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ORGANIC PEROXIDES /

Polymer crosslinking
 Organic peroxides product range for crosslinking
Storage
PHYSICAL Assay ACTIVE temperature
FAMILY NAME CHEMICAL NAME CHEMICAL FORMULA PRODUCT NAME CARRIER UN SADT PACKAGING
FORM (%) oxygen
 ARKEMA, Ts max Ts min
Innovative Chemistry LUPEROX® F Flakes solid flakes 96 min 9.1% - 3106 70°C 30°C - 20 kg bag in carton box
LUPEROX® FreeO solid flakes 96 min 9.1% - 3106 70°C 30°C - 20 kg bag in carton box
The Arkema group is one of the main LUPEROX® MIX paste 42 3.97% - 3077 90°C 40°C - 25 kg in plastic bin

global producers of organic peroxides. LUPEROX® F90P powder 90 8.2% Silica 3106 80°C 30°C - 20 kg bag in carton box

Its expertise also extend to glass coatings, LUPEROX® FreeO-40 granule NR


LUPEROX® F40P powder NR
additives for PVC, catalysts for synthesis 40 3.8% Calcium carbonate + Silica 80°C 30°C - 20 kg bag in carton box
1,3-1,4-bis(tert-butylperoxyisopropyl) LUPEROX® F40 granule NR
in fine chemicals, polyester resins and benzene LUPEROX® F40P-SP2 powder 3106
Cas N° 25155-25-3 LUPEROX® F40KEP powder
specialty epoxides. LUPEROX® F 40 3.8% Kaolin NR 80°C 30°C - 20 kg bag in carton box
Molecular weight: 338.5 g LUPEROX® F40KE granule
The Organic peroxides activity, Melting point: 37-54°C LUPEROX® F40MG pellet
headquartered in King of Prussia (United Active oxygen: 9.45% 25 kg bag in carton box
LUPEROX® F40MF sheet 40 3.8% EPM NR 80°C 30°C -
20 kg bags in big box
States), operates facilities throughout the LUPEROX® F40MG-SP pellet

world. Its products, services and LUPEROX® F40MGEVT pellet 25 kg bag in carton box
40 3.8% EPM + EVA + Silica NR 80°C 30°C -
LUPEROX® F40MFEVT sheet 20 kg bags in big box
technical support are available to LUPEROX® F40ED pellet
customers in Europe, North America, LUPEROX® F40EDF sheet 40 3.8% EPM + Calcium carbonate + Silica NR 80°C 30°C -
25 kg bag in carton box
20 kg bags in big box
Asia, Africa and the Middle East. LUPEROX F40M-SP
®
pellet
LUPEROX® DCP solid crystals 99 min 5.9% - 3110 80°C 30°C - 20 kg bag in carton box
Arkema is building the future of the LUPEROX® DC40P powder
chemical industry using a responsible, LUPEROX® DC40 granule 40 2.4% Calcium carbonate + Silica 3077 80°C 30°C - 20 kg bag in carton box
LUPEROX® DC40P-SP2 powder
innovation-based approach.
LUPEROX® DC40KEP powder
Dicumyl peroxide 40 2.4% Kaolin 3077 80°C 30°C - 20 kg bag in carton box
LUPEROX® DC40KE granule
France’s leading chemicals producer, Cas N° 80-43-3
LUPEROX® DC40MG pellet
Arkema is aiming to become one of the LUPEROX® DCP Molecular weight: 270,4 g LUPEROX® DC40MF sheet 40 2.4% EPM 3077 80°C 30°C -
25 kg bag in carton box
Melting point: > 39°C 20 kg bags in big box
LUPEROX® DC40M-SP2 pellet
global leaders in specialty chemicals. Active oxygen: 5.92%
LUPEROX® DC40MGF pellet 25 kg bag in carton box
With its 14,000 employees and LUPEROX® DC40MG-SP2 pellet
40 2.4% EPM + Calcium carbonate + Silica 3077 80°C 30°C -
20 kg bags in big box
91 industrial sites in 40 countries, Arkema 25 kg bag in carton box
LUPEROX® DC40MGPE pellet 40 2.4% EPM + LPDE 3077 80°C 30°C -
has a revenue of €6.4 billion. 20 kg bags in big box
The Arkema group was created in October LUPEROX® DC40PE powder 40 2.4% LPDE 3077 80°C 30°C - 25 kg bag in carton box

2004, following the reorganization of 2,5-dimethyl-2,5-di(tert-butylperoxy) LUPEROX 101


