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Title:
URETHANE POLYOLS AND THEIR POLYMERS
Document Type and Number:
WIPO Patent Application WO/2009/101535
Kind Code:
A2
Abstract:
A urethane polyol of formula (I) : A1-[B1 -[A2 -[B2-[T]q]p]n]m. Polymeric products obtained or obtainable from the urethane diol are also described. The polymeric products are useful in the production of polyurethane coatings.

Inventors:
JONES RICHARDS G (GB)
BOLTON LOUISE (GB)
Application Number:
PCT/IB2009/005050
Publication Date:
August 20, 2009
Filing Date:
February 09, 2009
Export Citation:
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Assignee:
BAXENDEN CHEM (GB)
JONES RICHARDS G (GB)
BOLTON LOUISE (GB)
International Classes:
C08G71/04; C09D167/04; C09D175/12
Domestic Patent References:
WO2005123808A12005-12-29
Foreign References:
US4588783A1986-05-13
US20050075476A12005-04-07
Download PDF:
Claims:

CLAIMS

1. A urethane polyol of formula ( 1 ): wherein m is an integer 2 or 3;

A 1 is a polycarbonyi moiety of formula (2a) or formula (2b):

wherein: o Y 1 is a single bond, a C|-C t i alkylenc group, C;-C| 2 alkenylene, Cj-Cu alkynylene, Ct-Cu arylene group or a C 2 -C 2 * aryl-alkylene group, each of which is unsubstirutcd or substituted with one or more substitυcnts selected from Ci-Ct 2 alkoxy, C 1 -Ci 2 alkylthio, Ci-C 12 alkyl and C 2 -C 13 alkoxycarbonyl; preferably Y 1 is a single bond or an unsubstituted C 1 -C4 alkylene group, more preferably Y 1 is a single bond or an unsubstituted methylene group;

0 Y 2 is a C|-C| 2 alkylene group, CyCu alkenylene, CJ-C J2 alkynylene, C t - CM arylene group or a C 2 -C;* aryl-alkylene group, each of which is unsubstituted or substituted with one or more substiruents selected from Ci-C,; alkoxy, CJ-CI 2 alkylthio, Ci-Ci 2 alkyl and Q-Cualkoxycarbonyl; each n is selected from the integers 1 and 2, and where there is more than one n, the values of n may be the same or different;

B 1 is the same or different and each B 1 is independently selected from a polyamino moiety of formula (3a) and formula (3b):

wherein: - R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different and each is independently selected from a hydrogen atom and a C)-C )2 alkyl group; preferably each R 1 and each K 2 are the same or different and is selected from a hydrogen atom and C 1 -C 4 alkyl, more preferably a hydrogen atom and methyl, ethyl or propyl, even more preferably a hydrogen atom; - X 1 is the same or different and is independently selected from a single bond, a C 1 -C 12 alkylene group, a C 2 -C 12 alkenylene group, a C 2 -C 12 allcynylene group, a C 6 -C 14 arylene group, a C 2 -C 26 aryl-alkylene group and a 5- to 14- membered heteroarylene group comprising 1, 2 or 3 hetcroatoms selected from N and O, each of which is substituted or unsubstirutcd with one or more substituents selected from halogen atoms and C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio groups, amino and mono-( C 1 -C 12 alkyl)amino. and wherein one or more non-adjacent, saturated carbon atoms of said C 1 -C 12 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; - X 2 is the same or different and is independently selected from a C 1 -C 12 alkylene group, a C 2 -C 12 alkenylene group, a C 3 -C 12 alkynylene group, a C 6 -C 14 arylene group, a C 2 -C 26 aryl-alkylene group and a 5- to 14- membered heteroarylene group comprising 1 , 2 or 3 hetcroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and Ci-Cj.. alkyl, C 1 -C 12 alkoxy, Cι-Ct 2 alkylthio groups, amino and mono-(C 1 - C 12 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said C 1 -C 12 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom;

each p is independently selected from 0 and the integers 1 and 2, and where there is more than one p, the values of p may be the same or different; A 2 is the same or different and each A 2 is independently selected from: o when p is 0, A 2 is terminal group T, wherein T is a hydrogen atom or a group D of formula (6): o

wherein: - each group D is the same or different and Z 1 is independently selected from a C2-C 1 2 alkyiene group, C 2 -C 12 alkenylene or C 2 -C12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more subsrituents selected from halogen atoms, hydroxy, C 1 -C 1 2 alkoxy and Q-C12 alkylthio groups; 0 when p is 1 , A 2 is a polycarbonyl moiety of formula (2c), wherein Y 1 is independently selected from a single bond, a Ci-Cu alkyiene group, CVC 12 alkenylene, C 2 -C1 2 alkynylene, a C0-C14 arylene group and a C2-C26 aryl- alkylcne group each of which is unsubstituted or substituted with one or more sυbstitucnts selected from Ci-C 12 alkoxy, Ct-Cn alkylthio, Cj-Ci2 alkyl and C 2 -C ijalkoxycarbonyl; and

0 when p is 2, A 2 is a polycarbonyl moiety of formula (2d). wherein Y 2 is independently selected from a Ci-Cu alkyiene group, C 2 -C 1 2 alkenylene, C3-C|2 alkynylene, a C6-Cu arylene group and a Cz-Cy, aryl-alkylenc group, each of which is unsubstituted or substituted with one or more sυbstituents selected from C1-C 1 2 alkoxy, C 1 -C 1 2 alkylthio, Ci-Cu alkyl and C 2 -C 13 alkoxycarbonyl;

each q is independently selected from O and the integers 1 and 2, and where there is more than one q, the values of q may be the same or different; B 2 is the same or different and each B 2 is independently selected from: o when q is 0, an unreacted leaving group lλ wherein L 1 is a hydroxy group, a Ci-Q alkoxy, a Ce-Cu aryioxy, a mono-(C|-C6 alkyl)amino or a di-{C|-

Cs alkyl)aτnino group; o when q is 1 , a polyamino moiety of formula (3c). wherein R ' and R 2 is each independently selected from a hydrogen atom and a Q-Cn alkyl group; and X 1 is independently selected from a single bond, a CI-CI 2 alkylene group, a C2-C 1 2 alkenylene group, a C 2 -Cn alkynyienc group, a C 6 -CH arylene group, a C2-C26 aryi-alkylene group and a 5- to 14- membered heteroaryiene group comprising 1 , 2 or 3 hcteroatoms selected from N and O, each of which is substituted or unsubstiruted with one or more substituents selected from halogen atoms and Ci-Cu alkyl, Ci-Cu alkoxy, C 1 -C 1 2 alkyithio groups, amino and mono-(C|-Ci2 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-C^ alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; and

0 when q is 2, a polyamino moiety of formula (3d), wherein R 4 , R 5 and R 6 is each independently selected from a hydrogen atom and a Ci-C 1 : alkyl group; and X 2 is independently selected from a Ci-Cn alkylene group, a C 2 -C 1 2 alkenylene group, a CrCn alkynylene group, a C fc -Cu arylene group, a C 2 -C 2 6 aryl-alkylcne group and a 5- to 14- membered heteroaryiene group comprising 1 , 2 oτ 3 hetcroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and C \ -Cn alkyl, C 1 -C 12 alkoxy,

C)-C| 2 alkyhhio groups, amino and mono-<C r Ci 2 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said C 1 -C 12 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; and

T is a terminal group, and where there is more than one T, T may be the same or different and each T is independently selected from: o a hydrogen atom; and o a group D of formula (6a):

wherein: - each group D is the same or different and Z 1 is independently selected from a Cj-Cu alkylene group, C 2 -C 12 alkcnylcnc or C 2 -C 12 alkynylcnc group, each of which is straight or branched and is unsubstituted or substituted with one or more substitucnts selected from halogen atoms, hydroxy, Cj-Cn alkoxy and C 1 -C 12 alkylthio groups; preferably Z 1 is a straight or branched C 2 -Q, alkylene group which is unsubstituted or substituted with 1, 2 or 3 substitucnts selected from halogen atoms, hydroxy. Ci -C\» alkoxy and Ci-Q alkylthio groups, more preferably Z 1 is an unsubstituted ethylene group; and wherein either:

(i) p is 0 at least twice and at least two A 2 groups arc a group D, wherein each D may be the same or different;

(u) q is 1 or 2 at least twice, when p is 1 or 2, and wherein at least two of the B 2 groups is each bonded to a group D, wherein each D may be the same or different; or (iii) at least one p is 0 and an A 2 group is a group D, and at least one q is 1 or 2, when p is I or 2, and a B 2 group is bonded to a group D, wherein D may be the same or different.

2. A urcthane polyol according to claim 1 of formula (7):

D-B 3 -<A J -BYD (7) wherein r is 1 or 2; preferably r is 1 ;

A 3 is a polycarbonyl moiety of formula (2a), and where there are more than one A 3 moieties, then they may be the same or different:

wherein o Y 1 is a single bond, a C1-C1 2 alkylenc group, Cr-Cu alkenylene, C 2 -C 12 alkynylene, Ce-Cu aryiene group or a C;-Cz 6 aryl-alkylene group, each of which is unsubstitυted or substituted with one or more substituents selected from Ci-Cu alkoxy, C)-Ci 2 alkylthio, Ci-Ci 3 alM ∞d Cz-Cu alkoxycarbonyl; preferably Y 1 is a single bond or an unsubstituted Q-d alkylene group, more preferably Y 1 is a single bond or an unsubstituted methylene group;

B* is the same or different and is a polyamine moiety of formula (3a)

wherein o R 1 and R 2 is the same or different and each R 1 and R 2 is independently selected from a hydrogen atom and a Ci-Cu alkyi group; preferably each R 1 and each R 2 are the same or different and is selected from a hydrogen atom and C t -C* alkyi, more preferably a hydrogen atom and methyl, ethyl or propyl, even more preferably a hydrogen atom; o X 1 is die same or different and each X 1 is independently selected a single bond, a Ci-Cu alkylene group, a Ci-Cu alkcnylcnc group, a C 2 -C 12 alkynylene group, a Q-C H aryiene group, a C 2 -C 2 6 aryt-alkylene group and a S- to 14- membered heteroaryiene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more sυbstitυcnts selected from halogen atoms and C1-C12 alkyl, Ci-Cu alkoxy, Ci-Cu alkylthio groups, amino and mono- (Cι-Cualkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-C u alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom;

D is the same or different and each D is a terminal group of formula (6)

wherein o Z 1 is the same or different and each Z 1 is independently selected from a CV Cu alkylene group, Ci-Cu alkenylene or CrCu alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substitυents selected from halogen atoms, hydroxy, Ci-Cu alkoxy and Ci-Cu alkyithio groups; preferably Z 1 is a straight or branched C 2 -C 6 alkylene group which is unsubstituted or substituted with 1 , 2 or 3 substitucnts selected from halogen atoms, hydroxy, C 1 -C 4 alkoxy and Q- C« alkylthio groups, more preferably Z 1 is an unsubstituted ethylene group.

A urethane polyol according to any one of the preceding claims wherein each

X 1 is a C1-C12 alkylcne group, which is υnsubstituted or substituted with one or more substituents selected from CrQ alky). Ci-C 6 alkoxy and C)-C 6 alkylthio groups, preferably each X J is a group of formula (8)

wherein the asterisks indicate the point of attachment to the nitrogen atoms in formula (3a).

4. A process for preparing a polymeric product, which process comprises the step of reacting a urcthane polyol as defined in any one of claims I to 3 with:

(a) a polyester;

(b) a polycarboxylic acid, ester or anhydride thereof;

(c) a compound of formula (9):

and

(d) a compound of formula ( 10):

wherein

L 2 is -O- or -NR 13 -;

L 3 iβ a halogen atom, the group -O-R H or -NR 14 R 15 ;

R M is a hydrogen atom, Ci-C* alky, group or Ci-C 4 acyi group; preferably R 14 is a hydrogen atom or CI-CO alkyl, more preferably a hydrogen atom; R 13 and R ιs are the same or different and each is independently selected from a hydrogen atom and a Cj-C\ alkyl group; R 1 ' is a C|-Ci2 alkylenc C 2 -C 12 alkenylene or C2-C 12 alkynylene group, each of which is straight or branched and is unsubstrtuted or substituted with one or more substitυents selected from halogen atoms, Ci-Cn alkoxy and Ci-C 12 alkyithio groups and wherein one or more non- adjacent, saturated carbon atoms of said alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; preferably R 1 ' is a C 1 -C12 alkylene group, more preferably a Ci-Q alkylenc group, wherein each of the said alkylene groups are unsubstituted or substituted with 1, 2 or 3 substitucnts selected from halogen atoms, Ci - C 4 alkoxy groups and Ci-C 4 alkyithio groups; R 12 is a C 2 -C 12 alkylene, C 3 -C 12 alkenylene or Cj-Ci2 alkynylene group, each of which is straight or branched and is unsubβu ' tutcd or substituted with one or more sυbstituenu* selected from halogen atoms and C 1 -C 12 alkoxy and Ci-Cu alkyithio groups and wherein one or more non- adjacent, saturated carbon atoms of said alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; preferably R 12 is a C2-C| 2 alkylenc group, more preferably a C 2 -C* alkylene group, wherein each of the said alkylene groups are unsubstituted or substituted with 1, 2 or 3 substituents selected from halogen atoms, Ci- C 4 alkoxy groups and C 1 -C 4 alkyithio groups, even more preferably R 12

IS -(CH 2 )S-;

L 4 is -O- or -NR 16 -; preferably L 4 is -O-; R 16 is a hydrogen atom or a CrC 6 alkyl group; and wherein the groups L 2 , L 3 , L 4 , R n , R 12 , R 13 , R 14 , R IJ and R 1 * may be the same or different in each compound of formula (9) or formula ( 1 U).

