, the stability of the polymerization reaction is mainly influenced by a large amount of heat release in the polymerization process, so that the reaction heat energy is removed in time or the risk of caking of a reaction kettle can be effectively reduced in the high-temperature reaction heat release process. Patent CN1856514B of Dow's sphere-of-Ring technology, Inc. discloses a Z-N catalyst system containing myristate compound as activity limiting agent, which has the function of controlling the exothermic process of high-temperature reaction in a polymerization kettle, but has large dosage and large influence on the activity of low-temperature polymerization (conventional polymerization temperature: 67-70 ℃). The invention develops a Z-N catalyst composition with stronger inhibition efficiency of high-temperature reaction activity and better low-temperature activity.
Disclosure of Invention
An object of the present invention is to provide a Z-N catalyst composition having a strong inhibitory effect on high-temperature activity and its use in propylene polymerization.
In order to achieve the above purpose, on one hand, the invention provides the following technical scheme:
a Ziegler-Natta catalyst composition comprises a main catalyst component, a cocatalyst component and an external electron donor component, wherein the main catalyst component comprises a titanium-containing compound, an ester or ether internal electron donor compound and a magnesium chloride carrier, the cocatalyst component comprises alkyl aluminum, the external electron donor component comprises a first external electron donor and a second external electron donor, the first external electron donor is an alkoxysilane stereo-selective control agent, and the second external electron donor is an unsaturated aliphatic ester high-temperature activity inhibitor.
Preferably, wherein the first type of external electron donor comprises one or more selected from the group consisting of methylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, and tetraethoxysilane; the mole percentage content of the first type in the external electron donor component is 1-99%.
Optionally, wherein the second type of external electron donor component comprises allyl acrylate, 3-butenoate, 3-pentenoate, 5-hexenoate-3-butenoate, 6-heptenoic-3-butenoate, 7-octenoic-4-pentenoate, 8-nonenoic-5-hexenoate, 9-decenoic-9-decenyl ester, 10-undecenoate-propenyl ester, 11-dodecenoic-2-butenoate, 11-dodecenoic-3-butenoate, 5-tridecenoic-4-octenyl ester, 13-tetradecenoic-4-hexenoate, 14-pentadecenyl-14-pentadecenyl ester, 15-hexadecenoic-15-hexadecenyl ester, hexadecenoic acid-4-hexenoate, 16-heptadecene-16-heptadecene ester, benzoic acid-allyl ester, 6-phenylhexenoic acid-allyl ester, 12-phenyldodecene-6 phenylhexenoic acid-allyl ester, 6-naphthylhexenoic acid-allyl ester, hexyl acrylate and 5-heptenoic acid phenethyl ester.
Preferably, wherein the titanium-containing compound is TiCl 4.
Preferably, wherein said cocatalyst is triethylaluminum.
Optionally, in the catalyst composition, the molar ratio of the aluminum element in the cocatalyst to the titanium element in the main catalyst is 10: 1-500: 1, preferably 10: 1-200: 1.
Preferably, in the internal electron donor compound, the ester compound is selected from one or more of ethyl benzoate, diisobutyl phthalate, di-n-butyl phthalate, diisobutyl 2, 3-diisopropylsuccinate and 2, 4-pentanediol ester; the ether internal electron donor compound is 9, 9-bis (hydroxymethyl) fluorene.
Preferably, in the catalyst composition, the internal electron donor compound accounts for 6 wt% to 15 wt% of the main catalyst.
Optionally, in the catalyst composition, a molar ratio of the first external electron donor to the titanium element in the main catalyst is 1:1 to 1000: 1.
Preferably, the molar ratio of the first external electron donor to the titanium element in the main catalyst is 10:1-100: 1.
In the external electron donor components of the catalyst composition, the first external electron donor is mainly matched with the main catalyst component to have the functions of adjusting and controlling the polypropylene isotacticity and hydrogen regulation sensitivity, and the second external electron donor can inhibit high-temperature reaction in the propylene gas-phase polymerization process so as to reduce the occurrence of high-temperature polymerization in a polymerization kettle.
