WO2018132960A1 - Process for the synthesis of (per) fluoropolyether-amino derivatives - Google Patents

Process for the synthesis of (per) fluoropolyether-amino derivatives Download PDF

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Publication number
WO2018132960A1
WO2018132960A1 PCT/CN2017/071476 CN2017071476W WO2018132960A1 WO 2018132960 A1 WO2018132960 A1 WO 2018132960A1 CN 2017071476 W CN2017071476 W CN 2017071476W WO 2018132960 A1 WO2018132960 A1 WO 2018132960A1
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Prior art keywords
chain
group
independently
carbon atoms
branched alkyl
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PCT/CN2017/071476
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French (fr)
Inventor
Zhen YAN
Fan Jiang
Patrizia Maccone
Pier Antonio Guarda
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Solvay Specialty Polymers Italy S.P.A
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Priority to PCT/CN2017/071476 priority Critical patent/WO2018132960A1/en
Priority to CN201780083982.7A priority patent/CN110248982B/en
Priority to JP2019537821A priority patent/JP7005634B2/en
Publication of WO2018132960A1 publication Critical patent/WO2018132960A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
    • C08G65/3255—Ammonia
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
    • C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus

Definitions

  • the present invention relates to a process for the synthesis of (per) fluoropolyether polymers (PFPE) comprising at least one amino group at their chain end (s) .
  • PFPE fluoropolyether polymers
  • PFPE fluoropolyether polymers
  • MRM magnetic recording media
  • US 6083600 discloses a lubricant suitable for being deposited onto a magnetic layer alloy film, wherein the lubricant comprises an amine-stabilized perfluoropolyether polymer.
  • a perfluoropolyether polymer Z-DOL, Z-DIAC from Montedison (IT) and Demnum (R) from Daikin (JP) are mentioned.
  • these polymers are said to break down in the disk drive environment.
  • these polymers may be capped with an amine end group, such as for example a secondary or tertiary amine end group.
  • conventional lubricants with hydroxy functionality may be capped with an amine compound.
  • the amine-group substituted perfluoropolyether derivatives can be prepared by first reacting the Z-DOL with sulfonyl-anhydrides or chlorides in the presence of a suitable acid accepter to form the ester of the Z-DOL; then the ester is isolated and the solvent is removed by distillation; as a further passage, the ester is treated with a mono- or di-functional diamine and the diamine in excess is removed.
  • US 6984759 discloses a process for the preparation of perfluoropolyether having reactive end groups, including notably -CH 2 NH 2 , by reduction of the corresponding perfluoropolyether having-CN end group, by using gaseous hydrogen in the presence of a catalyst constituted by Pd, Rh or Ru, supported on solid metal fluorides.
  • the Applicant faced the need of a process for the synthesis of amine derivatives of perfluoropolyether polymers that requires few synthetic steps, that has high selectivity (preferably of at least 90%or even higher) and high conversion (preferably of at least 70%or even higher) , while being easy and convenient on industrial scale.
  • amino derivatives of (per) fluoropoly-ether polymers can be advantageously prepared via direct amination starting from (poly) alkoxylated (per) fluoropolyether polymers.
  • the present invention relates to a process for the synthesis of a (poly) alkoxylated (per) fluoropolyether polymer [polymer (P N ) ] comprising a (per) fluoropolyether chain [chain (R pf ) ] having two chain ends, wherein at least one chain end bears a chain [chain (R N ) ] complying with the following formula:
  • each of J 1 and J 2 is independently selected from hydrogen atom; linear or branched alkyl chain comprising from 1 to 3 carbon atoms, preferably methyl; or aryl group, preferably phenyl; with the proviso that at least one of J 1 and J 2 is hydrogen atom; and
  • each of R 1 and R 2 is independently selected from hydrogen atom or linear or branched alkyl chain comprising from 1 to 6 carbon atoms;
  • J is independently straight or branched alkyl or aryl, preferably methyl, ethyl or phenyl, and
  • each of j1, j2 and j3 is, independently, an integer from 1 to 50;
  • each of R 1 and R 2 identical or different from each other, is selected from hydrogen atom or linear or branched alkyl chain comprising from 1 to 6 carbon atoms;
  • said chain (R pf ) is a chain of formula
  • z1 and z2, equal or different from each other, are equal to or higherthan 1;
  • X and X' equal or different from each other, are-F or-CF 3 , provided that when z1 and/or z2 are higher than 1, X and X’are-F;
  • D and D * are an alkylene chain comprising from 1 to 6 and even more preferably from 1 to 3 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms;
  • R f comprises, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of:
  • z1 and z2, equal or different from each other are from 1 to 10, even more preferably from 1 to 3.