5. A polymeric product obtained or obtainable from the process of claim 4.

6. λ polymeric product of formula (1 1 ):

A l -[B I -rA 2 -(B 2 -[CK(Pλ-HUI,lpl.]«

(H) wherein m is an integer 2 or 3;

A 1 is a polycarbony) moiety of formula (2a) or formula (2b):

wherein: o Y 1 is a single bond, a Ci-Ci 2 alkylene group, Cj-Cu alkenylene, Cj-Cn alkynylenc, CVCM arylene group or a Cj-C^ aryl-alkylene group, each of which is unsubstituted or substituted with one or more substitucnts selected from Ci-Ci 2 alkoxy, Ci-Ci 2 alkylthio, Ci-C) 2 alkyl and C 2 - C i jalkoxycarbonyl; preferably Y 1 is a single bond or an unsubstituted Ci- Gt alkylene group, more preferably Y 1 is a single bond or an unsubstituted methylene group; o Y 2 is a C|-Cj2 alkylene group, C 2 -C1 2 alkenyiene, C3-C12 alkynylene, CV C M arylene group or a C 2 -CK, aryl-alkylene group, each of which is unsubstituted or substituted with one or more substitυems selected from Ci-Ci 2 alkoxy, C1-C12 alkylthio, Ci-Cu alkyl and C 2 -Ci 3 alkoxycart>onyl; each n is selected from the integers 1 and 2, and where there is more than one ru the values of n may be the same or different;

B 1 is the same or different and each B 1 is independently selected from a polyamino moiety of formula (3a) and formula (3b):

wherein: - R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different and each is independently selected from a hydrogen atom and a C 1 -C) 2 alky] group; - X' is the same or different and is independently selected from a single bond, a Cι-Cj2 alkylcnc group, a C2-C 12 alkenylcne group, a C2-C 1 2 alkynylene group, a CVC 14 arylene group, a CrCav aryl-alkylene group and a 5- to 14* membered heteroarylcne group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and C 1 -C 12 alkyl, Ci-Cu alkoxy, C 1 -C 12 alkylthio groups, amino and mono-(C|-Ci2alky])amino, and wherein one or more non-adjacent, saturated carbon atoms of said C \ -Cn alkyiene group is optionally replaced with a nitrogen, oxygen or sulphur atom; - X 2 is the same or different and is independently selected from a C 1 -O 12 alkyiene group, a C2-C 1 2 alkenylene group, a C3-C 12 alkynylene group, a Cή-Ci4 arylene group, a C2-C 2 6 aryl-alkylene group and a 5- to 14- membered heteroaryiene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more sυbstitυcnts selected from halogen atoms and C 1 -C 12 alkyl, C 1 -C 12 alkoxy, Q-C 12 alkylthio groups, amino and mono-<C|- Cι:»alkyi)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Cι-C' 12 alkyiene group is optionally replaced with a nitrogen, oxygen or sulphur atom; each p is independently selected from 0 and the integers 1 and 2, and where there is more than one p, the values of p may be the same or different;

A 2 is the same or different and each A 2 is independently selected from: 0 when p is 0, a group of formula M-| (P) 1 -H] 0 , wherein u is independently

selected from the integers 1 and 2, and M is a Unking group, wherein: - when u is 1 , M is a linking group of formula (12a); • when u is 2, M is a linking group of formula (12b); and

(the asterisk indicates the point of attachment of M to the B 1 moiety); wherein:

7.} is independently selected from a C 2 -C 12 alkylene group, C 2 -C 12 alkenylenc or C 2 -C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, Ci-Oi 2 alkoxy and C 1 -C 12 alkylthio groups; " Z 2 is independently selected from a C 2 -C 12 alkylene, CyCu alkenylenc and a C 3 C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, Ci-C 12 alkoxy and Ci-C 12 alkyhhio groups;

• the side chain -(PX-H has formula (13), and each monomer unit P and the values oft when there is more than one side chain, may be the same or different;

wherein:

• t is the number of monomer units P in each side chain and has an average value of 1 to 50;

• R 11 is independently selected from a C 1 -C 1 2 alkylene, C 2 -C 1 2

alkenylene and C 2 -C) 2 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, Ci-C n alkoxy and Ci-Cu alkyhhio groups and wherein one or more non-adjacent saturated carbon atoms of said alkylcne, alkenytcnc or alkynylcnc group is optionally replaced with a nitrogen, oxygen or sulphur atom;

• L 2 is -O- or -MR 13 -;

• R 13 is independently selected rrom a hydrogen atom and a Ci-C 6 alkyl group; o when p is 0, A 2 is terminal group T, wherein T is a hydrogen atom or a group D of formula (6):

wherein: - each group D is the same or different and Z 1 is independently selected lfom a C 2 -C 12 alkylene group, C 2 -Cu alkenylene or C 2 -C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, Q-C12 alkoxy and C1-C 1 2 alkyltbio groups; 0 when p is 1 , A 2 is a polycarbonyl moiety of formula (2c), wherein Y 1 is independently selected from a single bond, a Ci-Cu alkylene group, C2-C 1 2 alkenylene, C 2 -C 12 alkynylene, a C 6 -CM arylene group and a C 2 -Ca* aryl- alkylene group each of which is unsubstituted or substituted with one or more substituents selected from C1-C 12 alkoxy, Ci-Ci; alkylthio, C 1 -C 1 2 alkyl and C2-Ci 3 alkoxycaτbonyl; and

0 when p is 2, A 2 is a polycarbonyl moiety of formula (2d), wherein Y 1 is independently selected from a Ci-Cu alkylene group, C 2 -Ci 2 alkenylene, CJ-C|2 alkynylene, a C 6 -Cu arylene group and a C2-C26 aryl-alkylcne group, each of which is unsubstituted or substituted with one or more substituents selected from CJ-CJ 2 alkoxy, Cj-Ci 2 alkylthio, C r Cι; alkyi

and CrCn alkoxyearbonyl;

each q is independently selected from 0 and the integers 1 and 2, and where there is more than one q, the values of q may be the same or different; B 2 is the same or different and each B 2 is independently selected from: o when q is 0, an unreacted leaving group L 1 , wherein L 1 is a hydroxy group, a C 1 -C 6 alkoxy, a Q-Cu aryloxy, a mono-iCj-Q alkyl)amino or a di-(C|- C 6 alkyl)amino group; o when q is 1 , a polyamino moiety of formula (3c), wherein R 1 and R 2 is each independently selected from a hydrogen atom and a Ci -C 12 alkyl group; and X 1 is independently selected from a single bond, a Cj-Ci ? alkytenc group, a Ci-Ci? alkenyiene group, a Q-C 1 2 alkynylene group, a Ce-Cu aryiene group, a Q-C 2 6 aryl-alkylene group and a 5- to 14- membercd heteroarytene group comprising 1 , 2 or 3 hcteroatoms selected from N and O, each of which is substituted or unsυbstitυted with one or more substirυcnts selected from halogen atoms and Ci-C) 2 alkyl, Q-C'12 alkoxy, Q-Q 2 alkylthio groups, amino and mono-(Cι-Cu alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said C 1 -C 12 alkyiene group is optionally replaced with α nitrogen, oxygen or sulphur atom; and 0 when q is 2, a polyamino moiety of formula (3d), wherein R 4 , R 5 and R 6 is each independently selected from a hydrogen atom and a C 1 -C12 alkyl group; and X" is independently selected from a Q-C 12 alkyiene group, a C- 2 -Q2 alkenyiene group, a Ci-Cn alkynylene group, a Q 1 -Cu arylenc group, a Q-Q* aryl-alkylene group and a 5- to 14- membered hctcroarylene group comprising 1.2 or 3 heteroatoms selected from N and

O, each of which is substituted or unsubstitυtcd with one or more

substituents selected from halogen atoms and Cj-Cu alkyl, Ci-C 12 alkoxy, Ci-C 12 alkylthio groups, amino and mono-(C|-Ci 2 alkyl)amJno, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-Cc alkylcnc group is optionally replaced with a nitrogen, oxygen or sulphur atom; and

each s is independently selected from 0 and the integers 1 and 2, and where there is more than one s, the values of s may be the same or different; C is the same or different and each C is independently selected from: o when s is 0, C is a terminal group T, wherein T is a hydrogen atom or a group D of formula (6a):

wherein: - each group O is the same or different and Z 1 is independently selected from a C 2 -C 11 alkylene group, CrC a alkenylene or Cj-Cu alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, C)-Cj 2 alkoxy and Cj-C^ alkylthio groups; 0 when s is 1 , C is a linking group of formula ( 12c); 0 when s is 2, C is a linking group of formula ( 12d);

(the asterisk indicates the point of attachment of C to the B 2 moiety); wherein:

• Z 1 is independently selected from a Ci-Cn alkylcne group, CrCι> allcenylene or C f Cn alkynylene group, each of which is straight or branched and is unsubstitufed or substituted with one or more subβtitυcnts selected from halogen atoms, hydroxy, Ci -Cc alkoxy and C i -C i 2 aJkylthio groups;

• Zr is independently selected from a Ci-C 1 2 alkyiene, C 2 -C 12 alkenylene and a C 3 -C 12 alkynylenc group, each of which is straight or branched and is umubstitυted or substituted with one or more sυbstituents selected from halogen atoms, hydroxy, C 1 -C 12 alkoxy and C)-C| 2 alkylthio groups; the side chain -(PVH has formula (13a), and each monomer unit P and the values oft when there is more than one side chain, may be the same or different;

wherein:

0 t is the number of monomer units P in each side chain and has an average value of 1 to 50; preferably up to 25;

0 R 1 ' is independently selected from a Ci-Cj 2 alkylcne, C 2 -Ci 2 alkenylene and C 2 -C 12 alkynylenc group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, C 1 -C 12 alkoxy and CJ-C I2 alkylthio groups and wherein one or more non-adjacent, saturated carbon atoms of said alkylene, alkenylene

or alkynylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; o L 2 is -0- or -NR"-; o R 13 is independently selected from a hydrogen atom and a Ci-C 6 alkyl group; and wherein either: (i) p is 0 at least twice and at least two A 2 groups are a group of formula

M-f(P)rH] u , wherein each group of formula M-I(P) 1 -H] 11 may be the same or different; (ϋ) q is 1 or 2 at least twice, when p is I or 2, and wherein at least two of the B 2 groups is each bonded to a group of formula Cf(P) 1 -I I],, where s is I or 2 and the values of s may be the same or different; or

(iii) at least one p is 0 and an A 2 group is a group of formula M-J(PX-H] 14 , wherein each group of formula M-I(P) 1 -H] n may be the same or different, and at least one q is 1 or 2, when p is 1 or 2, and a B 2 group is bonded to a group of formula -Q(P) 1 -H] 5 , where s is 1 or 2.

7. A polymeric product according to claim 6 having the structure ( 14):

H-(PX-C-B 3 -(A 3 -B J ) I -C-(PX-H (14) wherein r is 1 or 2; preferably r is 1 ;

A 3 is a polycarbon yi moiety of formula (2a), and where there are more than one A 3 moieties, then they may be the same or different:

wherein o Y 1 is a single bond, a C 1 -C 12 alkylene group, C 2 -C 12 alkenyicne. C 2 -Cu alkynylene, C 6 -C 14 arylene group or a C 2 -C 26 aryl-alkylene group, each of which is unsubstituted or substituted with one or more substituents selected

from Ci-C 12 alkoxy, C I -CI 2 alkylthio, Ci-Cn alley! and C 2 -Cu alkoxycarbonyl; preferably Y 1 is a single bond or an unsubstituted C 1 -C 4 alkylene group, more preferably Y 1 is a single bond or an unsubstituted methylene group;

B J is the same or different and is a polyamine moiety of formula

(3a)

wherein o R 1 and R 2 is the same or different and each R 1 and R 2 is independently selected from a hydrogen atom and a Ci-Cu alkyl group; preferably each R 1 and each R 2 are the same or different and is selected from a hydrogen atom and C 1 -C4 alkyl, more preferably a hydrogen atom and methyl, ethyl or propyl, more preferably a hydrogen atom;

0 X 1 is the same or different and each X 1 is independently selected from a single bond, a C I -CI 2 alkylene group, a C^-Cu alkenylene group, a C 2 -Ci 2 alkynyiene group, a G,-C M arylene group, a C 2 -C 26 aryl-alkylene group and a S- to 14- membered heteroarylene group comprising 1, 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and C I -C I2 alkyl, C J -CI 2 alkoxy, CI-CI 2 alkylthio groups, amino and mono- (C|-C| 2 alkyl)ainino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-C) 2 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; each C is the same or different and each C is a moiety of formula ( 12a):

(12a) wherein o Z 1 is the same or different and each Z 1 is independently selected from a C 2 -C 12 alkyJene group, C f Cn alkenylene or C 2 -C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, C(-C| 2 alkoxy and C 1 -C 12 alkyithio groups; preferably each Z 1 is a straight or branched C ^ -Q alkylene group which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from halogen atoms, hydroxy, C 1 -C 4 alkoxy and CrQ alkyithio groups, more preferably Z 1 is an unsubstituted ethylene group; -(PX-H is a side chain of formula (13), wherein each side chain may be the same or different, and wherein

) 0 t is the number of monomer units P in each side chain, t may be the same or different and has an average value of 1 to 50; 0 R 11 is independently selected from a C1-Q2 alkylene. C2-C 12 alkenylene and C2-C1 2 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, C 1 -Cu alkoxy and Cj-C, 2 alkyithio groups and wherein one or more non-adjacent, saturated carbon atoms of said alkylenc, alkenylene or alkynylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; 0 L 2 is -O- or -NR 13 -; 0 R 13 is independently selected from a hydrogen atom and a Ci-Ce alkyl group.

A polymeric product according to any one of the claims 6 to 7 wherein each X 1 C| 2 alkylene group, which is unsubstituted or substituted with one or more

substituents selected from C|-C« alkyl, Ci-C 6 alkoxy and Ci-C 6 alkyllhio groups, preferably each X 1 Ls a group of formula (8)

wherein the asterisks indicate the point of attachment to the nitrogen atoms in formula (3a).

9. A coating composition comprising (a) a polymeric product as defined in any one of claims 5 to 8: and

(b) one or more cross-linking agents; optionally together with one or more components selected from

(c) a catalyst;

(d) one or more solvents; (e) another polymer or polymers reactive with the cross-linking agent; and

(f) one or more chain extenders.

10. A process for coating an article which comprises

(i) applying a coating composition as defined in claim 9 to the surface of said article; and

(ii) curing said composition to produce a coated article.

1 1. A coated article obtained or obtainable by the process of claim 10.

