Process for manufacturing fluoropolymer hybrid composites
View Patent ↗The invention pertains to a process for manufacturing a fluoropolymer hybrid organic/inorganic composite comprising: (i) partially hydrolyzing and/or polycondensing, in the presence of an aqueous medium, a metal compound of formula (I): X4-mAYim, wherein X is a hydrocarbon group, Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, A is a metal selected from the group consisting of Si, Ti and Zr, and m is an integer from 1 to 4, so as to obtain an aqueous medium comprising a pre-gelled metal compound comprising one or more inorganic domains consisting of ≡A-O-A≡ bonds and one or more residual hydrolysable groups Y [compound (M)], and then (ii) reacting in the molten state at least a fraction of hydroxyl groups of a functional fluoropolymer [polymer (F)] with at least a fraction of hydrolysable groups Y of said pre-gelled metal compound [compound (M)], so as to obtain a fluoropolymer hybrid organic/inorganic composite. The invention also pertains to uses of said fluoropolymer hybrid organic/inorganic composite in several applications.
1. A process for manufacturing a fluoropolymer hybrid organic/inorganic composite, the process comprising:
(i) partially hydrolysing and/or polycondensing, in the presence of an aqueous medium, a metal compound of formula (I):
X 4-m AY m
wherein X is a hydrocarbon group, Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, A is a metal selected from the group consisting of Si, Ti and Zr, and m is an integer from 1 to 4, so as to obtain an aqueous medium comprising a pre-gelled metal compound comprising one or more inorganic domains consisting of ≡A-O-A≡ bonds and one or more residual hydrolysable groups Y [compound (M)], and
(ii) reacting in the molten state at least a fraction of hydroxyl groups of a functional fluoropolymer [polymer (F)] with at least a fraction of hydrolysable groups Y of said compound (M), so as to obtain a fluoropolymer hybrid organic/inorganic composite.
2. The process according to claim 1 , wherein the metal compound of formula (I) complies with formula (I-A):
R′ 4-m′ E(OR″) m′ (I-A)
wherein m′ is an integer from 1 to 4, E is a metal selected from the group consisting of Si, Ti and Zr, R′ and R″, equal to or different from each other and at each occurrence, are independently selected from C 1 -C 18 hydrocarbon groups, optionally comprising one or more functional groups.
3. The process according to claim 1 , wherein polymer (F) comprises recurring units derived from at least one fluorinated monomer and at least one comonomer comprising at least one hydroxyl group [comonomer (MA)].
4. The process according to claim 3 , wherein the polymer (F) comprises at least 0.01% by moles of recurring units derived from at least one comonomer (MA).
5. The process according to claim 4 , wherein polymer (F) comprises at least 0.1% by moles of recurring units derived from at least one comonomer (MA).
6. The process according to claim 3 , wherein polymer (F) comprises at most 20% by moles of recurring units derived from at least one comonomer (MA).
7. The process according to claim 5 , wherein polymer (F) comprises at most 3% by moles of recurring units derived from at least one comonomer (MA).
8. The process according to claim 3 , wherein comonomer (MA) is selected from the group consisting of (meth)acrylic monomers of formula (II) or vinylether monomers of formula (III):
wherein each of R 1 , R 2 and R 3 , equal to or different from each other, is independently a hydrogen atom or a C 1 -C 3 hydrocarbon group, and R OH is a hydrogen atom or a C 1 -C 5 hydrocarbon moiety comprising at least one hydroxyl group.
9. The process according to claim 1 , wherein polymer (F) is selected from the group consisting of:
polymers (F-1) comprising recurring units derived from at least one comonomer (MA), from at least one per(halo)fluoromonomer selected from tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE), and from at least one hydrogenated monomer selected from ethylene, propylene and isobutylene, optionally containing one or more additional comonomers, in amounts of from 0.01% to 30% by moles, based on the total amount of TFE and/or CTFE and said hydrogenated monomer(s); and
polymers (F-2) comprising recurring units derived from at least one comonomer (MA), from vinylidene fluoride (VDF), and, optionally, from one or more fluorinated monomers different from VDF.
10. The process according to claim 9 , wherein the polymers (F-2) comprise:
(a′) at least 60% by moles of vinylidene fluoride (VDF);
(b′) optionally, from 0.1% to 15% by moles of a fluorinated monomer selected from vinylfluoride (VF 1 ), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), perfluoromethylvinylether (PMVE) and mixtures thereof; and
(c′) from 0.01% to 20% by moles of at least one (meth)acrylic monomer of formula (II).
11. The process according to claim 10 , wherein polymers (F-2) comprise:
(a′) at least 75% by moles of vinylidene fluoride (VDF);
(b′) optionally, from 0.1% to 12% by moles of a fluorinated monomer selected from vinylfluoride (VF 1 ), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), perfluoromethylvinylether (PMVE) and mixtures thereof; and
(c′) from 0.05% to 18% by moles of at least one (meth)acrylic monomer of formula (II).
12. The process according to claim 10 , wherein polymers (F-2) comprise:
(a′) at least 85% by moles of vinylidene fluoride (VDF);
(b′) optionally, from 0.1% to 10% by moles of a fluorinated monomer selected from vinylfluoride (VF 1 ), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), tetrafluoroethylene (TFE), trifluoroethylene (TrFE), perfluoromethylvinylether (PMVE) and mixtures thereof; and
(c′) from 0.1% to 10% by moles of at least one (meth)acrylic monomer of formula (II).
13. The process according to claim 1 , wherein the aqueous medium of step (i) comprises at least one acid catalyst.
14. The process according claim 1 , wherein the aqueous medium of step (i) further comprises one or more organic solvents (S).
15. The process according to claim 1 , wherein the aqueous medium of step (i) consists of water, at least one acid catalyst and one or more alcohols.
16. The process according to claim 1 , wherein in step (i) the hydrolysis and/or polycondensation of the metal compound of formula (I) is carried out at room temperature or upon heating at temperatures lower than 100° C.
17. The process according to claim 1 , wherein in step (ii), polymer (F) and the aqueous medium comprising compound (M) are reacted in the molten state at temperatures between 100° C. and 300° C. as a function of the melting point of the polymer (F).
18. The process according to claim 17 , wherein in step (ii), polymer (F) and the aqueous medium comprising compound (M) are reacted in the molten state at temperatures between 150° C. and 250° C. as a function of the melting point of the polymer (F).
19. The process according to claim 1 , wherein in step (ii), polymer (F) is blended with a non-functional fluoropolymer prior to reaction with compound (M).
20. The process according to claim 1 , wherein an inorganic filler (I) is further used in step (i) and/or step (ii).