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US 2024/0327341 A1Published application
Polythiol compounds and process for preparation thereof
OwnerKenji Ito, Andreas Taden +4inventors
InventorsKenji Ito, Andreas Taden, Horst Beck, Adrian Brandt, Johannes Gerardus de Vries, Zahra Mazloomi
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Abstract
The present application is directed to a polythiol compound obtainable independently from a) eugenol, b) gallic acid, c) the adduct of guaiacol and vanillin or d) resveratrol and, respectively, having the general Formula VIA, VIB, VIC or VID, wherein: R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group; and R2 is H or methyl.
Claims18
1:
- A polythiol compound having a Formula VIA, VIB or VIC:
- wherein:
- R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group;
- and,
- R2 is H or methyl.
2 more elements
2:
- The compound according to claim 1, wherein:
- R1 is an unsubstituted C1-C12 alkylene group, preferably an unsubstituted C1-C4 alkylene group;
- and,
- R2 is H or Me.
1 more element
3:
- The compound according to claim 1 which is selected from VIAa, VIBa or VICa:
4:
- A process for preparing a compound having the general Formula VIA, VIB, VIC or VID
- wherein:
- R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group;
- and,
- R2 is H or methyl,
- said process comprising providing a compound having the general Formula IA, IB, IC or ID:
- and further comprising the steps of:
- a) reacting, in the presence of at least one base, said compound of general Formula IA, IB, IC or ID with a primary allyl compound (II) having the general Formula:
- X—(R1)—C R2)═CH2 (II)
- wherein:
- X is a halogen or an —OC(50 O)OR° group;
- R° is a C1-C4 alkyl group;
- R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group;
- and,
- R2 is H or methyl
- to form, respectively, a compound of Formula IIIA, IIIB, IIIC or IIID:
- b) reacting said compound of Formula IIIA, IIIB, IIIC or IIID with a thiol acid (IV) having the general Formula
- R3—C(50 O)—SH (IV)
- wherein:
- R3 is C1-C6 alkyl, C6-C18 aryl, C7-C18 alkylaryl or C7-C18 aralkyl,
- to form, respectively, a thioester compound of Formula VA, VB, VC or VD:
- and,
- c) deprotecting said thioester compound of Formula VA, VB, VC or VD to form, respectively, said polythiol compound of Formula VIA, VIB, VIC or VID.
20 more elements
5:
- The process according to claim 4, wherein said primary allyl compound (II) is characterized in that:
- R° is a C1-C2 alkyl;
- R1 is an unsubstituted C1-C12 alkylene group, preferably an unsubstituted C1-C4 alkylene group;
- and,
- R2 is H or Me.
2 more elements
6:
- The process according to claim 5, wherein said primary allyl compound (II) is selected from the group consisting of:
- 3-chloro-1-propene, 3-bromoprop-1-ene;
- 3-iodoprop-1-ene;
- methyl prop-2-enyl carbonate;
- and, ethyl prop-2-enyl carbonate.
2 more elements
7:
- The process according to claim 4, wherein said primary allyl compound (II) is reacted at a molar equivalency of from 1 to 2 relative to the number of moles of hydroxyl groups of Formula I.
8:
- The process according to claim 4, wherein said base is present in step a) in an amount of from 1 to 5 molar equivalents relative to the reactant compound IA, IB, IC or ID.
9:
- The process according to claim 4, wherein said base is selected from the group consisting of potassium carbonate, sodium carbonate and calcium carbonate.
10:
- The process according to claim 4, wherein said thiol acid (IV) is characterized in that:
- R3 is C1-C4 alkyl, C6 aryl, C7-C18 alkylaryl or C7-C18 aralkyl;
- and,
- wherein said thiol acid (IV) is selected from the group consisting of thioacetic acid, thiopropionic acid;
- thiobutyric acid, thioisobutyric acid, thiobenzoic acid, 2-methyl-thiobenzoic acid, 3-methyl-thiobenzoic acid, 4-methyl-thiobenzoic acid, 2,4-dimethyl-thiobenzoic acid and 3,5-dimethyl-thiobenzoic acid.