12. A compound of formula (4)

wherein m is an integer 2 or 3;

A 1 is a polycarbonyl moiety of formula (2a) or formula (2b):

wherein: o Y 1 is a single bond, a Cj-Ci 2 alkylene group, C 2 -C 12 alkenylene, C2-C 1 2 allcynyiene. C 6 -C 14 arylene group or a C 2 -C 26 aryl-alkylene group, each of which is unsubstituted or substituted with one or more substituents selected from C)-Cu alkoxy, CI-CJ 2 alkylthio, C 1 -C 12 alkyl and C 2 - Cijalkoxycarbonyl; preferably Y 1 is a single bond or an unsubstituted C> C4 alkylene group, more preferably Y* is a single bond or an unsubstituted methylene group;

0 Y 2 is a CJ-CI 2 alkylene group, C 2 -Cu alkenylene, C 3 -C 12 alkynyiene, CV Cu arylene group or a C 2 -C 2 * aryl-alkylene group, each of which is unsubstituted or substituted with one or more substituents selected from C 1 -C 1 2 alkoxy, Ci-Ci 2 alkylthio, Ci-Ci 2 alkyl and Cz-Cualkoxycarbonyl; each n is selected from the integers 1 and 2, and where there is more than one

IV the values of n may be the same or different;

B 1 is the same or different and each B 1 is independently selected from a polyamino moiety of formula (3a) and formula (3b):

0 wherein: - R 1 , R 2 , R 3 R 4 and R 5 may be the same or different and each is

independently selected from a hydrogen atom and a Ci-Ci 2 alky) group; preferably each R 1 and each R 2 arc the same or different and is selected from a hydrogen atom and Ci-Q alkyl, more preferably a hydrogen atom and methyl, ethyl or propyl, even more preferably a hydrogen atom;

• X 1 is the same or different and is independently selected from a single bond, a CI-CJ 2 alkylate group, a C 2 -C12 alkenylcnc group, a C 2 -C 1 2 alkynylene group, a (VCu arylene group, a C 2 -C 26 aryl-alkylcnc group and a 5- to 14- raembered heteroarylenc group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and C 1 -C12 alkyl, C1-C12 alkoxy, C1-C12 alkylthio groups, amino and mono-<CrCi 2 alkyl)amino, and wherein one or more non-adjacenU saturated carbon atoms of said Ci-C 12 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; - X 2 is the same or different and is independently selected from a Cj-Ci: alkylene group, a C 2 -C 12 alkenylcne group, a Cj-C); alkynylene group, a C*-C| 4 arylene group, a C 2 -C 26 aryi-alkylene group and a 5- to 14- membered heteroarylene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and Ci-C 12 alkyl, Ci-Cn alkoxy, C 1 -Cn alkylthio groups, amino and roono-(Cι- Cι:alkyl)aminø, and wherein one or more non-adjacent, saturated carbon atoms of said CI-CJ 2 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom: each p is independently selected from 0 and the integers 1 and 2, and where there is more than one p, the values of p may be the same or different;

A 2 is the same or different and each A 2 is independently selected from: 0 when p is 0, a hydrogen atom: 0 when p is 1 , A 2 is a polycarbonyl moiety of formula (2c), wherein Y 1 is independently selected from a single bond, a CI-CI 2 alkylene group, C2-Q2 alkcnyiene. C -Cϋ alkynylene, a C 6 -C 1 4 arylene group and a C 2 -C 24 aryl-

alkyiene group each of which is unsubstituted or substituted with one or more substituents selected from Ci-C^ alkoxy, Cj-Cu alkylthio, C|-Cι; alkyl and C:-Cπalkoxycarbonyl; and o when p is 2, A 2 is a polycarbonyl moiety of formula (2d), wherein Y 2 is independently selected from a CI-C I2 alkylcnc group, CJ-C I2 alkcnyienc, C 3 -C 12 alkynylenc, a CVCu arylene group and a C 2 -C 26 aryl-alkylene group, each of which is unsubstituted or substituted with one or more substituents selected from Ci-Cu alkoxy, C1-C12 alkylthio, Ci-Cu alkyl and Ca-Cijalkoxycarbonyl;

each q is independently selected from 0 and the integers 1 and 2, and where there is more than one q, the values of q may be the same or different; B 2 is the same or different and each B 2 is independently selected from: 0 when q is 0, an unreacted leaving group L 1 , wherein L 1 is a hydroxy group, a Ci-Cδ alkoxy, a CO-CM aryϊoxy, a mono-(C|-C6 alkyl )amino or a di-(Cr C 6 alkyl )amino group;

0 when q is 1 , a polyamino moiety of formula (3c), wherein R 1 and R 2 is each independently selected from a hydrogen atom and a C)-Ci 2 alkyl group; and X 1 independently selected from a single bond, a C 1 -C12 alkylcnc group, a C 2 -C 12 alkenylene group, a Q-Cu alkynylene group, a Ce-Cu arylene group, a C2-C 24 aryl-alkylene group and a 5- to 14- mcmbered heteroarylenc group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and C 1 -C 12 alkyl, C 1 -C1 2 alkoxy, C|-C|2 alkylthio groups, amino and mnno-(C\-Cn alkyi)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-Cu alkyiene group is optionally replaced with a nitrogen, oxygen or sulphur

atom; and o when q is 2, a polyamino moiety of formula (3d), wherein R 4 , R 5 and R 6 is each independently selected from a hydrogen atom and a Ci-Ci: alkyl group; and X 2 is independently selected from a Ct-Ci 2 alkylene group, a CrCi 2 alkenylenc group, a C3-C12 alkynylcne group, a C 6 -Cu arylene group, a C 2 -C 26 aryl-alkylene group and a 5- to 14- membered hetcroarytene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubβtituted with one or more substituents selected from halogen atoms and Ct-Cu alkyl, C I -CK alkoxy, C)-C| 2 alkylthio groups, amino and mono-<Cι-Cij alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-C 12 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom;

and wherein either (i) p is 0 at least twice and at least two A : groups are a hydrogen atom; (ii) q is 1 or 2 at least twice, when p is 1 or 2; or

(iii) at least one p is 0 and an A 2 group is a hydrogen atom, and at least one q is I or 2, when p is 1 or 2.

13. A compound according to claim 12 of formula (S):

H-B J -(A'-BVH

(5) wherein r is 1 or 2; preferably r is 1 ;

A* is a polycarbonyl moiety of formula (2a), and where there are more than one A 3 moieties, then they may be the same or different:

wherein o Y 1 is a single bond, aC 1 -C 12 allcylene group, C 2 -C 12 alkcnylcne, C 2 -Q 2 alkynylcne, C 6 -C 14 arylene group or a C 2 -C 26 aryl-alkylene group, each of which is unsubstituted or substituted with one or more substitυcnls selected from Ci-C 12 alkoxy, C 1 -Ci 2 alkyithio, C 1 -Ci 2 alkyl and C 2 -C 13 alkoxycarbonyl; preferably Y 1 is a single bond or an unsubstituted C 1 -C 4 alkylene group, more preferably Y 1 is a single bond or an unsubstituted methylene group;

B 3 is the same or different and is a polyaminc moiety of formula (3a)

wherein

0 R 1 and R 2 is the same or different and each R 1 and R 2 is independently selected from a hydrogen atom and a Ci-Cn alkyl group; preferably each R 1 and each R 2 are the same or different and is selected from a hydrogen atom and C 1 -C 4 alkyl, more preferably a hydrogen atom and methyl, ethyl or propyl, even more preferably a hydrogen atom;

0 X 1 is the same or different and each X 1 is independently selected from a single bond, a C 1 -C 12 alkylene group, a C 2 -C 12 alkcnylcne group, a C 2 -C 12 alkynylene group, a C 6 -C 14 arylcnc group, a C 2 -C 26 aryl-alkylenc group and a 5- to 14- membered hcteroarylenc group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more subsϋtυents selected from halogen atoms and C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkyithio groups, amino and mono- (C 1 -C 12 alky])amino, and wherein one or more non-adjacent, saturated

carbon atoms of said C I -C I2 alkylcne group is optionally replaced with a nitrogen, oxygen or sulphur atom.

14. A compound according to any one of the claims 12 or 13 wherein each X 1 is a Cj-Ci2 alkylcnc group, which is unsubstitutcd or substituted with one or more substituents selected from Cj-C 6 alkyl, Ci-C* alkoxy and Ci-C 6 alkylthio groups, preferably each X 1 is a group of formula (8)

wherein the asterisks indicate the point of attachment to the nitrogen atoms in formula (3a).

IS. A process for preparing a methane polyol, wlύch process comprises reacting an amine compound as defined in any one of claims 12 to 14 with at least two equivalents of a compound of formula (16):

wherein Z 1 is a C 2 -C 12 alkylcne group, C 2 -C 11 alkenylene or C 2 -C 11 alkynyfene group, each of which is straight or branched and is unsubstituted or substituted with one or more substkυents selected from halogen atoms, hydroxy, C 1 -C 12 alkoxy and C 1 -Q 2 alkylthio groups; preferably Z' is a straight or branched Q-Q alkytene group which is unsubstituted or substituted with 1 , 2 or 3 substkuents selected from halogen atoms and Q Q alkoxy and Q-Q alkyhhio groups, and preferably X 1 is an unsubstttuted ethylene group.

Description:

URETHANE POLYOLS AND THEIR POLYMERS

Reference to Previously Filed Application

This application claims priority to copending British Application No. 0802571.0, filed February 12, 2008. This document is incorporated by reference herein in its entirety.

Field of the Invention

The present invention relates to urethane-group containing polyol polymer products as well as a process for their production. The polymer products can be used in cross- linking reactions to produce coatings containing carbamate groups, for example pol yurethane coatings. The invention further provides amine compounds used in the preparation of the urethane-group containing polyol.

Background of the Invention

Polyester based polyurcthanes are well known and used widely for many applications, including surface coatings. These materials arc manufactured from polyester resins, typically produced by reacting dirunctional alcohols and difiinctional acids to produce hydroxy functional polyesters, which are then cross-linked with di- or tri-runctional isocyanatcs in order to produce polyurethanes. However, isocyanates are highly dangerous and there is increasing pressure to minimise the use of these materials for environmental, and health and safety reasons.

Various alternatives to isocyanate chemistry are already available but they do not offer the same benefits as the use of isocyanates. For example, mclaminc-bascd resins (and similar products such as ureas, benzoguanamine or glyooluπl resins) are widely used to cross-link hydroxy functional polyesters but this often leads to coatings which are too hard, brittle and/or inflexible, particularly when high hydroxy containing acrylic resins are used.

When the use of free isocyanatc is undesirable on health and safety grounds or for technical reasons, it is widely practised to incorporate isocyanatc prepolymer or polyisocyanate, either containing free isocyanate functionality or having chemically protected isocyanate ("blocked isocyanate"). However, whilst providing polyurethanes which are flexible and highly chemically resistant, blocked isocyanates are expensive materials and their use is therefore not always cost-effective. Further, even blocked isocyanates are becoming unfavoured from a safety point of view. Alternative routes to polyurethanes are therefore desired which arc not detrimental to the properties of the final polyurcthanc product, but avoid the safety issues connected with isocyanates and blocked isocyanates.

One such alternative route Ls described in WO 2005/123808, which is incorporated by reference herein in its entirety, which allows polyester based polyurethanes to be manufactured without involving isocyanate reagents. A urethane diol is used to initiate polymerisation of a lactone or lactam, leading to a polyester diol or polyol product containing a urethane linkage. The urethane diol is the product of a reaction between ethylene carbonate and an alkylene di-aminc, such as ethylene di-aminc or 1 ,6- hexancdi-aminc.

US 5,134,205, which is incorporated by reference herein in its entirety, describes an alternative method for the preparation of polyester based polyurethanes without the use of isocyanate reagents. The polyester based polyurethanc is prepared by reacting a polyester with a bis-hydroxyalkylcarbarnate of an alkylene di-amine, such as 2- methyi-1 ,5 pentanc di-amine (MPDA).

Summary of the Invention

The present inventors have developed new urethane polyol compounds for preparing polyester based polyurethanes. It has surprisingly been found that coatings prepared from such polymers have beneficial physical properties compared to other coatings that have been prepared from polyester based polyurethanes known in the art that were manufactured without the use of isocyanate reagents.

The urethane polyols of the invention provide the skilled person in the art with access to polymers having new and different combinations of properties. This may lead to improvements in the currently known applications such as coatings and adhesives and may further lead to new applications for polyurethanes. In addition, the urethane polyols of the present invention allow the preparation of polymers that are not possible to manufacture using the isocyanatc route.

Thus the present invention provides a urethane polyυl of formula ( 1 ):

wherein m is an integer 2 or 3;

A* is a polycarbonyl moiety of formula (2a) or formula (2b):

wherein: o Y 1 is a single bond, a C I -C I2 alkylate group, C 2 -Cu alkenylene, C 2 -C 12 alkynylcne, CVCu arylene group or a C 2 -C 26 aryl-alkylene group, each of which is υnsubstituted or substituted with one or more subsrituents selected from C 1 -Ci 2 alkoxy, Ci-Ca alkylthio, C 1 -C 12 alkyl and C 2 - Ciialkoxycarbonyl;

0 Y 2 is a Cι-Cj 2 alkylene group, C;-C| 2 alkenylene, CJ-C I2 alkynylene, C O - C M arylene group or a C 2 -C 2 * aryl-alkylene group, each of which is unsubstituted or substituted with one or more subsrituents selected from C1-C12 alkoxy, Ci-Cu alkylthio, C J -C J2 alkyi and CrCnalkoxycarbonyl; - each n is selected from the integers 1 and 2, and where there is more than one n, the values of n may be the same or different;

B 1 is the same or different and each B 1 is independently selected from a polyamino moiety of formula (3a) and formula (3b):

wherein: - R 1 , R 2 , R J , R 4 and R 5 may be the same or diflerent and each is independently selected from a hydrogen atom and a Ci -Cn alky! group: - X 1 is the same or different and is independently selected from a single bond, a C|-C| 2 alkyiene group, a Q-C 12 alkcnylene group, a Qt-Cu alkynylene group, a Q-Cu arylene group, a C2-C24 aryl-alkylene group and a 5- to 14- membered heteroarylene group comprising 1. 2 or 3 hetcroatoms selected from N and O, each of which is substituted or unsubβtituted with one or more substituents selected from halogen atoms and Ci-C| 2 alkyl. Cj-Cu alkoxy, Ci-Cu alkyithio groups, amino and mono-(Cι-Ci 2 alkyl)aimno, and wherein one or more non-adjacent, saturated carbon atoms ofsaid C|-Ci 2 alkyiene group is optionally replaced with a nitrogen, oxygen or sulphur atom; • X 2 is the same or different and is independently selected from a Ci-Cu alkyiene group, a C 2 -C1: alkenylene group, a C3-C1 2 alkynylenc group, a C*-C|4 arylene group, a Ci-Cz* aryl-alkylene group and a 5- to 14- membered heteroarylene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and Ci-Cu alkyl, C 1 -Q 2 alkoxy, Ci-Cu alkyithio groups, amino and mono-(C|- Ci 2 alkyl)ammo, and wherein one or more non-adjacent, saturated carbon atoms of said Q-Cu alkyiene group is optionally replaced with a nitrogen, oxygen or sulphur atom; each p is independently selected from 0 and the integers 1 and 2, and where

there is more than one p, the values of p may be the same or different; A 2 is the same or different and each A 2 is independently selected from: o when p is 0, A 2 is terminal group T, wherein T is a hydrogen atom or a group D of formula (6):

wherein: - each group D is the same or different and Z 1 is independently selected from a C 2 -C 12 alkylene group, C 2 -Ci 2 alleenylene or C2-C 1 2 allcynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, CJ-CJ: alkoxy and C1-C12 alkyhhio groups; o when p is 1 , A 2 is a polycarbonyt moiety of formula (2c), wherein Y 1 is independently selected from a single bond, a C]-Cu alkylene group, C 2 -Ci 2 alkenylcne, C2-C 1 2 alkynylene, a C*-C|4 arylene group and a C2-C24 aryl- alkylcne group each of which is unsubstituted or substituted with one or more substituents selected from Ct-C 12 alkoxy, Q-Cu alkylthio, Ci-C 12 alkyl and C2-C|jalkoxycarbonyl; and