®
liquid 94 min 10.4% - 3103 82°C 30°C 8°C 25 kg in plastic bin
hexane
Total’s Chemicals branch. Cas N° 78-63-7 LUPEROX 101XLS50
®
powder 50 5.5% Silica 3108 75°C 30°C - 20 kg bag in carton box
Thanks to innovation, targeted acquisitions LUPEROX® 101 Molecular weight: 290.4 g
Melting point: 8°C LUPEROX 101XL45
®
and investments in emerging countries, LUPEROX® 101XL45-SP2
powder 45 5.0% Calcium carbonate + Silica 3108 75°C 30°C - 20 kg bag in carton box
Active oxygen: 11.1%
it has become a recognized world player
Tert-butylcumylperoxide
in the field of specialty chemicals. Cas N° 3457-61-2
LUPEROX® 801 Molecular weight: 208.3 g LUPEROX® 801 liquid 95 min 7.4% - 3107 84°C 30°C 16°C 25 kg in plastic bin
Melting point: 11.3-19.5°C
Active oxygen: 7.7%

2,5-dimethyl-2,5-di(tertbutylperoxy)
hex-3-yne LUPEROX® 130MO85 liquid 85 9.5% White oil 3103 90°C 30°C 8°C 25 kg in plastic bin
Cas N° 1068-27-5
LUPEROX 130
®
Molecular weight: 286,42 g
Active oxygen: 11.2%
Note: this product only exists as LUPEROX® 130XL45 powder 45 5.0% Calcium carbonate + Silica 3106 90°C 30°C - 20 kg bag in carton box
extended grade

n-butyl-4,4-di(tert-butylperoxy)valerate Calcium carbonate + Sodium


Cas N° 995-33-5 LUPEROX® 230G40 granule 40 3.8% 3108 65°C 30°C - 20 kg bag in carton box
aluminium silicate
 CONTENTS LUPEROX® 230 Molecular weight: 334.4 g
Active oxygen: 9.57%
Note: this product only exists as LUPEROX® 230XL40 powder
p. 2/3 Product range for crosslinking 40 3.8% Calcium carbonate + Silica 3108 60°C 30°C - 20 kg bag in carton box
extended grade LUPEROX® 230XL40-SP powder

p. 4/5 Kinetic 1,1-di(tert-butylperoxy)


LUPEROX® 231G40 granule Calcium carbonate + Sodium
-3,3,5-trimethylcyclohexane 40 4.2% 3110 57°C 30°C - 20 kg bag in carton box
Cas N° 6731-36-8 LUPEROX® 231XL40 powder aluminium silicate
p. 6/7 Processing
LUPEROX® 231 Molecular weight: 302.4 g
Active oxygen: 10.58%
p. 8 Scorch protection solution Note: this product only exists as LUPEROX® 231XL40-SP powder 40 4.2% Calcium carbonate + Silica 3110 57°C 30°C - 20 kg bag in carton box
extended grade
p. 9 Smell free solution Di(2,4-dichlorobenzoyl) peroxide
Cas N° 133-14-2
p. 10/11 Application polymers LUPEROX DCBP
®
Molecular weight: 380.0 g
LUPEROX® DCBP paste 50 2.1% Silicone oil 3106 60°C 35°C - 25 kg in plastic bin
Active oxygen: 4.21%

2 3
kinetic kinetic

 Kinetic and Half-life time  Decomposition Rate


The half-life of a peroxide at any specified temperature is the time required at that temperature to affect a loss of one half It is possible to estimate the quantity of reacted organic peroxide as a function of time.
of the peroxide’s active oxygen content. In the following graphs various peroxides are compared for an easy selection based on decomposition rate at given temperatures.
Half-life data is essential for selecting the optimum peroxide for a specific time-temperature combination.
Peroxide half-life data is generated by studying their thermal decomposition in various solvents at low concentrations.
The polarity of the solvent used will influence the peroxide decomposition kinetics. Thus it is important to compare peroxide
half-life data generated in the same solvent and at the same concentration.  HIGH TEMPERATURE CURING ORGANIC PEROXIDES
% Remaining peroxide vs. time
at 180°C
100 %
Luperox® 130
90 % Luperox® 801
Half-life time/temperature curves
in n-decane or n-dodecane 80 % Luperox® 101

100,000 Luperox® F
Luperox® 130 70 %

% Remaining Peroxide
Luperox® DCP
Luperox® 801 60 %
10 Hours Luperox® 101 50 %
Luperox® F
40 %
Luperox® DCP
30 %
10,000 Luperox® 230
Luperox® 231 20 %