2 more elements
11:
- The process according to claim 4, wherein said thiol acid (IV) is reacted at a molar equivalency of from 1 to 2 relative to the allyl groups of said compound of Formula IIIA, IIIB, IIIC or IIID.
12:
- A process for preparing a compound having the general Formula VIB, VIC or VID
- wherein:
- R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group;
- and,
- R2 is H or methyl,
- said process comprising providing a compound having the general Formula IB, IC or ID:
- and further comprising the steps of:
- α) reacting, in the presence of at least one base, said compound of general Formula IB, IC or ID with a thiolate ester compound having general Formula VII:
- wherein:
- Y denotes a halogen;
- R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group;
- R2 is H or methyl;
- and,
- R3 is C1-C6 alkyl, C6-C18 aryl, C7-C18 alkylaryl or C7-C18 aralkyl,
- to form, respectively, a thioester compound of Formula VB, VC or VD:
- and,
- β) deprotecting said thioester compound of Formula VB, VC or VD to form, respectively, said polythiol compound of Formula VIB, VIC or VID.
14 more elements
13:
- The process according to claim 4, wherein said deprotection step (c), β)) is performed by acid-catalysed or base-catalysed hydrolysis, wherein said acid or base catalyst is preferably present in said deprotection step (c), β)) in an amount of from 0.05 to 0.25 moles per mole of said thioester of Formula VA, VB, VC or VD.
14:
- The process according to claim 13, wherein said deprotection step (c), β)) is performed by base-catalysed hydrolysis and further wherein said base is selected from the group consisting of:
- pyridine;
- dimethylaminopyridine (DMAP);
- proline;
- triazabicyclodecene (TBD);
- diazabicycloundecene (DBU);
- hexahydro methyl pyrimido pyridine (MTBD);
- diazabicyclononane (DBN);
- tetramethylguanidine (TMG);
- and, triethylenediamine (TED, 1,4-diazabicyclo[2.2.2]octane).
7 more elements
15:
- A curable composition comprising the polythiol compound as defined in claim 1.
16:
- A curable composition comprising:
- a) at least one polythiol compound having the general Formula VIA, VIB, VIC or VID:
- wherein:
- R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group;
- and,
- R2 is H or methyl;
- and,
- b) at least one thiol reactive compound, wherein the or each said thiol reactive compound has at least one functional group (F) selected from the group consisting of:
- epoxide groups;
- oxetane groups;
- cyclic carbonate groups;
- cyclic anhydride groups;
- 1-oxacycloalkan-2-one groups;
- ethylenically unsaturated groups;
- alkyne groups;
- and, isocyanate groups, wherein said thiol reactive compound b) is selected from the group consisting of include but are not limited to:
- epoxide compounds;
- ethylenically unsaturated compounds;
- epoxy (meth)acrylate compounds having at least one (meth)acrylate group and at least one epoxide group;
- and, polyisocyanates.
17 more elements
17:
- A compound of general Formula IIIC:
- wherein:
- R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group;
- and,
- R2 is H or methyl.
- where R1 is an unsubstituted C1-C12 alkylene group, an unsubstituted C1-C4 alkylene group;
- and R2 is H or Me,
- or R1 is methylene;
- and R2 is H.
6 more elements
18:
- A compound having a formula VID:
- wherein:
- R1 is a C1-C18 alkylene group, C2-C18 oxyalkylene group, C2-C18 thioalkylene group, C6-C18 arylene or C7-C18 aralkylene group;
- and,
- R2 is H or methyl;
- where R1 is an unsubstituted C1-C12 alkylene group, an unsubstituted C1-C4 alkylene group;
- and R2 is H or Me, and
- R1 is not a methylene group when R2 is H.
5 more elements