  • D and D * are a chain of formula -CH 2 -, -CH 2 CH 2 - or -CH (CF 3 ) -.
  • chain (R f ) complies with the following formula:
  • - X 1 is independently selected from -F and -CF 3 ,
  • - X 2 , X 3 equal or different from each other and at each occurrence, are independently -F, -CF 3 , with the proviso that at least one of X is -F;
  • g1, g2, g3, and g4 are independently integers ⁇ 0, such that g1+g2+g3+g4 is in the range from 2 to 300, preferably from 2 to 100; should at least two of g1, g2, g3 and g4 be different from zero, the different recurring units are generally statistically distributed along the chain.
  • chain (R f ) is selected from chains of formula:
  • - a1 and a2 are independently integers ⁇ 0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000; both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably comprised between 0.1 and 10;
  • b1, b2, b3, b4 are independently integers ⁇ 0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000; preferably b1 is 0, b2, b3, b4 are>0, with the ratio b4/(b2+b3) being ⁇ 1;
  • c1, c2, and c3 are independently integers ⁇ 0 chosen so that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000; preferably c1, c2 and c3 are all>0, with the ratio c3/(c1+c2) being generally lower than 0.2;
  • d is an integer>0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000;
  • Hal * is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom;
  • chain (R f ) complies with formula (R f -III) here below:
  • - a1, and a2 are integers>0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000, with the ratio a1/a2 being generally comprised between 0.1 and 10, more preferably between 0.2 and 5.
  • said chain (R N ) complies with one of the following formulae
  • R 1 and R 2 are as defined above.
  • said chain (R N ) complies with formula (R N -I * ) as represented above.
  • both R 1 and R 2 are hydrogen atom.
  • said chain (R O ) complies with the following formula:
  • j is an integer from 1 to 50, more preferably from 1 to 20, even more preferably from 1 to 10, still more preferably from 1 to 8;
  • each of J and J * is independently selected from hydrogen atom; linear or branched alkyl chain comprising from 1 to 3 carbon atoms, more preferably methyl; or aryl group, more preferably phenyl;
  • J and J * are independently selected from hydrogen atom and methyl. Even more preferably, both J and J * are hydrogen atom.
  • j is an integer from 1 to 6.
  • Embodiments of polymer (P N ) comprising a chain (R pf ) having two chain ends, wherein both its chain ends bear chain (R N ) as defined above are particularly preferred within the present invention.
  • polymer (P N ) comprises a chain (R pf ) wherein only one of its chain end bears a chain (R N ) as defined above and the other chain end bears a group selected from halogen atom, preferably a fluorine atom; perfluorinated alkyl group comprising from 1 to 6 carbon atoms, preferably -CF 3 , -C 2 F 5 , C 3 F 7 .
  • said polymer (P OH ) comprises a chain (R pf ) , which is as defined above for polymer (P N ) .
  • said chain (R OH ) complies with one of the following formulae
  • j1 and j2 are an integer from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, and still more preferably from 1 to 6;
  • j3, j4 and j (x) are integers higher than 1, such that the sum of j3 and j4 is from 2 to 15, more preferably from 3 to 15, even more preferably from 4 to 15, and still more preferably from 4 to 10; and
  • R 1 and R 2 are as defined above.
  • said chain (R OH ) complies with formula (R OH -I * ) as represented above, wherein j1 is an integer from 1 to 6.
  • said polymer (P OH ) has an average number molecular weight between 400 and 10,000, more preferably between 400 and 5,000.
  • Preferred polymers (P OH ) can be manufactured by chemical reduction of corresponding PFPE carboxylic acids or esters according to several methods known in the art, using reducing agents such as NaBH 4 , or by catalytic hydrogenation, as disclosed, for example, in US 6509509 (AUSIMONT S. P. A. ) 7/5/2001, US 6573411 (AUSIMONT S.P.A. ) 11/21/2002, WO 2008/122639 (SOLVAY SOLEXIS S. P. A. ) 10/16/2008.
  • Precursors of PFPE carboxylic acids or of PFPE esters can be manufactured according to different methods, e.g.
  • suitable polymers useful as starting material in the process according to the present invention are commercially available from Solvay Specialty Polymers Italy S.p.A. under the trade name
  • said compound (C) is based on at least one element selected in the group comprising, preferably consisting of iron, cobalt, ruthenium, rhodium, osmium and iridium. More preferably said compound (C) is based on ruthenium.
