SELF-REGULATING EXTERNAL ELECTRON DONOR-CONTAINING CATALYST USED FOR ALPHA-OLEFIN POLYMERIZATION, AND APPLICATION OF CATALYST

Abstract

Disclosed are a Z-N catalyst for -olefin polymerization and an application thereof, specifically, an industrial production catalyst consisting of (A) a solid catalyst component, (B) a cocatalyst organoaluminum compound and (C) an external electron donor compound and used for -olefin polymerization or copolymerization processes. The catalyst component is prepared from a transition metal such as titanium and magnesium and a composite aromatic diacid diester/1,3-diether as an internal electron donor. One or more organoaluminum compounds or a mixture thereof serve as the cocatalyst. One or more structure control agent hydrocarbyl alkoxysilicons are compounded with one or more activity regulator organic acid esters as the external electron donor capable of automatically adjusting the polymerization rate. The Z-N catalyst is used for -olefin polymerization/copolymerization, and can automatically adjust the polymerization rate at a higher polymerization temperature so as to maintain stable operation of a reactor.

Claims

1. A Z-N catalyst for preparing poly--olefins, comprising a catalyst component A formed by supporting an internal electron donor on magnesium chloride, a cocatalyst alkyl aluminum B, and an external electron donor C capable of automatically adjusting the catalyst activity, wherein: (1) the catalyst component A is composed of at least titanium ions and a composite internal electron donor aromatic diaciddialkyl ester and 1,3-diether supported on magnesium chloride; and the preparation method of the catalyst component A comprises: a) co-precipitation of a magnesium chloride alcoholate, a composite internal electron donor and titanium tetrachloride; b) supporting titanium tetrachloride and a composite internal electron donor on a spherical magnesium chloride alcoholate support; and c) supporting a composite internal electron donor on magnesium chloride generated by reaction of diethoxymagnesium and titanium tetrachloride; (2) the cocatalyst alkyl aluminum B is triethyl aluminum, triisobutyl aluminum or a mixture thereof; and (3) the external electron donor C capable of automatically adjusting the catalyst activity comprises a structure control agent and an activity regulator, used in combination or alone; the structure control agent is one or more hydrocarbylalkoxysilicons and the activity regulator is one or more fatty acid esters; a molar ratio of total moles of the external electron donor C capable of automatically adjusting the catalyst activity and metal titanium ions in the catalyst component A is 1-500:1.

2. The Z-N catalyst according to claim 1, wherein the structure control agent is hydrocarbylalkoxysiliconR.sub.nSi(OCH.sub.3).sub.(4-n) where n=1 or 2; wherein when n=1, R is a C.sub.1-10 linear or branched alkyl, C.sub.5-10cycloalkyl, alkylcycloalkyl or cycloalkylalkyl, C.sub.6-10 phenyl, phenylalkyl or alkylphenyl; and when n=2, R is two hydrocarbyl groups R.sup.1 and R.sup.2, which may be the same or different and are C.sub.1-6 linear or branched alkyl, C.sub.5-6cycloalkyl, C.sub.1-6 alkyl and cycloalkyl, or phenyl.

3. The Z-N catalyst according to claim 2, wherein the hydrocarbylmethoxysilicon is selected from: propyltrimethoxysilicon, phenyltrimethoxysilicon, diisopropyldimethoxysilicon, diisobutyldimethoxysilicon, methylcyclohexyldimethoxysilicon, dicyclopentyldimethoxysilicon, and diphenyldimethoxysilicon.

4. The Z-N catalyst according to claim 1, wherein the activity regulator fatty acid ester or fatty diaciddiester comprises C.sub.10-20 linear fatty acid C.sub.3-6 branched alkyl ester or C.sub.4-16 linear fatty diacid C.sub.2-6 linear or branched dialkyl ester.

5. The Z-N catalyst according to claim 4, wherein the activity regulator is selected from esters of natural fatty acids, including isopropyl laurate, isoamyllaurate, isopropyl myristate, isoamylmyristate, isopropyl palmitate, isopropyl stearate; and the fatty diaciddiester is selected from diethyl adipate, di-n-butyl adipate, di-isobutyl adipate, diethyl suberate, di-n-butyl suberate, diisobutylsuberate, diethyl sebacate, di-n-butyl sebacate, and diisobutylsebacate.

