Process for preparing high-performance polypropylenes

Patent metadata

Field	Value
Publication number	US-10544242-B2
Application number	US-201514710007-A
Country	US
Kind code	B2
Filing date	May 12, 2015
Priority date	Apr 20, 2006
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

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-uniformness 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.

First claim

What is claimed is:

1. A process for preparing a polypropylene having a polydispersity index of from 3 to 10, the process comprising at least the following two stages of polymerization: a first stage of polymerization, which is homopolymerization of propylene carried out in the presence of a Ziegler-Natta catalyst and a lesser amount of a molecular weight control agent, to provide a high molecular weight fraction of the polypropylene; and a second stage of polymerization, which is homopolymerization of propylene carried out in the presence of resulting polymer from the first stage of polymerization and a larger amount of the molecular weight control agent, to provide a low molecular weight fraction of the polypropylene, wherein: (1) no external electron donor compound is used in the first stage of polymerization, while an external electron donor compound is used in the second stage of polymerization; (2) an amount of an external electron donor compound is used in the first stage of polymerization, while an amount of the external electron donor compound, which is larger than that employed in the first stage of polymerization, is used in the second stage of polymerization; or (3) an external electron donor compound providing a polymer having a first isotacticity is used in the first stage of polymerization, while an external electron donor compound providing a polymer having a second isotacticity, which is higher than the first isotacticity, is added in the second stage of polymerization, to give a final polymer having an isotacticity higher than that of the polymer produced in the first stage of polymerization, wherein a ratio of the output of the first stage of polymerization to the output of the second stage of polymerization is in a range of from 30:70 to 70:30, wherein a ratio of a MFR value of the final polymer to a MFR value of the propylene polymer prepared in the first stage of polymerization is in a range of from 5 to 15; and wherein a weight ratio of an organic aluminum compound to an organic silicon compound in the first stage of polymerization is 2 to 20 times larger than that in the second stage of polymerization.

2. The process according to claim 1 , wherein a ratio of the isotacticity of the final polymer to the isotacticity of the propylene polymer prepared in the first stage of polymerization is larger than 1 but less than or equal to 1.2.

3. The process according to claim 1 , wherein the Ziegler-Natta catalyst used in the first stage of polymerization is a reaction product of: a solid catalyst component comprising magnesium, titanium, a halogen and an internal electron donor as essential components, an organic aluminum compound, and an organic silicon compound, with a weight ratio of the organic aluminum compound to the organic silicon compound being in a range of from 10 to 300, and wherein an additional amount of the organic silicon compound is added in the second stage of polymerization so as to give a weight ratio of the organic aluminum compound to the organic silicon compound less than that in the first stage of polymerization.

4. The process according to claim 3 , wherein the weight ratio of the organic aluminum compound to the organic silicon compound in the first stage of polymerization is 2 to 20 times larger than that in the second stage of polymerization.

5. The process according to claim 1 , wherein the ratio of the output of the first stage of polymerization to the output of the second stage of polymerization is in a range of from about 35:65 to about 55:45, polymerization temperatures in the two loop reactors are controlled at 60 to 80° C., and the polymerization is conducted in a liquid phase bulk process.

6. The process according to claim 1 , wherein the process comprises successively performing homopolymerization of propylene in two loop reactors in series in the presence of a Ziegler-Natta catalyst, which comprises a reaction product of an active titanium-containing solid catalyst component, an organic aluminum compound, and an organic silicon compound, to produce a propylene homopolymer having an isotactic index of more than 93%, wherein in the first loop reactor, a weight ratio of the organic aluminum compound to the organic silicon compound is in a range of from 10 to 300; an additional amount of the organic silicon compound is added in the second loop reactor so that a weight ratio of the organic aluminum compound to the organic silicon compound in the second loop reactor is less than that in the first loop reactor; a concentration of a molecular weight control agent in the second loop reactor is larger than that in the first loop reactor; a ratio of the output of the first loop reactor to the output of the second loop reactor is in a range of from about 35:65 to about 55:45; polymerization temperatures in the two loop reactors are controlled at 60 to 80° C.; and the polymerization is a liquid phase bulk polymerization.

7. The process according to claim 6 , wherein the weight ratio of the organic aluminum compound to the organic silicon compound in the first loop reactor is 2 to 20 times larger than that in the second loop reactor.

8. A polypropylene prepared by the process as claimed in claim 1 .

9. A polypropylene prepared by the process as claimed in claim 6 .

10. The polypropylene of claim 8 , which has a polydispersity index of 3 to 10, and of which the isotacticity of the low molecular weight fraction is higher than the isotacticity of the high molecular weight fraction.

11. Biaxial oriented films, tubings, flat fibers, or injection mould articles prepared from the polypropylene as claimed in claim 8 .

12. Biaxial oriented films, tubings, flat fibers, or injection mould articles prepared from the polypropylene as claimed in claim 9 .

13. Biaxial oriented films, tubings, flat fibers, or injection mould articles prepared from the polypropylene as claimed in claim 10 .

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp
• China Petroleum & Chemical Corporation And Beijing Res Institute Of Chemical Industry

Inventors

• Song Wenbo
• Guo Meifang
• Qiao Jinliang
• Yang Zhichao
• Zhang Shijun
• Yu Luqiang

Classifications

• Y10T428/139

  Open-ended, self-supporting conduit, cylinder, or tube-type article · CPC title

• C08F2/40

  using retarding agents · CPC title

• C08F110/06

  Propene · CPC title

• C08F110/02 Primary

  Ethene · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title