  • said compound (P) complies with the following formula (P-I) :
  • n zero or 1;
  • each of R1, R2, R3, R4, R5 and R6 is independently selected from linear or branched alkyl chain comprising from 1 to 10 carbon atoms, alkyl-diphenyl-phosphine wherein the alkyl chain comprises from 1 to 4 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 3- to 10- membered heterocyclyl group comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryl group optionally comprising at least one heteroatom selected from N, O and S; the above groups being optionally substituted with one substituent [group (S) ] selected from fluorine atom, chlorine atom, bromine atom, hydroxy group, cyano group, -NH 2 and linear or branched alkyl chain comprising from 1 to 10 carbon atoms;
  • Y 1 , Y 2 and Y 3 are, each independently, asigma bond or an alkylene group selected from methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, said alkylene group being optionally substituted with one or more group (S) as defined above;
  • A is a group selected from optionally substituted N, O, P, C 1 -C 6 alkyl, C 3 -C 10 cycloalkyl optionally comprising one heteroatom selected from N, O and S, C 5 -C 14 aromatic group optionally comprising one heteroatom selected from N, O and S, or a group complying with one of the following formulae (A-I) and (A-II) :
  • R 8 and R 9 are, each independently, selected from the group comprising liner or branched alkyl chain comprising from 1 to 10 carbon atoms, fluorine atom, chlorine atom, bromine atom, -OR 7 group or-N (R 7* ) 2 group wherein R 7 and R 7* are each independently selected from hydrogen atom, linear or branched alkyl chain comprising from 1 to 10 carbon atoms and aryl group comprising 5 to 10 members;
  • X 1 and X 2 are, each independently, selected from NH, O and S;
  • X 3 is a sigma bond or a divalent group selected from: -N (R 10 ) -, -O-, -S-, -C (R 11 ) (R 12 ) -wherein R 10 is linear or branched alkyl chain comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 3-to 10-membered heterocyclyl group comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryl group optionally comprising at least one heteroatom selected from N, O and S; the above groups being optionally substituted with one or more group (S) as defined above;
  • R 11 and R 12 are, each independently, selected from linear or branched alkyl group comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 3-to 10-membered cycloalkoxy, 3-to 10-membered heterocyclyl comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryloxy group optionally comprising at least one heteroatom selected from N, O and S; the above groups being optionally substituted with one or more groups (S) as defined above.
  • said compound (P) complies with the formula (P-I) as represented above, wherein:
  • n zero or 1;
  • each of R1, R2, R3, R4, R5 and R6 is independently selected from linear or branched alkyl chain comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 5-to 14-membered aryl group;
  • Y 1 , Y 2 and Y 3 are, each independently, asigma bond or an alkylene group selected from methylene, ethylene and trimethylene;
  • A is C 1 -C 6 alkyl, C 3 -C 10 cycloalkyl or a divalent or trivalent group of formula:
  • X 2 is O
  • X 3 is a sigma bond or a divalent group of formula-C (R 11 ) (R 12 ) -wherein R 11 and R 12 are, each independently, selected from linear or branched alkyl group comprising from 1 to 10 carbon atoms.
  • said compound (P) is selected in the group comprising, preferably consisting of: 1, 2-bis (diphenylphosphino) ethane (diphos or dppe) ; 1, 2-bis (dicyclohexylphosphino) ethane; 1, 3-bis(diphenylphosphino) propane (dppp) ; 1, 4-bis (diphenylphosphino) butane (dppb) ; 2, 3-bis (dicyclohexylphosphino) ethane (dcpe) ; 4, 5-bis (di-phenylphosphino) -9, 9-dimethylxanthene (xantphos) ; 1, 1’ - [2, 7-bis (1, 1-dimethylethyl) -9, 9-dimethyl-9H-xanthene-4, 5-diyl] bis (1, 1diphenyl) phosphi (t-bu-xantphos) ; and 1, 1, 1-tris (diphenyl)
  • step (a) of the process according to the present invention is performed in the presence of a complex between said compound (C) and said compound (P) .
  • a complex comprising ruthenium and xantphos.
  • said solvent is selected from polar solvents, non-polar solvents and mixtures thereof.
  • said non polar solvents are selected in the group comprising: saturated and unsaturated hydrocarbons, such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and mesitylene; linear and cyclic ethers, such as tetrahydrofuran (THF) , diethyl ether, 1, 4-dioxane, tert-butyl methyl ether (MTBE) , diglyme and 1, 2-methoxyethane.
  • saturated and unsaturated hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and mesitylene
  • linear and cyclic ethers such as tetrahydrofuran (THF) , diethyl ether, 1, 4-dioxane, tert-butyl methyl
  • said polar solvent is selected in the group comprising polar protic and aprotic solvents.
