a better idea for scrap - pro india recycling · - pre-compounding with intensive mixer - increased...

The Dow Chemical Company

A Better Idea for Scrap

February 2015 Ritika Kalia Brian Walther

®™Trademark of The Dow Chemical Company

Barrier Materials - Market Growth & Drivers

2

Global Barrier Materials (thousand metric tons)

Material 2011 2016 CAGR 2011-

2016 PET Film 2,687 3454 5.1%

Aluminum Foil 2,449 3175 5.3% Nylon Resin 1,909 3023 9.6%

Metallized Film 1,569 2013 5.1% PVDC resin 545 580 1.3% EVOH resin 465 677 7.8%

Transparent Oxide-Coated Film 294 409 6.8%

Other 187 295 6.4% 10,107 13625 6.1%

Demand Drivers: •Consumer Convenience

(microwaveable, single

serve (lidstock), retort)

• Food waste / availability

(farm to fork & beyond)

• Food safety concerns

• Shelf appeal

Dow: A proven track record of Innovation

3

• Very high puncture, tear

• Cold temp impact

’40s-’50s ’60s-’70s 1990-’95 1996-’99

• Excellent impact

and sealing

• Enhanced PE

• Distinct combinations

such as impact

AND modulus

’80s 2000-’05

• Propylene Based

Plastomers

• Distinct heat and

tensile properties

• Advanced ZN

• Increased toughness

and excellent optics

• Elasticity and High

Service Temp

• Tough resins

made tougher

• Excellent impact and

processibility

2010 2009 2014

• High performance polymers

with enhanced service

standards to meet the needs

of the Healthcare industry

• Advanced Technology – post

metallocene LLDPE resins

• Excellent physical and

processing properties

• Broad design space

ROBOND™PS Pressure Sensitive Adhesives

ROBOND™L Laminating Adhesives

ADCOTE™

MOR-FREE™

SERFENE™

• Ziegler-Natta

• Solution Technology

• High tear and

puncture

• Free-radical initiated

• High pressure

reactors

Solventless Adhesives

• Polyolefin Elastomers

• Excellent impact resistance

• Laminating

Adhesives

• Barrier Adhesives

TYMOR™

• Tie Layers

(Rohm & Haas) ®™Trademark of The Dow Chemical Company

New Innovation for AMPLIFY™ Portfolio

Solved a long standing challenge of capturing value from recycle

streams

- Barrier films are not recyclable like conventional polyethylene

- Converters either burn, landfill, or use in ultra low value applications

Developed technology that enables a transformation in performance

4 ®™Trademark of The Dow Chemical Company

Challenge of Conventional vs. Barrier Film Recycle

Conventional film scrap is easily incorporated

back into multi-layer structure - Typically “buried” in an inner layer as a blend

with prime resin

- Minimal shift in properties or optics by

incorporating the film scrap

Barrier film scrap often contains EVOH and

nylon (polyamide) in a multi-layer structure

- EVOH and nylon are incompatible with unmodified

polyolefin

- Immiscibility leads to high haze structures with

considerable surface defects

5

Taking a Closer Look at a Barrier Recycle Film

Domains of EVOH and nylon are large

enough to scatter light in a polyolefin

continuous phase

Surface defects act as point defects and

the physical properties are degraded

Conclusion: EVOH and nylon must be

compatibilized into the matrix

Details: Blown film, 2.2 BR, 2.0 mil thickness

monolayer films – 10% EVOH + 90% Dowlex 2056

6

TEM

Optical Microscopy


Conventional Compatibilizer Chemistry

Compatibilize the EVOH and nylon using

conventional maleic anhydride tie layer

molecule - Example: PE-g-MAH, 2 MI, 1% MAH

The grafted polymer should solubilize the

EVOH and nylon and eliminate these

large domains

N H

O

R

R 1

C H 3

CH 3

O

O

O

CH 3

O

O-

O

N+

O

R

R 1

CH 3

H

CH 3

O-

O

N+

O

R

R 1

C H 3

O

H

CH 3 N O

R

R 1

C H 3

O

OH

O

N H

O

R

R 1

C H 3

CH 3

O

O

O

CH 3

O

O-

O

N+

O

R

R 1

CH 3

H

CH 3

O-

O

N+

O

R

R 1

C H 3

O

H

CH 3 N O

R

R 1

C H 3

O

OH

O

In situ

reaction

Non-polar Polar

Conventional Compatibilizer Chemistry

Conventional compatibilizer improved the

dispersion but not sufficient to make a high

quality film

Other attempts to improve dispersion - Pre-compounding with intensive mixer

- Increased levels of MAH based modifier

- Different types of EVOH or nylon

What is the basic physics/chemistry of what

is going on?


