Process for the preparation of high performance polypropylene

Inactive Publication Date: 2009-12-31
CHINA PETROCHEMICAL CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0027]In the process for preparing polypropylenes having broad molecular weight distribution according to the invention, the first and second stages of polymerization are performed under different concentrations of a molecular weight control agent, for example, hydrogen gas, in order to make the final propylene polymers having broadened molecular weight distribution. In general, melt flow rate (MFR) of a final polymer may be controlled depending on the intended use of the polymer, and the MFR of the propylene polymer produced in the first polymerization stage can be so controlled that a ratio of the MFR of the final propylene polymer to the MFR of the propylene polymer produced in the first polymerization stage is in a range of from about 5 to about 15. For example, when the final polymer will be used as a tubing material, the MFR of the propylene polymer produced in the first polymerization stage can be controlled as being in a range of from 0.01 to 0.03 g/10 min., and the MFR of the final propylene polymer can be controlled as being in a range of from 0.1 to 0.3 g/10 min.; and when the final polymer will be used as a film material, the MFR of the propylene polymer produced in the first polymerization stage can be controlled as being in a range of from 0.2 to 0.4 g/10 min., and the MFR of the final propylene polymer can be controlled as being in a range of from 2 to 4 g/10 min. The MFR values are measured according to ISO1133, at 230° C., under 2.16 kg loading.
[0028]In the process according to the invention, a ratio of the output of the first stage of polymerization to the output of the second stage of polymerization may be in a range of from 30:70 to 70:30, preferably from 35:65 to 55:45.
[0029]The polymerization can be carried out in a liquid phase process, or in a gas phase process, or in a combination process of gas phase and liquid phase. In the case where the polymerization is carried out in liquid phase, polymerization temperature is in a range of from 0° C. to 150° C., and preferably from 40° C. to 100° C., and polymerization pressure is higher than saturated vapor pressure of propylene at the corresponding polymerization temperature. In the case where the polymerization is carried out in gas phase, polymerization temperature is in a range of from 0° C. to 150° C., and preferably from 40° C. to 100° C., and polymerization pressure may be normal pressure or higher, and preferably in a range of from 1.0 to 3.0 MPa (gauge, similarly hereinafter).
[0030]Comonomers which may copolymerize with propylene in the process according to the invention include ethylene and C4-C12 α-olefins, for example, 1-butene, 1-hexene, and 1-octene.
[0031

Problems solved by technology

Such polymers may have many defects in the practical applications.
For example, the fractions having low molecular weight and low isotacticities tend to migrate out from the interior of the materials during processing and during long-term use of articles, and thus adversely affect the performance and use of the articles.
And the fractions having high molecular weight and high isotacticities tend to form thick lamellar crystal in the materials, and this is disadvantageous for some applications of propylene polymers.
For example, when su

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

[0039]A main catalyst (active titanium-containing solid catalyst component) was prepared by the process described in Example 1 of Chinese patent application CN93102795. The main catalyst was found to have a Ti content of 2.4 wt %, a Mg content of 18.0 wt %, and a di-n-butyl phthalate content of 13 wt %.

[0040]Polymerization was performed in a polypropylene pilot plant using two 75 L loop polymerization reactors. The main catalyst, cocatalyst (i.e., triethylaluminum), and external electron donor (i.e., cyclohexyl methyl dimethoxy silane) pre-contacted with each other at 10° C. for one minute, and then were continuously fed into a 2 L prepolymerization reactor to conduct prepolymerization. Flow rate of each raw material fed into the prepolymerization reactor was 5.29 g / hr for triethyl aluminum, 0.13 g / hr for cyclohexyl methyl dimethoxy silane, 0.01 g / hr for the main catalyst, and 11 kg / hr for propylene. Prepolymerization temperature was 15° C., prepolymerization pressure was 4.1 MPa, a...

example 2

[0043]The procedure as described in the Example 1 was followed, except that the flow rate of cyclohexyl methyl dimethoxy silane fed to the prepolymerization reactor was changed to 0.06 g / hr so that Al / Si weight ratio in the first loop reactor was 80, and additional cyclohexyl methyl dimethoxy silane was fed into the second loop reactor at a flow rate of 0.47 g / hr, so that Al / Si weight ratio in the second loop reactor was 10. The results of property measurement are shown in the Table 1.

example 3

[0044]The procedure as described in the Example 1 was followed, except that the hydrogen concentration in the feed to the first loop reactor was controlled at 80 ppm by volume, and the hydrogen concentration in the feed to the second loop reactor was controlled at 5200 ppm by volume. The results of property measurement are shown in the Table 1.

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Abstract

The invention discloses a process for preparing high-performance propylene polymers, the process utilizing a high activity, highly stereoselective Ziegler-Natta catalyst and two or more stages of polymerization carried out under different hydrogen concentrations to prepare propylene polymers having broad molecular weight distribution, wherein non-unifomess of isotacticity of molecular chains of the final propylene polymers is improved by adjusting or controlling stereoselectivity of catalytic active sites under different hydrogen concentrations, namely, making the low molecular weight fraction of the polymers having a higher isotacticity and making the high molecular weight fraction of the polymers having a lower isotacticity, thereby overcoming the drawbacks of the propylene polymers having broad molecular weight distribution known in the art. The resulting final polymers have excellent combined properties, in particular, remarkably improved mechanical properties.

Description

CROSS REFERENCE OF RELATED APPLICATION[0001]The present application claims the priority of the Chinese Patent Application No. 200610076310.7, filed on Apr. 20, 2006, which is incorporated herein by reference in its entirety and for all purposes.FIELD OF THE INVENTION[0002]The present invention relates to a process for preparing high-performance polypropylenes, and more specifically, to a process for preparing polypropylenes having excellent performance and broad molecular weight distributions, of which high molecular weight fraction has a lower isotacticity and low molecular weight fraction has a higher isotacticity.BACKGROUND OF THE INVENTION[0003]In general, polypropylene resins having broad molecular weight distributions (of which polydispersity indexes as measured by a rheological method are typically larger than 4.0) exhibit better performance, because high molecular weight fraction of the resins imparts better mechanical strength, creep resistance, etc. to the resins, while lo...

Claims

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Application Information

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IPC IPC(8): C08F2/01C08F4/42
CPCC08F10/00C08F110/06C08F2/001C08F2500/04C08F2500/15C08F4/6465Y02P20/52Y10T428/139C08F10/06C08F2/38C08F2/00C08F2/40C08F110/02
Inventor SONG, WENBOGUO, MEIFANGQIAO, JINLIANGYANG, ZHICHAOZHANG, SHIJUNYU, LUQIANG
Owner CHINA PETROCHEMICAL CORP
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