0 when p is 2, A 2 is a polycarbonyl moiety of formula (2d), wherein Y 2 is independently selected from a C t -Cu alkylene group, C 2 -Ci 2 alkenylene, CJ-CJ 2 alkynylene, a C6-Cu arylene group and a C2-C2 6 aryi-alkylene group, each of which is unsubstituted or substituted with one or more substituenls selected from C)-Ci 2 alkoxy, Ct-Cv alkylthio, C 1 -Ci 2 alkyl and Cj-Cijalkoxycarbonyl;

(2c) (2d) each q is independently selected from 0 and the integers 1 and 2, and where there is more than one q, the values of q may be the same or different; B 3 is the same or different and each B 2 is independently selected from: o when q is 0, an unreactod leaving group L 1 , wherein L 1 is a hydroxy group, a Ci-Ce alkoxy, a Ce-Ci.) aryloxy, a mono-(C|-C6 alkyl)amino or a di-(Cι-

C(, atkyl)amino group; o when q is 1 , a polyamino moiety of formula (3c), wherein R* and R 2 is each independently selected from a hydrogen atom and a Ci-Ci 2 alley] group; and X 1 is independently selected from a single bond, a Ci-Cn alkylenc group, a Cr-Cn alkenylene group, a C 2 -C^ alkynylene group, a Ce-Cu aryiene group, a C^-Cv, aryl-alkyiene group and a 5- to 14- membered heteroarylene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and C1-C12 alkyi, C1-C 1 2 alkoxy, Ci-Cu alkylthio groups, amino and momMCi-Cu alkyl)amino, and wherein one or more non-adjacent saturated carbon atoms of said C 1 -C 1 2 alkylenc group is optionally replaced with a nitrogen, oxygen or sulphur atom; and

0 when q is 2, a polyamino moiety of formula (3d), wherein R 4 , R $ and R 6 is each independently selected from a hydrogen atom and a C 1 -C 1 2 alkyi group; and X 2 is independently selected from a Ci-Cu alkyiene group, a C 2 -C 12 alkenyiene group, a C 3 -C 12 alkynylene group, a Q-Cu arylene group, a C2-C 26 aryi-alkylenc group and a 5- to 14- mcmbcrcd heteroarylene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and C)-Cn alkyl, Ci-Cn alkoxy, C 1 -C 1 2 alkylthio groups, amino and mono-(C|-Ci 2 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-Cu alkyiene group is optionally replaced with a nitrogen, oxygen or sulphur atom; and

T is a terminal group, and where there is more than one T, T may be the same or different and each T is independently selected from: o a hydrogen atom: and o a group D of formula (6a):

wherein: - each group D is the same or different and Z 1 is independently selected from a Cr-Cn alkylene group, C 2 -C 12 alkenylene or Qr-Cu alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substitucnts selected from halogen atoms, hydroxy, C 1 -C 12 alkoxy and Ci-Cu alkylthio groups; and wherein either:

(i) p is 0 at least twice and at least two A 2 groups are a group D, wherein each D may be the same or different;

(ii) q is 1 or 2 at least twice, when p is 1 or 2, and wherein at least two of the B 2 groups is each bonded to a group D, wherein each D may be the same or different; or

(Ui) at least one p is 0 and an A 2 group is a group D, and at least one q is 1 or 2, when p is I or 2, and a B 2 group is bonded to a group D, wherein D may be the same or different.

The present invention also provides a polymerisation process for producing polymeric products of the invention, which process involves reacting a urethane polyol of the

invention as a monomer. In particular, the process comprises the step of reacting the υrethane polyol with a compound having a functional group capable of reacting with an active hydrogen compound. The compound having a functional group capable of reacting with an active hydrogen compound must be suitable for, or capable of, forming a polymer.

The invention also relates to polymeric products obtained or obtainable from the process above. In one aspect of the invention, the polymeric product of the invention has the formula (U ):

wherein m is an integer 2 or 3; - A 1 Ls a polycarbonyl moiety of formula (2a) or formula (2b):

wherein: o Y 1 is a single bond, a CI-CJ 2 alkylcne group, Q>-C|2 alkenylenc, C 2 -Ci 2 alkynylene, Q-Cu arylene group or a C 2 -C 26 aryl-alkylene group, each of which is υnsubstituted or substituted with one or more substituents selected from C-C12 alkoxy, Ci-Ci 2 alkylthio, C 1 -Ci 2 alky! and C 2 - C 1 jalkox ycarbonyl ;

0 Y 2 is a C 1 -C12 alkyiene group, C 2 -Ci 2 alkenylene, Cj-Ci 2 alkynytene, CV CM arylene group or a C 2 -C 2 * aryl-alkylene group, each of which is unsubstituted or substituted with one or more substituents selected from Ci-Ci 2 alkoxy, CI-CI 2 alkylthio, Ci-Ci 2 alkyl and C 2 -C ι 3 alkoxycarbonyl; each n is selected from the integers 1 and 2, and where there is more than one

n, the values of n may be the same or different;

B 1 is the same or different and each B 1 is independently selected from a polyamino moiety of formula (3a) and formula (3b):

wherein: - R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different and each is independently selected from a hydrogen atom and a Ci-Cu alley! group; - X' is the same or different and is independently selected from a single bond, a Cj -Cjj alkylene group, a Cj-Cu alkenylene group, a C2-C 1 2 alkynylene group, a C 6 -Cu arylene group, a C 2 -C 2 * aryl-alkylene group and a S- to 14- membered heteroaryiene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more sαbstitυents selected from halogen atoms and C 1 -C 1 2 alkyl, Ci-C) 2 alkoxy, C 1 -C 12 alkylthio groups, amino and mono-(C|-Ci2alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Cj-Q alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; - X is the same or different and is independently selected from a Ci-C 1J alkylene group, a C;-Ci2 alkenylene group, a Cj-C 12 alkynylene group, a C 6 -CH arylene group, a C 2 -C26 aryl-alkylene group and a 5- to 14- membered heteroaryiene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substitυents selected from halogen atoms and Ci-Ci 2 alkyl, C 1 -C 12 alkoxy, C1-C 12 alkylthio groups, amino and mono-(Cj- Ci^alkyijamino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-Ci? alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; each p is independently selected from 0 and the integers 1 and 2, and where

there is more than one p. the values of p may be the same or different; A 2 is the same or different and each A 3 is independently selected from: o when p is 0, a group of formula M-[(PV H] n , wherein u is independently selected from the integers 1 and 2, and M is a linking group, wherein: - when u is 1 , M is a linking group of formula (12a); - when u is 2, M is a linking group of formula ( 12b); and

(the asterisk indicates the point of attachment of M to the B 1 moiety); wherein:

• Z 1 is independently selected from a Ct-Cn alkylcne group, C 2 -Ci; alkenylene or Ci-Cn alkynylene group, each of which is straight or branched and is unsubstitutcd or substituted with one or more substiruenls selected from halogen atoms, hydroxy, Ci-Cn alkoxy and C 1 -C 12 alkylthio groups;

• Z 2 is independently selected from a C 2 -C 12 alkylene, C 2 -C 1 2 alkenylcne and a C 3 -C1 2 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substiluents selected from halogen atoms, hydroxy, C)-CJ: alkoxy and C 1 -C 12 alkylthio groups; - the side chain -(PVH has formula (13), and each monomer unit P and the values oft when there is more than one side chain, may be the same or different;

wherein:

• t is the number of monomer units P in each side chain and has an

average value of 1 to 50;

R 11 is independently selected from a C 1 -C 1 2 alkviene, C2-C 1 2 alkenylene and Cj-C 12 alkynylene group, each of which is straight or branched and is υnsubstituted or substituted with one or more substituents selected from halogen atoms. Ci-Cu allcoxy and Cj-Cu alkylthio groups and wherein one or more non-adjacent, saturated carbon atoms of said alkylene, alkenyiene or alkynylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; • L 2 is -O- or -NR 13 -; " R 13 is independently selected from a hydrogen atom and a C 1 -C 6 alkyl group; when p is 0, A 2 is terminal group T, wherein T is a hydrogen atom or a group D of formula (6):

wherein: - each group D is the same or different and Z 1 is independently selected from a C2-C 1 ; alkylene group, C2-C 1 2 alkenylene or C 2 -C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more βubstitucnts selected from halogen atoms, hydroxy, Ci-Cu alkoxy and C)-Cu alkylthio groups; when p is 1 , A" is a polycarbonyl moiety of formula (2c), wherein Y 1 is independently selected from a single bond, a C 1 -C 12 alkylene group, C 2 -C 12 alkenylene, C 2 -C 1 2 alkynylene. a C^-Cj 4 arylene group and a C2-C2 4 aryi- alkylene group each of which is unsubstituted or substituted with one or more substituents selected from C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, Ci-Cc alkyl and C2-C|jalkoxycarbonyl; and when p is 2, A 2 is a polycarbonyl moiety of formula (2d), wherein Y 2 is independently selected from a Ci-Cc alkylene group, C2-C 1 2 alkenylene, Cj-C I 2 alkynylene, a CVCM arylene group and a C 2 -C26 aryl-alkylcnc

group, each of which is unsubstitutcd or substituted with one or more subsrituents selected from Ci-Cu alkoxy, C 1 -C 1 2 alkylthio, Ci-Cu alkyl and C2-Ci 3 alkoxycarbonyl;

each q is independently selected from 0 and the integers 1 and 2, and where there is more than one q, the values of q may be the same or different;

B 2 is the same or different and each B 2 is independently selected from: 0 when q is 0, an unreacted leaving group L 1 , wherein L 1 is a hydroxy group, aC 1 -C 6 alkoxy, a C 6 -C 14 aryioxy, a rnono-(C 1 -C 6 alkyl)amino or a di-(C 1 - C 6 alkyi)amino group; 0 when q is 1 , a polyamino moiety of formula (3c), wherein R 1 and R 2 is each independently selected from a hydrogen atom and a Ci-C u alkyl group; and X 1 is independently selected from a single bond, a C 1 -C 12 alkylene group, a C 2 -C 12 alkenylene group, a C 2 -C 1 2 alkynyiene group, a C 6 -C 14 arylene group, a C 2 -C 26 aryl-alkylcne group and a 5- to 14- membered hcteroarylcne group comprising 1. 2 or 3 heteroaioms selected from N and O, each of which is substituted or unsubstituled with one or more subtstituents selected from halogen atoms and Ci-Cu alkyl, Ci-Cc alkoxy, C 1 -C 12 alkylthio groups, amino and mono-(C 1 -C 12 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said C 1 -C 12 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; and

0 when q is 2, a polyamino moiety of formula (3d), wherein R 4 , R 5 and R 6 is each independently selected from a hydrogen atom and a Ci-Ci 2 alkyl group; and X 2 is independently selected from a Cj-Cu alkylene group, a C 2 -C 12 alkenylene group, a C 3 -C u alkynyiene group, a C 6 -C 14 arylene group, a C 2 -C 26 aryj-alkylene group and a 5- to 14- membered

hetcroaryiene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubslituted with one or more substituents selected from halogen atoms and Ci-Cu alky!, Ci-Cu alkoxy, C|-Ci 2 alkylthio groups, amino and mono-(C|-Ci 2 alkyOamino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-C^ alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; and

each s is independently selected from U and the integers 1 and 2, and where there is more than one s, the values of s may be the same or different; C is the same or different and each C is independently selected from: o when s is 0, C is a terminal group T, wherein T is a hydrogen atom or a group D of formula (6a):

wherein: - each group D is the same or different and Z 1 is independently selected from a C 2 -C» 2 alkylene group, C 2 -C 12 alkenyiene or C 2 -C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, Cι-Cι> alkoxy and C1-Q2 alkylthio groups; 0 when s is 1 , C is a linking group of formula ( 12c); 0 when s is 2 t C is a linking group of formula ( 12d);

(the asterisk indicates the point of attachment of C to the B 3 moiety); wherein:

• Z 1 is independently selected from a Cj-C i> alkylcne group, C 2 -C 12 alkcnyiene or CrCi 2 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, C I -C I2 alkoxy and C 1 -C 12 alkylthio groups; ■ Z 2 is independently selected from a CyCu alkylene, Q.-C 12 alkenytene and a Cj-Cu alkynylene group, each of which is straight or branched and is imsubstituted or substituted with one or more substituents selected from halogen atoms, hydroxy, Cj -C 12 alkoxy and C 1 -C 12 alkyithio groups; the side chain -(PVH has formula (13a), and each monomer unit P and the values of t when there is more than one side chain, may be the same or different;

wherein:

0 t is the number of monomer units P in each side chain and has an average value of 1 to 50;

0 R 11 is independently selected from a Ci-Ct 2 alkylene, Q>-C 1 2 alkcnyiene and C 2 -C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, C 1 -C12 alkoxy and C)-Cn alkylthio groups and wherein one or more non-adjacent, saturated carbon atoms of said alkylene, alkenylene

or alkynyiene group is optionally replaced with a nitrogen, oxygen or sulphur atom; o L 2 is -O- or -NR 13 -; o R n is independently selected from a hydrogen atom and a Q-Q, alkyl group; and wherein either, (i) p is 0 at least twice and at least two A~ groups are a group of formula

M-ftPVHJu, wherein each group of formula M-[(P)rH Ju may be the same or different; (ii) q is 1 or 2 at least twice, when p is 1 or 2, and wherein at least two of the B 2 groups is each bonded to a group of formula Cf(F) I -H],. where s is 1 or 2 and the values of s may be the same or different; or

(iii) at least one p is 0 and an A 3 group is a group of formula M-[(P),-H J u , wherein each group of formula M-I(P) 1 -H] 1 , may be the same or different, and at least one q is 1 or 2, when p is 1 or 2, and a B 2 group is bonded to a group of formula -CftPVH],, where s is 1 or 2.

