FORMULATING RIGID / SEMI-

RIGID PVC: ACRYLIC

MODIFIERS
KEVIN YOCCA
ARKEMA INC., ACR PLASTICS ADDITIVES

VINYLTEC 2019, AKRON

OCTOBER 1, 2019
 CONTENTS
Acrylic Impact Modifiers
● Core / Shell impact modifier design
● Modes of failure and formulation
● Processing and impact performance

Acrylic Process Aids

● Process aid chemistry and functionality
● Selecting process aid technology
● Applications in semi-rigid and flexible PVC

PVC Formulation by market segment

● Rigid weatherable
● Substrate
● Cellular PVC

© ARKEMA 2019
IMPACT MODIFIERS
CORE-SHELL PARTICLE TECHNOLOGY
THE GOAL OF IMPACT MODIFIERS

To lower the DBTT (ductile-brittle transition temperature) of the material

● As temperature decreases, a material’s ability to absorb a specific
amount of energy without fracturing decreases
● Make your matrix tougher!

To assist in the absorption of energy

● Act as stress concentrators
● Initiate crazing
● Act as sites for shear-banding
● Cavitate to create new surfaces
● De-bond to facilitate crazing and/or shear banding

© ARKEMA 2019
METHODS OF IMPACT MODIFICATION

Blends
Plasticizers
Fibrous materials
Minerals
Rubbery materials
● Linear Molecules
● Core-shells
● Network polymers

© ARKEMA 2019
 CORE / SHELL TECHNOLOGIES

Methacrylate – Butadiene – Styrene Acrylic Impact Modifiers

(MBS) (AIM)

pBd core (Tg ~ -80°C) pBA core (Tg ~ -45°C)

pMMA shell pMMA shell

• Excellent low temperature impact • Good low temperature impact

• Excellent colorability • Good colorability
• Poor UV Stability • Good UV stability
• Acceptable thermal stability • Good thermal stability

© ARKEMA 2019
 CORE/SHELL AIM SYNTHESIS, STRUCTURE, AND KEY PARAMETERS
Monomers AIM Latex AIM Powder

Isolation
Emulsion and
Polymerization drying

Key performance parameters

- Rubber content
- CS particle size (80-500 nm)
- Core X-linking level
- Core Tg
- Chemistry improving PVC
compatibility

AIM CS primary particle AIM Powder grain

© ARKEMA 2019
 CORE/SHELL VS POWDER GRAIN PARTICLES
AIM CS primary particle

Ideal schematisation More realistic view AIM CS primary particle AIM Powder grain
D50≈ 200 nm D50≈ 200 µm

Rubber content can vary from 60 to > 90% There are about 1 billion of active CS AIM
and remain a free-flowing powder  particles into a single AIM powder grain!
improved shell chemistry improves anti-  Easily released and dispersed into the PVC
matrix during the extrusion step
blocking properties

PVC Window Profile

© ARKEMA 2019
CORE-SHELL PARAMETERS - BROADLY

Core Shell
Low Tg materials provide impact Because of the high Tg, it provides
modification by allowing stress excellent powder properties (i.e.
concentration flowabilitiy)
General rule of thumb is impact Allows for improved dispersion of the
modifiers work to about 50°C above the primary particles into the polymer
core Tg matrix
Mechanisms differ from matrix to matrix The shell facilitates energy transfer
so particle size and crosslink density between the matrix and the rubbery
become critical for success core – can help affect gelation!
Required particle size of the core differs pMMA exhibits fairly good compatibility
by resin matrix, for example: with many polymers (PVC, PC, and
● PVC: 80 – 300 nm others), which can be improved by the
● Polycarbonate: 150 – 400 nm incorporation of functional monomers
● HIPS: 700 nm + (i.e. tailor selectivity)

© ARKEMA 2019
 PRINCIPLE OF IMPACT MODIFICATION

Nano / Micro-structure Approach

● Particle size
● Mechanical properties
● Polymerization techniques
Microscopic Scale
● Theory of micro-mechanical damage and fracture
● Modifier / resin interactions
● Observations of microscopic deformation via AFM / TEM / SEM
Macroscopic Scale
● Fracture behavior
● Ductile to brittle transition temperature

Inclusions are the key to toughening polymers. They play the role of
inducing crazing, initiating shear yielding of the matrix as well as ending the
propagation of cracks.

