Ethylene Polymer Blends with Controlled Long-Chain Branching

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Solution Overview

Problem

The high-temperature solution process for making ethylene polymers lacks the ability to introduce controlled long-chain branching, which is desirable for applications like shrink-film, and existing catalysts such as metallocenes are prone to deactivation by trace impurities and have low thermal stability.

Innovation Solution

A high-temperature solution process using a Ziegler-Natta catalyst comprising titanium, magnesium, and aluminum, in the absence of hydrogen, produces a first ethylene polymer component with substantial long-chain branching, while a second component with little or no long-chain branching is produced under different conditions, allowing the blend's long-chain branching to be controlled by adjusting the relative amounts of these components.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If metallocene catalysts are used to introduce long-chain branching, then long-chain branching is achieved, but the catalyst is easily poisoned by trace impurities and has low thermal stability

Engineering Contradiction:
Improvelong-chain branching controlVSAvoidcatalyst stability
Core Design Contradiction:
Manufacturing precisionVSReliability

Solution Approach 1:

The patent changes the catalyst system parameters from metallocene to Ziegler-Natta catalysts (Ti/Mg/Al combination), and changes the reaction condition parameter by introducing hydrogen to suppress long-chain branching in one reactor while allowing it in another, thereby achieving controlled long-chain branching without catalyst deactivation issues

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent divides the polymerization process into two separate reaction zones with different catalyst systems and hydrogen conditions. The first zone produces polymer with minimal long-chain branching using Ziegler-Natta catalyst with hydrogen, while the second zone produces polymer with controlled long-chain branching using Ziegler-Natta catalyst without hydrogen, allowing independent optimization of each zone

Inventive Principle:
Principle #1Segmentation

2Productivity

If Ziegler-Natta catalysts are used to produce linear ethylene polymers, then high activity and comonomer incorporation are achieved, but long-chain branching cannot be introduced

Engineering Contradiction:
Improvecatalyst activityVSAvoidlong-chain branching control
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The patent segments the polymerization process into two reaction zones with different hydrogen conditions. The first zone uses Ziegler-Natta catalyst with hydrogen to produce high-activity linear polymer, while the second zone uses the same catalyst type without hydrogen to produce polymer with long-chain branching, thereby maintaining catalyst activity while achieving branching control

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent changes the hydrogen parameter in the reaction conditions. By removing hydrogen in the second reaction zone while maintaining the Ziegler-Natta catalyst system, the process enables long-chain branching formation without sacrificing catalyst activity or comonomer incorporation capabilities

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This process enables the production of ethylene polymer blends with a predetermined degree of long-chain branching using readily available Ziegler-Natta catalysts and conventional equipment, improving the polymer's properties and processability without requiring new catalysts or extensive equipment modifications.

Implementation Method 1

ethylene is polymerized in the presence of a first Ziegler-Natta catalyst comprising titanium, magnesium, and aluminum

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentUS8697808B2Process for making ethylene polymer blends with controlled long-chain branching
Publication Date: 2014.04.15 EQUISTAR CHEMICALS LP

AI summary

A high-temperature solution process for making an ethylene polymer blend having a controlled degree of long-chain branching is disclosed. Ethylene is polymerized in the presence of a first Ziegler-Natta catalyst comprising titanium, magnesium, and aluminum in the absence of hydrogen to produce a first ethylene polymer component having substantial long-chain branching. A second ethylene polymer component having little or no long-chain branching is also prepared. Both polymerizations are performed at a temperature from 140° C. to 250° C. The first and second ethylene polymer components are combined to give a polymer blend. The degree of long-chain branching in the blend is controlled by adjusting the relative amounts of the first and second ethylene polymer components. The invention enables the preparation of valuable products having a pre-determined degree of long-chain branching using readily available Zeigler-Natta catalysts, commercially practiced techniques, and conventional equipment.