The Value in Recycled Polyamides

Polyfunc)onal  Chain  Extenders  

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Overview

•  Background - Industry, Materials, Technical Objectives

•  Technical Data - Rheological Analysis - Mechanical Analysis

•  Conclusion & Recommendation - Discussion, Product Comparisons

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Background - Industry Objectives

•  “Developing market-based solutions for the recycling and reuse of post-consumer carpet” – Carpet America Recovery Effort slogan

•  Voluntary initiative by industry/government to prevent burdening landfills

•  Plan to achieve 40% landfill diversion by 2012

•  2002 diversion goal, 178 million pounds (3.8%) •  1.3 billion pounds diverted since 2002, 92% of which has gone into

other value added products •  Estimated 5 billion pounds landfilled, annually •  5 billion pounds can support the NA injection molding market

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Background – Materials, Availability

*Courtesy of Phantom Plastics

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Background - Value-Added Process

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Background - Limiting Factor

Specifications

Mechanical Properties

Molecular Weight

Recycled Nylon

1

1

Virgin Fiber Grade

2

2

Injection Molding

3

3

Specifications

Mechanical Properties

Molecular Weight

Recycled Nylon

Low

Low

Virgin Fiber Grade

Med

Med

Injection Molding

High

High

Degradation

Added Value

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Technical Objectives

•  Objective #1: Improve the mechanical properties of reprocessed recycled nylon derived from carpet using a functional additive

•  Objective #2: Impart value added properties to recycled nylon that stay within a low cost model

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Theory - Recycled Nylon

Low Mw High Mw

FA

FA FA

FA FA FA

2. Melt Processing

1. Dry Blending

5. Chain Extended

3. Homogenizing

4. Reaction

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Materials

•  Yan et al. documented the importance of diffusion of reactive species •  Hargreaves et al. described the reaction between amino group and anhydride

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Materials

Model Formulation •  98 to 99% r-PA (N66, >95% purity) •  1 to 2% Chain Extender*

* LPBD were prepared on a porous silica at 70% active

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Results

•  Grafted MA yielded more chain extension reactions •  Low viscosity LBPD likely integrated more efficiently •  Mobility of low Mw SMA led to shorter induction times

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Optimization Results

•  Low shear viscosity attributed to increased branched structure •  Increased long chain branching or MWD •  Reactivity of graft versus in-chain anhydride

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Results

•  SMA improved mechanical properties more than LPBD •  Homogenization an important factor in additive selection •  Chain extended r-PA has properties encroaching on virgin PA

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Results

•  Thermal characteristic improved with low/high Tg additive •  Extent of branching suggested by improvement in HDT •  SMA more efficient at restoring properties of r-PA

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Conclusion

•  Significant improvements in r-PA using low molecular weight anhydride functional additives

•  Anhydride grafted LPBD gave the greatest extent of

reaction as shown by increased melt characteristics

•  Low molecular weight additives were deemed more beneficial due to increased mobility in the melt

•  Homogenizing the melt involved balance of reactivity and mobility

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•  Leading global supplier of hydrocarbon resins, diene-based resins, and specialty monomers - Wingtack® and Norsolene® (C5 & C9 tackifiers)

- Poly bd®, KrasolTM and Ricon® (low molecular weight liquid

polybutadiene resins)

- SMA® (styrene-maleic anhydride copolymer resins) - DymalinkTM (metal centered monomers)

•  Annual sales over $350 million and has more than 340 employees worldwide

•  Company’s more than 250 products are manufactured at 9 sites in 4 countries

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Upstream Downstream Chemicals

Focus •  Oil & gas exploration •  Production •  Gas & power •  Alternative energy

•  Trading & shipping •  Refining & marketing •  Commodity & specialty fluids

•  Base chemicals •  Industrial & consumer market specialty chemicals

Sales (billion) $24.6 $163.4 $23.2

Employees 17,192 32,631 41,658

Total, a partner in your challenges

Cray Valley HSC A Division of Total SA

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Rubb

er

•  Performance additives

•  Tire & hose applications

• Co-curing agents Ad

hesiv

es

•  Pressure sensitive

• Reactive adhesives

•  Insulated Glass Sealants G

row

th M

arke

ts •  Printed

circuit boards

•  Pigment Dispersants

• Mineral Dispersants

Cray Valley HSC Focus Markets

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Cray Valley HSC Global Presence

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•  For additional information about Cray Valley, its products or its work in Hydrocarbon Specialty Chemicals,

visit www.CVPolymerAdditives.com