Advanced MaterialsA Review of What is Applicable in SUT

Amy Plancon, Jayanthi Grebin, and James Hicks

Panel Organizer: Eva Heintz, Ph.D.

Thermoplastics: General Polyolefins

Amy Plancon

Sabic

July 14, 2017

POLYETHYLENE (C2)

POLYPROPYLENE (C3)

LDPE & PP

• Offer a range of properties, and may be suitable for a wide range of applications

• Versatile materials

• Depends on polymer type and additives

• Some materials such as LDPE can be made “additive-free,” depending on polymerization process

• Can meet pharmacopoeia standards (EP, USP, DMF)

POLYCARBONATE

• High impact strength

• Inherent ‘water-clear’ transparency

• High heat resistance

• Unlimited colors – transparent, translucent, opaque

• FDA & Biocompatibility

• Very good processability and design versatility

• Multiple sterilization options

CHEMICAL PROPERTIES: TYPES OF ADDITIVES

Additives are used to improve processing of polymers and to

enhance their properties

Modifiers

• Impact modifiers

• Nucleating agents/clarifiers

• Organic peroxides

• Plasticizers

Property Extenders

• Antioxidants

• Antistatic agents

• Heat stabilizers

• Light stabilizers

Processing Aids

• Anti-blocking agents

• Lubricants/mold release

• Slip agents

• Improves film toughness

• Inhibits gels

• Increases gamma

stability

• Facilitates bag opening

• Minimizes blocking

SUMMARY

Input

• LDPE

• HDPE

• PP

• PC

• Additives

Process

• Injection molding

• Extrusion

• Film (blown, cast)

• Printing

• Filling

• Sterilization

Output (SUT)

• Mechanical

• Modulus

• Impact

• Rupture

• Chemical

• Extractables & leachables

Sin

gle

Use T

ech

no

log

y

Influencing Single Use Technology

Thermoplastics: Fluoropolymers

Jayanthi Grebin & Mike Johnson

Entegris

July 14, 2017

Fluoropolymer Applications

•Consumer Electronics

•Food Processing

•Industrial Coatings

•Semiconductor Manufacturing

Source: ASME-BPE 2016

Single-Use Innovation

Source: ASME-BPE 2016

Source: ASME-BPE 2016

Polytetrafluoroethylene or PTFE (1938)

•PTFE, later trademarked as Teflon®, was discovered by Dr. Roy Plunkett in 1938.

•The fluorine atoms prefer their own kind, drawing to each other while repelling other kinds of molecules.

•C-C and C-F bonds are among the strongest in single bond organic chemistry, accounting for many of its unique properties.

Source: https://www.chemours.com/Teflon/en_US/products/history.html

Teflon® is a trademark of The Chemours Company.

F

C

F

F

C

Fn

Carbon

Fluorine

Fluorine

Fluoropolymers

• Nonstick

• Low coefficient of friction

• Wide Temperature resistance

• Unique electrical properties

• Cryogenic stability

• Universal chemical resistance

Chemical Resistance

Fluoropolymers’ unmatched chemical resistance is suitable for just about any pharmaceutical or bioprocessing application

•Strong mineral acids

•Inorganic bases

•Salt solutions

•Organic acids

•Alcohols

•Esters

•Aldehydes

Source: Compass Publications Chemical Resistance Guide for Plastics, ©2000

260

120

80

70

45

-240

-60

-60

-70

-18

-300 -200 -100 0 100 200 300

Fluoropolymer

PVDF

EVA

HDPE

PP

Temperature Use Range (°C)

Polymer Compounds

•Polymer additives• Antioxidants• Photostabilizers• Plasticizers• Lubricants• Acid scavengers• Pigments/colorants• Cross linking agents

•Adhesives (i.e. tie layer)

•Catalysts

Potential sources of E&L in many polyolefins

Polyester (PET) Layer

Tie Layer

EVOH Layer

Tie Layer

ULDPE Contact Layer

Polymer Compounds

•Polymer additives• Antioxidants• Photostabilizers• Plasticizers• Lubricants• Acid scavengers• Pigments/colorants• Cross linking agents

•Adhesives

•Catalysts

Potential sources of E&L in fluoropolymers

Fluoropolymer Contact Layer

Summary

Compatibility

◦ Outperforms other polymers as very few chemicals have an effect on fluoropolymers

Strength

◦ Maintains mechanical properties across a wide range of process temperatures

Extractables

◦ No additives to base resin result in extremely low extractable profile

James Hicks

Solvay Specialty Polymers

July 14, 2017

Thermoplastics: High Performance Aromatic Based Polymers and

High Barrier PVDC

• Commodity Polymers

• PE, PP, PVC, PS

• >75% of manufactured polymers are in this category.