© ARKEMA 2019
 MODES OF ENERGY ABSORPTION: MECHANICAL FAILURE
3 criteria for micromechanisms of damage RT-PMMA (TEM analysis)

Cavitation
● Particle / matrix debonding SBS (Optical microscopy)
● Voids in rubbery domains
● Stress-whitening zone

Shear Banding
● Sliding of molecules due to shear stress
● Favored by plane stress
● Distortion of material, constant volume process
● Best for high fracture toughness

Crazing
● Localized high alignment of polymer
● Voids and fibrils
● Favored by plane strain
● Mostly for brittle polymers
HIPS (Traction
under AFM)

© ARKEMA 2019
 APPLICATIONS PERSPECTIVE: PROCESSING AND RHEOLOGY
Gelation vs Fusion
● Any PVC material will become ductile above a certain level of impact modifier OR gelation level
● At the transition, it will randomly break brittle or ductile: high standard deviation
● The position of the transition depends on several factors: Gelation, MW of PVC, impact test, modifier type, °C / °F

Rheology can make it even more complicated

● Increasing modifier levels generally expedite fusion
● Increased fusion can lead to increased gelation
● Better gelation does not necessarily mean better impact properties

3000
2500

Torque (g.m)
e
2000 d
Impact Strength

Under-gelation Over-gelation c
1500 b
a
1000
Standard requirement AIM %
Optimum
500
0 50 100 150 200 250 300 350 400
Time (s)
Processing
window (a)=4.5 phr; (b) = 5.5 phr; (c)=6.5 phr; (d)=7.5 phr;
(e)=8.5 phr
Melt temperature, gelation level

© ARKEMA 2019
PROCESSING: DISPERSION OF CORE-SHELL PARTICLES

Processing plays a key

role in achieving success
with impact modifiers

An impact modifier is only

as good as the process
that disperses it

Y. Kayano et al., Polymer 37 (1996) 4505-4515. © ARKEMA 2019

HOW DO CORE-SHELL AIM WORK IN RIGID PVC?

Stress concentration
Rubber core must exist as a separate phase
● Large modulus differences versus PVC matrix

Large numbers of particles well dispersed in the PVC

matrix actually induce a stress field in the PVC article
● Stress field actually lowers the bulk stress required to
initiate response from the glassy matrix
● When deformation load is applied, shear flow and bulk
yielding of the matrix occur due to energy absorption by
the impact modifier particles

Stress field depends primarily on the concentration

and separation of impact modifier particles (volume
fraction) and not their absolute size

© ARKEMA 2019
OPTIMAL DISPERSION OF MODIFIERS

Overlapping stress zones is optimal

Dispersion becomes crucial
Size, volume fraction (interparticle distance), testing
conditions

Izod Impact Response for a PVC Siding Substrate

Formulation

100
75
% Ductile
50 K67 Resin
Failures
25
0

0 5 10

Loading (PHR)

© ARKEMA 2019
IMPACT PERFORMANCE VS. PROCESSING PARAMETERS

Impact modifier loading level alone will not determine final PVC article mechanical properties
PVC formulation, impact modifier selection, or equipment may change process window

Effect of Melt Temperature on Izod Impact of Rigid PVC

8
7

Izod impact, joules/cm

6
5
4
3
2
1
0
175 180 185 190 195 200
Melt temp. ºC

CM55 twin screw extrusion

© ARKEMA 2019
 CORE/SHELL AIM SIDE EFFECTS: OTHER KEY APPLICATION PROPERTIES

Gelation promotion

Corner Weld Strength (CWS) AIM acts as rheology modifier

(particulate system + shell
Plate-out processing aid effect)

Surface gloss

Dehydrochlorination (DHC)
● Small amounts of acidic species can be released
without any effect on real thermo-stability of PVC
profiles

These differences between AIM grades generally

remain within the technical specifications…

© ARKEMA 2019
ACRYLIC PROCESS AIDS
HIGH MOLECULAR WEIGHT COPOLYMERS
 PROCESS AIDS FOR RIGID PVC: WHAT / WHY / HOW?
Copolymers synthesized by Emulsion Polymerization
Based on acrylic or specialty monomers
Excellent compatibility with polar polymer matrices, especially PVC
Impart metal release properties based on co-monomer selection
Molecular weights < 1MM – 10 MM+ g/mol vs. PVC molecules < 100k
g/mol

Process aids started with one goal – enhance fusion:

● Force and shear transfer between primary PVC particles

© ARKEMA 2019
 VISUAL APPLICATIVE IMPROVEMENTS

High efficiency for various processes

● Processing aid (PA) can be used for injection, calendaring and all extrusion processes