In another aspect, the present invention provides an olefin polymerization process comprising: olefins are contacted with the Z-N catalyst composition having high temperature activity inhibition described herein in a polymerization reactor under polymerization conditions.
On the other hand, the invention provides the following technical scheme:
preferably, the homopolymerization or copolymerization of olefins is homopolymerization of propylene or copolymerization of propylene with other olefin monomers.
More preferably, the homopolymerization or copolymerization is a gas phase, bulk or slurry polymerization.
To better illustrate the efficacy of the present invention, a concentration variation factor is used to calculate the "normalized activity", which is defined as the activity at temperature T multiplied by a concentration correction factor, where P (67) is the propylene concentration at 67 ℃ and P (T) is the propylene concentration at temperature T. The normalized activity equation is:
the concentration correction factor for propylene was: 67 ℃ (correction factor of 1), 90 ℃ (correction factor of 1.67), 100 ℃ (correction factor of 1.93), 110 ℃ (correction factor of 2.16), 120 ℃ (correction factor of 2.57).
The normalized activity ratio AT/A67, calculated by calculating the normalized activity AT AT the temperature T, can be taken as an indication of the variation of the activity with temperature, and it has been found that, in the liquid phase polymerization of propylene, when the temperature reaches 100 ℃, the normalized activity ratio A100/A67 is less than or equal to 0.35, indicating that the catalytic system has self-extinguishing properties, meaning that the external electron donor has a high temperature activity inhibiting effect.
The inventor unexpectedly finds that the normalized activity ratio A100/A67 of the catalyst composition containing the unsaturated aliphatic ester compound as the external electron donor is within the range of 0.15-0.26, is obviously smaller than the normalized activity ratio A100/A67 of the catalyst composition adopting other monoesters as the external electron donor, and can ensure that the low-temperature activity of the polymerization reaction is higher when the unsaturated aliphatic ester is adopted. This indicates that the catalyst composition of the present invention has a stronger high-temperature activity inhibition effect and does not affect the low-temperature reaction activity. The experimental process further proves that compared with the catalyst composition adopting other monoesters as external electron donors, the catalyst composition containing unsaturated aliphatic ester as external electron donors can effectively control the exothermic process of high-temperature reaction in a polymerization kettle, and ensure the stable reaction.
The procatalyst of the present invention may be prepared by conventional methods known in the art. Preferably, the carrier of the main catalyst is a porous magnesium chloride carrier, the main catalyst can be prepared by reacting an magnesium ethoxide carrier or an ethanol-magnesium chloride carrier with titanium tetrachloride, and can also be prepared by using a recrystallization method of an alcohol compound of magnesium chloride-alcohol in titanium tetrachloride. The method for producing the main catalyst is not limited to the above two methods. For example, the main catalyst of the present invention can be obtained by the catalyst preparation method provided in patent application CN1320644A or patent application CN 1453298A.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
The following examples are set forth to better illustrate the present invention and are not intended to limit the same.
The test method comprises the following steps:
1. the isotacticity of polypropylene is determined by using a heptane extraction method, 3-5g of polypropylene is placed in a Soxhlet extractor, extracted with boiling heptane for 6 hours, the remaining polymer is dried to constant weight, and the ratio of the weight of the polypropylene after extraction to the weight of the polypropylene before extraction is weighed and calculated, namely the isotacticity of the polypropylene resin.
2. The melt flow index (MFR) of the product was determined according to the test standard ASTM D1238 under the experimental conditions 2.16Kg, 230 ℃.
Examples 1 to 16
Heating and vacuumizing a 5L high-pressure reaction kettle, replacing 3 times by nitrogen, and then adding a TiCl4 main catalyst component loaded by MgCl2 with the internal electron donor being diisobutyl phthalate, wherein the content of Ti element in the main catalyst is 2.5 wt% based on the weight of the main catalyst, and the content of the internal electron donor being diisobutyl phthalate is 8.6 wt% based on the weight of the main catalyst. The cocatalyst and the external electron donor are added in sequence, a small amount of hydrogen and 1200g of propylene are added, and the molar ratio of the hydrogen to the propylene is 0.004/1. And (3) rapidly heating the kettle to 67 ℃, starting polymerization, discharging unreacted propylene after 1h of reaction, taking out a product, and weighing and testing, wherein the specific experimental conditions are shown in table 1, and the polymerization results are shown in table 2.