The present invention therefore also provides a process for preparing a polyurethane comprising curing a polymeric product of the invention in the presence of a cross- linking agent, as well as a polyurethane obtained or obtainable thereby.

The polymeric products of the invention are envisaged to be particularly useful in the production of coatings. The invention therefore also provides a coating composition comprising

a) a polymeric product of the invention; and b) one or more cross-linking agents; optionally together with one or more components selected from c) a catalyst; d) one or more solvents; e) another polymer or polymers reactive with the cross-Unking agent; and f) one or more chain extenders.

The coating composition of the invention can be used to form a coated article by

i) applying the coating composition to the surface of the article; and ii) curing said composition to produce a coated article.

The present invention therefore also provides a process for coating an article as set out above as well as a coated article obtained or obtainable thereby.

The coatings produced in accordance with the present invention have the advantages of flexibility and chemical resistance that are usually associated with coatings produced using isocyanates. In addition, the polyurethanes and coatings of the invention have beneficial chemical and physical properties, such as improved hardness, compared to polyurethanes prepared using other methods that do not involve the use of isocyanate reagents that are known in the art.

The urethane polyotβ of the invention are formed of at least two di-amine or tri-amine units that arc linked by at least one di-carbonyl or tri-carbonyl moiety. The presence of a polycarbonyl moiety linking the polyamine groups is believed to provide additional hydrogen bonding sites within the resulting polymer structure. Moreover, the di-carbonyi or tri-carbonyl moiety provides an additional hard segment within the resulting polymer structure, which affects the distribution of hard and soft segments through the backbone of the polymer. The effect of the distribution of hard and sotf segments in a polymer is described further in "Polyurcthanc" 2 nd edition (Gunter Oertel, published Carl Hanser Verlag, 1994) pages 37 to 46, which is incorporated by reference herein in its entirety.

The invention also relates to amine compounds and salts thereof of formula (4)

wherein m is an integer 2 or 3;

A 1 is a polycarbonyl moiety of formula (2a) or formula (2b):

wherein: o Y 1 is a single bond, a Ci-Cu alkylene group, C 2 -C 12 alkenytene, C 2 -Ci 2 alkynylenc, C 6 -Cu arylene group or a C 2 -C 26 aryl-alkylene group, each of which is unsυbstitυted or substituted with one or more substitυents selected from Cj-C 12 alkoxy, Ci-Ci 2 alkyhhio, C 1 -C 12 alkyl and C 2 - C 13 alkoxycarbony I ; o Y 2 is a C 1 -CI 2 alkylene group, Ci-Cj 2 alkenylenc, C3-CU alkynylene, CV CM aryiene group or a C 2 -C 26 aryi-alkylene group, each of which is unsubβtituted or substituted with one or more subβtituents selected from C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C|-C )2 alkyl and Ci-Cijalkoxycarbonyi, each n is selected from the integers 1 and 2, and where there is more than one n, the values of n may be the same or different;

B 1 is the same or different and each B 1 is independently selected from a polyamino moiety of formula (3a) and formula (3b):

o wherein: - R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different and each is independently selected from a hydrogen atom and a Ci-C 12 alkyl group; - X 1 is the same or different and is independently selected from a single bond, a C 1 -C 1 2 alkylene group, a Q-C 12 alkenylene group, a C 2 -Cj 2 alkynylene group, a C 6 -C 14 arylene group, a CVC 26 aryl-alkylene group

and a 5- to 14- membered heteroaryiene group comprising 1 , 2 or 3 hetcroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and C 1 -C 12 alkyl, C 1 -C 1 2 alkoxy, Cj-C'u alkylthio groups, amino and mono-(C|-Ci2alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said C 1 -C12 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; - X 2 is the same or different and is independently selected from a Ci-Cu alkylene group, a CVCu alkenylene group, a CJ-CJ 2 alkynyicnc group, a Ce-Cu arylene group, a C 2 -C 2 ^ aryl-alkyiene group and a 5- to 14- merabered heteroaryiene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substituents selected from halogen atoms and Ci-Cu alkyl, Ci-Cu alkoxy, Ci-C 12 alkylthio groups, amino and mono-(C|- Ci 2 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said CrC^ alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; each p is independently selected from 0 and the integers 1 and 2. and where there is more than one p, the values of p may be the same or different; - A 2 is the same or different and each A 2 is independently selected from:

0 when p is 0, a hydrogen atom:

0 when p is 1 , A 2 is a polycarbonyl moiety of formula (2c), wherein Y 1 is independently selected from a single bond, a Ci-Cu alkylene group, C 2 -Ci: alkenylene, Q-Cu alkynylene, a Q-Cu arylene group and a C 2 -C26 aryl- alkylene group each of which is unsubstituted or substituted with one or more substituents selected from Ci-Cu alkoxy, Ci-Cu alkylthio, Cj-Cu alkyl and CVCoalkoxycarbonyl; and

0 when p is 2, A 2 is a polycarbonyl moiety of formula (2d), wherein Y 2 is independently selected from a Cj-Cu alkylene group, Cj-Ci: alkenylene, Cj-C U alkynylene, a Ce-Cu arylene group and a C 2 -C 26 aryl-alkyϊene group, each of which is unsubstituted or substituted with one or more substituents selected from Ci-Cu alkoxy, Ci-Cu alkylthio, Ci-Cu alkyl

and C2-Ci3alkoxycart>onyl;

each q is independently selected from O and lhe integers 1 and 2, and where there is more than one q, the values of q may be the same or different; B 2 is the same or different and each B 2 is independently selected from: o when q is O, an unreacted leaving group L 1 , wherein L 1 is a hydroxy group, a Ci-C 6 alkoxy, a Ce-Cw aryloxy, a mono-<Cι-C« alkyl)amino or a di-(C|- Ce alkyl)amino group; o when q is I , a polyamino moiety of formula (3c), wherein R 1 and R 2 is each independently selected from a hydrogen atom and a Ci-Cu alM group; and X 1 independently selected from a single bond, a Ci-Ci 2 alkylene group, a C2-C 1 2 alkenylene group, a C2-C 12 alkynylene group, a C 6 -Cu aryiene group, a C 2 -C 26 aryi-alkylene group and a 5- to 14- membered heteroarylene group comprising 1 , 2 or 3 heteroatoms selected from N and O, each of which is substituted or uasubstituted with one or more substituents selected from halogen atoms and C 1 -C 12 alkyl, Ci-Cu alkoxy. Cι-Ci2 alkylthio groups, amino and mono-{C|-Ci> alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci -C 12 alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; and 0 when q is 2, a polyamino moiety of formula (3d), wherein R 4 , R 5 and R 6 is each independently selected from a hydrogen atom and a Ci-Cu alkyl group; and X~ is independently selected from a Ci-Cu alkylene group, a C 2 -C 12 alkenylene group, a C 3 -C 12 alkynylene group, a C 1 -CM arylcnc group, a C2-C2 6 aryi-alkyienc group and a 5- to 14- membered heteroarylene group comprising 1 , 2 or 3 heteroatoms selected from N and

O, each of which is substituted or unsυbstituted with one or more

sυbstitucnts selected from halogen atoms and C 1 -C 12 alkyi, C 1 -Q 2 alkoxy, C|-C)2 alkylthio groups, amino and mυno-<C|-Ci2 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-C) 2 alkyiene group is optionally replaced with a nitrogen, oxygen or sulphur atom;

and wherein either

(i) p is 0 at least twice and at least two A 2 groups are a hydrogen atom; (ii) q is 1 or 2 at least twice, when p is 1 or 2; or

(iii) at least one p is 0 and an A 2 group is a hydrogen atom, and at least one q is 1 or 2, when p is 1 or 2.

A further aspect of the invention is a process for preparing the urethane polyol, which process comprises reacting a compound of formula (4) with at least two equivalents of a compound of formula (16):

wherein Z 1 is a Cj-Cjj alkyiene group, C2-C)2 alkenylene or C 2 -C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substiruents selected from halogen atoms, hydroxy. C|-C ( i alkoxy and C 1 -C12 alkylthio groups.

Detailed Description of the Invention

Y 1 and Y 2 in the structures and formulae above represent the backbone of the polycarbonyl compound. Y 1 is preferably a single bond or an υnsubstituted C \ -CA alkylcne group, more preferably Y* is a single bond or an unsubstiluted methylene group. Y 2 is preferably a C«-Cj2 alkylene group, or a C 6 -Ci 0 arylene group. More preferably, Y 2 is an unsubstituted phenyl group.

R.\ R 2 , R 3 , R 4 and R 5 are the sυbstituents attached to the nitrogen atoms in the urethane polyols, polymeric products or other compounds or products of the invention. Preferably each R 1 , R 2 , R 3 , R 4 and R $ group is the same or different and may be a hydrogen atom or C 1 -C 4 alkyl, more preferably a hydrogen atom, methyl, ethyl or propyl group, and most preferred is a hydrogen atom.

Preferably X 1 is a C 1 -C 12 alkylene group, which includes a C 3 -C 1 2 cycloallcylcne group, each of which is unsubstituted or substituted with one or more substituents selected from Cy-Ci, alkyl, Ci-Ce alkoxy and Cj-C<, alkylthio groups. It is preferred that X 1 in formula (3a) above is a group of formula (8):

It is preferred that X 2 is a Ci-Cu alkylene group, which includes a C 3 -C1 2 cycloalkγlene group, wherein one non-adjacent saturated carbon atom of said alkylene group is optionally replaced with a nitrogen atom. Also preferred is when X" is a 6- membered heteroaryl ring. Most preferably X 2 is triazine or the group N((CH?)2-)3.

It is preferred that Z 1 is a straight or branched C 2 -C 6 alkylene group which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from halogen atoms, hydroxy groups, Q-C4 alkoxy and C 1 -C4 alkylthio groups. Preferably Z 1 is an

υrøubstituted ethylene group. 7? is preferably a Q-C 4 alkylene group.

The urethane polyols of lhe invention have at least two hydroxy groups that may be used to propagate or extend a polymer chain. Thus, the hydroxy groups of the urethane polyol may react with suitable compounds having one or more carboxylic acid, ester, anhydride or amide functional groups.

The present invention provides a process for producing the polymeric products of the invention. The process comprises the step of reacting a urethane polyol of the invention with a compound that is capable of, or suitable for, forming a polymer and which has a functional group capable of reacting with an active hydrogen compound. The compound thai is capable of, or suitable for, forming a polymer may itself be a polymer or a monomer and preferably is selected from:

(a) a polyester. (b) a polycarboxylic acid, ester or anhydride thereof;

(c) a compound of formula (9):

; and

(d) a compound of formula (10):

wherein - L 2 is -O- or -NR 13 -;

L J is a halogen atom, the group -O-R 14 or -NR M R 15 ; R 14 is a hydrogen atom, C)-Q alkyl group or C) -Ce acyl group; each R 1} and R 15 is independently selected from a hydrogen atom and a Ci-C 6 alkyl group;

R u is a Cj-Ci2 alkylene, C∑-CJZ alkenyicne or Cj-Cu alkynyiene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, Ci -C 12 alkoxy and Ci-Cn alkylthio groups and wherein one or more non- adjacent, saturated carbon atoms of said alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; R 12 is a C 2 -C 1 2 alkyiene, Cj-Cu alkenyϊene or Cj-C 1 2 alkynyiene group, each of which is straight or branched and is unsubstituted or substituted with one or more substitυents selected from halogen atoms and Ci -Cu alkoxy and C1-C 12 alkylthio groups and wherein one or more non- adjacent, saturated carbon atoms of said alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; L 4 is -O- or -NR 1 *-; R 16 is a hydrogen atom or a Cy-C f , alkyl group; and wherein each of the groups L 2 , L\ L 4 , R 11 , R 12 , R π , R M , R 15 and R 16 may be the same or different in each compound of formula (9) or formula (10).

Polymeric products of the invention are obtained or obtainable from a process involving reacting a urethane polyol with a prc- formed polyester. The urethane polyol is able to react with a terminal ester moiety in the polyester to extend the polymer chain and form a polyester based polyurcthanc. Alternatively, when the polyester has terminal alcohol groups, the urethane polyol may be reacted with the polyester in the presence of a polycarboxylic ester. Suitable polyesters can be prepared from suitable diols or polyols, such as trioln or tetrols, and an aromatic or aliphatic polycarboxylic acid, particularly a di- or tricarboxylic acid. The polyester can also be prepared by polymerising a hydroxyalkyl carboxyhc acid or lactone, such as caprolactone, using methods known in the art.

Suitable diols that may be used to prepare the polyester include ethylene glycol, propylene glycol, 1,3-butylcneglycol, 1,4-butyleneglycol, neopentylglycol, dicthyleneglycol, dipropytenegiycol, eyelohexane dimethanol and 1,6 hcxanediol. Suitable polyols that may be used include trimethylol propane, trimethylol ethane,

glycerine and pentaerythritol. The diols and polyols may be used either singly or in combination with one another.

Examples of suitable aliphatic polycarboxylic acids that can be used to make 5 polyesters include malonic, succinic, glutaric, adipic, pimclic, suberic azclaic acids and mixtures thereof. Aliphatic polycarboxylic acids having a non-aromatic, unsaturated moiety, such as an ethylene group, are also suitable. Examples of such non-aromatic, unsaturated aliphatic polycarboxylic acids include malcic, fumaric, aconitic, itaconic acids and mixtures thereof. Examples of suitable aromatic 0 polycarboxylic acids include o», m-, p-phthalic acid, trimellitic acid and mixtures thereof. Mixtures of aliphatic (saturated and unsaturated) and aromatic polycarboxylic acids may also be used.

Esters of the polycarboxylic acids described may also be used either instead of, or in 5 combination with, the polycarboxylic acids to prepare polyesters for use in the invention. If an ester is used, then the polyester will be formed by a transestehfication reaction using a standard method known in the art. The esters are preferably alkyi esters of the polycarboxylic acids mentioned above. Anhydrides of the polycarboxylic acids may also be used, if available. It is preferred that the polyester is prepared from0 an aliphatic polycarboxylic acid, ester or anhydride thereof.

The polyesters for use in the invention may also be prepared from hydroxyalkyl carboxylic acids and/or lactones using methods known in the art. It is not necessary to include diols or polyols as a monomer in a reaction for preparing a polyester fromS hydroxyalkyl carboxylic acids and/or lactones because the hydroxyalkyl carboxylic acid or lactone monomer is able to propagate the polyester polymer chain by itself.