No PA added

With 1 phr PA

Jetting and gate blush Smoother Rolling banks Smoother surface,

Prevention Better additives dispersion Shark skin prevention,
Higher process stability

© ARKEMA 2019
 VISUAL APPLICATIVE IMPROVEMENTS

High efficiency for various processes

● Processing aid (PA) can be used for injection, calendaring and all extrusion processes

No PA added

With > 1 phr PA

Product improvement Decrease in melt necking Higher melt strength

for thermoforming for extruded sheet

© ARKEMA 2019
PROCESS AIDS AND PVC RHEOLOGY

25
Process aid composition and rheology control
20
● Process aid Tg can control fusion time with all other
57C

Time (min)
processing conditions and formulation components 15
75C
remaining constant Tg
84C
10
● Flexibility in emulsion polymerization allows for a broad 92C effect
range of compositional and structural changes to the 5 105C
co-polymers
● Generally, lowering process aid Tg will accelerate 0
fusion 140 150 160 170 180 190
Temp (Deg C)

Process aid selection is often a combination of 100

considerations conv. Mw HMw UHMw
● Molecular weight effects complicate Tg effects 80

● Increased torque can lead to accelerated fusion Mw

Torque (Nm)
60
● Molecular weight effects can lead to issues with effect
dimensional stability and flow changes, especially for
40
dimensionally complicated tooling Mw
20

0
0 60 120 180 240 300 360 420 480 540 600
Time (s)

© ARKEMA 2019
 MELT STRENGTH: PROCESS AID SELECTION
Rheotens: Melt Strength Evaluation 2 x40 MW
Process Aid 4 g/mol PA
1.8
Process Aid 3
1.6 Process Aid 2
x20 MW
Process Aid 1
1.4 g/mol PA

Die 1.2

Force (N)
orifice x10 MW
1 g/mol PA
0.8

0.6

Control PA
Pull-off 0.4
wheels
0.2

* Goettfert® Rheotens 71.97 0

10 20 30 40 50 60 70 80 90 100
Draw Down Velocity (mm/s)

PVC
melt Process aid melt strength evolution based on molecular weight:
strand
● Force versus Velocity: drawing down the strand out of the die (load cell)
● Remember: the curves represent PVC foam compound melt strength (PVC K-value = 58)
● The differences in melt strength are caused by process aid selection

© ARKEMA 2019
 MELT STRENGTH: CELLULAR PVC PERFORMANCE

Process Aid 4
1.8 Cell structure based on
Process Aid 1 x40 MW g/mol PA available melt strength:
1.6
● Melt strength largely
1.4 determined by acrylic
process aid selection
1.2
Force (N)

● Capturing and surviving

1 gas evolution most
important during cellular
0.8
PVC processing
0.6 ● If MW chosen is too low,
large voids will appear in
0.4
Control PA the foam structure
0.2
throughout the PVC article

0
10 20 30 40 50 60 70 80 90 100

Draw Down Velocity (mm/s)

© ARKEMA 2019
OPTIMIZING CELL STRUCTURE DENSITY REDUCTION
2.0
Conventional PA
Molecular weight for cellular 1.8 High MW PA
applications is critical: Ultra-high MW PA
● Generally, increasing 1.6

molecular weight is
desirable for improved 1.4

efficiency and final PVC melt

performance 1.2 strength
● Drawbacks of ultra-high Force [N]
1.0
MW technology are
possible with diminished
0.8
melt flow and high
extrusion torque
0.6
● Process aid selection
based on understanding
0.4
processing needs is
essential PVC melt strength and cell structure uniformity as Mw
0.2

*cellular PVC formulations w/ 5 phr PA

0.0
20 40 60 80 100 120 140
Pull-off speed [mm/s]

© ARKEMA 2019
 MELT STRENGTH: CELLULAR PVC PERFORMANCE
2.0

1.8

Cell structure control by 1.6

process aid type:
1.4
● Smallest, most consistent
Ultra-high MW
cell structure with ultra- Avg = 55 µm
1.2
high MW process aid
Force [N]

● Lower molecular weight 1.0

process aids allow cell
coalescence and collapse 0.8
High MW
● Proper selection based on Avg = 67 µm
0.6
application and density
targets for the final PVC
0.4
article Traditional
High MW
0.2 Traditional
Ultra-high MW
Avg = 77 µm
0.0
0 10 20 30 40 50 60 70 80 90

Pull-Off Speed [mm/s]

