Novel hydrocarbon-based polymers bearing dithiocyclocarbonate end groups

Patent metadata

Field	Value
Publication number	US-2018051130-A1
Application number	US-201715677153-A
Country	US
Kind code	A1
Filing date	Aug 15, 2017
Priority date	Aug 16, 2016
Publication date	Feb 22, 2018
Grant date	—

Abstract

1) Hydrocarbon-based polymer of formula (I):

in which F 1 and F 2 have the respective formulae (IIa) and (IIb) or (II′a) and (II′b):

a process for its preparation, and use as an adhesive.

First claim

1 . Hydrocarbon-based polymer comprising two dithiocyclocarbonate end groups, said hydrocarbon-based polymer having the formula (I):

in which:
F 1 and F 2 are monovalent radicals of respective formulae (IIa) and (IIb):

or alternatively F 1 and F 2 are monovalent radicals of respective formulae (II′a) and (II′b):

in which:
g1 and d1, which may be identical or different, represent an integer equal to 0, 1, 2 or 3;
g2 and d2, which may be identical or different, represent an integer equal to 1, 2 or 3;
A represents a divalent C 1 -C 9 alkylene radical;
Z is such that:
the divalent group -A-Z— is the group -AC(═O)O— and the divalent group —Z-A- is the group —OC(═O)-A- with the proviso that g1 and d1 are each other than 0; or alternatively
the divalent group -A-Z— is the group -A-OC(═O)— and the divalent group —Z-A- is the group —C(═O)O-A-;

each carbon-carbon bond of the main chain of the polymer, denoted , represents a double bond or a single bond, in accordance with the valency rules of organic chemistry;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , which may be identical or different, represent:
a hydrogen or halogen atom; or
a radical comprising from 1 to 22 carbon atoms chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy or alkenylcarbonyloxy, it being possible for the hydrocarbon-based chain of said radical to be optionally interrupted with at least one oxygen atom or one sulfur atom; in addition:
at least one of the R 1 to R 8 groups can form, with at least one other of the R 1 to R 8 groups and with the carbon atom or atoms to which said groups are linked, a 3- to 10-membered, optionally substituted, saturated or unsaturated hydrocarbon-based ring or heterocycle; and
at least one of the pairs (R 1 , R 2 ), (R 3 , R 4 ), (R 5 , R 6 ) and (R 7 , R 8 ) can form, with the carbon atom to which said pair is linked, a carbonyl group C═O or a group of two carbon atoms linked by a double bond: C═C, the other carbon atom of which bears two substituents chosen from a hydrogen atom and a C 1 -C 4 alkyl radical;

x and y are integers, which may be identical or different, within a range extending from 0 to 4, the sum x+y being within a range extending from 0 to 4;
R 9 , R 10 , R 11 and R 12 , which may be identical or different, represent:
a hydrogen or halogen atom; or
a radical comprising from 1 to 22 carbon atoms which is chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy and alkylcarbonyloxyalkyl, it being possible for the hydrocarbon-based chain of said radical to be optionally interrupted with at least one oxygen atom or one sulfur atom; in addition:
at least one of the R 9 to 12 12 groups can form, with at least one other of the R 9 to 12 12 groups and with the carbon atom or atoms to which said groups are linked, a 3- to 10-membered, optionally substituted, saturated or unsaturated hydrocarbon-based ring or heterocycle; and
at least one of the pairs (R 9 , R 10 ) and (R 11 , R 12 ) can form, with the carbon atom to which said pair is linked, a group of two carbon atoms linked by a double bond: C═C, the other carbon atom of which bears two substituents chosen from a hydrogen atom and a C 1 -C 4 alkyl radical; and
the carbon atom bearing one of the groups of the pair (R 9 , R 10 ) may be linked to the carbon atom bearing one of the groups of the pair (R 11 , R 12 )a double bond, it being understood that, in accordance with the valency rules, only one of the groups of each of these two pairs is then present;

R 13 represents:
an oxygen or sulfur atom, or
a divalent radical —CH 2 —, —C(═O)— or —NR 0 — in which R 0 is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms;

n1 and n2, which may be identical or different, are each an integer or equal to 0, the sum of which is denoted by n;
m is an integer greater than or equal to 0;
p1 and p2, which may be identical or different, are each an integer or equal to 0, the sum p1+p2 of which is non-zero and adheres to the equation:
p 1 +p 2 =q ×( z+ 1)

in which:
q is an integer greater than 0; and
z is an integer ranging from 1 to 5; and

n1, n2, m, p1 and p2 also being such that the number-average molecular mass Mn of the polymer of formula (I) is within a range extending from 400 to 100 000 g/mol and its polydispersity index is within a range extending from 1.0 to 3.0.

2 . Hydrocarbon-based polymer according to claim 1 , characterized in that:
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms; the integers x and y are within a range extending from 0 to 2, the sum x+y being within a range extending from 0 to 2; x is equal to 1 and y is equal to 1; R 9 , R 10 , R 11 and R 12 represent a hydrogen atom or a radical, the hydrocarbon-based part of which comprises from 1 to 14 carbon atoms; z is an integer equal to 1 or 2; and/or the number-average molecular mass Mn is within a range extending from 1000 to 50 000 g/mol.

3 . Hydrocarbon-based polymer according to claim 1 , characterized in that:
when m is non-zero and when n1 and n2 are each equal to 0, then the ratio: m/(p1+p2+m) is within the interval ranging from 30 to 70%; or when m is equal to 0 and when the sum n1+n2 is non-zero, then at least one of the groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is other than a hydrogen atom, and the ratio: (n1+n2)/(p1+p2+n1+n2) is within the interval ranging from 30 to 70%; or when m is non-zero, when the sum n1+n2 is non-zero and when each of the groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a hydrogen atom, then the ratio: m/(p1+p2+n1+n2+m) is within the interval ranging from 30 to 70%; or when m is non-zero, when the sum n1+n2 is non-zero and when at least one of the groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is other than a hydrogen atom, then the ratio: (m+n1+n2)/(p1+p2+n1+n2+m) is within the interval ranging from 30 to 70%.

4 . Hydrocarbon-based polymer according to claim 1 , characterized in that it has the formula (I′) below:

in which the bond is a bond geometrically oriented on one side or the other relative to the double bond.

5 . Hydrocarbon-based polymer according to claim 1 , characterized in that m is equal to 0, the polymer being of formula (II) below:

6 . Hydrocarbon-based polymer according to claim 5 , characterized in that it has the formula (II′) below:

7 . Hydrocarbon-based polymer according to claim 1 , characterized in that n1 and n2 are each equal to 0, the polymer being of formula (III) below:

8 . Hydrocarbon-based polymer according to claim 7 , characterized in that it has the formula (III′) below:

9 . Hydrocarbon-based polymer acc

Assignees

• Bostik Sa
• Univ Rennes
• Centre Nat Rech Scient

Inventors

• Michaud Guillaume
• Simon Frederic
• Fouquay Stephane
• Vanbiervliet Elise
• Guillaume Sophie
• Carpentier Jean Francois

Classifications

• C08G2261/11

  Homopolymers · CPC title

• C08G2261/3323

  derived from other monocyclic systems · CPC title

• C08G2261/12

  Copolymers · CPC title

• C09J165/00

  Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09J107/00 - C09J157/00, C09J161/00 take precedence); Adhesives based on derivatives of such polymers · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title