6. The Z-N catalyst according to claim 1, wherein in the catalyst component A, the mass fraction of titanium is 2.0-3.8%, the mass fraction of magnesium is 15.0-20.0%, the mass fraction of 1,3-diether is 1-13%, and the mass fraction of the aromatic diaciddialkyl ester is 1-8%.

7. The Z-N catalyst according to claim 6, wherein in the catalyst component A, the aromatic diaciddialkyl ester is di-n-(iso)butyl phthalate; the 1,3-diether is 9,9-bis(methoxymethyl) fluorene; and the composite internal electron donor is di-n-(iso)butyl phthalate and 9,9-bis(methoxymethyl) fluorene.

8. The Z-N catalyst according to claim 7, wherein a molar ratio of di-n-(iso)butyl phthalate and 9,9-bis(methoxymethyl) fluorene is 1-9.9:10.

9. The Z-N catalyst according to claim 1, wherein a molar ratio of the structure control agent and the activity regulator is 0-10:10.

10. The Z-N catalyst for preparing poly--olefins according to claim 1, wherein the preparing poly--olefins comprises: propylene polymerization, 1-butene polymerization, ethylene and propylene copolymerization, ethylene and 1-butene copolymerization, or propylene and 1-butene copolymerization.

11. A method of application of the Z-N catalyst according to claim 1 in preparing poly--olefins, wherein the tacticity of polypropylene is 95-99%; the polymerization and the copolymerization of -olefins are continuous polymerization, and a reactor for continuous polymerization is more than one reactor in series, or a reactor for continuous polymerization is a fluidized bed reactor.

12. The method of the Z-N catalyst in preparing poly--olefins according to claim 11, wherein the polymerization and the copolymerization of -olefins are continuous gas-phase polymerization, and a reactor for continuous gas-phase polymerization is more than one reactor in series, or a reactor for continuous gas-phase polymerization is a fluidized bed reactor.

13. The method according to claim 12, wherein in the polymerization and the copolymerization of -olefins, the structure control agent and the activity regulator are added into a reactor in a variety of ways: the structure control agent and the activity regulator are together or separately added into a reactor simultaneously with the catalyst component A or the cocatalyst component B; in the process with more than one reactor in series, the structure control agent and the activity regulator are together or separately added into a first reactor simultaneously with the catalyst component A or the cocatalyst component B, or the structure control agent is added into the first reactor and then the activity regulator is added into a different reactor.

14. The method of claim 11, wherein the Z-N catalyst is according to claim 9.

15. The method of claim 11, wherein the Z-N catalyst is according to claim 10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0037] The following non-limiting examples are used to illustrate the combination and properties of the structure control agent and the activity regulator suitable for the present catalyst system, to enable those skilled in the art to understand the present invention more fully. However, these examples are not meant to limit the claimed invention in any way.

[0038] Various structure control agents and activity regulators supplied in the market are designed to form several structure control agent/activity regulator combination groups. Each combination group is formulated into a 10% hexane solution, and unless otherwise indicated, the mass ratio of the structure control agent and the activity regulator is 20:80; the structure control agent or the activity regulator alone is also formulated into a 10% hexane solution; reproducibility of each experiment is ensured. The experiments are performed in a 5 L autoclave by bulk polymerization. Each experiment follows the following procedure, and the experiments using only the structure control agent or the structure control agent/activity regulator combination are carried out respectively. For each experiment, an amount of polypropylene generated before reaching the polymerization temperature is made first: when the temperature of the polymerization reactor is raised at a uniform speed to reach the polymerization temperature, propylene in the reactor is immediately vented, and dry polypropylene is weighted. Then, the polymerization experiment is performed, and when the temperature of the polymerization reactor is raised at a uniform speed to reach the polymerization temperature, recording time is started. After 1 h reaction, propylene in the reactor is immediately vented, and dry polypropylene is weighted. When the catalyst activity is calculated, the amount of polypropylene generated before reaching the polymerization temperature is subtracted. The pressure of the reactor before stopping the polymerization for each time is the saturated vapor pressure of propylene at the polymerization temperature, otherwise, the experiment needs to be done again. Each experiment is repeated three times and the average is taken. The polymer samples are preserved and determined for other performance data.

[0039] The catalyst activity of the present application is an average after a number of corrections, and is referred to as standard catalytic activity.