© ARKEMA 2019
FLEXIBLE AND SEMI-RIGID PVC APPLICATIONS

Promotion of the Gelation of PVC

● Effect on fusion time by:
PA Molecular Weight (M.W.) PA loading

M.W of PA No PA
PA content

Formulation: 30 phr plasticizer

● Higher MW or higher PA content leads to faster fusion of PVC formulations

© ARKEMA 2019
FLEXIBLE AND SEMI-RIGID PVC APPLICATIONS

Promotion of the Gelation of PVC

● PAs differ by composition and molecular weight
Formulation: 70 phr plasticizer - 2 phr of PA

● PA always reduces the gelation time of PVC formulations

● Reduction to a great extent depending on the nature of the plasticizer

© ARKEMA 2019
 FLEXIBLE AND SEMI-RIGID PVC APPLICATIONS

Calendering process
● Effect of plasticizer content on rolling bank
No PA 3 phr PA

30 phr Plasticizer

50 phr Plasticizer

Test run on Two-Roll mill

80 phr Plasticizer Collin (Ø 150) @ 160°C

● Addition of PA improves rolling bank quality, even at high plasticizer content

© ARKEMA 2019
SEMI-RIGID AND FLEXIBLE PVC APPLICATIONS

Calendering process
● Effect of processing aid loading level on rolling bank
Formulation: 30 phr plasticizer

Test run on Two-Roll mill

Collin (Ø 150) @ 160°C

● Increasing the PA content significantly improves the rolling bank quality

© ARKEMA 2019
 SEMI-RIGID AND FLEXIBLE PVC APPLICATIONS
Filler incorporation by process 4000

aid selection 130°C, 50 RPM and 80 g sample

● Added process aid promotes 3500

fusion with high loading levels of

filler 3000
● Process aid chemistry can
determine effectiveness
2500

Component phr

Torque (m g)
SE850 (0.82 IV) Resin 100 2000

DOTP 20 Process Aid 1

1500
Epoxidized SBO 10 Process Aid 2
Process Aid 3
CaZn stabilizer 2.5 1000
Process Aid 4
Stearic acid 0.2 Process Aid 5
500
No Process Aid
Process Aid 3.0
Calcium carbonate (3 µm) 150 0
0 1 2 3 4 5 6 7 8
Titanium dioxide 2.5 Time (min)

© ARKEMA 2019
 SEMI-RIGID AND FLEXIBLE PVC APPLICATIONS

Rheology of high filled PVC formulation

● Addition of various processing aid and effect of loading content

Up to 10 MM g/mol

PA4

PA3
Molecular
Weight
PA2

PA1

Min. ~ 1,000,000 g/mol

Formulation with 30 phr plasticizer & 200 phr CaCO3 (LVT type formulation)

● Melt strength increases with addition of PA and when increasing loading content ~up to 10 phr

© ARKEMA 2019
SEMI-RIGID AND FLEXIBLE PVC APPLICATIONS

Effect on PVC Dry blend

● Variation of loading and Tg 1.5 phr PA

of the PA
(into high speed mixer
reaching 110 °C)

● PA can behave
like a flow aid additive
5 phr PA

Medium Tg High Tg

© ARKEMA 2019
THANK YOU!
Plastics Additives Support
ARKEMA
King of Prussia R&D Center
900 First Avenue,
King of Prussia, PA 19406
Contact: Kevin Yocca
New Business Development Manager
kevin.yocca@arkema.com
610 878 6911 (office)
484 343 8055 (mobile)

Acknowledgements
Mark Lavach, Manager ASR, Jason Lyons, Business Manager Kepstan®
Frederic Malet and Alexandre Vermogen, Plastics Additives R&D
The statements, technical information and recommendations contained herein are believed to be accurate as of the date hereof. Since the conditions and methods of use
of the product and of the information referred to herein are beyond our control, Arkema expressly disclaims any and all liability as to any results obtained or arising from any
use of the product or reliance on such information; NO WARRANTY OF FITNESS FOR ANY PARTICULAR PURPOSE, WARRANTY OF MERCHANTABILITY, OR ANY OTHER WARRANTY,
EXPRESS OR IMPLIED, IS MADE CONCERNING THE GOODS DESCRIBED OR THE INFORMATION PROVIDED HEREIN. The information provided herein relates only to the specific
product designated and may not be applicable when such product is used in combination with other materials or in any process. The user should thoroughly test any
application before commercialization. Nothing contained herein constitutes a license to practice under any patent and it should not be construed as an inducement to
infringe any patent, and the user is advised to take appropriate steps to be sure that any proposed use of the product will not result in patent infringement.
© 2019 Arkema Inc.

© ARKEMA 2019