10 %
1 Hour
0%
0 5 10 15 20
Time (minutes)
1,000
Time (seconds)

 low TEMPERATURE CURING ORGANIC PEROXIDES


100 % Remaining peroxide vs. time
1 Min at 160°C
100 %
Luperox® DCP
90 % Luperox® 230
80 % Luperox® 231
10
70 %

% Remaining Peroxide
60 %

50 %

40 %

1 30 %
100 120 140 160 180 200 220
Temperature (°C) 20 %

10 %

0%
0 5 10 15 20
Time (minutes)

4 5
processing processing

 Crosslinking density  Cure time


These data were generated using an ODR2000E rheometer. MH (Nm) is a torque measurement which is proportional to the These data were generated using an ODR2000E rheometer.
relative amount of crosslinking bonds created by the peroxide. It is an indication of the mechanical properties to be expected.
This graph shows the cure time represented by T90, which is the time needed at a specific temperature to get 90% of the
peroxide decomposed. This key feature of the peroxide is to be taken into account when selecting the proper peroxide.

Crosslinking efficiency in an EPDM compound at 185°C


T90 vs. temperature
(except for Luperox® 230 and 231 at 170°C)
in an EPDM compound
5.00
Luperox® F 25:00
Luperox® 101
4.75 Luperox 101
®
Luperox® F
Luperox® 801
4.50 20:00 Luperox® 801
Luperox® 231
Luperox® DCP
4.25 Luperox® DCP
15:00 Luperox® 230
MH (N m)

Luperox® 230

T90 (min:s)
4.00 Luperox® 231

3.75 10:00

3.50
05:00
3.25

3.00
00:00
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
130 150 170 190 210
Quantity of peroxide (phr)
Temperature (°C)

 Suggested dosage rate of LUPEROX ®


Organic Peroxides  scorch time
in some polymers

The below data were generated using a Mooney viscometer. TS05 is the scorch time at the processing temperature (usually at the
luperox ®
luperox ®
luperox ®
luperox ®
luperox ®
luperox ®
luperox ®
luperox ® polymer extrusion temperature).
phr of active substance This value represents the time during which the vulcanizable compound can be safely processed before unwanted crosslinking
F DCP 101 130 801 230 231 DCBP
or “scorch” takes place. TS05 is defined by the time needed at a specific temperature to obtain a 5 Mooney Unit increase in the
LDPE 1.2 - 1.8 1.5 - 2.5 1.4 - 2.0 1.2 - 2.0 viscosity as measured from the MV or minimum viscosity.
Low Density Polyethylene

HDPE LUPEROX® MIX


0.5 - 1.2 0.5 - 1.2
High Density Polyethylene 0.8 - 1.6
Mooney scorch TS05 vs. temperature
EVA 0.8 - 1.6 1.2 - 2.0 1.2 - 2.0 1.0 - 1.6 1.4 - 2.6 1.2 - 2.3 in an EPDM compound
Ethyl-Vinyl Acetate
25:00
EPM/EPDM 1.6 - 3.2 2.4 - 5.4 1.7 - 3.4 3.2 - 6.3 2.4 - 6.0
Luperox® 801
Ethylene-Propylene Monomers
Luperox® F
CM 1.5 - 2.4 2.4 - 3.8 2.5 - 4.0 3.3 - 6.0 3.0 - 5.5 20:00 Luperox® 101
Chlorinated polyethylene
Luperox® DCP

Scorch Time TS05 (min:s)


Q 0.2 - 1.0 0.5 - 2.0 0.4 - 1.5 1.4 - 2.0
Silicone rubbers 15:00 Luperox® 230

NBR Luperox® 231


0.5 - 1.5 0.9 - 1.7 1.1 - 2.0 1.2 - 2.2 1.0 - 2.0
Butadiene acrylonitrile rubber
10:00
SBR 0.4 - 1.0 0.7 - 1.5 0.7 - 1.2 0.8 - 1.8 0.7 - 1.6
Styrene Butadiene Rubber
05:00

Example: Typically, 1.6 to 3.2 phr of Luperox® F are used in an EPM/EPDM compound.
For formulated peroxide, this quantity has to be divided by the peroxide content. 00:00
Therefore, 4 to 8 phr of Luperox® F40 is the typical range of quantities used for an EPM/EPDM compound. 90 100 110 120 130 140 150 160 170
SP grades are used at same dosage rate as standard peroxides. Temperature (°C)

