In-situ Polymerization of Trans-1,4-Polybutadiene and Syndiotactic 1,2-Polybutadiene

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Solution Overview

Problem

Current methods for producing blends of syndiotactic 1,2-polybutadiene and trans-1,4-polybutadiene are inefficient due to high processing costs, inadequate mixing, and polymer degradation at elevated temperatures, particularly exacerbated by the high vinyl content of syndiotactic 1,2-polybutadiene.

Innovation Solution

A process involving the polymerization of 1,3-butadiene in the presence of a lanthanide-based catalyst to form trans-1,4-polybutadiene, followed by the introduction of an iron-based catalyst within the same polymerization mixture to form syndiotactic 1,2-polybutadiene, allowing for the production of a blend without the need for isolating trans-1,4-polybutadiene or purifying the mixture.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If high-temperature mixing procedures are used to produce blends of syndiotactic 1,2-polybutadiene and trans-1,4-polybutadiene, then the polymers can be mixed together, but polymer degradation and crosslinking occur particularly severely due to the high vinyl content of syndiotactic 1,2-polybutadiene

Engineering Contradiction:

Improvemixing capabilityVSAvoidpolymer stability

Core Design Contradiction:

Ease of manufactureVSReliability

Solution Approach 1:

The invention changes the temperature parameter from high-temperature mixing to low-temperature polymerization (below 100°C, preferably 0-50°C). This parameter change allows the syndiotactic 1,2-polybutadiene to be formed without thermal degradation while maintaining mixing capability through in-situ polymerization in the presence of trans-1,4-polybutadiene

Inventive Principle:

Principle #35Parameter changes

Solution Approach 2:

The invention replaces the mechanical mixing system (extruder, Banbury mixer, Brabender mixer, or kneader) with a chemical polymerization system using lanthanide-based and iron-based catalysts. This substitution eliminates the need for high-temperature mechanical mixing while achieving homogeneous blends through controlled polymerization

Inventive Principle:

Principle #28Mechanics substitution (Replace mechanical system)

2Ease of manufacture

If solvent dissolution under high temperatures is used to prepare polymer blends, then the two crystalline polymers can be dissolved and recovered, but the process is inconvenient and time consuming

Engineering Contradiction:

Improveblend formationVSAvoidprocessing time

Core Design Contradiction:

Ease of manufactureVSLoss of time

Solution Approach 1:

The invention implements continuous polymerization where syndiotactic 1,2-polybutadiene is formed in-situ within the trans-1,4-polybutadiene matrix without interruption. This continuous process eliminates the time-consuming steps of solvent dissolution, heating, and recovery operations required by conventional methods

Inventive Principle:

Principle #20Continuity of useful action

Solution Approach 2:

The invention extracts and eliminates the solvent from the process by using bulk polymerization or polymerization in minimal inert medium. This removal of solvent eliminates the need for dissolution and recovery steps, significantly reducing processing time and inconvenience

Inventive Principle:

Principle #2Taking out (Extraction)

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 method enables the efficient production of a blend with improved mixing and reduced polymer degradation, facilitating the use of the blend in tire components and air spring bellows while maintaining the desirable properties of both polymers.

Implementation Method 1

polymerizing 1,3-butadiene in the presence of a lanthanide-based catalyst to form a polymerization mixture including trans-1,4-polybutadiene

Methodology Applied

Scientific EffectCatalysis: Catalysis

Implementation Method 2

polymerizing 1,3-butadiene in the presence of an iron-based catalyst within the polymerization mixture including trans-1,4-polybutadiene to form syndiotactic 1,2-polybutadiene

Methodology Applied

Scientific EffectCatalysis: Catalysis

Data Source

PatentUS10035908B1Process for preparing blends of trans-1,4-polybutadiene and syndiotactic 1,2-polybutadiene

Publication Date: 2018.07.31 BRIDGESTONE CORP

AI summary

A process for preparing a blend of trans-1,4-polybutadiene and syndiotactic 1,2-polybutadiene, the process comprising the steps of (i) polymerizing 1,3-butadiene in the presence of a lanthanide-based catalyst to form a polymerization mixture including trans-1,4-polybutadiene, where the lanthanide-based catalyst includes (a) a lanthanide-containing compound, and (b) an organomagnesium compound; and (ii) polymerizing 1,3-butadiene in the presence of an iron-based catalyst within the polymerization mixture including trans-1,4-polybutadiene to form syndiotactic 1,2-polybutadiene within the polymerization mixture including trans-1,4-polybutadiene and thereby produce a blend of trans-1,4-polybutadiene and syndiotactic 1,2-polybutadiene; where the iron-based catalyst includes (a) an iron-containing compound, (b) an organomagnesium compound, and (c) a silyl phosphonate.