PRODUCT DATASHEET

BlocBuilder MA regulator
TECHNOLOGY FOR CONTROLLED STRUCTURE POLYMERS

BlocBuilder MA regulator is an alkoxyamine joining a methacrylic acid-based radical initiating species with the nitroxide-based reaction controller, known as SG1, in one molecule (Fig.1). This attribute eliminates the need for an external initiation source and the perfect initiator-to-controller ratio facilitates synthesis of polymers of reduced polydispersity as initiation is virtually simultaneous and occurs at low temperature (T>30-40C).

Numerous manufacturing/process options are practical with BlocBuilder MA regulator including bulk, solvent, and aqueous-phase polymerization processes, including emulsion and suspension. Polymerization temperatures depend on the monomer(s) used and typically range from 25 to 125C. Typical polymerization temperatures for polymerizing styrene-, acrylate-, and methacrylatebased monomers and obtainable conversions are listed in Table 1. These temperatures achieve a reasonable balance between polymerization kinetics and maintaining an acceptable level of control.

Fig.1: BlocBuilder MA decomposition to Initiator + Controller

BlocBuilder MA c ontroller Heat P O N O P O O

Table 1: Typical range of polymerization temperature

Monomer Type Styrene Acrylate Temperature (C) 90-120 110-120 Conversion (%) 90+ 90+ 50 (pure) 90+ (mix*)

HO O

N O O

HO O

Alkoxyamine

Initiator

S G1

Methacrylate

BlocBuilder MA regulator can be easily converted to a multifunctional alkoxyamine in a onestep process, allowing for synthesis of a rich assortment of chain architectures (Fig. 2). Symmetric ABA type triblock copolymers or multiarmed star polymers for example, are easily synthesized in a simple 2-step process with multifunctional alkoxyamines.

* Methacrylate plus a small amount of a styrenic comonomer.

The versatile BlocBuilder MA regulator enables synthesis of a substantial array of polymer structures, as highlighted hereafter. Structures as simple as polymers having controlled molecular weight and low polydispersity and gradient copolymers, to more complex block structures including diblock and both symmetric or

Product Data Sheet- BlocBuilder MA regulator February 2011-Version 5

Arkemas BlocBuilder MA regulator technology is a unique nitroxide-based technology capable of controlling free radical polymerizations. BlocBuilder MA regulator technology allows tailoring of polymer composition as well as control of polymer molecular weight, polydispersity, and copolymer sequencing. BlocBuilder MA regulator is patented technology providing a practical and robust method for the design of novel materials spanning rich architectures (e.g., block, graft/comb, and gradient copolymers, etc.) and tailored end-use application properties; opening up tremendous possibilities for a wide range of polymer markets.

Fig. 2: One step synthesis of (multi)functional alkoxyamines 1-2 addition of (multi)functional acrylates on BlocBuilder MA
O + + HO O SG1 + O O R O R O O
1-2 Addition

O HO

O O SG1 R R' O

O OH SG1 O

O
1-2 Addition

O
O HO SG1 O O O R

OH SG1 O
O SG1 OH

90-110

PRODUCT DATASHEET
asymmetric triblock polymers, to even more complicated structures such as graft, comb, star or even hyperbranched polymers are possible (Fig. 3). Its tolerance of functional groups also facilitates synthesis of functionalized polymers with controlled group placement allowing the design of polymers with tailored reactivity, polarity, or miscibility.
Fig. 3: Example of structures achievable while using BlocBuilder MA regulator

BlocBuilder MA CAS no. ELINCS/REACH TSCA Properties Appearance Acid number Water content (%) Shelf-life

654636-62-1 449-920-8 Conform Values (1) White solid 145 < 0.5 2 years at T<15C

01-0000019001-870000 Methods Visual Titration Karl-Fisher

1

H NMR

Low PDI

AB diblock

ABA triblock Graft/Comb

(1)

Data non-intended for specification purposes.

Gradient Functionalized Copolymers

ABC triblock

Packaging BlocBuilder MA is available in drums (containing 3* 5kg sealed bags) Please contact us for other requirements. Storage and handling Please refer to the safety data sheet before any use The recommended storage temperature is strictly below 15C to maintain the performances of the product.

BlocBuilder MA regulator can help create unique polymers for a broad range of applications, including: Toughening Agents and Impact Modification Compatibilizers Dispersants and Rheology Modifiers Adhesives Paints and Coatings Amphiphilics for Controlled Release and Surface Modification Properties can be readily tailored based on end-use application needs through basic polymer structure/property relationships, which allows customers to develop commercially viable products using straight-forward free-radical polymerization processes and assets.

Product specifications
Table 2: Registration/Properties
Contact:

info.blocbuider@arkema.com

From simple polymers to more complex structures

A
Group 1 or as a blend with Group2 and/or Group3

A: Group 1 or as a blend with few % of Group2 and/or Group3 B: Group1, Group 2 or as a blend with Group3

A: Group 1 or as a blend with few % of Group2 and/or Group3 B: Group1, Group 2 or as a blend with Group3

A, B: Group 1 or as a blend with few % of Group2 and/or Group3 C: Group1, Group 2 or as a blend with Group3

Group 1: Recommended as main polymer backbone (styrenics and acrylates families)

OCH3 O
Styrene CAS no.: 100-42-5 Methyl acrylate CAS no.: 96-33-3

OC2H5 O
Ethyl acrylate CAS no.: 140-88-5

O-nC4H9 O
n-Butyl acrylate CAS no.: 141-32-2

O-tC4H9 O
t-Butyl acrylate CAS no.: 1663-39-4
O S
-

O , Na+

Styrene sulfonate sodium salt CAS no.: 2695-37-6

H OH O O
p-methyl styrene CAS no.: 622-97-9 2-hydroxyethyl acrylate CAS no.: 818-61-1

O O C2H5
O
2-Ethyl hexyl acrylate CAS no.: 103-11-7

nC4H9
O-nC12H25
O
n-octyl acrylate CAS no.: 2499-59-4 n-dodecyl acrylate CAS no.: 2156-97-0

O-nC8H17

Group 2: Recommended as last block (alone or with 5 wt-% of styrene as additive)

OCH3 O
Methyl methacrylate CAS no.: 80-62-6
O O CH2 CF3

O O O
PEG (meth)acrylate of various DP

MATRIFE CAS no.: 352-87-4

Group 3: Recommended as functional monomer

(CH3)

H
O NH O
O

H N

O S

OH O

O O
OH O

N O O

O
2-Acrylamido-2-

Maleic anhydride CAS no.: 108-31-6

(Meth)acrylic acid CAS no.: 79-10-7 or 79-41-4 t-Butylaminoethyl methacrylate CAS no.: 3775-90-4

Dimethylacrylamide CAS no.: 2680-03-7

methylpropanesulfonic acid CAS no.: 15214-89-8

Glycidyl methacrylate CAS no.: 106-91-2

The information contained in this document is based on trials carried out by our Research Centers and data selected from the literature, but shall in no event be held to constitute or imply any warranty, undertaking, expressed 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, EXPRESSED 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.