EXAMPLES 1-8

[0040] The catalyst component A was prepared by co-precipitation.

[0041] Using 0.02 g the catalyst component A containing 17.17% of magnesium, 2.24% of titanium, 1.68% of di-isobutyl phthalate, and 5.0% of 9,9-bis(methoxymethyl) fluorene, 1.5 ml the cocatalyst triethyl aluminum, and the external electron donor C comprising the structure control agent hydrocarbyl alkoxysilicon and the activity regulator fatty acid ester, the experiment results are shown in Table 1.

TABLE-US-00001 TABLE 1 External electron Standard catalyst Structure Activity donor/titanium/ activity At C./ Melt index/ A.sub.t C./ Experiment control agent regulator (molar ratio) Temperature/ C. kgpp/gcat Tacticity/% g/10 min A.sub.70 C./% A.sub.0 Diisobutyl- None 20 70 40.0 97.2 9.75 dimethoxysilicon A.sub.1 Diisobutyl- Isopropyl 20 70 37.0 95.4 50.95 100 dimethoxysilicon palmitate A.sub.2 Diisobutyl- Isopropyl 20 100 24.7 95.5 66.8 dimethoxysilicon palmitate A.sub.3 Diisobutyl- Isopropyl 20 110 11.0 95.8 29.7 dimethoxysilicon palmitate A.sub.4 Diisobutyl- Isopropyl 20 120 5.0 13.5 dimethoxysilicon palmitate B.sub.0 Methylcyclohexyl- None 20 70 26.0 95.5 11.46 dimethoxysilicon B.sub.1 Methylcyclohexyl- Isopropyl 20 70 34.0 95.7 39.56 100 dimethoxysilicon stearate B.sub.2 Methylcyclohexyl- Isopropyl 20 100 30.0 95.3 111.1 88.2 dimethoxysilicon stearate B.sub.3 Methylcyclohexyl- Isopropyl 20 110 10.3 95.0 30.3 dimethoxysilicon stearate C.sub.0 Phenyltrimethoxy- None 30 70 22.0 98.1 5.6 silicon C.sub.1 Phenyltrimethoxy- Isopropyl 30 70 35.0 98.1 100 silicon myristate C.sub.2 Phenyltrimethoxy- Isopropyl 30 100 25.0 98.2 28.1 71.4 silicon myristate C.sub.3 Phenyltrimethoxy- Isopropyl 30 110 16.0 45.7 silicon myristate F.sub.0 Propyltrimethoxy- None 20 70 25.0 97.1 9.39 silicon F.sub.1 Propyltrimethoxy- Isopropyl 20 70 37.0 97.2 100 silicon myristate F.sub.2 Propyltrimethoxy- Isopropyl 20 100 21.0 96.8 41.3 56.8 silicon myristate F.sub.3 Propyltrimethoxy- Isopropyl 20 110 18.0 97.2 48.6 silicon myristate G.sub.0 Dicyclopentyl- None 20 70 36.1 97.4 17.14 dimethoxysilicon G.sub.1 Dicyclopentyl- Isopropyl 20 70 41.7 97.3 12.76 100 dimethoxysilicon myristate G.sub.2 Dicyclopentyl- Isopropyl 20 100 29.0 97.5 28.9 69.5 dimethoxysilicon myristate G.sub.3 Dicyclopentyl- Isopropyl 20 110 9.3 96.4 22.3 dimethoxysilicon myristate H.sub.0 Dicyclopentyl- None 30 70 36.0 96.6 17.14 dimethoxysilicon H.sub.1 Dicyclopentyl- Diethyl 30 70 41.3 97.1 10.62 100 dimethoxysilicon suberate H.sub.2 Dicyclopentyl- Diethyl 30 100 28.8 97.9 25.0 69.7 dimethoxysilicon suberate H.sub.3 Dicyclopentyl- Diethyl 30 110 7.4 96.6 17.7 dimethoxysilicon suberate I.sub.1 Dicyclopentyl- Dibutyl 30 70 39.4 97.4 16.75 100 dimethoxysilicon sebacate I.sub.2 Dicyclopentyl- Dibutyl 30 100 28.0 97.9 21.22 71.0 dimethoxysilicon sebacate I.sub.3 Dicyclopentyl- Dibutyl 30 110 9.6. 97.0 24.4 dimethoxysilicon sebacate J.sub.0 Diisopropyl- None 20 70 32.0 97.5 15.29 dimethoxysilicon J.sub.1 Diisopropyl- Isopropyl 20 70 36.0 96.5 29.37 100 dimethoxysilicon myristate J.sub.2 Diisopropyl- Isopropyl 20 100 28.0 96.3 76.71 77.8 dimethoxysilicon myristate Note: mass ratio of phenyltrimethoxysilicon and isopropyl myristate: 2:98; mass ratio of dicyclopentyldimethoxysilicon and diethyl suberate: 20:40; mass ratio of dicyclopentyldimethoxysilicon and dibutyl sebacate: 20:40.

