Chain Transfer Agents

Technical brochure

Chain Transfer Agents

Thiochemicals and Chain Transfer Agents

Main CTA:
n-octyl mercaptan n-dodecyl mercaptan Tertiary-dodecyl mercaptan (NOM) (NDM) (TDM)
Primary mercaptan

CH 2

SH

Secondary mercaptan

R1
Other Light & Heavy Mercaptans
Methyl mercaptan Ethyl mercaptan Tertio-butyl mercaptan Benzyl mercaptan Tertio-nonyl mercaptan (MM) (EM) (TBM) (BZM) (TNM)

CH R2 SH

Tertiary mercaptan

R1 R2 R3 SH

Chain Transfer Agents

Other mercaptans
Water soluble CTA: Thioglycolic acid

TGA

O HS CH2 C O R TGA : R=H IOTG : R = iso-C8H17 EHTG : R = CH2-CH(C2H5)-nC4H9

Functional CTA: Iso-octyl thioglycolate 2-ethylhexyl thioglycolate

IOTG EHTG

Dithio coumpounds: 1,8 Dimercapto 3,5 dioxaoctane DMDO HS-CH2-CH2-O-CH2-CH2-O-CH2-CH2-SH

Thioglycolic acid and derivatives are odorless in comparison with the other mercaptans
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Thiochemicals A Global Business

Europe 2 R&D centers: GRL (Lacq, F) CRRA (Lyon, F) 3 Plants: Lacq (F), Mourenx (F) Rotterdam (Nl)

North America 1 R&D center: KoP (Pa) 4 Plants:) Houston (Tx) Beaumont (Tx) Mobile (Al)

Asia 1 R&D center: KTC (Kyoto, J) 4 Logistic Hubs: Japan, Singapore Taiwan China

Chain Transfer Agents

Mercaptan (=Thiols) Processes

NOM, NDM: photochemical process

R CH 2
H2S h

R S H

TDM: catalytic process

H2S catalyst

SH

Chain Transfer Agents

Specifications

Product Appearance

NOM No turbudity or suspended matter 21.6 Potentiometry 98.5 Chromatography

NDM No turbudity or suspended matter 15.5 Potentiometry 98.5 Chromatography

TDM Clear

Mercaptan Sulfur (wt-%) + Method

15.6 Potentiometry 98.5 Calculated from Mercaptan Sulfur 15 Spectrophotometer

Purity (wt-%) + Method

Color APHA

15 Spectrophotometer

20 Spectrophotometer

Chain Transfer Agents

Solubility parameters

Solubility TDM Insoluble in water (20 C) NDM Insoluble in water (20 C) <1mg/mL Hydrocarbons Alcohols (slightly) NOM Practically Insoluble in water (20 C) 4mg/mL Hydrocarbons Alcohols Ethyl ether Alcohols Ethers TGA Completely soluble (20 C)

Hydrocarbons

Chain Transfer Agents

Odor Detection limits of some thio compounds

Detection limit (ppb vol) 25

Detection limit (ppb vol) 1.25

20

15

0.75

10

0.5
5

0.25

og en D su im lfi et hy de ls D ul ie fid th D e yl in s -p ul ro f py ide D ls ii -p ul f ro py ide D l im su et lfi hy de ld D is ie ul th Et fid yl hy e di lm su et l f id hy e D im l dis et ul fid hy e lt ris D ie u th lfi Te de yl tra tr i hy su dr lfi ot de hi op he ne

H yd r

0
m er ca pt an m ne rc pr ap op ta yl n m e i-p rc ap ro py ta n lm e nrc bu ap ty ta lm n er ca i-b pt ut an yl m er t-b ca pt ut an yl m er ca pt an Et hy l

These products smell at ppb concentrations because human nose is very sensitive to thiols.
F.V. Willby, 35 persons panel

Ex: MeSH Human Olfactory Threshold = 1 ppb = 0.001 ppm Threshold Limit Value - Short Term Exposure Limit = 0.5ppm
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M et hy l