  • Suitable polar aprotic solvents are selected in the group comprising dimethylformamide, formamide and acetonitrile.
  • said polar protic solvent is selected from water and alcohols.
  • Suitable alcohols are selected in the group comprising: 3, 3-dimethyl-1-butanol, 3, 3, -dimehtyl-2-butanol, 2-trifluoromethyl-2-propanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2, 3-dimethyl-2-butanol.
  • step (a) is performed by mixing together said at least one polymer (P OH ) with said at least one compound (C) and said at least one compound (P) .
  • step (a 0 ) is performed, which comprises mixing together said at least one compound (C) , said at least one compound (P) and said solvent to provide a mixture [mixture (CP) ] , and then contacting in step (a) said mixture (CP) with said at least one polymer (P OH ) and said compound of formula HNR 1 R 2 as defined above.
  • said step (a 0 ) is performed under heating, more preferably at a temperature of from 50°C to 200°C, even more preferably from 100°C to 180°C.
  • said step (a 0 ) is performed under pressure, more preferably at a pressure from about 1.5 to 3 atm.
  • said step (a 0 ) is performed under inert atmosphere, more preferably using argon, nitrogen gas or a mixture thereof.
  • said compound (C) is used in an amount higherthan 0.01 wt. %based on the total weight of said polymer (P OH ) , more preferably from 0.05 to 10 wt. %, and even more preferably from 0.1 to 1.0 wt. %
  • step (a) is performed by reacting at least one polymer (P OH ) as defined above, with at least one compound of formula HNR 1 R 2 , wherein each of R 1 and R 2 , identical or different from each other, is selected from hydrogen atom or linear of branched alkyl chain comprising from 1 to 3 carbon atoms, with the proviso that at least one of R 1 and R 2 is hydrogen atom.
  • both R 1 and R 2 are hydrogen atoms.
  • step (a) is performed under heating, more preferably at a temperature of from 60°C to 210°C, even more preferably from 110°C to 190°C.
  • the autoclave was opened and 2 ml (3.0 g) of polymer (I) were added under an argon atmosphere.
  • the autoclave was closed and again evacuated with a vacuum pump.
  • 1.0 g of NH 3 was condensed into the autoclave from a gas cylinder while cooling the autoclave in iced water.
  • the mixture was then heated under stirring at 160°C and maintained at the same temperature for 12 hours.
  • the autoclave was vented slowly, the reaction mixture was evaporated under reduced pressure on a rotary evaporatorto remove the solvent. The remaining liquid was filtered and analysed with 13 C-NMR.
  • Example 2 The same procedure described in Example 1 was repeated starting from polymer (I) and using 0.012 g (0.0125 mmol) of CAS 16971-33-8 and 0.0087 g (0.015 mmol) of CAS 161265-03-8.

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Abstract

Provided is a process for the synthesis of (per) fluoropolyether polymers (PFPE) comprising at least one amino group at their chain end (s).

Description

Process for the synthesis of (per) fluoropolyether-amino derivatives Technical Field
__________________________________________________________________________
The present invention relates to a process for the synthesis of (per) fluoropolyether polymers (PFPE) comprising at least one amino group at their chain end (s) .
Background Art
__________________________________________________________________________
(Per) fluoropolyether polymers (PFPE) are widely known and used as lubricants. Among the others, the magnetic recording media (MRM) industry uses derivatives of (per) fluoropolyether polymers for lubricating the magnetic disks. For this application, (per) fluoropolyether polymers comprising at their chain end (s) an amino group are typically used.
Among the others, US 6083600 (INTERNATIONAL BUSINESS MACHINES CORPORATION) discloses a lubricant suitable for being deposited onto a magnetic layer alloy film, wherein the lubricant comprises an amine-stabilized perfluoropolyether polymer. As suitable perfluoropolyether polymers, Z-DOL, Z-DIAC from Montedison (IT) and Demnum (R) from Daikin (JP) are mentioned. However, these polymers are said to break down in the disk drive environment. Hence, to stabilize the lubricant, these polymers may be capped with an amine end group, such as for example a secondary or tertiary amine end group. Among the others, conventional lubricants with hydroxy functionality may be capped with an amine compound. The amine-group substituted perfluoropolyether derivatives can be prepared by first reacting the Z-DOL with sulfonyl-anhydrides or chlorides in the presence of a suitable acid accepter to form the ester of the Z-DOL； then the ester is isolated and the solvent is removed by distillation； as a further passage, the ester is treated with a mono- or di-functional diamine and the diamine in excess is removed.
