Luperox® for Polymerization of Ethylene

 Luperox® initiators are available worldwide to offer solutions for polymerization of ethylene and copolymers.


Selecting the proper Luperox® organic peroxide is a critical parameter to consider for polymerization. The "initiator package" affects directly the polymer properties and also the productivity (% conversion, cost per unit of monomer converted).


Polymerization is propagating macroradicals building polymer chains to generate short or long branched structure.  Short segments affect mechanical performance of the finished polymer while longer branched chains affect the rheological behavior.  The reaction takes place at temperatures between 100 to 300°C and at high pressure (1200-3000 bars). At these pressures ethylene liquefies and acts as a solvent under supercritical conditions.


Molecular weight and density is regulated by controlling the temperature and pressure, and by the addition of a chain transfer agent (e.g. propane).

Peroxide Selection

In order to maximize productivity, multiple peroxides should be introduced throughout the various zones of both tubular and autoclave processes.  This will help start, or "light-off" the polymerization, but also maximize productivity as the temperature and pressure reach the maximum in each reactor zone. 


The criteria for selecting peroxides for various zones is described by the peroxide half-life:


  • Short half-life peroxides alone provide fast light-off, but lower peak temperature.
  • Long half-life peroxides alone provide high peak temperature, but are slower to light-off.

Peroxide Benefits

The benefits of peroxide initiation over oxygen initiation:

  • Lower initiation temperatures
  • Extended cooling zones preventing max peak lagging
  • Increased conversion rate of ethylene + 20 %
  • More efficient use of reactor length

Effect of Temperature

Molecular structure is primarily determined by pressure and temperature. Below summarizes how these parameters impact molecular weight and branching.

 Molecular WeightSCB*LCB**
Temp. ↑ ↓↓ ↑↑ ↑↑
Pressure ↑

* Short Chain branching
** Long Chain Branching


Productivity is proportional to gas inlet and outlet temperatures but temperature profiles impact both properties and productivity.

 ProductivityMelt IndexDensityClarity
Temp. ↑ ↑↑ ↑↑ ↓↓


Tubular Process

In the tubular process, polymerization takes place in a long tube (>1000 m) at high pressure. Peroxide is introduced at different zones to optimize productivity. The reaction temperature profile is controlled by the dose and reactivity of the initiators. Addition of peroxide in various zones can increase the conversion rate of ethylene (+ 20 %) over oxygen initiation alone.


Chart of Staged Peroxide Injection / Tubular Process

Peroxide Injection
Reactor length cooling zone

Autoclave Process

In the autoclave process, polymerization takes place in a series of stirred reactors (2 to 6). Peroxide is introduced in each of the reactors to optimize productivity and performance. The reaction temperature is controlled by the peroxide dose.  Conversion of ethylene to polymer is proportional to the T outlet / T inlet ratio.  Quality is dependent on the mean polymerization temperature, but independent of T outlet.

Chart of Staged Peroxide Injection / Autoclave Process

Autoclave Peroxide Injection

Browse products and solutions

Choose a recommended product and see available formulations or get technical assistance:

Luperox® 554

tert-amyl peroxypivalate



Luperox® 11

tert-butyl peroxypivalate



Luperox® 219




Luperox® 26

tert-butyl peroctoate



Luperox® DEC

didecanoyl peroxide



Luperox® 331

1,1-di-(tert-butylperoxy) cyclohexane



Luperox® 270

tert-butylperoxy isononanoate



Luperox® 7

tert-butyl peroxyacetate



Luperox® P

tert-butyl peroxybenzoate



Luperox® 223

di-(2-ethylhexyl) peroxydicarbonate



Luperox® 10

tert-butyl peroxyneodecanoate



Find the right product for your application!

Contact the Luperox® salesperson in your region to learn more

North America

Jay Divyesh SHAH
Digital & Market Manager

Central America

Monserrat ALVAREZ
Sales Manager
Arkema Mexico SA de CV
Gustavo Baz 2160 - 3, La Loma, Tlalnepantla, Mexico 54070

South America

Business Unit Manager
Arkema Quimica LTDA
Avenida Ibirapuera 2033 4° Andar - Bairro Moema CEP 04029-901 SÃO PAULO (SP) BRASIL

Europe and Africa

Business Manager
420 rue d'Estienne d'Orves 92705 Colombes Cedex FRANCE


Sales Manager
Arkema Peroxides India Private Ltd
1st Floor, Balmer Lawrie House 628, Anna Salai, Teynampet, Chennai (Madras), India 600 018

Southeast Asia

Regional Manager
10 Science Park Rd #01-01A, The Alpha, Singapore Science Park II, Singapore 117684

Far East

Jonathan CHANG
Greater China Sales Director
Arkema Changshu Chemical Co Ltd
7F Block 1, Life Hub@Daning 1868 Gonghexin Rd. Shanghai 20072 CHINA

Middle East

Sales Manager
ARKEMA FRANCE, Middle East Office
Unit 2801 Indigo Icon Tower, Dubai UAE