PHA Modifiers as Polymeric Plasticizers and Process Aids

1. PHA Modifiers as Polymeric
Plasticizers and Process Aids
Vinyltec 2014
Indianapolis
October 20-22, 2014
Allen Padwa
Sr. Science Fellow

2. © 2014 Metabolix2
Metabolix Core PHA Technology
Versatile 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
Performance
Additives
Metabolix Biopolymers
Biobased Chemicals
P4HB
P3HP
PHA
Core PHA
Bioscience

3. © 2014 Metabolix3
PHA Biopolymer Portfolio
Key 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

4. © 2014 Metabolix4
Metabolix PHA Family of Copolymers
Amorphous
Range
Progress has Extended PHA Technology
into the Amorphous Region

5. © 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 Focus
Additives Approach
Additives, Modifiers

6. © 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

7. © 2014 Metabolix7
PVC / PHA Miscibility
DMA tg δ as a function of temperature (with 18 phr DIDP):
PHA
PVC
PVC/10 phr PHA blend
61 ºC-9 ºC
53 ºC
Fox equation confirms miscibility
1
𝑇𝑔𝑏
=
𝑊1
𝑇𝑔1
+
𝑊2
𝑇𝑔2

8. © 2014 Metabolix8
PHA as Polymeric Modifier
Comparison 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)

9. © 2014 Metabolix9
Shore D Response
PHA 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

10. © 2014 Metabolix10
Factor slope
DINP - 0.43
TOTM - 0.42
a-PHA - 0.07 *
ECR +0.02 *
(* weak effects)
r2 = 0.87
Torque Response
Polymeric additives display no significant impact on torque
ECR

11. © 2014 Metabolix11
Migration Study
Specimens 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

12. © 2014 Metabolix12
Migration Study
Modeling 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

13. © 2014 Metabolix13
Migration Response
a-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

14. © 2014 Metabolix14
Migration Response
Calculated plasticizer loss in 1 year at 70º C

15. © 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