US 6984759 (SOLVAY SOLEXIS S.P.A. ) discloses a process for the preparation of perfluoropolyether having reactive end groups, including notably -CH2NH2, by reduction of the corresponding perfluoropolyether  having-CN end group, by using gaseous hydrogen in the presence of a catalyst constituted by Pd, Rh or Ru, supported on solid metal fluorides.
Process for the synthesis of primary amines by amination of starting materials comprising at least one–OH group have been disclosed for example in US 8946463 (EVONIK DEGUSSA GMBH) , US 20120232292 (BASF SE (DE) ) and US 20120232309 (BASF SE (DE)) .
However, none of the above mentioned patent documents either discloses nor mentions that the direct amination can be performed starting from macromolecules having high molecular weight, such as for example (per) fluoropolyether polymers. Also, none of the above mentioned patent documents suggests that a high conversion and selectivity rate can be obtained when the synthesis starts from (per) fluorinated macromolecules having high molecular weight.
Summary of invention
__________________________________________________________________________
The Applicant noted that the methods known in the art typically used for the synthesis of PFPE amino derivatives, such as for example the one described in US 6083600 cited above, require several steps, with high costs and low conversion rate. In addition, also the process disclosed in US 6984759 showed the drawback of requiring several synthetic steps, in order to obtain the polymer comprising -CN end group.
The Applicant faced the need of a process for the synthesis of amine derivatives of perfluoropolyether polymers that requires few synthetic steps, that has high selectivity (preferably of at least 90％or even higher) and high conversion (preferably of at least 70％or even higher) , while being easy and convenient on industrial scale.
Surprisingly, the Applicant found that amino derivatives of (per) fluoropoly-ether polymers can be advantageously prepared via direct amination starting from (poly) alkoxylated (per) fluoropolyether polymers.
Thus, in a first aspect, the present invention relates to a process for the synthesis of a (poly) alkoxylated (per) fluoropolyether polymer [polymer (PN) ] comprising a (per) fluoropolyether chain [chain (Rpf) ] having two chain ends, wherein at least one chain end bears a chain [chain (RN) ] complying with  the following formula:
-CH (J1) CH (J2) -NR1R2
wherein
each of J1 and J2 is independently selected from hydrogen atom； linear or branched alkyl chain comprising from 1 to 3 carbon atoms, preferably methyl； or aryl group, preferably phenyl； with the proviso that at least one of J1 and J2 is hydrogen atom； and
each of R1 and R2 is independently selected from hydrogen atom or linear or branched alkyl chain comprising from 1 to 6 carbon atoms；
and wherein said chain (Rpf) and said chain (RN) are linked together via a (poly) alkoxylated chain [chain (RO) ] ；
said process comprising the following step:
(a) reacting at least one (per) fluoropolyether polymer [polymer (POH) ] comprising a (per) fluoropolyether chain [chain (Rpf) ] having two chain ends, wherein at least one chain end bears a chain [chain (ROH) ] complying with one of the following formulae:
(ROH-I)     - [CH2CH2O] j1-H,
(ROH-II)    - [CH2CH (J) O] j2-H or
(ROH-III)   - [CH (J) CH2O] j3-H,
wherein
J is independently straight or branched alkyl or aryl, preferably methyl, ethyl or phenyl, and
each of j1, j2 and j3 is, independently, an integer from 1 to 50；
with at least one compound of formula HNR1R2, wherein each of R1 and R2, identical or different from each other, is selected from hydrogen atom or linear or branched alkyl chain comprising from 1 to 6 carbon atoms；
in the presence of:
(i) at least one catalyst [compound (C) ] based on at least one element belonging to Group 8 or 9 of the Periodic Table of the Elements；
(ii) at least one organo-phosphorous compound [compound (P) ] and
(iii) at least one solvent.
Description of embodiments
___________________________________________________________________________
For the purpose of the present description and of the following claims:
- the use of parentheses around symbols or numbers identifying the formulae, for example in expressions like “polymer (P) ” , etc., has the mere purpose of better distinguishing the symbol or numberfrom the rest of the text and, hence, said parenthesis can also be omitted；
- the acronym “PFPE” stands for" (per) fluoropolyether” and, when used as substantive, is intended to mean eitherthe singular orthe plural from, depending on the context；
- the term " (per) fluoropolyether” is intended to indicate fully or partially fluorinated polymer.