Polyesters suitable for use in the invention typically have an average molecular weight of between 300 and 3,500, preferably between 500 and 2500. 0

The reaction of a urethane polyol with a polyester is typically performed at a temperature from 120 °C to 200 °C, preferably from 140 °C to 160 °C. The reaction

may be performed in the presence of an estcrification catalyst, which is present in an amount of 0.005 % to 5 % by weight, of the reactants, more preferably 0.01 % to 1 % by weight of the reactants. Particularly preferred esten ficarion catalysts include organotin compounds and titanium (FV) alkoxide complexes. Suitable titanium (FV) alkoxide complexes include titanium (IV) ethoxidc, titanium (IV) n-propoxidc, titanium (IV) lsopropoxide, titanium (IV) n-butoxide. titanium (IV) isobutoxide, titanium (FV) ethylhexoxidc, titanium (IV) butoxy isopropoxy complexes, and mixtures thereof. Suitable organotin compounds include dibutyltin di acetate, dibutyitin dilaurate, dibutyltin maleate, dibutyltin diacetate, dilauryltin diacetate, dioctyitin diacetate and mixtures thereof. Preferably the catalyst is dibutyltin dilaurate.

For some combinations of urethanc polyols and polyesters, the reaction conditions used, particularly the temperature, may cause discoloration or degradation of the ester. Thus, it is preferred that polymeric products of the invention are obtained or obtainable from a process that involves the step of reacting a urethanc polyol as a monomelic component with other compounds that are able to generate or propagate a polyester chain in situ. Thus, the urethanc polyol may be reacted directly with a lactone or a polycarboxyiic acid, a hydroxycarboxylic acid or an ester or anhydride thereof.

In one embodiment, the urethane polyol is reacted in a first step with a polycarboxyiic acid, ester or anhydride thereof, without the presence of a diol or polyol. The urethane diol may be added to a reaction vessel comprising a polycarboxyiic acid, ester or anhydride thereof, or vice-versa. Alternatively, the urethane polyol and polycarboxyiic acid, ester or anhydride may be added to the reaction vessel at the same time. Once the reaction between the urethane polyol and polycarboxyiic acid, ester or anhydride is near or has gone to completion, a diol or polyol may then be added to react with any remaining carboxylic acid, ester or anhydride functional groups.

The order of addition of the urethanc polyol and polycarboxyiic acid, ester or

anhydride thereof, as well as the amounts of those compounds are selected, as is known in the art, to obtain a polymeric product having the desired distribution of monomer units. For example, one equivalent of a urethane diol may be reacted with one equivalent of a dicarboxylic add, ester or anhydride thereof, such that the resulting polymeric product has repeating units that alternate between that derived from the urethane diol and that derived from the poiycarboxytic acid, ester or anhydride thereof. Alternatively, a polymeric product comprising a relatively low number of urethane groups may be desired. If such a polymeric product is desired, then, for example, a urethane diol is reacted with a large molar excess of the polycarboxylic acid, ester or anhydride. Typically, the urethane diol would also be added to a reaction vessel containing the polycarboxylic acid, ester or anhydride.

In an alternative embodiment, the process of the invention involves the step reacting a urethane polyol and a diol or polyol with a polycarboxylic acid, ester or anhydride thereof. The diol or polyol may be added to a reaction vessel containing the polycarboxylic acid, ester or anhydride, or vice-versa, before the urethane polyol is added. Alternatively, the urethane polyol may be added at the same time as the diol or polyol to a reaction vessel containing the polycarboxylic acid, ester or anhydride. Further, the urethane polyol may be added at the same time as, but separately to, the polycarboxylic acid, ester or anhydride to a reaction vessel containing a diol or polyol.

One embodiment of the invention relates to a process, which comprises the step of reacting a urethane polyol of formula (1 ) with a compound of formula (9). This reaction is shown in scheme 1 below, by way of example, for urethane diols of formula (7a).

Scheme 1

In scheme 1 above, the groups A 3 , B\ D, Z\ L", L 3 , R n and the parameters t and r are as defined herein.

The class of compounds represented by formula (9) have a carbonyl- functional group (represented by L 3 C(O)-) that is capable of forming an ester group with the hydroxy group of the urethane polyol. It also has an active hydrogen functional group represented by -L 2 -H that is capable of reacting with the L 3 C(O)- functional group of another molecule of a compound of formula (9), which may be present in the reaction mixture. Formula (9) represents compounds such as hydroxy alkyl carboxylic esters, primary or secondary aminoalkyl carboxylic amides, which are commercially available or may be prepared using a method known in the art

The molar ratio of urethane polyol to the compound of formula (9) will depend on the number of hydroxy groups present in the urethane polyol. Generally, one equivalent of the urethane diol, for example, is reacted with at least two equivalents of a compound of formula (9) in order to obtain polymeric products of the invention.

When L 3 is a halogen atom, it is preferred that the halogen atom is chlorine or bromine, more preferably chlorine. It is preferred that L 2 is -O- and L 3 is -O-R 14 , particularly when R 14 is a CrQ, alkyi group or a hydrogen atom. Typically, R" is preferably a Ci-Ci 2 alJcyicne group, more preferably a Ci-Q alkylene group, which is unsubstituted or substituted with 1, 2 or 3 substituents selected from halogen atoms, Ci-O aflcoxy groups and C 1 -C 4 alkyithio groups. R 1 ' preferably has the same definition as that of R ι: set out below.

It is preferred that the urethane polyol is of formula (7):

D-B 3 -(A 3 -BVD

(7) wherein r is 1 or 2; - A 3 is a polycarbonyl moiety of formula (2a), and where there are more than one A 3 moieties, then they may be the same or different:

(2a) wherein

0 Y 1 is a single bond, a C1-C12 alkylene group, C 2 -C 12 alkcnylene, C 2 -C1 2 alkynylene, Q-CM arylcne group or a C 2 -C 2 6 aryl-alkylene group, each of which is unsubstituted or substituted with one or more substituents selected from C 1 -C 12 alkoxy, CI-CI 2 alkyithio, C 1 -C 12 alkyl and C 2 - Cualkoxyearbonyl;

B 3 is the same or different and is a polyamine moiety of formula (3a)

R 1 R 2

(3a)

wherein o R 1 and R 2 is (he same or different and each R 1 and R 2 is independently selected from a hydrogen atom and a Ci-Cn alkyJ group; o X 1 is the same or different and each X 1 is independently selected from a single bond, a Ci-Cu allcylene group, a C2-C 1 2 allcenylenc group, a C 2 -C 12 alkynylene group, a CG-CM arylene group, a C 2 -C 2 * aryl-alkylene group and a S- to 14- memhered hetcroarylene group comprising 1 , 2 or 3 hetcroatoms selected from N and O, each of which is substituted or unsubstituted with one or more substiruents selected from halogen atoms and C 1 -C 12 alkyl, C 1 -C1 2 alkoxy, Ci-Cn alkylthio groups, amino and mono-

(C|-Ci>alkyJ)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-C 12 alkyiene group is optionally replaced with a nitrogen, oxygen or sulphur atom;

D is the same or different and each D is a terminal group of formula (6)

wherein

0 Z 1 is the same or different and each Z 1 is independently selected from a CN- Cj 2 alkyiene group, C 2 -C 12 alkenylene or C 2 -C 12 alkynylene group, each of which is straight or branched and is unsυbstituled or substituted with one or more substituents selected from halogen atoms, hydroxy, C 1 -C 12 alkoxy and C|-C| 2 alkylthio groups.

Another embodiment of the invention is a process which comprises the step of reacting a urethane polyol of the invention with a lactone or lactam of formula (10), as shown in scheme 2 below.

Scheme 2

Jn the above scheme 2, A J , B J , D, Z 1 , L 4 , R 12 , t and r have the meanings set out above. The reaction is typically carried out in the presence of a Lewis acid catalyst or at a pH of less than 7 and at a temperature of approximately 50-1SO°C.

The lactone or lactam (10) should be present in sufficient quantities to provide the desired values oft in the product (14b). For example, when the reaction is performed with a urethane diol and each t is about 3, six equivalents of lactone or lactam (10) are required for each equivalent of compound (7a). At least two equivalents of lactone or lactam (10) must be used in any case. The lactams and lactones (10) are typically available commercially. For example, a preferred compound of formula (10) is caprolactonc which is widely available.

It is noted that the reaction of scheme 2 is carried out at relatively low temperatures, particularly when compared with typical temperatures for carrying out a conventional polyesterification, i.e. up to 240°C, typically from 220 to 240 11 C. The use of low

temperatures avoids possible degradation of the urethane polyoL which might otherwise discolour the final polymer. Also, the lower reaction temperatures compared to that of conventional polyesterification allows the use of thermally sensitive compounds of formula (10), which would otherwise decompose or react in an undesirable manner at higher temperatures.

In the process of the invention, R 12 is typically a C 2 -C 12 alkylene group, preferably a Ci-Q, alkylene group, which is unsubstituted or substituted with 1 , 2 or 3 substitucnts selected from halogen atoms, C 1 -C 4 alkoxy groups and C1-C 4 alkytthio groups. More preferably R 12 is -(CH^-. H is also preferred that the compound of formula (10) is a lactone i.e. L 4 is -O-.

It is preferred that the amine compound of formula (4) above is a compound of formula (5): H-B 3 -(A 3 -BVH

(5) wherein r is 1 or 2;

A 3 is a polycarbonyl moiety of formula (2a), and where there are more than one A 3 moieties, then they may be the same or different:

wherein

0 Y 1 is a single bond, a Ci-Cn alkylene group, Q-Cu alkenylene, C2-C 1 2 alkynylcne, C 6 -Cu arylenc group or a CrC^ aryl-alkylene group, each of which is unsubstituted or substituted with one or more substituents selected from C 1 -C 1 2 alkoxy, C 1 -Cu alkylthio, C 1 -Ci 2 alkyi and C 2 - Cijalkoxycarbonyl; B* is the same or different and is a polyamine moiety of formula (3a)

wherein o R 1 and R 2 is the same or different and each R 1 and R 3 is independently selected from a hydrogen atom and a Cj-Cu alkyl group; o X 1 is the same or different and each X 1 is independently selected from a single bond, a C 1 -Cu alkylene group, a C 2 -C 1 2 alkenylene group, a Cj-Ci 2 alkynyiene group, a Q-Cu arylene group, a Q-C^ aryl-alkylene group and a S- to 14- raembered heteroarylene group comprising 1, 2 or 3 heteroatoms selected from N and O, each of which is substituted or unsubstitυtcd with one or more substitucnts selected from halogen atoms and C|-Ci 2 alkyi, Cι-C' 12 alkoxy, Ci-Cu alkyithio groups, amino and mono-

(C|-Ci 2 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ct-Cu alkylene group is optionally replaced with a nitrogen, oxygen or sulphur atom.

It is preferred that r in the compounds of formulae (5), (7) and ( 14) is 1.

The above polymerisation processes of the invention can, if desired, be carried out using an enzymatic polymerisation process such as that described in GB-B-2 272 904 and EP-B-O 670906. each of which is incorporated by reference herein in its entirety.

The polymerisation processes of the invention can be promoted by any type of esterifjcation catalyst known in the art. Particularly attractive are metal oxides, halides or carboxylates, the metals of which contain free p, d or f orbitals of a favourable energy, e.g. Mg, Ti, Zr, Zn, Sn, Al, Y, La, Hf and rare earth atoms such as Sm, in the presence of protic species such as alcohols, amines, thiols and water. Preferably, the catalyst is a titanium (IV) alkoxide complex, zinc acetate, magnesium acetate or an organotin compound. Suitable titanium (IV) alkoxide complexes include titanium (IV) ethoxide, titanium (IV) n-propoxide, titanium (IV) isopropoxide, titanium (FV) n-

butoxide, titanium (IY) isobutoxide. titanium (IV) ethylhexoxide, titanium (IV) butoxy isopropoxy complexes, and mixtures thereof. Suitable organotin compounds include dibutyltin diacctate, dibutyltin dilaurate, dibutyltin maleale, dibutyltin di acetate, dilauryltin diacetate, dioctyitin di acetate, dibutylbis(laurylthio)stannate, dibutyUinbi^isooctylmercapto acetate), dibutylunbisfisooctylinalcatc), stannous octoate and mixtures thereof. It is however preferred that the polymerisation process employs stannous octoate as catalyst, which has the structure shown below.

As will be readily understood (and is capable of being determined) by one skilled in the art, the precise concentration of the catalyst to be employed in the process of the present invention may be varied as needed to obtain the polymer which is desired to be obtained thereby.

In all of the above processes, the conditions arc selected to avoid or minimise side reactions involving the amide moiety or carbamate moiety of the urcthane polyol e.g. hydrolysis or amide/ester exchange reactions. It is therefore preferable to avoid the use of carboxylic acids since their use may lead to hydrolysis of the amide or carbamate moieties in the urcthane diol.

The polymeric products of the invention typically have average molecular weights (Mw) in the region of 400 to 5000 and, preferably 500 to 2500 when measured by GPC with reference to a polystyrene standard.

The polymeric products of the present invention are typically produced by a polymerisation reaction of a lactone or lactam with a urcthane diol. Preferred polymeric products of the invention therefore have the formula (14):

H-(P\-C-B 3 -(A 3 -B 3 ),-C-(PX-H

wherein r is 1 or 2;

A i is a polycarbonyl moiety of formula (2a), and where there arc more lhan one A* moieties, then they may be the same or different:

wherein o Y* is a single bond, a C1-C12 alkylene group, CVC12 alkenylene, C 2 -C 12 alkynylene, CVCu arylene group or a C2-C26 aryl-alkylene group, each of which is unsubstitutcd or substituted with one or more substituents selected from C|-C|> alkoxy, Ci-C 12 alkylthio, C 1 -Ci 2 alkyl and C r C 1 jalkoxycarbonyl ;

B 3 is the same or different and is a polyaminc moiety of formula (3a)

wherein

0 R 1 and R 2 is the same or different and each R ' and K 2 is independently selected from a hydrogen atom and a Ci-C 12 alkyl group;

0 X 1 is the same or different and each X 1 is independently selected from a single bond, a C 1 -C12 alkylene group, a CrC^ alkenylene group, a C 2 -C 12 alkynylene group, a Q-Cu arylene group, a C 2 -C 26 aryl-alkylene group and a 5- to 14- mcmbcrcd hetcroarylene group comprising 1 , 2 or 3 beteroatoms selected from N and O, each of which is substituted or unsubstiruted with one or more substitucnts selected from halogen atoms and Cj-Ci 2 alkyl, Ci-Cc alkoxy, C1-C12 alkylthio groups, amino and mono- (C|-Ci 2 alkyl)amino, and wherein one or more non-adjacent, saturated carbon atoms of said Ci-Cu alkylene group is optionally replaced with a

nitrogen, oxygen or sulphur atom: each C is the same or different and each C is a moiety of formula (12a):

wherein o Z 1 is the same or different and each Z 1 is independently selected from a C 2 -C 12 alkyiene group, C 2 -C 12 alkenyienc or C 2 -C 12 alkynylcne group, each of which is straight or branched and is unsυbstiruted or substituted with one or more substituents selected from halogen atoms, hydroxy, C 1 -C 12 alkoxy and C 1 -C 12 alkyithio groups; -(P)rH is a side chain of formula ( 13), wherein each side chain may be the same or different, and wherein

o I is the number of monomer units P in each side chain, t may be the same or different and has an average value of 1 to 50; o R 11 is independently selected from a C 1 -C 12 alkyiene, C 2 -C 12 alkenyienc and C 2 -C 12 alkynylene group, each of which is straight or branched and is unsubstituted or substituted with one or more substituents selected from halogen atoms, C 1 -C 12 alkoxy and C 1 -C 12 alkyithio groups and wherein one or more non-adjacent, saturated carbon atoms of said alkyiene, alkenylene or alkynylene group is optionally replaced with a nitrogen, oxygen or sulphur atom; o L 2 is -O- OT -NR"-; o R 13 is independently selected from a hydrogen atom and a C 1 C 6 alkyi group.