EXAMPLES 9-10

[0042] The catalyst component A was prepared by co-precipitation.

[0043] Using 0.02 g the catalyst component A containing 17.17% of magnesium, 2.24% of titanium, 1.68% of di-isobutyl phthalate, and 5.0% of 9,9-bis(methoxymethyl) fluorene, 1.5 ml the cocatalyst triethyl aluminum, and the external electron donor C which is the activity regulator fatty acid ester, the polymerization results are shown in Table 2.

TABLE-US-00002 TABLE 2 External electron Standard catalyst Structure Activity donor/titanium/ activity At C./ Melt index/ A.sub.t C./ Experiment control agent regulator (molar ratio) Temperature/ C. kgpp/gcat Tacticity/% g/10 min A.sub.70 C./% D.sub.1 None Isopropyl 20 70 36.7 96.1 100 laurate D.sub.2 None Isopropyl 20 100 25.0 96.1 40.59 68.1 laurate E.sub.1 None Isopropyl 30 70 35.7 96.2 100 myristate E.sub.3 None Isopropyl 30 100 31.0 96.5 44.37 75.6 myristate

EXAMPLES 11-12

[0044] The catalyst component A was prepared by supporting titanium and a composite internal electron donor on a spherical magnesium chloride alcoholate.

[0045] Using 0.02 g the catalyst component A containing 18.23% of magnesium, 3.11% of titanium, 3.07% of di-isobutyl phthalate, and 5.14% of 9,9-bis(methoxymethyl) fluorene, 1.5 ml the cocatalyst triethyl aluminum, and the external electron donor C comprising the structure control agent alkylalkoxysilicon and the activity regulator fatty acid ester, the polymerization results are shown in Table 3.

TABLE-US-00003 TABLE 3 External electron Standard catalyst Structure Activity donor/titanium/ activity At C./ Melt index/ A.sub.t C./ Experiment control agent regulator (molar ratio) Temperature/ C. kgpp/gcat Tacticity/% g/10 min A.sub.70 C./% A.sub.0 Propyltrimethoxy- None 70 41.0 95.8 12.13 silicon A.sub.1 Propyltrimethoxy- Isopropyl 20 70 40.0. 95.5 12.8 100 silicon myristate A.sub.2 Propyltrimethoxy- Isopropyl 20 100 32.0. 95.5 33.55 80.0 silicon myristate A.sub.3 Propyltrimethoxy- Isopropyl 20 110 25.0. 62.5 silicon myristate B.sub.0 Methylcyclohexyl- None 20 70 43.0. 95.0 10.88 dimethoxy silicon B.sub.1 Methylcyclohexyl- Isopropyl 20 70 39 95.4 15.32 100 dimethoxysilicon myristate B.sub.2 Methylcyclohexyl- Isopropyl 20 100 29 95.0 21.40 74.4 dimethoxysilicon myristate

EXAMPLES 13-20

[0046] The catalyst component A was prepared by supporting an internal electron donor on magnesium chloride generated by reaction of diethoxymagnesium and titanium chloride.

[0047] Using 0.02 g the catalyst component A containing 18.16% of magnesium, 3.14% of titanium, 5.32% of di-isobutyl phthalate, and 11.89% of 9,9-bis(methoxymethyl) fluorene, 1.5 ml the cocatalyst triethyl aluminum, and the external electron donor C comprising the structure control agent alkylalkoxysilicon and the activity regulator fatty acid ester, the propylene polymerization results are shown in Table 4.