Preferably, said chain (Rpf) is a chain of formula
-O-D- (CFX) z1-O (Rf) (CFX’ ) z2-D*-O-
wherein
z1 and z2, equal or different from each other, are equal to or higherthan 1；
X and X', equal or different from each other, are-F or-CF3, provided that when z1 and/or z2 are higher than 1, X and X’are-F；
D and D*, equal or different from each other, are an alkylene chain comprising from 1 to 6 and even more preferably from 1 to 3 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms；
(Rf) comprises, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of:
(i) -CFXO-, wherein X is F or CF3；
(ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is F or CF3, with the proviso that at least one of X is –F；
(iii) -CF2CF2CW2O-, wherein each of W, equal or different from each other, are F, Cl, H；
(iv) -CF2CF2CF2CF2O-；
(v) - (CF2) j-CFZ-O- wherein j is an integerfrom 0 to 3 and Z is a group of general formula -O-R (f-a) -T, wherein R (f-a) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen among the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-,  -CF2CF2CF2CF2O-, with each of each of X being independently F or CF3 and T being a C1-C3 perfluoroalkyl group.
More preferably, z1 and z2, equal or different from each other, are from 1 to 10, even more preferably from 1 to 3.
More preferably, D and D*, equal or different from each other, are a chain of formula -CH2-, -CH2CH2- or -CH (CF3) -.
Preferably, chain (Rf) complies with the following formula:
(Rf-I)
- [ (CFX1O) g1 (CFX2CFX3O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4] -
wherein
- X1 is independently selected from -F and -CF3,
- X2, X3, equal or different from each other and at each occurrence, are independently -F, -CF3, with the proviso that at least one of X is -F；
- g1, g2, g3, and g4, equal or different from each other, are independently integers≥0, such that g1+g2+g3+g4 is in the range from 2 to 300, preferably from 2 to 100； should at least two of g1, g2, g3 and g4 be different from zero, the different recurring units are generally statistically distributed along the chain.
More preferably, chain (Rf) is selected from chains of formula:
(Rf-IIA)    - [ (CF2CF2O) a1 (CF2O) a2] -
wherein:
- a1 and a2 are independently integers≥0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000； both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably comprised between 0.1 and 10；
(Rf-IIB)    - [ (CF2CF2O) b1 (CF2O) b2 (CF (CF3) O) b3 (CF2CF (CF3) O) b4] -
wherein:
b1, b2, b3, b4, are independently integers≥0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000； preferably b1 is 0, b2, b3, b4 are>0, with the ratio b4/(b2+b3) being≥1；
(Rf-IIC)    - [ (CF2CF2O) c1 (CF2O) c2 (CF2 (CF2) cwCF2O) c3] -
wherein:
cw＝1 or 2；
c1, c2, and c3 are independently integers≥0 chosen so that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000； preferably c1, c2 and c3 are all>0, with the ratio c3/(c1+c2) being generally lower than 0.2；
(Rf-IID)    - [ (CF2CF (CF3) O) d] -
wherein:
d is an integer>0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000；
(Rf-IIE) - [ (CF2CF2C (Hal*) 2O) e1- (CF2CF2CH2O) e2- (CF2CF2CH (Hal*) O) e3] -
wherein:
- Hal*, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom；
- e1, e2, and e3, equal to or different from each other, are independently integers≥0 such that the (e1+e2+e3) sum is comprised between 2 and 300.
Still more preferably, chain (Rf) complies with formula (Rf-III) here below:
(Rf-III)    - [ (CF2CF2O) a1 (CF2O) a2] -
wherein:
- a1, and a2 are integers>0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000, with the ratio a1/a2 being generally comprised between 0.1 and 10, more preferably between 0.2 and 5.
Preferably, said chain (RN) complies with one of the following formulae
(RN-I*) to (RN-III*) :
(RN-I*)      -CH2CH2-NR1R2
(RN-II*)     -CH2CH (CH3) -NR1R2
(RN-III*)    -CH (CH3) CH2-NR1R2
wherein
R1 and R2 are as defined above.
More preferably, said chain (RN) complies with formula (RN-I*) as represented above.
More preferably, both R1 and R2 are hydrogen atom.
Preferably, said chain (RO) complies with the following formula:
- [ (CH (J) CH (J*) O] j-
wherein
j is an integer from 1 to 50, more preferably from 1 to 20, even more preferably from 1 to 10, still more preferably from 1 to 8；
each of J and J* is independently selected from hydrogen atom； linear or branched alkyl chain comprising from 1 to 3 carbon atoms, more preferably methyl； or aryl group, more preferably phenyl；
with the proviso that at least one of J and J*is hydrogen atom.
According to a preferred embodiment, J and J*are independently selected from hydrogen atom and methyl. Even more preferably, both J and J* are hydrogen atom.
According to a preferred embodiment, j is an integer from 1 to 6.