Typically, the polymeric product comprises a number of different compounds of

formula (14), each of which can be prepared by polymerisation of Ae same starting materials. Thus, a polymeric product may, for example, contain a number of compounds which differ only in terms of their value oft in formula (14).

The polymeric products of the invention can be further reacted using known techniques to produce cured polyurethancs. The process comprises curing a polymeric product of the invention in the presence of a cross-linking agent. Typically, the polymer products arc combined with a cross-linking agent and one or more solvents, optionally together with one or more chain extenders, such as polyolβ or polyamincs, and a catalyst system. Further polymer(s) reactive with the cross-linking agent(s) may also be added. The composition thus produced is subsequently cured to produce a final polyurethane product.

Suitable cross-linking agents are known in the art Preferred cross-linking agents are non-isocyanate containing components such as aminotriazine compounds, in particular mclamine, ureas, benzoguanamine or glycoluril; the resins can be alkylated or partially alkylated. Such resins and their chemistry arc described in "Organic Coatings Science and Technology" 2 nd Edition (edited by Wicks, Jones and Papas), Pub. Wiley lntcrscience. 1999, (hereinafter "Wicks, et al."), which is incorporated by reference herein in its entirety. Chapter 9 p 162-179 is devoted entirely to these resins. Melaminc type cross-linkers are, for instance, manufactured by Cytec (wwvv.cvteccom). However, isocyanate and blocked isocyanate cross-linking agents can be employed if desired. Suitable catalyst systems, solvents and chain extenders will also be well known to the skilled person in the art. An example of a suitable catalyst system is p-toluene sulfonic acid in methanol/isopropanol at a pH of 5.7 to 6.5.

The polymer products of the invention are particularly useful in the production of polyurethane coatings, for example clear coatings for the automobile industry and coil coatings. An article is coated by (i) applying a coating composition containing the polymer products of the invention to the article to be coated, and (ii) curing the applied coating. The application and curing steps can be carried out by techniques generally

known in the art For example, the curing step is typically carried out by heating up to approximately 15O°C for up to 1 hour.

The coating compositions of the invention comprise (a) the polymer product of the invention, (b) one or more cross-linking agents, optionally (c) a catalyst, optionally (d) one or more solvents, optionally (e) another polymer or polymers reactive with the cross-linker (eg. a hydroxy-functional acrylic polymer) and optionally (f) one or more chain extenders (for instance amino-functiona) chain extenders such as diethyl toluene dt-amine and hydroxy-functional chain extenders such as butane diol). Preferred coating compositions comprise (a) the polymer product of the invention, (b) one or more cross-linking agents and (d) one or more solvents. Further preferred coating compositions comprise (c) a catalyst in addition to components (a), (b) and (d). Suitable coating composition formulations are known in the art and are described, for example, in Wicks, et al., see in particular page 4.

Whilst the polymer products of the invention are particularly useful in the production of coatings, other uses can also be envisaged. For example, the polymer products can be employed as adhesives, foams and moldings.

The urethane polyols of formula ( I ) can be produced from an amine compound of formula ( 15) by reaction with a cyclic carbonate of formula (16). The reaction is shown in scheme 3, by way of example, for a compound for formula ( 15). In the reaction shown, typically, an equivalent of the di-aroine is reacted with at least two equivalents of the carbonate of formula (16).

Scheme 3

In the above scheme 3, B 3 A 3 , D, R 1 , R 2 , X 1 , Z 1 and r are as defined herein. This reaction can be earned out in an inert organic solvent such as toluene and at a temperature of approximately 50 °C. or in accordance with any techniques known in the art. For example, it may be necessary to deprotonate the amino group or groups in the compound of formula (4) or formula (5) using a strong base (e.g. sodium hydride) before performing the reaction with a carbonate.

The carbonates of formula ( 16) are commercially available or can be produced by techniques well known to the skilled chemist. Examples of suitable carbonates of formula ( 16) that can be used to make urethane polyols include ethylene carbonate, propylene carbonate, butylcnc carbonate, amylene carbonate and also hydroxy- substituted carbonates, such as glycerine carbonate. The presence of additional hydroxy groups in a hydroxy substituted carbonate, such as glycerine carbonate, allows further hydroxy groups to be incorporated into the urethane polyol.

Compounds of formula (4), and formula (5) above, may be prepared by reacting a di- amine or tri-amine with a polycarbonyl compound. Scheme 4 below shows, by way of

example, the reaction of a di-aminc with a di-carbonyl compound.

Scheme 4

Y 1 , R 1 , R 2 and X 1 in the scheme above have the same definitions as set out above. The reaction shown in scheme 4 is the formation of an amide from a primary or secondary amine and experimental methods known in the art may be used to perform this reaction. In scheme 4, the compound of formula (19) may itself react further a compound ( 17), followed by a compound of formula (18). depending on the molar ratio of the di-carbonyl compound to the di-amme.

Typically, L 1 is a leaving group that is capable of being displaced by a polyamine having primary or secondary amino groups. Each sυbstituent L 1 may be the same or different and examples of suitable L 1 sυbstituents include halogen atoms, particularly chlorine or bromine, Ci-Q alkoxy, CVCM aryloxy, mono-(C|-Q alkyl)amino and di- (Ci-Q alkyi)amino group. Preferably, L 1 is a Cj-Q alkoxy group, Q-C 1 4 aryloxy or Cj-Cu cycloalkoxy group, more preferably Q-Q alkoxy group, particularly ethoxy or methoxy. The compounds of formula (XI) are typically commercially available di- ester or tri-ester compounds.

Examples of suitable aliphatic di-esters include the esters of oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid, such as di-methyl oxalate, di-ethyl oxalate, di-n-propyl oxalate, di-isopropyl oxalate, di-n-butyl oxalate, di-isobutyl oxalate, di- phenyl oxalate, di-cyclohexyl oxalate, di-methyl malonate, di-ethyl malonate, di-n- propyl malonate, di-isopropyl malonate, di-n-buryl malonate, di-isobutyl malonate, di- phenyl malonate, di-cyclohexyl malonate, di-methyl succinate, di-ethyl succinate, di- n-propyl succinate, di-isopropyl succinate, di-n-butyl succinate, di-isobutyl succinate,

di-phcnyi succinate, di-cyclohexyl succinate, di-methyl gJutaratc, di-ethyl glutarate, di-n-propyl glutarate, di-isopropyl glularate, di-n-butyl glutarate, di-isobutyl glutarate, di-phenyl glutarate, di-cyclohexyl ghitaratc, di-methyl adipatc, di-ethyl adipate, di-n- propyl adipate, di-isopropyl adipate, di-n-butyl adipate, di-isobutyl adipate, di -phenyl adipatc and di-cyclohexyl adipate. Preferably, the compound of formula (X) is an ester of oxalic acid or malonic acid.

Other suitable types of di -esters or tri-esters, though less preferred, include the esters of ethylenically unsaturated aliphatic carboxylic acids, such as maieic, rumaric, aconitic and itaconic acids. Esters of di- or tri-aromatic carboxylic acids arc also suitable, although they arc lees preferred than the esters of ethylenically unsaturated aliphatic acids, and examples the esters of o-, m-, p-phthaJic acid and melHtic acid.

Polyamincs of formula (XII) are also commercially available. Examples of suitable aliphatic di-amines include but are not limited to 1 ,2-ethylencdiamine (EDA), 1 ,2- propanediamine 1 ,3-propanediamine, 1 ,4-butanediamine (BDA), 1 ,6-hcxamethylene diamine (HDA), 2-methyi 1 ,5-pcntanc diamine; 2-cthyl 1 ,4-tetramethylene diamine; 2,2,4-trimeihyl 1 ,6-hexane diamine; 2,4,4-trimethyl hexamethylene diamine; cyclohexane-l,3-diamine, cyclohexane-l,4-di-amine and any mixture of its isomers (CHDA), 3-aranomethyl-3,5,5.5-rrimdhylcyclohexylamine (isophoronc diamine, IPDA), 2,2-diaminodicyclohexylmethane, 2,4-diaminodicyclohexyhnethane, 4,4- diaminodicyciohexyrrnethane and any mixture of its Isomers (H^MDA), 1,8 mcnthane diamine and mixtures thereof. Preferred di-amines arc EDA, BDA, HDA, CHDA, IPDA and H^MDA. Most preferably the di-amine is isophorone di-amine (IPDA).

Other suitable types of polyamines, though less preferred, include aliphatic tri-amines, aromatic di- or tri-amines, and heterocyclic di- or tri-amines. Examples of suitable aliphatic tri-amines include diethylene triamine and triethylene triamine. Other examples of suitable aromatic di-amines or heterocyclic tri-amines include o-, πv. p- phenyienediaminc and melamine.

The reaction in scheme 4 may be performed by heating the compound of formula (17)

with (he polyamine under azeotrυpic distillation conditions. ITK reaction may be performed in the presence of a suitable esterification or amidation catalyst Examples of suitable catalysts include titanium (IV) alkoxide complexes and organotin compounds.

Suitable titanium (IV) alkoxide complexes include titanium (IV) ethoxide, titanium (IV) n-propoxide, titanium (IV) isopropoxide, titanium (IV) n-butoxide, titanium (IV) isobutoxide, titanium (IV) ethylhexoxide, titanium (IV) butoxy isopropoxy complexes, and mixtures thereof. Suitable organotin compounds include dibutyttin diacetate, dibutyltin dilaurate, dibutyttin malcatc, dibutyltin diacetate, dilauryltin diacetate, dioctyltin diacetate and mixtures thereof.

Preferably the catalyst is dibutyltin dilaurate. The catalysts are employed in small amounts, for example from about 0.001 percent to about 5 percent, based on weight of the reaction mixture.

It may be necessary to use higher temperatures and/or one or more esterification or amidation catalysts for some combinations of esters and polyamines. Typically, higher temperatures are required for tri-esters.

The amine in scheme 4 may also be deprotonated using a strong base (e.g. sodium hydride) before it is reacted with a compound of formula (17) having a suitable leaving group L 1 . Deprotonation of the amine may be necessary when performing the reaction with some amine compounds having lower reactivity, such as aromatic di- amines.

The molar ratio of the polyamine to the polycarbonyl compound of formula ( 17) in the reaction influences the nature of the products that are obtained. In principle any molar ratio of polyamine to polycarbonyl compound of formula (17) can be used, but preferably reaction conditions are selected to minimise or prevent the formation of a poiyamide. For example, in the case where the polycarbonyl compound is a diester and is reacted with a di -amine, a molar ratio of di-amine to di-ester of J : 1 favours the

formation of a polyamide polymer. Preferred ratios of polyaminc to polycarbonyl compound will depend on bom the number of amino groups in the polyamine rcactant and the number of carbonyt groups in the polycarbonyl compound. It is preferred that the length of the side chain attached to the polycarbonyl compound core does not exceed 3 alternating units in length i.e. [carbonyl core]-[aminc)-[cabonyi)-[amincj. Preferred molar ratios are set out in the table below.

The use of a di-aminc and a di-carbonyl compound is most preferred in the ratio of 3:2 to 2:l .

Amide compounds of formulae (5) which are produced from reacting a di-carbonyl compound of formula (17) where Y 1 is a single bond and the polyamine compound is either hydrazine, ethylene diamine, 1,2 diaminopropane, 13 diaminopropane, 1 ,6 hcxanediaminc, 1,8-mcnthanediamine or aminoethyl piperazine, are less preferred.

Definitions

The term alkyl, as used herein and unless otherwise defined, refers to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of a hydrocarbon compound having from 1 to 12 carbon atoms (unless otherwise specified) and is a saturated, straight or branched aliphatic or an alicyclic group. Thus, the term alkyl includes the sub-class cycloalkyl below. The alkyl group is a C1-C12 alkyl group, typically a Ci-Cg alkyl group and more preferably a C)-Ce alkyl group. Preferably the alkyl group is an unbranched, straight group. Examples of alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-penryl and n-hexyl.

The term alkylene, as used herein and unless otherwise defined, refers to a bidentatc or tridentate moiety obtained by removing two or three hydrogen atoms, either from the same carbon atom, or from different carbon atoms, of a hydrocarbon compound having from 1 to 12 carbon atoms (unless otherwise specified) and is a saturated, straight or branched aliphatic or an alicyclic group. Thus, the term alkylene includes the sub-class cycloalkyiene below, which may be unsaturated. The alkylene group is a Ci-Ci2 alkylene group, typically a Ci-Cu alkylene group and more preferably a C]-C 6 alkylene group. Preferably the alkylene group is an aliphatic group, particularly an unbranched, straight aliphatic group. Examples of alkylene groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene and n-hexylene.

As used herein, an arylene group refers to a bidentate or tridentate moiety obtained by removing two or three hydrogen atoms, one from each of two or three different aromatic ring atoms of an aromatic compound, which moiety has from 3 to 14 ring carbon atoms (unless otherwise specified). Preferably, each ring has from 5 to 7 ring carbon atoms. In this context, the prefixes (e.g. C^-Cu. Gs-C io etc) denote the number of ring carbon atoms. For example, the term C« arylene, as used herein, refers to an arylene group having 6 ring carbon atoms e.g. benzene. Examples of groups of arylene groups include o-, m- and p-phenylene.