6 7
scOrtch prOtectiOn sOlutiOn sMell free sOlutiOn

 scOrch prOtectiOn technOlOgy  luperOx ®


freeO: safer and OdOurless sOlutiOn fOr fOaMed eva

Arkema Scorch Protection technology is a unique technology that provides outstanding protection against scorch both at mixing Luperox® FreeO offers to footwear manufacturers an alternative to current technologies commonly used. Sport shoes with soles made of
and crosslinking temperatures. expanded EVA are known for releasing a strong and persistent odour in manufacturing plants, as well as in retail outlets. This smell is
due to the crosslinking agent and its VOCs (Volatile Organic Compounds), in particular acetophenone.
By increasing the scorch time during mixing and extrusion of the rubber compound, "SP" peroxides are the right technology which allows:
better process control; Luperox® FreeO offers:
higher product quality; small amounts of VOC released;
higher productivity. no release of unpleasant odor;
outstanding crosslinking efficiency (up to 40% lower dosage);
The "SP2" peroxide is the ultimate generation of scorch protection, designed for very scorchy elastomers such as HNBR and very
easy use thanks to its flakes form.
challenging curing conditions such as high injection molding temperature. The Arkema Scorch protection system is an Arkema’s patent.
Luperox® FreeO is a bis isopropyl benzene peroxide.

50:00
Luperox® F40M-SP
45:00 Luperox® F40ED
40:00
Solution to solve
Scorch Issues,  sMell free  excellent cOst/
35:00
to improve quality perfOrMance features
Under typical working conditions organic peroxide
30:00
decomposes in different molecules. Thanks to its characteristics, Luperox® FreeO is an
TS05 (min:s)

25:00 Solution Dicumyl peroxide decomposes in acetophenone excellent crosslinking agent for a large range of rubbers
x3 to improve (52% of total amount), cumyl alcohol and methane. allowing reduction of peroxide consumption up to 37%.
20:00
productivity Acetophenone is characterised by a strong
15:00 Luperox® FreeO is available as pure in flakes form and it
and persistent smell.
allows easy handling and easy weighing.
10:00 Luperox® FreeO decomposes in molecules different in
x2
+ 12°C composition and properties. These decomposition products Luperox® FreeO-40 is the diluted version on calcium
05:00
are considered neither smelling nor persistent volatiles. carbonate in granule form.
00:00 Luperox® FreeO does not contain additives added to mask
115 120 125 130 135 140 145 150 155 160 165
the odour.
Temperature (°C)

 prOductivity increase Benefit  higher crOsslinking efficiency  lOwer vOc generatiOn


As it allows to work at higher process temperature without generating scorch, the Arkema Scorch Protection technology allows xl density of eva foamed compound Luperox® FreeO does generate 68% lower VOC than DCP.
the increase of process speed leading to the increase of productivity in all applications, including extrusion and moulding. as function of peroxide dosage
Luperox® FreeO decomposition products are methane,
24 acetone and ter-butanol, characterised by low boiling point.
22
Thanks to its higher efficiency and its composition,
20
Luperox® FreeO generates much lower organic volatiles

MH-ML (dN.m)
 8 phr perOxide in epdM cOMpOund 18 than other peroxides.
Equivalent crosslinking
16
density
ts2 at moulding temperature (min:s) t90 at moulding temperature (min:s) Luperox®
14
0.85 1.35 unit DCP
FreeO
00:30 04:00 12
Compound EVA PHR 115 115
10
00:25 03:43 0.5 0.8 1.1 1.4 1.7 2.0 Peroxide PHR 1.35 0.85
03:00 Dosage (phr) Peroxide ppm 11760 7404
00:20 03:00
00:21 00:21 00:21 FreeO Dicumyl peroxide
VOC*: acetophenone
00:15 02:00
02:16 ppm 11760
Crosslinking density test demonstrate that Luperox® FreeO cumyl alcohol, methane

00:10 does provide the same crosslinking density at 37% lower VOC*: methane, acetone,
ppm 3766
01:00 loading, or higher crosslinking density at the same loading t-butanol
00:05 rate.
* VOC definition accordingly to D.2004/42/EC

00:00 00:00
F40 @ F40M-SP @ F40P-SP2 @ F40 @ F40M-SP @ F40P-SP2 @
183°C 186°C 190°C 183°C 186°C 190°C

8 9
applicatiOn pOlyMers applicatiOn pOlyMers

 selectiOn / suggested Mixing technOlOgy  aspect / physical fOrM

MASTERbATCHES LIQUID gRADES gRANULES POWDERS


Masterbatch in pellets
Soaking of polymer pellets

Internal mixer

Open mill

Direct peroxide injection

Direct screw compounding without injection

200

 applicatiOn
180
180
160

140
Compounding time (s)

120
120 pOlyMers that can Be crOsslinked
100
Granules
80
100 ABS Acrylonitrile butadiene styrene copolymer
AU/EU Polyurethane rubber
60 75
70 BR Polybutadiene rubber
40 CM Chlorinated polyethylene
45
35 CR Polychloroprene rubber
20 30
CSM Chlorosulfonyl polyethylene
0 EBA Ethylene butylacrylate copolymer
EPM Ethylene propylene copolymer
< s

