US 5,489,654 AGranted

Polymers containing thiuram disulfide groups and their preparation

AssigneeAtochem

InventorGilbert Clouet

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Abstract

The invention is directed to polymers containing thiuram disulfide groups and their preparation. These polymers are iniferters in radical polymerization of vinyl monomers. Macroiniferters (having one thiuram disulfide group in their main chain) and polyiniferters (having more than one thiuram disulfide group in their main chain) result respectively, in triblock copolymers PA--PB--PA and diblock copolymers. --PA--PB).sub.z, z having a value from 2 to 25.

Claims15

Dependent claims

A polymer of the formula:

##STR68## wherein:
said polymer is thiuram disulfide group containing, each of P.sub.1 and P.sub.2 denotes a polyoxyalkylene polymer block;
A denotes:
(1) an ##STR69## residue in which R.sub.1 denotes a linear or branched alkyl group optionally comprising (i) at least one hetero atom and/or (ii) at least one ##STR70## residue, in which each of R.sub.2, R.sub.3 and R.sub.4 denotes an alkyl,-cycloalkyl or aryl group, R.sub.2, R.sub.3 and R.sub.4 optionally bearing at least one functional group;
(2an ##STR71## residue wherein:
G denotes:
(a) --(CR.sub.5 R.sub.6).sub.a --in which each of R.sub.5 and R.sub.6, independently, of each other, denotes a hydrogen atom or an alkyl group, which alkyl group optionally comprises (i) at least one hetero atom and/or (ii) at least one ##STR72## group in which R.sub.7 is an alkyl, cycloalkyl or aryl group, and "a" denotes an integer from 1 to 6;
or
(b) the residue of an aliphatic ring which may contain at least one hetero atom;
E and J, independently of each other, each denote
(a) an alkyl group optionally comprising (i) at least one hetero atom and/or (ii) at least one ##STR73## group in which R.sub.8 is an alkyl, cycloalkyl or aryl group;
(b) a cycloalkyl group;
(c) an aryl group;
(d) a --K--L group in which K denotes (i) a single bond;
(ii) an alkylene group optionally comprising (.alpha.) a hetero atom and/or (.beta.) at least one ##STR74## group in which R.sub.9 is an alkyl, cycloalkyl or aryl group;
(iii) a cycloalkylene group;
or (iv) an arylene group;
and L denotes a functional group, each of E, J, R.sub.8 and R.sub.9 optionally bearing at least one functional group, or
(e) E and J are joined and the ##STR75## group forms a nitrogenous heterocyclic ring or represents:
##STR76## wherein:
b denotes an integer from 1 to 12;
each of R.sub.10 and R.sub.11, independently of each other, denotes (1) a hydrogen atom or (2) a C.sub.1 -C.sub.12 -alkyl group which optionally comprises (i) at least one hetero atom and/or (ii) at least one ##STR77## group in which R.sub.13 is an alkyl, cycloalkyl or aryl group;
E' and J' have the same meanings as E and J, respectively;
=T is present or absent and when present T denotes an oxygen or sulfur atom;
R.sub.12 denotes a C.sub.1 -C.sub.12 -alkyl or -alkoxy, a C.sub.3 -C.sub.12 -cycloalkyl or -cycloalkoxy, an aryl or an aryloxy group, each of which groups optionally bears a substituent;
each of c, d, e and f independently denotes an integer from 1 to 3;
g denotes an integer from 10 to 40;
n has a value from 1 to 20,
and wherein each functinoal group independently is
OH;
OR.sub.23, R.sub.23 denoting an alkyl, cycloalkyl or aryl group;
COOH;
COOR.sub.24, R.sub.24 denoting an alkyl, cycloalkyl or aryl group;
Si(R.sub.25).sub.2 H, R.sub.25 denoting an alkyl, cycloalkyl, alkoxy, aryl or aryloxy group;
##STR78## in which:
each of R.sub.26 and R.sub.27, which are identical or different, denotes an alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy or ##STR79## group (each or R.sub.28 and R.sub.29 independently denoting alkyl, cycloalkyl or aryl), for each of the groups R.sub.26, R.sub.27, R.sub.28 and R.sub.29 optionally being substituted by at least one halogen atom;
T denotes an oxygen or sulfur atom;
U denotes a single bond, --O-- or ##STR80## R.sub.30 being alkyl, cycloalkyl or aryl;
o ranges from 0 to 12;
CN;
or ##STR81## R.sub.31 and R.sub.32 each denoting a C.sub.6 -C.sub.10 aromatic group, a C.sub.5 -C.sub.10 cycloaliphatic group or a C.sub.1 -C.sub.6 aliphatic group.