Comparative examples 1 to 10
The polymerization process is the same as that in example 1, except that the types of the added external electron donor and internal electron donor, the molar ratio between the first type of external electron donor and the second type of external electron donor, the weight percentage of the internal electron donor in the main catalyst, the molar ratio of the aluminum element in the cocatalyst to the titanium element in the main catalyst, the molar ratio of the second type of external electron donor to the titanium element in the main catalyst, and the polymerization temperature are changed, the specific experimental conditions are shown in table 1, and the polymerization results are shown in table 2.
TABLE 1 kinds of external electron donors and internal electron donors and polymerization temperatures employed in examples 1 to 16 and comparative examples 1 to 10
TABLE 2 polymerization results of examples 1 to 16 and comparative examples 1 to 10
In actual production, when the activity value at low temperature (67 ℃) is lower than 30KgPP/g, the polymerization activity is lower, the reaction is slow, the production yield is influenced, meanwhile, when the normalized activity ratio A100/A67 is lower than 0.35, the high-temperature reaction in the polymerization process is inhibited, and the lower the normalized activity ratio A100/A67 is, the better the activity inhibition of the first type of external electron donor is, so that the fluctuation of the reaction is avoided, and the production stability is ensured.
As can be seen from the experimental results in Table 1-2, the type and amount of the second type of external electron donor has a large influence on the polymerization activity,
through examples 1-16 (containing the second type of external electron donor) and comparative examples 9-10 (not containing the second type of external electron donor), it can be found that the addition of the second type of external electron donor component has a slight influence on the low-temperature polymerization activity of the catalyst, but has a significant inhibition effect on the high-temperature polymerization activity.
As shown by the polymerization experimental results of the examples 1-2 and the comparative examples 1-2, the examples 3-4 and the comparative examples 3-4, and the examples 5-16 and the comparative examples 7-8, the addition of the olefine acid alkene ester external electron donor can ensure the low-temperature (67 ℃) polymerization activity of the catalyst and obtain a better high-temperature activity inhibition function, and the ratio of A100/A67 is obviously lower than isopropyl myristate, which indicates the activity inhibition function of the olefine acid alkene ester compound.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. A Ziegler-Natta catalyst composition comprises a main catalyst component, a cocatalyst component and an external electron donor component, wherein the main catalyst component comprises a titanium-containing compound, an ester or ether internal electron donor compound and a magnesium chloride carrier, the cocatalyst component comprises alkyl aluminum, the external electron donor component consists of a first external electron donor and a second external electron donor, the first external electron donor is an alkoxysilane stereoselective control agent, and the second external electron donor is a high-temperature activity inhibitor and is selected from acrylic ester, 3-butenoate, 3-pentenoate, 5-hexenoic acid-3-butenoate, 6-heptenoic acid-3-butenoate, 7-octenoic acid-4-pentenoate, 8-nonenoic acid-5-hexenoate, 9-decenoic acid-9-decenyl ester, 10-undecenoic acid-propenyl ester, 11-dodecenoic acid-2-butenyl ester, 11-dodecenoic acid-3-butenyl ester, 5-tridecenoic acid-4-octenyl ester, 13-tetradecenoic acid-4-hexenyl ester, 14-pentadecenyl ester, 15-hexadecenoic acid-15-hexadecenyl ester, and 16-heptadecenyl acid-16-heptadecenyl ester.
2. The ziegler-natta catalyst composition of claim 1 wherein the first type of external electron donor comprises one or more selected from the group consisting of methylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, and tetraethoxysilane; the mole percentage content of the first type in the external electron donor component is 1-99%.
3. The ziegler-natta catalyst composition according to claim 1 wherein the titanium-containing compound is TiCl4。
4. Ziegler-Natta catalyst composition according to any of claims 1 to 3, the cocatalyst being triethylaluminium and the molar ratio of the aluminium element of the cocatalyst to the titanium element of the procatalyst being from 10:1 to 200: 1.
