ENCORE ® PRIME

Styrene Free resin system Th. Foussard – G. Cledat

Pole Européen de la Plasturgie

Innov’ days

Outline of the presentation

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STYRENE regulation

Spray-Up application

Curing In Place Pipe (CIPP)

SMC automotive application

3

Styrene Regulation

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In Europe : DNEL will be for all Europe @ 20 ppm

Today : - UK : 100 ppm

- France : 50 ppm

- Germany : 20 ppm

- Sweden : 10 ppm for new installation

In France : The Decree of 9 May 2012 which sets limit values for

occupational exposure to some chemicals published in the Official Journal of

10 May 2012

No longer mentions styrene (when he appeared in the original project as a

TWA*/8h 23.0 ppm to meet before 01/07/2014).

(*)TWA = Time Weighted Average

Styrene regulation: VOC Reduction

Dangerous Substance Directive /

Dangerous Preparations Directive

(before 2015)

Classification Labelling

Packaging

(at least in 2015)

New hazard classification

of styrene

Reprotoxic cat 3 Reprotoxic cat 2

Disclosure Threshold

(reprotoxic substance)

≥ 1% ≥ 0,1%

Classification Threshold

(reprotoxic substance)

≥ 5% ≥ 3%

Classification and

labeling

Xn, Harmful

R10 - Flammable

R48/20 - Harmful: danger of serious

damage to health by prolonged

exposure through inhalation

R20 - Harmful by inhalation

R36/37/38 - Irritating to eyes, respiratory

system and skin

R63 - Possible risk of harm to the

unborn child

Danger

Flam. Liq cat 3 - H226: Flammable liquid

STOT RE 1 - H372: Causes damage to

organs through prolonged or repeated

exposure

Acute inhalation tox. Cat 4 - H332:

Harmful if inhaled

Skin irrit cat 2 - H315: Causes skin

irritation

Eye irrit cat 2 - H319: Causes serious

eye irritation

STOT SE3 - H335: May cause respiratory

irritation

Reprotox cat 2- H361: Suspected of

damaging fertility or the unborn child

Styrene regulation: Impact on classification

NEW

NEW

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Development of Styrene-Free technology in

several market sectors:

- Spray-Up application : Blend styrene with other

reactive monomers to reduce VOC emissions:

LVOC UPR

- Curing In Place Pipe: Styrene free solution to

decrease VOC and Odor with ENCORE® PRIME

for CIPP

- Automotive: UPR and LP additives for SMC

compliant with automotive request with

ENCORE® PRIME for SMC

Our solution to answer:

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Spray-Up application at room temperature

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Spray up application Characteristics of Resins

Methods Reference LVOC UPR

Specific Weight (g/cm3) 1,10 1,10

Viscosity BK -25°C-SP3V50 (dPa.s) 7-9 7-9

Volatils content (%) 34-36 35-37

Reactivity 23°C-2%MEKP-100g

-Gel time (mn) 29-34 29-34

-Peak time (mn) 78-90 78-90

-Temperature at peak (°C) 60-70 90-110

LVOC UPR

REFERENCE

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Spray up application Characteristics of Resins

0

5

10

15

20

25

30

35

40

0 2 4 6 8

bar

col

time (hours)

LVOC UPR

REFERENCE

Curing Gel time drift

Barcol hardness 4 layers at 23°C Exotherm on laminates

DSC Reference LVOC UPR

4 hrs after

peak

79% 78%

R127 T 0 T0 + 34

days

Gel time 31 min 32 min

20

30

40

50

60

70

4 5 6 7 8 9 10 11 12

temperature °C

Layers

REFERENCE

LVOC UPR

Spray up application Characteristics of Resins

Hydrolysis resistance

ISO-62 test 60 days at 60°C (comparative)

Water desorption

Determination of water desorption Samples placed in a non-ventilated

oven for 10 days at 105 ° C

0

0,5

1

1,5

2

2,5

0 10 20 30 40 50 60 70

%

Immersion time in days

LVOC UPR

REFERENCE

Reference LVOC UPR

Sample N°1 0,42% 0,40%

Sample N°2 0,41% 0,43%

Average 0,415% 0,415%

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on pure resin – catalyst system : 0.15% Co 6% + 1.2% MEKP50 – Post cured 16h at 40°C

Reference LVOC UPR

TENSILE

ISO 527

Tensile strength (MPa) 51 MPa 50 MPa

Elongation at break (%) 2.1 % 2.2 %

FLEXURAL

ISO 178

Flexural modulus (MPa) 3 500 MPa 3 300 MPa

Flexural strength (MPa) 80 MPa 105 MPa

HDT (°C) - ISO 75-2 – Method Ae – Post-cured 40°C 60°C 55°C

Spray up application Mechanical properties

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Projection step

0

50

100

150

200

250

0 5000 10000 15000

pp

m

secondsSPRAY-UP

resin/glass fiber

1st SIDE

Pause

SPRAY-UP resin/glass fiber

1st SIDE

SPRAY-UP resin/glass fiber

2nd SIDE

Pause

Preparation

step

TOTAL TIME = 3h50

SPRAY-UP

resin/glass fiber

2nd SIDE

Spray up application Projection step: styrene emission measurement

LVOC UPR

Reference

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Reference LVOC UPR

PROJECTION

STEP

MOLDING

STEP

PROJECTION

STEP

MOLDING

STEP

STYRENE EMISSION

average value

Mini RAE (3h00) 43 ppm 91.2 ppm 30.7 ppm 34.6 ppm

STYRENE EMISSION

average value

measure with a Charcoal trap +

pump during 1 work day (7h30) A

120 ppm 85 ppm 38 ppm 24 ppm

Spray up application Projection step: styrene emission results

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Curing In Place Pipe (CIPP)