Embodiments of polymer (PN) comprising a chain (Rpf) having two chain ends, wherein both its chain ends bear chain (RN) as defined above are particularly preferred within the present invention.
According to another embodiment, polymer (PN) comprises a chain (Rpf) wherein only one of its chain end bears a chain (RN) as defined above and the other chain end bears a group selected from halogen atom, preferably a fluorine atom； perfluorinated alkyl group comprising from 1 to 6 carbon atoms, preferably -CF3, -C2F5, C3F7.
Preferably, said polymer (POH) comprises a chain (Rpf) , which is as defined above for polymer (PN) .
Preferably, said chain (ROH) complies with one of the following formulae
(ROH-I*) to (ROH-III*) :
(ROH-I*)      - (CH2CH2O) j1-H
(ROH-II*)     - [CH2CH (CH3) O] j2-H
(ROH-III*)    - [ (CH2CH2O) j3- (CH2CH (CH3) O) j4] j (x) -H
wherein
j1 and j2, each independently, are an integer from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, and still more preferably from 1 to 6；
j3, j4 and j (x) are integers higher than 1, such that the sum of j3 and j4 is  from 2 to 15, more preferably from 3 to 15, even more preferably from 4 to 15, and still more preferably from 4 to 10； and
R1 and R2 are as defined above.
More preferably, said chain (ROH) complies with formula (ROH-I*) as represented above, wherein j1 is an integer from 1 to 6.
Preferably, said polymer (POH) has an average number molecular weight between 400 and 10,000, more preferably between 400 and 5,000.
Preferred polymers (POH) can be manufactured by chemical reduction of corresponding PFPE carboxylic acids or esters according to several methods known in the art, using reducing agents such as NaBH4, or by catalytic hydrogenation, as disclosed, for example, in US 6509509 (AUSIMONT S. P. A. ) 7/5/2001, US 6573411 (AUSIMONT S.P.A. ) 11/21/2002, WO 2008/122639 (SOLVAY SOLEXIS S. P. A. ) 10/16/2008. Precursors of PFPE carboxylic acids or of PFPE esters can be manufactured according to different methods, e.g. by oxypolymerization of fluoroolefins or by ring opening polymerization of HFPO (hexafluoropropylene oxide) , as taught in US 3847978 (MONTEDISON S.P.A. ) 11/12/1974, US 3766251 (MONTEDISON S.P.A. ) 10/16/1973, US 3715378 (MONTEDISON S.P.A. ) 2/6/1973, US 3665041 (MONTEDISON S.P.A. ) 5/23/1972, US 4647413 (MINNESOTA MINING) 3/3/1987, EP 151877 A (MINNESOTA MINING) 8/21/1985, US 3442942 (MONTEDISON S.P.A. ) 5/6/1969, US 577291 (AUSIMONT S.P.A. ) 7/7/1998, US 5258110 (AUSIMONT S.R.L. ) 11/2/1993 or US 7132574 (SOLVAY SOLEXIS S.P.A. ) 11/7/2006.
For example, suitable polymers useful as starting material in the process according to the present invention are commercially available from Solvay Specialty Polymers Italy S.p.A. under the trade name
Figure PCTCN2017071476-appb-000001
Preferably, said compound (C) is based on at least one element selected in the group comprising, preferably consisting of iron, cobalt, ruthenium, rhodium, osmium and iridium. More preferably said compound (C) is based on ruthenium.
Preferably, said compound (P) complies with the following formula (P-I) :
Figure PCTCN2017071476-appb-000002
wherein
n is zero or 1；
each of R1, R2, R3, R4, R5 and R6 is independently selected from linear or branched alkyl chain comprising from 1 to 10 carbon atoms, alkyl-diphenyl-phosphine wherein the alkyl chain comprises from 1 to 4 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 3- to 10- membered heterocyclyl group comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryl group optionally comprising at least one heteroatom selected from N, O and S； the above groups being optionally substituted with one substituent [group (S) ] selected from fluorine atom, chlorine atom, bromine atom, hydroxy group, cyano group, -NH2 and linear or branched alkyl chain comprising from 1 to 10 carbon atoms；
Y1, Y2 and Y3 are, each independently, asigma bond or an alkylene group selected from methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, said alkylene group being optionally substituted with one or more group (S) as defined above；
A is a group selected from optionally substituted N, O, P, C1-C6 alkyl, C3-C10 cycloalkyl optionally comprising one heteroatom selected from N, O and S, C5-C14 aromatic group optionally comprising one heteroatom selected from N, O and S, or a group complying with one of the following  formulae (A-I) and (A-II) :
(A-I)
Figure PCTCN2017071476-appb-000003
(A-II)
Figure PCTCN2017071476-appb-000004
wherein
m and q are, each independently, zero or an integer from 1 to 4, R8 and R9 are, each independently, selected from the group comprising liner or branched alkyl chain comprising from 1 to 10 carbon atoms, fluorine atom, chlorine atom, bromine atom, -OR7 group or-N (R7*) 2 group wherein R7 and R7* are each independently selected from hydrogen atom, linear or branched alkyl chain comprising from 1 to 10 carbon atoms and aryl group comprising 5 to 10 members；
X1 and X2 are, each independently, selected from NH, O and S；
X3 is a sigma bond or a divalent group selected from: -N (R10) -, -O-, -S-, -C (R11) (R12) -wherein R10 is linear or branched alkyl chain comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members,  3-to 10-membered heterocyclyl group comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryl group optionally comprising at least one heteroatom selected from N, O and S； the above groups being optionally substituted with one or more group (S) as defined above；
R11 and R12 are, each independently, selected from linear or branched alkyl group comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 3-to 10-membered cycloalkoxy, 3-to 10-membered heterocyclyl comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryloxy group optionally comprising at least one heteroatom selected from N, O and S； the above groups being optionally substituted with one or more groups (S) as defined above.