38 more elements

A polymer containing at least one thiuram disulfide group in its main chain, of the formula:

##STR100## wherein:
each of P.sub.1 and P.sub.2 is (1) a polymer block originating from at least one monomer vinyl or dienic monomer, in which p=1, or (2) a polyoxyalkylene, polyester or polyamide block, in which p=0;
A is:
(1) an ##STR101## residue, optionally bearing at least one functional group, R.sub.1 is a linear or branched alkyl group optionally containing (a) at least one heteroatom, (b) ##STR102## (c) ##STR103## or (d) a combination thereof, in which R.sub.2, R.sub.3 and R.sub.4 are an alkyl, cycloalkyl or aryl group;
(2) an ##STR104## residue wherein:
G is:
(a) --(CR.sub.5 R.sub.6).sub.a -- in which a is 1-6, R.sub.5 and R.sub.6 are each independently (i) a hydrogen atom or (ii) an alkyl residue optionally containing (.alpha.) at least one hetero atom and/or (.beta.) at least one ##STR105## residue, in which R.sub.7 is an alkyl, cyclo-alkyl or aryl group, or (b) the residue of an aliphatic ring which optionally contains at least one hetero atom;
E and J are each independently:
(a) an alkyl group optionally containing (i) at least one hetero atom and/or (ii) at least one ##STR106## residue, in which R.sub.8 is alkyl, cycloalkyl or aryl;
(b) a cycloalkyl group;
(c) an aryl group;
(d) a -K-L group in which L is a functional group and K is (i) a single bond;
(ii) an alkylene group optionally containing (.alpha.) a hereto atom and/or (.beta.) at least one ##STR107## residue, in which R.sub.9 is an alkyl, cycloalkyl or aryl group;
(iii) a cycloalkylene group;
or (iv) an arylene group;
each of the groups E, J, R.sub.8 and R.sub.9 optionally having at least one functional group,
(e) E and J of the ##STR108## group optionally being joined to form a nitrogenous heterocyclic ring;
or the ##STR109## group in (2) is:
##STR110## in which:
b is an integer from 1 to 12;
R.sub.10 and R.sub.11 are each independently hydrogen or a C.sub.1 -C.sub.12 -alkyl residue optionally containing (a) at
least one hetero atom and/or (b) at least one ##STR111## residue, in which R.sub.13 is alkyl, cycloalkyl or aryl;
E' and J' have the same meanings as E and J, respectively;
T is an oxygen or sulfur atom, .dbd.T optionally being absent;
R.sub.12 is a substituted or unsubstituted C.sub.1 -C.sub.12 alkyl or alkoxy, C.sub.3 -C.sub.12 cycloalkyl or cycloalkoxy, aryl or aryloxy;
c, d, e and f independently denotes an integer from 1 to 3;
and
g is an integer from 10 to 40;
(3) if P.sub.1 is a vinyl or dienic block, A is optionally a ##STR112## residue in formula (I) in which:
M, joined to D, is ##STR113## Q is a single bond or an alkylene, cycloalkylene or arylene group;
and R is COOH;
COOR.sub.14, in which R.sub.14 is alkyl, cycloalkyl or aryl;
OH;
a phosphorus-containing group;
--CN or an ##STR114## imine residue, in which R.sub.15 and R.sub.16 are each independently a C.sub.6 -C.sub.10 aromatic group, a C.sub.5 -C.sub.10 cycloaliphatic group or a C.sub.1 -C.sub.6 aliphatic group;
and
D is a single bond or an alkylene, cycloalkylene or arylene group;
n is 1-20,
each functional group independently is
OH;
OR.sub.23, R.sub.23 denoting an alkyl, cycloalkyl or aryl group;
COOH;
COOR.sub.24, R.sub.24 denoting an alkyl, cycloalkyl or aryl group;
Si(R.sub.25).sub.2 H, R.sub.25 denoting an alkyl, cycloalkyl, alkoxy, aryl or aryloxy group ##STR115## in which:
each of R.sub.26 and R.sub.27, which are identical or different, denotes an alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy or ##STR116## group (each or R.sub.28 and R.sub.23 independently denoting alkyl, cycloalkyl or aryl), for each of the groups R.sub.26, R.sub.27, R.sub.28 and R.sub.29 optionally being substituted by at least one halogen atom;
T denotes an oxygen or sulfur atom;
U denotes a single bond, --O-- or ##STR117## R.sub.30 being alkyl, cycloalkyl or aryl;
o ranges from 0 to 12;
CN;
or ##STR118## R.sub.31 and R.sub.32 each denoting a C.sub.6 -C.sub.10 aromatic group, a C.sub.5 -C.sub.10 cycloaliphatic group or a C.sub.1 -C.sub.6 aliphatic group
with the provisos that:
A is not an ##STR119## residue in I if P.sub.1 is a polyamide or polyester block from a polyester terminated by an acidic or ester functional group;
A is not an ##STR120## residue in II unless P.sub.2 is a polyoxyalkylene or polyester block from a polyester terminated by an OH group;
D is a single bond if M is CH.