> s

< s

> s

< s

> s

< s

> s
55

55

55

55

55

55

55

55
A nd

A nd

A nd

A nd

A nd

A nd

A nd

A nd
EPDM Ethylene propylene diene terpolymer
e u

e u

e u

e u

e u

e u

e u

e u
or po

or po

or po

or po

or po

or po

or po

or po
EVA Ethylene vinylacetate copolymer
sh om

sh m

sh m

sh m

sh m

sh om

sh m

sh m
co

co

co

co

co

co
c

FKM Fluoro rubber


ft

ft

ft

ft

d
ar

ar

ar

ar
So

So

So

So

HNBR Hydrogenated butadiene acrylonitrile rubber


H

IR Polyisoprene rubber
NBR Butadiene acrylonitrile rubber
NR Natural rubber
PE Polyethylene

 selectiOn / why tO use MasterBatch POE


Q
Polyolefin elastomer
Silicone rubber
SBR Styrene butadiene rubber
T Polysulfide rubber
EEA Ethylene ethyl acrylate
Experiments were performed with an EPDM compound in a Brabender type
internal mixer.
Standard deviation of MH was determined using an ODR2000E rheometer after Free-flowing powder pOlyMers that cannOt Be crOsslinked
different times of compounding. The times reported in this graph are the mixing
times required to obtain an acceptable standard deviation in MH from batch to ACM Polyacrylate rubber
batch, comparing the various commercially available forms of di-(t-butylperoxy) CIIR Chlorobutyl rubber
diisopropylbenzene. CO Epichlorohydrin rubber
Pre-dispersed peroxide masterbatches dramatically shorten mixing time and ECO Epichlorohydrin copolymer
improve the quality of the elastomer by avoiding premature crosslinking or IIR Butyl rubber
“scorch” in hard or soft compounds. PB Polybutene-1
The final elastomeric composition exhibits a desirably lower and more consistent PIB Polyisobutene
viscosity, essential to molding and extrusion operations. PVC Polyvinylchloride
Masterbatch peroxides are preferred in technical rubber articles production because PP Polypropylene
they provide uniform peroxide dispersion and consistent physical properties. Crystals

10 11
Arkema - A limited liability company with capital of 625 388 180 euros - Nanterre Company and Commercial Registry No. 445,074,685
DIRCOM 4343E / 09.2013 / 10 - ADDI - Photos: Arkema, Thinkstock - Agency: VU DU TOIT
 EUROPE  USA
Arkema Arkema Inc.
420, rue dʼEstienne dʼOrves King of Prussia, PA
92705 Colombes Cedex 900 First Avenue
France King of Prussia, PA 19406
Tél. : 33 (0)1 49 00 80 80 Corp Phone: 610-205-7000
Fax : 33 (0)1 49 00 83 96 R&D Phone: 610-878-6500

A global chemical company and France’s leading chemicals producer, arkema is building the future of the chemical industry every day. Deploying a responsible,
innovation-based approach, we produce state-of-the-art specialty chemicals that provide customers with practical solutions to such challenges as climate change, access
to drinking water, the future of energy, fossil fuel preservation and the need for lighter materials. With operations in more than 40 countries, some 14,000 employees
and 10 research centers, Arkema generates annual revenue of approximately 6.4 billion, and holds leadership positions in all its markets with a portfolio of internationally
recognized brands.

The information contained in this document is based on trials carried out by our Research Centres and data selected from the literature, but shall in no event be held to
constitute or imply any warranty, undertaking, express or implied commitment from our part. Our formal specifications define the limit of our commitment. No liability
whatsoever can be accepted by Arkema with regard to the handling, processing or use of the product or products concerned which must in all cases be employed in
accordance with all relevant laws and/or regulations in force in the country or countries concerned.

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.
See MSDS for Health & Safety Considerations.

420, rue d’Estienne d’Orves


92705 Colombes Cedex – France
Tel.: 33 (0)1 49 00 80 80
Fax: 33 (0)1 49 00 83 96
luperox.com arkema.com

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