monolayer films – 10% EVOH + 80% Dowlex 2056 + !0% tie layer

8

TEM

Optical Microscopy


Reaction of Grafted Polymer to Nylon / EVOH

9

MAH

graft

+

PE-g-MAH EVOH Polymer EVOH grafted to PE

Conventional PE Grafted Processing

•Multiple grafting locations per chain of a conventional grafted polymer

will result in higher melt viscosity vs. the matrix

•Leads to poorer dispersion

•How to resolve this challenge?

1. One graft per chain

Double the Mw and would increase viscosity

2. Alternate approach would be to make something radically new

Low Mw and high graft level

10

Reaction of New Grafted Polymer to Nylon / EVOH

11

MAH

graft

+

PE-g-MAH EVOH Polymer EVOH grafted to PE


RETAIN™ for EVOH & PA barrier films

Reactive ultra-low viscosity compatibilizer

– Low viscosity = fast mixing

– Reactive groups will “coat” the polar components, encapsulate into

micro-domains and enable excellent dispersion

Nylon/EVOH

Non-polar matrix

Ccompatibilizer

Polar component


Compatibility of Technology with Conventional Process

13

RC

film

RC

pellets

New

RC

A layer in a

multilayer blown

film structure

• Closer look at recycle material stream

- Blown film production - edge trim and scrap

polymer

- Pellets combined in-line on blown film line


Compatibility of Technology with Conventional Process

14

RC

film

RC

pellets

A layer in a

multilayer blown

film structure

• More efficient use of RETAIN™

- Addition at the initial pelletization step

- Components added at the time of initial

densification

New

RC


Film Results Using RETAIN™

New compatibilizer improves the dispersion

effectively eliminating all of the larger

domains

Polar polymers are dispersed but not

eliminated – what is the effect on - Optical properties?

- Physical properties?


monolayer films – 10% EVOH + 80% Dowlex 2056 + !0% tie layer

15

TEM

Optical Microscopy


RETAIN™ - EVOH Based Recycle Stream

6x clarity improvement Optical Properties

2 mil films; DOWLEX™ 2056G/recyle stream with 10% EVOH/Dowlex™ 2056G (15:70:15)


RETAIN™ - EVOH Based Recycle Stream

Physical Properties Maintain Tear Increase Dart

2 mil films; DOWLEX™ 2056G/recyle stream with 10% EVOH/Dowlex™ 2056G (15:70:15)


Incorporating compatibilizer

allows you to achieve the same

clarity as the control film

Optical Properties

RETAIN™ - Performance w/ PA Recycle Stream

1

8

2 mil films; DOWLEX™ 2056G/recyle stream with 30% PA6/Dowlex™ 2056G (15:70:15)

Incorporating compatibilizer

allows you to achieve the

same key physical properties

Barrier properties match

polyethylene

Physical Properties


Evaluation of Sample Films

Question: Could using a recycle stream alter Taste and Odor

Properties?

Evaluation: Produced sample film and evaluated the properties

19

Evaluation of Recycled Film

• Use trained panelist, instructed and taught to focus on only one attribute at a time

• Use partitions and neutral surroundings to minimize distractions

• Use random sample presentation

Result – No preference

20 ®™Trademark of The Dow Chemical Company

Loading Level will Vary

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Compatibilizer loading decision tree

• Recycle Stream containing EVOH − EVOH typically used at 5% or less

− Add RETAIN™ at 5% maximum

• Recycle Stream containing PA: − PA typically added at 10-30%

− Add RETAIN™ at 15% maximum


Solution: Recycle Compatibilizer

EVOH / PA

LLDPE

LLDPE

Tie Layer

Tie Layer

Core Layer: Recycle Stream/PE/

Recycle Compatibilizer

Skin

Sealant Profitability& Sustainability!

BARRIER FILMS SCRAP (Edge Trim)

Recycle compatibilizer eliminates waste and transforms scrap into a high value film !


Recycle Compatibilizer

23

Cost Savings & Sustainability!


a better idea for scrap - pro india recycling · - pre-compounding with intensive mixer - increased...

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