51 more elements

Dependencies are inferred from the claim text.

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Abstract

A polymer of the formula:

##STR68## wherein:
said polymer is thiuram disulfide group containing, each of P.sub.1 and P.sub.2 denotes a polyoxyalkylene polymer block;
A denotes:
(1) an ##STR69## residue in which R.sub.1 denotes a linear or branched alkyl group optionally comprising (i) at least one hetero atom and/or (ii) at least one ##STR70## residue, in which each of R.sub.2, R.sub.3 and R.sub.4 denotes an alkyl,-cycloalkyl or aryl group, R.sub.2, R.sub.3 and R.sub.4 optionally bearing at least one functional group;
(2an ##STR71## residue wherein:
G denotes:
(a) --(CR.sub.5 R.sub.6).sub.a --in which each of R.sub.5 and R.sub.6, independently, of each other, denotes a hydrogen atom or an alkyl group, which alkyl group optionally comprises (i) at least one hetero atom and/or (ii) at least one ##STR72## group in which R.sub.7 is an alkyl, cycloalkyl or aryl group, and "a" denotes an integer from 1 to 6;
or
(b) the residue of an aliphatic ring which may contain at least one hetero atom;
E and J, independently of each other, each denote
(a) an alkyl group optionally comprising (i) at least one hetero atom and/or (ii) at least one ##STR73## group in which R.sub.8 is an alkyl, cycloalkyl or aryl group;
(b) a cycloalkyl group;
(c) an aryl group;
(d) a --K--L group in which K denotes (i) a single bond;
(ii) an alkylene group optionally comprising (.alpha.) a hetero atom and/or (.beta.) at least one ##STR74## group in which R.sub.9 is an alkyl, cycloalkyl or aryl group;
(iii) a cycloalkylene group;
or (iv) an arylene group;
and L denotes a functional group, each of E, J, R.sub.8 and R.sub.9 optionally bearing at least one functional group, or
(e) E and J are joined and the ##STR75## group forms a nitrogenous heterocyclic ring or represents:
##STR76## wherein:
b denotes an integer from 1 to 12;
each of R.sub.10 and R.sub.11, independently of each other, denotes (1) a hydrogen atom or (2) a C.sub.1 -C.sub.12 -alkyl group which optionally comprises (i) at least one hetero atom and/or (ii) at least one ##STR77## group in which R.sub.13 is an alkyl, cycloalkyl or aryl group;
E' and J' have the same meanings as E and J, respectively;
=T is present or absent and when present T denotes an oxygen or sulfur atom;
R.sub.12 denotes a C.sub.1 -C.sub.12 -alkyl or -alkoxy, a C.sub.3 -C.sub.12 -cycloalkyl or -cycloalkoxy, an aryl or an aryloxy group, each of which groups optionally bears a substituent;
each of c, d, e and f independently denotes an integer from 1 to 3;
g denotes an integer from 10 to 40;
n has a value from 1 to 20,
and wherein each functinoal group independently is
OH;
OR.sub.23, R.sub.23 denoting an alkyl, cycloalkyl or aryl group;
COOH;
COOR.sub.24, R.sub.24 denoting an alkyl, cycloalkyl or aryl group;
Si(R.sub.25).sub.2 H, R.sub.25 denoting an alkyl, cycloalkyl, alkoxy, aryl or aryloxy group;
##STR78## in which:
each of R.sub.26 and R.sub.27, which are identical or different, denotes an alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy or ##STR79## group (each or R.sub.28 and R.sub.29 independently denoting alkyl, cycloalkyl or aryl), for each of the groups R.sub.26, R.sub.27, R.sub.28 and R.sub.29 optionally being substituted by at least one halogen atom;
T denotes an oxygen or sulfur atom;
U denotes a single bond, --O-- or ##STR80## R.sub.30 being alkyl, cycloalkyl or aryl;
o ranges from 0 to 12;
CN;
or ##STR81## R.sub.31 and R.sub.32 each denoting a C.sub.6 -C.sub.10 aromatic group, a C.sub.5 -C.sub.10 cycloaliphatic group or a C.sub.1 -C.sub.6 aliphatic group.

38 more elements