Allylic chain transfer agents

Details Allylic chain transfer agents Allylic chain transfer agents

1996-08-01

1998-06-30

Zitomer, Fred

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

526 78, 526 79, 526 82, 526 83, 526 84, 526209, 526213, 526214, 526216, 526217, 560129, 560155, 560170, C08F 238

Patent

active

057735433

DESCRIPTION:

BRIEF SUMMARY
This invention relates to processes for radical-initiated polymerization of unsaturated species and for the control of molecular weight of the polymers produced from such processes. Polymers of low molecule weight, or oligomers, are important as precursors in producing other polymeric materials and such polymers have been found to be useful in a variety of products, for example, in the production of high solids (low VOC) surface coatings, in adhesives and as plasticizers in polymeric composites.
In conventional polymerization practice, the manufacture of oligomers requires the use of an initiator which acts as a free radical source, and of a chain transfer agent. The chain transfer agent controls the molecular weight of the polymer by reacting with the propagating polymer radical to terminate its growth. It then initiates a new polymer chain thus transferring the growth process from one discrete polymer molecule to another discrete polymer molecule.
The most commonly used chain transfer agents are alkanethiols, which normally are associated with an objectionable odour and lead to a wide distribution of molecular weight with certain monomers. Also, the residual thiols and the end thio-ether linkage of the polymers may have an adverse effect on the properties of the ultimate product from the polymer.
The present invention helps overcome the disadvantages of polymerizations regulated with thiols by using alternative polymerization regulators. These regulars have good stability and shelf life while maintaining many of the advantages over thiols. In the majority of cases, the materials that are part of the present process present a different range of chain transfer activities, allowing more opportunity for an optimal process to be selected for a given polymerization system of monomers and polymerization conditions. The chain transfer constant that a given regulator possesses is an important consideration in selecting the optimum process for producing low molecular weight polymers.
This invention provides a process for the free radical polygon of unsaturated species to provide polymers with lower molecular weight and narrower polydispersity characterised by the use of compounds of Formula (I) as chain transfer agents. ##STR2## wherein
X is selected from hydrogen; CN; optionally substituted aryl; COOH; COOR; C(O)NHR.sup.6 ; C(O)NR.sup.7 R.sup.8 ; and halogen;
Q is selected from COOR.sup.1 ; CN; and C(O)NR.sup.7 R.sup.8 ;
Y is selected from hydrogen; C.sub.1 to C.sub.6 alkyl; C.sub.1 to C.sub.6 alkyl substituted with one or more substituents selected from hydroxy, amino, C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 alkoxycarbonyl, halogen, CN and optionally substituted aryl; C.sub.1 to C.sub.6 alkenyl; and C.sub.1 to C.sub.6 alkynyl;
Z is selected from COOR.sup.2 ; CN; and optionally substituted aryl;
R.sup.3 and R.sup.4 may be the same or different and are selected from hydrogen, C.sub.1 to C.sub.4 alkyl and halogen; or R.sup.3 and R.sup.4 together with the carbon atom to which they are attached form part of a carbocyclic or heterocyclic ring structure;
R is selected from C.sub.1 to C.sub.18 alkyl; C.sub.1 to C.sub.12 alkyl substituted with one or more substituents selected from hydroxy, amino, C.sub.1 to C.sub.6 alkoxy, phenyl halogen, NCO, CN, and COOR.sup.5 ;
R.sup.1 and R.sup.2 may be the same or different and are selected from C.sub.1 to C.sub.18 alkyl; C.sub.1 to C.sub.12 alkyl substituted with one or more substituents selected from hydroxy, C.sub.1 to C.sub.6 acyloxy, C.sub.1 to C.sub.6 alkoxy, amino, halogen, Si(R.sup.9).sub.3, Si(OR.sup.9).sub.3, optionally substituted aryl, CN and NCO;
R.sup.5 is selected from hydrogen and C.sub.1 to C.sub.6 alkyl;
R.sup.6 is selected from hydrogen and C.sub.1 to C.sub.18 alkyl;
R.sup.7 and R.sup.8 may be the same or different and are selected from C.sub.1 to C.sub.18 alkyl; and
R.sup.9 is selected from C.sub.1 to C.sub.18 alkyl; C.sub.1 to C.sub.18 cycloalkyl; and optionally substituted aryl.
A preferred group of compounds of Formula I are the malonates with Q=COOR.su

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