5. The ziegler-natta catalyst composition according to any of claims 1 to 3, wherein said ester internal electron donor compound is selected from one or more of ethyl benzoate, diisobutyl phthalate, di-n-butyl phthalate, diisobutyl 2, 3-diisopropylsuccinate and 2, 4-pentanediol ester; the ether internal electron donor compound is 9, 9-bis (hydroxymethyl) fluorene.
6. Ziegler-Natta catalyst composition according to any of claims 1 to 3, wherein the internal electron donor compound represents from 6% to 15% by weight of the procatalyst.
7. Ziegler-Natta catalyst composition according to any of claims 1 to 3, wherein the molar ratio of the first type of external electron donor to the titanium element of the procatalyst is from 1:1 to 1000: 1.
8. Use of a ziegler-natta catalyst composition according to any of claims 1 to 7 in the homopolymerisation of propylene or in the copolymerisation of propylene with at least one copolymerizable monomer.
9. Use according to claim 8, wherein the homo-or co-polymerisation is a gas phase, bulk or slurry polymerisation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180712A (en) * | 1997-11-18 | 1998-05-06 | 化学工业部北京化工研究院 | Catalyzer for ethylene polymerization and copolymerization and preparaing method thereof |
| JP3429901B2 (en) * | 1995-05-12 | 2003-07-28 | 昭和電工株式会社 | Modified polypropylene |
| CN100339399C (en) * | 2003-01-23 | 2007-09-26 | 三星阿托菲纳株式会社 | Method of polymerization and copolymerization of ethylene |
| CN101848946A (en) * | 2007-08-24 | 2010-09-29 | 陶氏环球技术公司 | Gas phase polymerization process |
| CN104371046A (en) * | 2013-08-16 | 2015-02-25 | 中国石油化工股份有限公司 | Catalyst system used for olefin polymerization and propylene copolymer |
| CN105524192A (en) * | 2015-12-09 | 2016-04-27 | 大唐国际化工技术研究院有限公司 | Polypropylene catalyst composition with high-temperature activity inhibitory effect and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3429901B2 (en) * | 1995-05-12 | 2003-07-28 | 昭和電工株式会社 | Modified polypropylene |
| CN1180712A (en) * | 1997-11-18 | 1998-05-06 | 化学工业部北京化工研究院 | Catalyzer for ethylene polymerization and copolymerization and preparaing method thereof |
| CN100339399C (en) * | 2003-01-23 | 2007-09-26 | 三星阿托菲纳株式会社 | Method of polymerization and copolymerization of ethylene |
| CN101848946A (en) * | 2007-08-24 | 2010-09-29 | 陶氏环球技术公司 | Gas phase polymerization process |
| CN104371046A (en) * | 2013-08-16 | 2015-02-25 | 中国石油化工股份有限公司 | Catalyst system used for olefin polymerization and propylene copolymer |
| CN105524192A (en) * | 2015-12-09 | 2016-04-27 | 大唐国际化工技术研究院有限公司 | Polypropylene catalyst composition with high-temperature activity inhibitory effect and application thereof |
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Effective date of registration: 20230118 Address after: 200233 room 405G, floor 4, building 33, No. 680, Guiping Road, Xuhui District, Shanghai Patentee after: PULAN POLYOLEFIN TECHNOLOGY DEVELOPMENT (SHANGHAI) Co.,Ltd. Patentee after: Puenejing New Energy Materials (Shanghai) Co.,Ltd. Address before: 200233 Room 401, block B, 410 Guiping Road, Xuhui District, Shanghai Patentee before: PULAN POLYOLEFIN TECHNOLOGY DEVELOPMENT (SHANGHAI) Co.,Ltd. |
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Effective date of registration: 20230608 Address after: Room 702, Building 56, No. 248, Guanghua Road, Minhang District, Shanghai, 201108 Patentee after: Puenejing New Energy Materials (Shanghai) Co.,Ltd. Address before: 200233 room 405G, floor 4, building 33, No. 680, Guiping Road, Xuhui District, Shanghai Patentee before: PULAN POLYOLEFIN TECHNOLOGY DEVELOPMENT (SHANGHAI) Co.,Ltd. Patentee before: Puenejing New Energy Materials (Shanghai) Co.,Ltd. |