TABLE-US-00004 TABLE 4 External electron Standard catalyst Structure Activity donor/titanium/ activity At C./ Melt index/ A.sub.t C./ Experiment control agent regulator (molar ratio) Temperature/ C. kgpp/gcat Tacticity/% g/10 min A.sub.70 C./% A.sub.0 Diisopropyl- None 70 18.0 96.5 dimethoxysilicon A.sub.1 Diisopropyl- Isopropyl 20 70 32.0 96.9 15.95 100 dimethoxysilicon myristate A.sub.2 Diisopropyl- Isopropyl 20 100 15.0 97.1 49.32 46.9 dimethoxysilicon myristate A.sub.3 Diisopropyl- Isopropyl 20 110 13.0 40.6 dimethoxysilicon myristate B.sub.0 Phenyltrimethoxy- None 20 70 18.0 98.3 15.44 silicon B.sub.1 Phenyltrimethoxy- Isopropyl 20 70 34.1 97.2 50 100 silicon myristate B.sub.2 Phenyltrimethoxy- Isopropyl 20 100 20.0 96.1 56.7 silicon myristate B.sub.3 Phenyltrimethoxy- Isopropyl 20 110 12.5 95.7 36.7 silicon myristate D.sub.0 Propyltrimethoxy- None 20 70 30.0 97.5 12.89 silicon D.sub.1 Propyltrimethoxy- Isopropyl 20 70 32.0. 96.1 31.1 100 silicon myristate D.sub.2 Propyltrimethoxy- Isopropyl 20 100 19.0 96.9 59.4 silicon myristate D.sub.3 Propyltrimethoxy- Isopropyl 20 110 8.2. 97.3 25.9 silicon myristate G.sub.0 Dicyclopentyl- None 30 70 30.0 96.6 17.14 dimethoxysilicon E.sub.1 Dicyclopentyl- Dibutyl 30 70 32.0. 98.3 27.62 100 dimethoxysilicon sebacate E.sub.2 Dicyclopentyl- Dibutyl 30 100 16.0 98.2 30.42 50.0 dimethoxysilicon sebacate F.sub.1 Dicyclopentyl- Isopropyl 20 70 31.6. 96.7 10.61 100 dimethoxysilicon myristate F.sub.2 Dicyclopentyl- Isopropyl 20 100 17.0 98.2 17.60 53.8 dimethoxysilicon myristate A.sub.0 Diisobutyl- None 20 70 36.0 97.2 9.75 dimethoxysilicon G.sub.1 Diisobutyl- Isopropyl 20 70 38.0. 96.4 100 dimethoxysilicon palmitate G.sub.2 Diisobutyl- Isopropyl 20 100 18.0 96.5 47.4 dimethoxysilicon palmitate H.sub.0 Methylcyclohexyl- None 20 70 15.0 98.2 19.60 dimethoxysilicon H.sub.1 Methylcyclohexyl- Isopropyl 20 70 43.0. 96.4 24.12 100 dimethoxysilicon stearate H.sub.2 Methylcyclohexyl- Isopropyl 20 100 16.0 96.4 36.42 37.2 dimethoxysilicon stearate H.sub.3 Methylcyclohexyl- Isopropyl 20 110 11.8. 95.8 48.54 27.4 dimethoxysilicon stearate

EXAMPLES 21-22

[0048] The catalyst component A was prepared by supporting an internal electron donor on magnesium chloride generated by reaction of diethoxymagnesium and titanium chloride.

[0049] Using 0.02 g the catalyst component A containing 18.16% of magnesium, 3.14% of titanium, 5.32% of di-isobutyl phthalate, and 11.89% of 9,9-bis(methoxymethyl) fluorene, 1.5 ml the cocatalyst triethyl aluminum, and the external electron donor C which is the activity regulator fatty acid ester, the propylene polymerization results are shown in Table 5.

TABLE-US-00005 TABLE 5 External electron Standard catalyst Structure Activity donor/titanium/ activity At C./ Melt index/ A.sub.t C./ Experiment control agent regulator (molar ratio) Temperature/ C. kgpp/gcat Tacticity/% g/10 min A.sub.70 C./% C.sub.1 None Isopropyl 20 70 39.3 95.3 100 myristate C.sub.2 None Isopropyl 20 100 30.0 95.5 76.3 myristate I.sub.1 None Isopropyl 20 70 34 95.9 28.4 100 laurate I.sub.2 None Isopropyl 20 100 12.0 96.4. 35.3 laurate