Main application domains of Thiols

TDM (butadiene based copolymers) Rubber (SBR/NBR) Latex (SB latex/XSBR) Plastics (ABS/PS) Resins (Toner/MBR) Reaction Medium Bulk Solution Gas phase Homogeneous

NDM

Rubber (neoprene) Plastics (ABS/PMMA)

NOM Plastics (ABS/PMMA)

Each process/recipe is optimized with a specific chain transfer agent. Process Unit Continuous

Semi-continuous

Heterogeneous Suspension Emulsion

Batch

Chain Transfer Agents

Chain Transfer Agents

Mechanism & Performances

Chain Transfer Agents

Free Radical Polymerization Mechanism

MW

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FRP with Chain Transfer Agent

Transfer to thiol (=mercaptan)

MW

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Main CTA characteristics

The efficiency of a chain transfer agent (CTA) is characterized by a chain constant: Ctr
Transfer rate coefficient (ktr) Propagation rate coefficient (kp)

Ctr=

Ctr is directly impacted by the monomer (or mixture of monomers) Propagation rate and MW distribution are also impacted by re-initiation step

Case 1 2 3 4

Kinetics kp>>ktr and kikp kp<<ktr and kikp kp>>ktr and ki<kp kp<<ktr and ki<kp

Effect Normal Transfer Telomerization Retardation Degradative Transfer

Rp None None

MW

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RSH characteristics
SBL (75/25) polym erization

Primary thiols are much reactive than secondary and tertiary

RSH Consumption

1 NDM TDM 0.75

0.5

0.25

The shorter the chain, the faster the transfer

0 0 0.25

SBL (75/25) polymerization 1 n-C8 n-C12 n-C14 n-C16

0.5 Monomer Conv.

0.75

SBL (75/25) polymerization 1 t-C8 t-C12 t-C14 t-C16

0.75 RSH Consumption

0.75 RSH Consumption

0 0.25 0.5 0.75 Monomer Conv. 1

0.5

0.5

0.25

0.25

0 0 0.25 0.5 0.75 Monomer Conv. 1

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New Chain Transfer Agents for RAFT polymerization

Mechanism & Performances

Chain Transfer Agents

Controlled Radical Polymerization (CRP) versus FRP

MW

MW

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* RAFT: Reversible Addition Fragmentation Transfer

Random Copolymerization

MW

MW

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Block copolymerization

MW

MW

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DiBenzylTriThioCarbonate (DBTTC) for RAFT Polymerization

Under development at Arkema
Product Formula
S S S

Registration ELINCS registration (done for V<1T) And outside E.U. zone (on request) TSCA registration (on going) Legal part Arkema holds IP patent rights (license + sublicense) for the use of RAFT agents in some specific polymerization processes and their applications Product available under secrecy agreement

RN CAS : 26504-29-0 Purity > 95 % Physical state: solid (mp 27-30 C) Degradation temperature > 250 C Almost odorless product Irritant Available for sampling or purchase Already synthesized at pilot scale

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Thiochemical Innovators
Our technological expertise Sulfur chemistry synthesis starting from S, H2S,NaSH or CS2 Application knowledge in refining, steamcracking, polymerization, gas odorization, metal plating, mining and lubrication

Address us your request for new CTA

Our industrial development equipment Arkema operates several pilot and multipurpose plants managed under ISO9001 and ISO14001 standards, with a total reactor capacity exceeding 75m3, either glass-lined or stainless steel These facilities, staffed with senior scientist, engineers and project managers, can apply a large range of reactions and process capabilities They allow Arkema a fast scale-up of new molecules from the lab to industrial production

Our lab tools Analytical means especially developed for Thiochemicals and heavy general analytical capabilities Olfactometric laboratory to help your address issues linked to odors in your application Application testing equipment: flotation cell, polymerization equipment, plating cells, tribological testing tools, polymer characterization, steam cracking and hydrotreatment lab pilots

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