PHA Modifiers as Polymeric

Plasticizers and Process Aids

Vinyltec 2014

Indianapolis

October 20-22, 2014

Allen Padwa

Sr. Science Fellow

© 2014 Metabolix2

Metabolix Core PHA TechnologyVersatile Technology Addresses Chemicals and Polymers Markets

Manufacturing technology proven

Biopolymers: Gaining traction in the performance additives; focusing on unique polymer properties and product forms in all biopolymer segments

Biobased Chemicals: Option to Leverage PHA platform and breakthrough “FAST”

process for chemicals

Sugars, Natural Oils

Fermentation

Polymer Recovery

Biopolymers

Acrylic (C3),

GBL/BDO (C4)“FAST”

Recovery

Compostables,

Degradables

PerformanceAdditives

Metabolix Biopolymers

Biobased Chemicals

P4HB

P3HP

PHA

Core PHA

Bioscience

© 2014 Metabolix3

PHA Biopolymer PortfolioKey Features

~100% Bio-based – Made from renewable raw materials– Can use industrial sugars and non-food plant oils

Copolyester polymer – Wide range of MW (200,000 - 700,000)– Semi-crystalline to amorphous (Tg: - 30 to +5ºC, Tm: 120 to 180ºC)

FDA food contact: FCN1119 for PHA copolymers– Single use (conditions B through H)– In preparation for new copolymers (FDA, EFSA)

Biodegrade in most environments having microbial activity– Hot to cold aerobic conditions: composting, soil, marine– Meso & thermophilic anaerobic conditions: high & low solids

Effective additive and modifier in leading polymer systems

© 2014 Metabolix4

Metabolix PHA Family of Copolymers

Amorphous

Range

Progress has Extended PHA Technology

into the Amorphous Region

© 2014 Metabolix5

Sharpen emphasis on value and performance we can

deliver to customers

Strategically selective

Established application spaces

Critical mass

Key areas of focus

PVC

PLA

Micropowders

PHA-based latex

Biopolymers FocusAdditives Approach

Additives, Modifiers

© 2014 Metabolix6

I6003rp/M0000 - PVC Recycle Enhancer

Maintain properties without losing flexibility

Lower Process Torque

Improved homogeneity

I6002 - Toughening Flexible & Semi-rigid PVC

Excellent miscibility process aid – Dispersion & Fusion

Low Tg, high MW rubber property modifier – Toughness, Elongation, Permanence, No migration

Bio-based Modifiers for PVC Take Advantage of Inherent PHA Miscibility in PVC

© 2014 Metabolix7

PVC / PHA Miscibility

DMA tg δ as a function of temperature (with 18 phr DIDP):

PHA

PVC

PVC/10 phr PHA blend61 ºC-9 ºC

53 ºC

Fox equation confirms miscibility

1

𝑇𝑔𝑏=𝑊1

𝑇𝑔1+𝑊2

𝑇𝑔2

© 2014 Metabolix8

PHA as Polymeric ModifierComparison with Plasticizers and Ethylene Copolymer Resin (ECR)

Response factors for PVC with:

– Plasticizer (DINP or TOTM)

– a-PHA – Bio-based high MW polymeric modifier

– ECR – Conventional high MW synthetic polymeric modifier

Basic Flexible PVC Formulation:– CPM vs. a-PHA modifier

– Bio-based plasticizer/stabilizer - ESO

– Conventional plasticizers - DINP or TOTM

Processing on two-roll mill at 180ºC

Response variables: Torque, Shore D hardness, Extractability

Analyzed by JMP (from SAS Institute)

© 2014 Metabolix9

Shore D ResponsePHA and ECR display similar plasticization effect; but at lower rate than the primary plasticizers (DINP, TOTM)

Factor Slope

DINP -1.24

TOTM -1.16

a-PHA -0.75

ECR -0.72

r2 = 0.97

ECR

© 2014 Metabolix10

Factor slope

DINP - 0.43

TOTM - 0.42

a-PHA - 0.07 *

ECR +0.02 *

(* weak effects)

r2 = 0.87

Torque ResponsePolymeric additives display no significant impact on torque

ECR

© 2014 Metabolix11

Migration StudySpecimens were tested for migration response

ISO 177 migration protocol

Sandwich construction

– PVC disk – 50 mm diameter, 3 mm thick

– LDPE disk – 60 mm diameter, 1.6 mm thick

– Wrap in aluminum foil

– 5 kg weight

– Samples run in triplicate

– Heat age in oven at 70º C

– Samples removed at 1, 5, 15 and 29 days

© 2014 Metabolix12

Migration StudyModeling of data

Loss of plasticizer is limited by diffusion

Plots of ‘Weight Loss’ vs Time0.5 are linear

Slope is proportional to the rate of weight loss

© 2014 Metabolix13

Migration Responsea-PHA and ECR display lower migration responses and potential favorable impact on conventional plasticizers

Factor slope

DINP 1.4e-4

a-PHA 4.5e-5

ECR 4.3e-5

DINP*(a-PHA) 9.9e-7

DINP*(ECR) 1.2e-6

r2 = 0.88

Slope = % wt loss/day

ECRa-PHA

© 2014 Metabolix14

Migration ResponseCalculated plasticizer loss in 1 year at 70º C

© 2014 Metabolix15

Conclusions

PHAs display similar performance to an ethylene copolymer resin (ECR)

– lower migration response than conventional plasticizers

– favorable impact on conventional plasticizer material performance

PHA modifiers are inherently miscible in PVC

>> More easily processed and incorporated than synthetics

PHAs are 100% bio-based and food-contact approved

>> Increases bio-content, supports broad range of applications