• Engineered Polymers

• PC, ABS, PA, PEX, PET

• High structural properties and/or other unique properties not available with commodity polymers.

• High Performance Polymers

• PSU, PES, PPSU, PARA, PPA

• Engineered polymers taken to the next level.

• Ultra Polymers

• PEEK, PAI

• Specially design polymers capable of meeting multiple demanding criteria.

A Review of the Categories of Thermoplastics

Sulfone polymer base

PEEK polymer base

PVC polymer base

Nylon (PA) polymer base

Conversion to High Performance Plastics

METALS

COMMODINITY AND

ENGINEERING

PLASTICS

• Increase Chemical

Resistance – Acidic or

Alkaline conditions

• Lower Costs to

manufacture

• Weight Reduction

• Consolidation of parts

• Increase Chemical

Resistance

• Increase Mechanical

Performance

• Increased Thermal

Performance

ULTRA AND HIGH

PERFORMANCE

PLASTICS

Drivers for Thermoplastics to Metal Conversions

• Weight / Ergonomics

• Colorability / Transparency

• Design flexibility

• Part consolidation

• Lower cost manufacturing

Sterilization Methods

Not all Plastics can Withstand a wide range of Sterilization Methods

Steam (up to 134°C for 18 minutes)

Ethylene Oxide

Hydrogen Peroxide

Gamma Radiation

10 cycles

500 cycles

1,000 cycles

100 cycles

200 cycles

40-50 kGy

PC - Polycarbonate ✓ ✓ ✓ ✓

PARA – Aromatic Nylon ✓ ✓ ✓

PSU - Polysulfone ✓ ✓ ✓ ✓ ✓

PPSU - Polyphenylsulfone ✓ ✓ ✓ ✓ ✓ ✓

PEEK - Polyetheretherketone ✓ ✓ ✓ ✓ ✓ ✓

Sulfone and PEEK based polymers - Compliance Profile

• EU Regulation No 10/2011 on plastic materials and articles intended to come into contact to foodstuffs(2)

• U.S.: approvals for Food and Drug Administration (FDA) 21 CFR Part 176.170(1)

• USP VI Compliance

• ISO 10993 Complaince(2)

• NSF Std 51 and 61

• Low extractables and leachables

1) Information on current listings for specific grades is available from your Solvay representative

2) Sectional complaince varies with product and grades

Most base grades have:

Polyvinylidene Chloride - PVDC: Strong Properties by Chemistry

Flame Resistance: High LOI

Copolymer: Tailor-made

Functionality:

Steric hindrance:

Crystallinity:H2O Vapor Barrier

O2 BarrierHF Sealability

Polarity:

Low melt T:

Low Tg: ThermoformingShrink

Flexibility

( ) X( )

VDC-Monomer

H

C

H

Cl

C

Cl

H

C

H

Cl

C

Cl

XComonomer(s)

Polymerization

Source: Statoil

Source: brasilien.de

Printability Adhesion

Heat Sealability

Salt

Optional: Ethylene via

Biomass

Oil

Oxygen and Water Vapor Comparison

PVDC provides both outstanding water vapor and oxygen barrier

Water Vapor38 ºC / 90% rel. humidity

g · µm / (m²·d)1)

Oxygen Dry: 25 ºC/ 0% rel. humidity

LDPE

HDPE

OPP

R-PVC

PA 6-6

PETP

PAN

EVOH (EVAL)

Cellophane

PVOH (PVAL)

ca. 200000

ca. 60000

ca. 50000

2500 - 3000

1500 - 2500

ca. 1500

100 - 300

5 -80

300 - 500

3 - 4 > 500000

ca. 100000

1500 - 3500

1500 - 2000

ca. 800

1000 - 2000

600 - 900

100 - 200

ca. 150

300 - 500

PVDC 10 - 230 7 - 80

cm3 · µm/ (m²·d·bar)1)

1) Film thickness: 1 µm (= intrinsic permeability)

PVDC - Compliance Profile

• U.S.: PVDC approvals for Foodand Drug Administration (FDA) 21 CFR Part 170-199(1)

• European Pharmacopeia

• EU Regulation No 10/2011 on plastic materials and articlesintended to come into contactto foodstuffs(2)

1) Information on current listings for specific grades is available from your Solvay representative

2) Including EU Regulation No 1282/2011