As used herein, a heteroarylene group refers to a bidentate or tridentate moiety obtained by removing two or three hydrogen atoms, one from each of two or three different carbon atoms of an aromatic heterocyclic compound, which moiety has a 5 to 14 mcmbered ring (unless otherwise specified). Preferably, there are at least 1 , 2 or 3 heteroatoms in the heterocyclic compound, which are selected from N and O. More preferably, the heteroarylene group is a 5 to 6 mcmbered ring having L 2 or 3 nitrogen heteroatoms. An examples of a 6- membered heteroarylene group having 3 nitrogen atoms is the group formed from triazine, which is triazinylene.

As used herein, an alkyl group or alkylene moiety wherein one or more non-adjacent, saturated carbon atoms of said alkyl group is replaced with a nitrogen, oxygen or

sulfur atom, is typically a group of formula -(C 1 -C 4 alkylene)-Q-(C|-C« alkyi(enc)) wherein Q is N, O or S. Examples include -(CH 2 VCHCi-C 2 alkyl(cncϊ), -(CH 2 VNH-(Ci-C 2 alkyl(ene)) and -(CH 2 VS-(C-C 2 alkyl(ene)), wherein each z is (he same or different and is 1 or 2.

A 8 used herein, an alkenytene or an alkynyiene group refer to a bidentatc or tridcntate moiety obtained by removing two or three hydrogen atoms, cither from the same carbon atom, or from different carbon atoms, of a hydrocarbon compound having from 1 to 12 carbon atoms (unless otherwise specified) that is an unsaturated, straight or branched aliphatic group. The term alkenylene refers to a moiety having carbon- carbon doable bond. The term alkynyiene refers to a moiety having a carbon-carbon triple bond.

As used herein, an aryl-aOcylene group refers to a bidentate or tridentate moiety obtained by removing two or three hydrogen atoms, either both from the same carbon atom, or from different carbon atoms, of a hydrocarbon compound containing both aliphatic carbon atoms and an aromatic carbocyclic ring. At least one hydrogen atom is removed from a carbon atom of a saturated, aliphatic group. The remaining hydrogen atom or atoms may be removed from a different carbon atom of a saturated, aliphatic group or the aromatic ring. The aliphatic part or parts of the group typically have a total of from I to 12 carbon atoms and the aromatic ring has from 6 to 14 ring atoms (unless otherwise specified). 1 * hus, the aryl-alkylene group may be represented as CrC 2 * aryl-alkylene. Preferably, the aromatic group has from 6 to 10 ring carbon atoms, and more preferably is phenyl or phenyl ene. Preferably, the aliphatic part or parts of the group have a total of from 1 to 8 carbon atoms, more preferably a total of 1 to 6 carbon atoms. Examples of aryl-alkylene groups include methylenebenzene (- C^H 4 -CH 2 -), groups derived from xylene (e.g. -CH 2 -(O^)-CH 2 -, the o-, m- and p- isomers) and groups derived from trimethyibenzcne (e.g. the isomers of C 6 HWCH 2 -),).

The term cycloalkyl, as used herein and unless otherwise defined, refers to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of a

hydrocarbon compound having from 3 to 14 carbon atoms (unless otherwise specified) and which contains an alicyclic ring. Thus, the term encompasses alicyclic rings that are saturated or partially unsaturated. 1 , 2, 3, 4 or more Ci -C« alkyl groups may be attached to the alicyclic ring, wherein the alkyl group is as defined above and the number of carbon atoms in the alky) group is not included in the number of carbon atoms defining the cycloalkyl group. The point of attachment of the cycloalkyl group (obtained when a hydrogen atom is removed from a carbon atom of a hydrocarbon compound) may be directly at the alicyclic ring or via an alkyl group, such as in a cyclopropylmethyl group.

The cycloalkyl group is a Cj-Cu cycloalkyl group, typically a C 5 -C 10 cycloalkyl group. Preferably the cycloalkyl group is a saturated group. Typically, the cycloalkyl group is not attached or substituted by a Ci-Q alkyl group or is substituted by 1 or 2 Ci-C f alkyl groups, more preferably the cycloalkyl group is not attached to a Ci-Cg alkyl group. Examples of cycloalkyl groups include cycloprυpyl, cycloburyi, cyclopentyi, decahydronaphthalenyl, methytcyclopropyl. dimethylcyclohexyl, ethylcyclohexyl, (methylcyclohexyl)cthyl, cyclopentylenyl and methylcyclohexylenyl.

The term cycloalkylene, as used herein and unless otherwise defined, refers to a bidentate or tridentate moiety obtained by removing two or three hydrogen atoms, either both from the same carbon atom, or from different carbon atoms, of a hydrocarbon compound having from 3 to 12 carbon atoms (unless otherwise specified) which has an alicyclic ring. Thus, the term encompasses alicyclic rings that are saturated or partially unsaturated. 1 , 2, 3, 4 or more Ci-C 1 alkyl groups may be attached to the alicyclic ring, wherein the alkyl group is as defined above and the number of carbon atoms in the alkyl group is not included in the number of carbon atoms defining the cycloalkyl group. The cycloalkylene group (obtained when two hydrogen atoms arc removed from the same or different carbon atoms of a hydrocarbon compound) may be attached as a substituent by one or two carbon atoms in the alicyclic ring or by one or two of the carbon atoms of an alkyl group attached to the ring.

The cycloalkylene group is a Cy-Cn cycloalkylenc group and preferably a Q-Qo cycloalkyiene group. Prefcrably the cycloalkylenc group is a saturated group. Typically, the cycloalkylene group is not attached or substituted by a Cj-Q alkyl group or is substituted by 1 or 2 Cj-Q alkyl groups, more preferably the cycloalkylene group is not attached to a CJ-C S alkyl group. Examples of saturated C 3 -C 14 cycloalkylene groups include cyclopcntyicne (e.g. cyclopent-l,3-ylene), cyclohexylene (e.g. cyclohex-l ,4-ylene), 4-methylcyclopent-l,2-ylene and cyclohexyi- 2-cthylcne. Examples of partially unsaturated Cj-Cu cycloalkylene groups include cyclopentenylene (e.g. 4-cyclopenren-l ,3-ylenc), cyclohexenylenc (e.g. 2-cyclohexen- 1 ,4-ylene; 3-cyclohexen- 1 ,2-ylene; 2,5-cyclohexadien- 1 ,4-ylene).

A Q-Q 2 alkoxy or Q-Cn alkylthio group is typically a C,-Cj 2 alkyl group as defined above attached to an oxygen or sulfur atom respectively. Examples of Q-Q2 alkoxy groups include methoxy, ethoxy, n-propoxy and i-propoxy. Examples of Q-C12 alkylthio groups include methyKhio, ethyUhio, n-propylthio and i-propylthio.

A C^-C 14 aryloxy group is an aryl-O- substituent The term aryL as used herein, refers to a monovalent moiety obtained by removing a hydrogen atom from an aromatic ring atom of an aromatic carbocyclic compound, which moiety has from 6 Io 14 ring carbon atoms (unless otherwise specified). Preferably, each ring has from 5 to 7 ring carbon atoms. The aromatic carbocyclic compound may contain two aromatic rings, such as in a biphcnyl group, and the two ring may also be fused, as in naphthalene. Examples of aryi groups include benzene (i.e. phenyl) and naphthalene (i.e. naphthyl). Most preferably the aryl group is phenyl.

As used herein and unless otherwise defined, a C 2 -Q 2 alkcnyiene group refers to a bidentate moiety obtained by removing two hydrogen atoms, either both from the same carbon atom, or one from each of two different carbon atoms, of a hydrocarbon compound having from 2 to 12 carbon atoms (unless otherwise specified) containing one or more double bonds. The Q-Q> alkenylene group is either straight or branched, preferably straight, and is typically a Q-Q alkenylene group, more preferably a Q-Q group. Examples of Q-C 12 alkenylene groups include ethenylene, n-propenylene, n-

butenyfene, n-pentenyienc and n-hexenylcne.

As used herein and unless otherwise defined, a C 2 -C 12 aJkynylene group refers to a bidentatc moiety obtained by removing two hydrogen atoms, either both from the same carbon atom, or one from each of two different carbon atoms, of a hydrocarbon compound having from 2 to 12 carbon atoms (unless otherwise specified) containing one or more triple bonds. The C 2 -Cu alkynyiene group is either straight or branched, preferably straight, and is typically a C 2 -C 8 alkynyiene group, more preferably a C2-Q alkynyiene group. Examples of Ci-Cj ? alkynyiene groups include ethynylene, n- propynylene, n-butynylene, n-pcntynylene and n-hexynylene.

As used herein and unless otherwise defined, an acyl group refers to a -CC=O)R substituent (i.e. a keto group), wherein R is an alkyl group. The number of carbon atoms defining the acyl group, e.g. Cj-Q acyl, refers to the number of carbon atoms in the alkyl group R (i.e. Ci -CV alkyl) and does not include the carbonyl carbon atom. Thus, a Ci-Cb acyl group is a carbonyl group with a Ci-C^ alkyl group attached to it.

As used herein and unless otherwise defined, an alkoxycarbonyl group refers to a - C( 1 O)OR' substituent (i.e. an ester group), wherein -OR' is an alkoxy group as defined above. The number of carbon atoms in the term C 2 -C 13 alkoxycarbonyl includes the total number of carbon atoms in the alkoxy group and the carbon atom of the carbonyl group.

The terms mono-(Ci-Q alkyl)amino and di -(Ci-C t , alkyl)amino as used herein refer to a group of the formula -NR*R b . In a mono-(Cj-C 6 alkyl )amino group, one of R* and R b is a hydrogen atom and the other is a Ci-C 6 alkyl group, wherein the alkyl group is as defined above. In a di-(C|-C« alkyl )amino, R" and R b are each a Ci-C, alkyl group, which may be the same or different.

As used herein, a halogen atom is a fluorine, chlorine or bromine atom.

It may be convenient or desirable to prepare, purify, and/or handle a corresponding salt of a urethanc diol or polyaminc compound of the invention. For example, the urethane diol contains two hydroxy groups, which may be deprotonated to form an anionic salt with a cation. Examples of suitable cations include, but are not limited to, alkali metal ions such as Na * and K. * , alkaline earth cations such as Ca" f and Mg 2 * , and other cations such as A1 +3

Similarly, a cationic compound may be formed by protonating one or more of the amine groups in the polyamine compound of the invention, such that a salt will be formed with an anion. Examples of suitable inorganic anions include, but are not limited to, those derived from the following inorganic acids: hydrochloric, hydrobromic, hydroiodic, sulfuric, sulfurous, nitric, nitrous, phosphoric, and phosphorous. Examples of suitable organic anions include those derived from the following organic acids: acetic, benzoic, camphorsυlfonic, ethancdisulfonic, ethanesul tonic, rumaric, methancsυlfbnic, oxalic, phenylacctic, phenylsulfonic, propionic and toluenesυlfonic.

Examples

Example 1 : Preparation of a polvamine

To a reaction vessel equipped with a reflux condenser and Dean-Stark trap was charged IPDA (433Jg; 2.544 moles), diethylmalonate, (266.7g; 1.665 moles), toluene (300g), p-toluene suφhonic acid (1.Og) and dibutyltin dilaurate (0.5g). The reaction temperature was raised to reflux. After 5 hours, the solvent was then distilled off. The reaction temperature was raised and maintained at 140°C for a further 1 hour to give a highly viscous liquid residue, which solidified on cooling.

Example 2: Preparation of a urethane containing diol

40Og of the residue prepared in Example 1 was charged to a reaction flask, followed by ethylene carbonate (82.Og) and toluene ( 12O.5g). The temperature was raised to

70-80°C whilst the mixture was stirred. After approximately 6 hours, thin layer chromatography analysis indicated that all the ethylene carbonate had reacted. On cooling the mixture separated into two layers. The upper layer (toluene) was separated and discarded. The lower layer solidified on standing.

Example 3: Preparation of a polyester based polvurethane

171.9 g of the material obtained from the lower layer in Example 2 was charged to a flask, followed by n-methylpyrrolidonc, (20Og). The temperature was raised to 60- 70°C and stirred until the mixture became homogeneous. Caprolactone (128.Ig) and stannous octoate (0.2Sg) were added and then the temperature was raised to 100 °C. The reaction mixture was heated at this temperature for approximately 30 hours, until no caprolactone was detected by thin layer chromatography. The resulting cooled material was a medium viscosity liquid

Example 4: Preparation of a cured coating

A preparation was made up according to the following formulation

The mixture was coated onto substrate, allowed to air dry for approximately 10 minutes and then heated in an oven at 14O°C for 30 minutes.

The cured coating showed the following characteristics (test methods described below):

(TTS ∞ through to substrate)

The coating showed a combination of good flexibility, solvent resistance and hardness and demonstrates that the urethanc containing diol of the invention is suitable for the application.

Example 6

A polyester based polyurcthane according to the invention was prepared using substantially the same process set out in Example 3, except that the urethane diol was prepared from diethyloxalate, instead of diethylrnalonate as set out in Examples 1 and 2.

Comparative Example 7

A urethane diol was prepared from IPDA and ethylene carbonate using a method analogous to that described in Example 2. The resulting urethane diol was reacted with caprolactone using the method of Example 3 and the polymer obtained was cured using the method of Example 4.

A cured coating (coating D) was prepared from a polycaprolactone (1000 Mw) having no urethane groups using substantially the same method of Example 4.

Cured coatings of the invention were prepared from the polyester-based polyurethanes of Examples 3 and 6 using the method of Example 4.

The cured coating showed the following characteristics (test methods described below):

A « IPDA; B = IPDA/diethyt malonate; C - IPDA/diethyl oxalate; D « polycaprolactone (1000 Mw, with no urethane groups).

Coatings B and C have improved solvent resistance and hardness compared to the coatings of the prior art.

Test Methods

"MEK Rubs" A ball of cotton wool is soaked in methyiethyl ketone (butan-2- onc). The cotton wool is manually rubbed backwards and forwards over the surface of the coating under test, exerting the maximum pressure possible. Each backward and forward cycle Ls one "double rub". The surface is rubbed continuously (re-soaking the cotton after 50 cycles), observing any deterioration in the surface (for instance scratching, marking or dissolution of the coating) up to a maximum of 250 double rubs. (In the coatings tested in the present examples the number of double rubs is recorded on penetration through to the

coating substrate.) "Koenig hardness" ASTM 4366 "Mandrel Bend" AS 3900 E 1 "Adhesion" ISO cross-cut adhesion test, BS 3900 E6