JPWO2021204720A5

JPWO2021204720A5 -

Info

Publication number: JPWO2021204720A5
Application number: JP2022561084A
Authority: JP
Publication date: 2024-04-12

Claims

1. A process for the preparation of a polyurea or polyurethane organopolysiloxane block copolymer (I) having a silicone content of at least 90% by weight, based on the total weight of the organosiloxane block copolymer, comprising the steps of:
1) The following compound:
a) Formula (A):

long chain hydroxyl or amino difunctionalized polysiloxanes of the formula:
b) Formula (B):

a chain extender which is a short chain hydroxyl or amino difunctionalized polysiloxane of the formula:
c) Formula (C):

at least one diisocyanate of
d) optionally a compound of formula (D):

a branching agent which is a hydroxyl or amino monofunctional polysiloxane of the formula:
e) and a catalyst (E),
Providing
2) adding Nb moles of a chain extender of formula (B), Nc moles of at least one diisocyanate of formula (C), and optionally Nd moles of a branching agent of formula (D) to Na moles of a long chain hydroxyl or amino difunctionalized polysiloxane of formula (A);
In the formula,
-Q-, -T- and -X- are the same or different and finally represent a (C1-C20) alkylene group in which one or more -CH ₂ - are replaced by -O-, or a (C6-C22) arylene group;
-M, -W and -Z are the same or different and represent -OH or -NHR', where -R' represents -H, a (C1-C10) alkyl group, or a (C6-22) aryl group;
-U represents a (C1-C20) alkyl group, in which one or more -CH ₂ - are ultimately replaced by -O-, or a (C6-C22) aryl group;
--Y-- represents a (C1 to C36) alkylene group, a (C6 to C13) arylene group, or an organopolysiloxane;
-R1, -R2 and -R3 are the same or different and represent a (C1-C20) alkyl group which is ultimately substituted with one or more -F and/or -Cl groups;
a is an integer ranging from 30 to 1000,
b is an integer ranging from 2 to 15,
c is an integer ranging from 10 to 200,
d is an integer ranging from 10 to 200,
the ratio a/b ranges from 2 to 200;
the molar ratio Nb/(Na+Nb+Nd) is in the range of 5% to 60%;
the molar ratio Nc/(Na+Nb+Nc+Nd) is in the range of 45-55%;
the molar ratio Nd/(Na+Nd) is in the range of 0 to 20%, and the hard segment ratio is in the range of 1 to 94%, the hard segment ratio being defined as HS=(Nb*Mb+Nc*Mc)/(Na*Ma+Nb*Mb+Nc*Mc+Nd*Md), Ma, Mb, Mc and Md respectively represent the molecular weights of the compounds of formulae (A), (B), (C) and (D),
Method.

The method of claim 1, wherein -R1, -R2 and -R3 are the same or different and represent (C1-C10) alkyl groups, and in particular methyl groups which are ultimately substituted with -F and/or -Cl.

The method according to claim 1 or 2, wherein -Q-, -T- and -X- are the same or different and represent a (C1-C10) alkylene group.

The method according to any one of claims 1 to 3, wherein -M, -W and -Z are the same and preferably represent -NHR', with -R' preferably representing -H.

The method according to any one of claims 1 to 4, wherein -Y- represents (C3 to C13) alkylene.

The method according to any one of claims 1 to 5, wherein only one diisocyanate of formula (C) is used.

The method according to any one of claims 1 to 6, wherein at least one diisocyanate of formula (C) is present in stoichiometric proportions compared to the compounds of formulae (A), (B) and, if present, (D), meaning that the value of the stoichiometric exponent ratio Ic is equal to 1, the stoichiometric exponent ratio being defined by Ic = 2Nc / (2Na + 2Nb + Nd).

The method according to any one of claims 1 to 6, wherein at least one diisocyanate (C) is present in a non-stoichiometric proportion compared to the compounds of formulae (A), (B) and, if present, (D), meaning that the value of the stoichiometric exponential ratio Ic is different from 1 and in particular exceeds 1, the stoichiometric exponential ratio being defined by Ic = 2Nc / (2Na + 2Nb + Nd), and preferably the diisocyanate (C) is present in excess such that 1 < Ic ≤ 1.10.

The method according to any one of claims 1 to 8, wherein the catalyst (E) is selected from the group consisting of copper-based catalysts, zirconium-based catalysts, tin-based catalysts and titanium-based catalysts.

The method according to any one of claims 1 to 9, wherein the reaction is carried out in a chemical reactor.

The method according to claim 10, in which the long-chain polysiloxane of formula (A) is dissolved in a solvent or mixture of solvents, followed by the addition of a chain extender of formula (B), at least one diisocyanate of formula (C), optionally a branching agent of formula (D), and a catalyst (E).

The method according to claim 10 or 11, wherein the chain extender of formula (B), at least one diisocyanate of formula (C), the branching agent of formula (D), if present, and catalyst (E) are added simultaneously to the long-chain polysiloxane of formula (A).

The method according to claims 10 to 11, wherein the chain extender of formula (B), at least one diisocyanate of formula (C), if present, the branching agent of formula (D), and the catalyst (E) are added successively, in any order, to the polysiloxane of formula (A).

10. The process according to claims 1 to 9, wherein the reaction is carried out in an extruder, preferably a twin-screw extruder, and the long-chain hydroxyl or amino difunctionalized polysiloxane of formula (A) is introduced into the first heating zone of said extruder.

15. The method of claim 14, wherein the polysiloxane of formula (A), the chain extender of formula (B), at least one diisocyanate of formula (C), the branching agent of formula (D), if present, and the catalyst (E) are all introduced into the first heating zone of the extruder.

15. The method of claim 14, wherein the polysiloxane of formula (A) is introduced into a first heating zone of the extruder, and at least one of the chain extender of formula (B), at least one diisocyanate of formula (C), if present, the branching agent of formula (D), and the catalyst (E) are introduced into a second or subsequent heating zone of the extruder.

A polyurea or polyurethane organopolysiloxane block copolymer (I) obtained by the method according to any one of claims 1 to 16.

The polyurea or polyurethane organopolysiloxane block copolymer (I) according to claim 17, having a hardness in the range of 0 to 60 Shore A.

The polyurea or polyurethane organopolysiloxane block copolymer (I) according to claim 17 or 18, having an elongation at break of at least 200% and preferably at least 500%.

The polyurea or polyurethane organopolysiloxane block copolymer (I) according to any one of claims 17 to 19, having a melting temperature in the range of 70 to 140°C.

21. The polyurea or polyurethane organopolysiloxane block copolymer (I) according to any one of claims 17 to 20, having a melt flow index in the range of 1 to 100 ^cm3.10 min ^-1 at 120°C under 2.16 kg.

A method for producing a 3D article by additive technology using the polyurea or polyurethane organopolysiloxane block copolymer (I) according to any one of claims 17 to 21.

23. The method of claim 22, wherein the 3D article is produced with a 3D printer selected from a fused filament fabrication printer, a syringe extrusion printer, a droplet deposition printer, a selective laser sintering printer, a selective laser melting printer, and a material jet printer.