Star polymers and compositions thereof
The invention provides a composition comprising: (a) a star polymer comprising: (i) a core portion comprising a polyvalent (meth)acrylic monomer, oligomer or polymer thereof or a polyvalent divinyl non-acrylic monomer, oligomer or polymer thereof; and (ii) at least two arms of polymerized alkyl(meth)acrylate ester; and (b) an oil of lubricating viscosity, wherein the core portion further comprises a functional group of formula (I): —CH 2 —C(R 1 )(C(═O)A)-Y— (I) wherein R 1 is hydrogen, a linear or branched alkyl group containing 1 to 5 carbon atoms; A is nitrogen or oxygen; and Y is a free radical leaving group selected from the group consisting of one or more atoms or groups of atoms which may be transferred by a radical mechanism under the polymerization conditions, a halogen, an —O—N═ group and an —S—C(═S)— group. The invention further provides the use of the composition in an oil of lubricating viscosity as a dispersant, a viscosity modifier or a precursor to a dispersant viscosity modifier.
1. A process for preparing an ATRP star-polymer having greater than five, up to 40 arms, comprising the steps of:
(1) contacting:
(i) a radically polymerisable monomer, wherein the radically polymerisable monomer consisting of an alkyl (meth)acrylate ester, wherein the alkyl (meth)acrylate ester is:
(a) a mixture of an alkyl ester group containing 10 to 15 carbon atoms present in at least 50% to 100% of the alkyl groups;
(b) an alkyl ester alkyl group containing 6 to 9 carbon atoms present at 0% to 20% of the alkyl groups;
(c) an alkyl ester alkyl group containing 1 to 5 carbon atoms present at 0% to 30% of the alkyl groups;
(d) an alkyl ester group containing 16 to 30 carbon atoms present at 0% of the alkyl groups; and
(e) a nitrogen containing monomer present at 0 wt % to 10 wt %;
(ii) a transition metal catalyst;
(iii) a nitrogen or phosphorus containing ligand;
(iv) a halogen initiator that contains one or more atoms or groups of atoms which may be transferred by a radical mechanism under the polymerisation conditions, wherein the halogen initiator is represented by formulae (III)-(X):
R 5 R 6 R 7 C—X; (III)
R 5 C(═O)—X; (IV)
R 5 R 6 R 7 Si—X; (V)
R 5 R 6 N—X; (VI)
R 5 N—X 2 ; (VII)
(R 5 ) n P(O) m —X 3-n ; (VIII)
(R 5 O) n P(O) m —X 3-n ; and (IX)
(R 5 )(R 6 O)P(O) m —X, (X)
wherein
n is 0, 1 or 2;
m is 0 to 1;
X is Cl, Br, I, OR 4 , SR 8 , SeR 8 , OC(—O)R 8 , OP(—O)R 8 , OP(—O)(OR 8 ) 2 , OP(═O)OR 8 , O—N(R 8 ) 2 , S—C(—S)N(R 8 ) 2 ;
R 4 is
an alkyl group with 1 to 20 carbon atoms and containing at least one halogen, in which each hydrogen atom in said alkyl group independently may be replaced by a halide;
an alkenyl group with 2 to 20 carbon atoms and containing at least one halogen, or
an aralkyl(aryl-substituted alkyl and containing at least one halogen, in which the aryl group is phenyl or substituted phenyl and the alkyl group represents an alkyl with 1 to 6 carbon atoms;
R 8 is an aryl group or a straight-chain or branched alkyl group with 1 to 20 carbon atoms and containing at least one halogen, or R 8 is a ring containing at least one halogen functional group; and
R 5 , R 6 and R 7 are independently hydrogen, halogens or hydrocarbyl groups, or a cycloalkyl group with 3 to 8 carbon atoms; and
(v) optionally a free radical mediator, to form a polymer chain;
(2) contacting the polymer chain of step (1) with a polyvalent coupling agent to form a star-polymer, wherein the polyvalent coupling agent is a divalent (meth) acrylic monomer, oligomer or polymer thereof or a divalent divinyl non-acrylic monomer, oligomer or polymer thereof;
and at least one of steps (3) to (4);
(3) contacting the polymer prepared by step (1) or step (2) with a polymerisation inhibitor;
(4) mixing the polymer prepared by step (2) or step (3) with an oil of lubricating viscosity to form a lubricating composition.
2. The process of claim 1 , wherein the radically polymerisable monomer is free of styrene.