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CIPP Process

- Thickenable resin thixo or non thixo for customers that prepare liner.

Photoiniators used mainly for this process

Glass fiber Liner prepare by

winding of

impregnate fiber Liner is installed by UV

cured UV light

UV curing

Hot water or steam curing system

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CIPP: Styrene and its disadvantages

At this stage the main issue is :

The odor

Very low odor threshold :

~0.1 ppm = 1 drop per 100 m3

(1 room 40 m²)

Smell "gas" according to some people

TWA / 8 h : 50 ppm

Certainly 20 ppm in a near future

REQUIREMENTS

17 -

CIPP The solution

Development of UPR & VER styrene-free resins:

ENCORE ® PRIME product range

- No styrene odor for installer

- Comfort for residents

- Better working conditions in the workshops for liner impregnation

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Reactivity R 149*

Gel time ( >70°C) 29mn20s

Peak time 31mn05s

Peak T°C 169°C

Viscosity Brookfield

Spindle 4 Speed 50 8.9 dPa.s

Thix Index 2.2

Pot life @ 20°C

Gel time 13hrs

Viscosity Brookfield after 1 week

Spindle 4 Speed 50 9 dPa.s

Thix Index 2

*Reactivity R149 (60°C)

1 g TRIGONOX 42S (AKZO) = peroxy-3,5,5-trimethyl

hexanoate de ter butyl

0.8 g PERKADOX 16 (AKZO) = bis(4-tertiobutylcyclohexyl)peroxydicarbonate

After 1 week, no bubble,

no sedimentation

CIPP

ENCORE®PRIME VER for CIPP

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Styrene Free SMC formulations

for Automotive applications

ENCORE ® PRIME for SMC

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Automotive application Styrene free resin system: ENCORE ®PRIME for SMC

Context :

- Requirements of automotive OEMs are more and more severe regarding

odor

- Preliminary studies have shown that complete substitution of styrene is

required to get significant odor reduction

- Styrene have been orange or black listed by few European OEMs

Aim :

- Development of low odor and low tox resin and LPA for Low Profile SMC

formulation for automotive application (Tailgate or floor board for instance)

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Automotive application Choice criteria for alternative monomers

Large panel of alternative

allylic, vinylic, (meth)acrylic

monomers, according to

several choice criteria :

- Toxicity (eco/tox labeling), odor,

flashpoint

- Viscosity cut, curing at

high/medium temp. (~150°C),

volatility, impact on thickening w/

MgO

- Availability, cost

Styrene diluted

UPR

Encore ®

Prime

Risks

Xn,

R10, R48/20,

R36/38

None

Flash point 32°C > 110°C

OEM* black list KO OK

Comments OdorMedium

odor

Viscosity cut Best OK

Cost 1 2 from 2,5

* Renault, PSA, DM, BMW (VDA), Scania, Volvo substance

black/grey/orange lists

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Automotive application ENCORE ® PRIME for SMC/BMC

Development of a comprehensive ENCORE ® PRIME range

of resin and LPA (based on PVAc, PMMA and Saturated

polyester)

Diluted in methacrylates

Covering a large panel of applications (standard LP

formulation, LS pigmented formulation)

Development of pigment (black) paste with partner in order to

limit VOC emission from conventional paste resin systems

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Same kind of shrinkage control compare to standard SMC

from 0.8 to - 0.5%

according to low profile additive type and content and SMC

formulation

Mechanical properties (Flexural modulus and strength,

impact resistance …) very similar to conventional SMC

formulation

Lower CTE ( ~14 . 10-6 K-1 @ 20°C), very close to steel

alloys

Automotive application ENCORE ® PRIME for SMC/BMC Shrinkage, mechanical and thermal properties

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Automotive application ENCORE ® PRIME for SMC/BMC Odor and VOC emissions

VOC emission reduced by a magnitude 2.5

(VDA 278 standard / Renault D 423109)

Dramatic reduction of BTXES emission: - 76%

About 2/3 of COV emission coming from initiators

Odor evaluated at 2.9 (scale from 0 to 5) (Renault D 493001)

standard LP SMC formulation rated at 3.7 by the same panel

CONCLUSION

ENCORE ® PRIME is a styrene free solution

dedicated to many market sectors

VOC emission can be reduced up to 70%

Odor is limited

ENCORE ® PRIME is available for SMC and

CIPP applications in UPR and VER

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