Hyperbranched Polymethacrylate Synthesis via Haloinimer SCVP

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Solution Overview

Problem

Current methods for synthesizing hyperbranched polyacrylates and polymethacrylates often result in side reactions, limiting the production of a wide variety of these polymers with desired properties.

Innovation Solution

The development of methods involving self-condensing vinyl polymerization (SCVP) and copolymerization using inimers with free alkyl ester substituents and alpha-halofunctional groups to produce hyperbranched polymethacrylates with a high degree of branching, including steps such as reacting halohydrins with anhydrides and chlorinating agents to form pre-inimers and subsequently esterifying them to create inimers for polymerization.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional polymerization methods are used to synthesize hyperbranched polyacrylates and polymethacrylates, then polymer production is achieved, but side reactions occur that limit the production of polymers with desired properties

Engineering Contradiction:
Improvepolymer synthesis reliabilityVSAvoidside reactions
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The patent changes the chemical parameters of the monomer structure by introducing alpha-halofunctional groups and free alkyl ester substituents. This structural modification enables selective reactivity during polymerization, allowing the terminal vinyl group to react preferentially while the substituent vinyl groups remain dormant, thereby eliminating side reactions and achieving reliable synthesis of hyperbranched polymers with controlled architecture

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs an inimer as an intermediary molecule that contains both initiating and monomer functionalities. The inimer structure with alpha-halofunctional groups acts as a self-condensing vinyl polymerization initiator, mediating the formation of hyperbranched architecture through controlled sequential reactions. This intermediary enables precise architectural control and prevents unwanted side reactions that occur with conventional initiators

Inventive Principle:
Principle #24Intermediary (Mediator)

2Shape

If inimers with alpha-halofunctional groups and free alkyl ester substituents are used for polymerization, then hyperbranched polymers with high degree of branching are produced, but the synthesis process becomes more complex

Engineering Contradiction:
Improvedegree of branchingVSAvoidsynthesis process complexity
Core Design Contradiction:
ShapeVSDevice complexity

Solution Approach 1:

The patent applies preliminary action by pre-synthesizing inimers with specifically designed alpha-halofunctional groups and free alkyl ester substituents before polymerization. This pre-functionalization step establishes the precise molecular architecture needed for high-degree branching, allowing the subsequent polymerization to proceed automatically with controlled hyperbranching without requiring complex in-process interventions

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The inimer structure is designed to be self-sufficient, containing both the initiating functionality (alpha-halofunctional group) and monomer units (vinyl groups) within a single molecule. During polymerization, the inimer automatically initiates its own polymerization and drives the self-condensing vinyl polymerization process, eliminating the need for separate initiators and complex multi-component systems

Inventive Principle:
Principle #25Self-service

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 approach allows for the synthesis of hyperbranched polymers with high branching and versatility in substituents, reducing side reactions and enabling the production of architecturally analogous linear polymethacrylates, suitable for biomedical and industrial applications.

Implementation Method 1

reacting a halohydrin containing a carboxylic acid group with an anhydride in the presence of an acid catalyst, to form a pre-inimer that contains a carboxylic acid group

Methodology Applied
Scientific EffectChemical Bonding: Chemical Bonding

Implementation Method 2

reacting the pre-inimer with a chlorinating agent to form an acid chloride

Methodology Applied
Scientific EffectChemical Bonding: Chemical Bonding

Implementation Method 3

reacting the acid chloride with an alcohol in the presence of trimethylamine to esterify the acid chloride and form an inimer

Methodology Applied
Scientific EffectChemical Bonding: Chemical Bonding

Implementation Method 4

polymerizing the inimer to form a hyperbranched polyacrylate or polymethacrylate polymer by self-condensing vinyl polymerization

Methodology Applied
Scientific EffectPolymerization: Photopolymerisation

Data Source

PatentUS11981777B2Synthesis of hyperbranched polymethacrylates and polyacrylates by a haloinimer approach
Publication Date: 2024.05.14 THE UNIVERSITY OF AKRON
  • US11981777B2 patent drawing
  • US11981777B2 patent drawing
  • US11981777B2 patent drawing

AI summary

A new synthetic pathway for hyperbranched polyacrylates and polymethacrylates including the steps of preparing an inimer and polymerizing the inimer to form hyperbranched polymers or copolymers.