More preferably, said compound (P) complies with the formula (P-I) as represented above, wherein:
n is zero or 1；
each of R1, R2, R3, R4, R5 and R6 is independently selected from linear or branched alkyl chain comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 5-to 14-membered aryl group；
Y1, Y2 and Y3 are, each independently, asigma bond or an alkylene group selected from methylene, ethylene and trimethylene；
A is C1-C6 alkyl, C3-C10 cycloalkyl or a divalent or trivalent group of formula:
(A-II*)
Figure PCTCN2017071476-appb-000005
wherein
X2 is O；
X3 is a sigma bond or a divalent group of formula-C (R11) (R12) -wherein R11 and R12 are, each independently, selected from linear or branched alkyl group comprising from 1 to 10 carbon atoms.
Even more preferably, said compound (P) is selected in the group comprising, preferably consisting of: 1, 2-bis (diphenylphosphino) ethane (diphos or dppe) ； 1, 2-bis (dicyclohexylphosphino) ethane； 1, 3-bis(diphenylphosphino) propane (dppp) ； 1, 4-bis (diphenylphosphino) butane (dppb) ； 2, 3-bis (dicyclohexylphosphino) ethane (dcpe) ； 4, 5-bis (di-phenylphosphino) -9, 9-dimethylxanthene (xantphos) ； 1, 1’ - [2, 7-bis (1, 1-dimethylethyl) -9, 9-dimethyl-9H-xanthene-4, 5-diyl] bis (1, 1diphenyl) phosphi (t-bu-xantphos) ； and 1, 1, 1-tris (diphenylphosphinomethyl) ethane (triphos) . Xantphos being particularly preferred.
According to a particularly preferred embodiment, step (a) of the process according to the present invention is performed in the presence of a complex between said compound (C) and said compound (P) . Surprising results in terms of conversion and selectivity have been obtained performing step (a) in the presence of a complex comprising ruthenium and xantphos.
According to a preferred embodiment, said solvent is selected from polar solvents, non-polar solvents and mixtures thereof.
Preferably, said non polar solvents are selected in the group comprising: saturated and unsaturated hydrocarbons, such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and mesitylene； linear and cyclic ethers, such as tetrahydrofuran (THF) , diethyl ether, 1, 4-dioxane, tert-butyl methyl ether (MTBE) , diglyme and 1, 2-methoxyethane.
Preferably, said polar solvent is selected in the group comprising polar protic and aprotic solvents.
Suitable polar aprotic solvents are selected in the group comprising dimethylformamide, formamide and acetonitrile.
More preferably, said polar protic solvent is selected from water and alcohols. Suitable alcohols are selected in the group comprising: 3, 3-dimethyl-1-butanol, 3, 3, -dimehtyl-2-butanol, 2-trifluoromethyl-2-propanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2, 3-dimethyl-2-butanol.
Good results have been obtained using at least one alcohol.
Preferably, step (a) is performed by mixing together said at least one polymer (POH) with said at least one compound (C) and said at least one compound (P) .
Optionally, before performing step (a) , step (a0) is performed, which comprises mixing together said at least one compound (C) , said at least one compound (P) and said solvent to provide a mixture [mixture (CP) ] , and then contacting in step (a) said mixture (CP) with said at least one polymer (POH) and said compound of formula HNR1R2 as defined above. Preferably, said step (a0) is performed under heating, more preferably at a temperature of from 50℃ to 200℃, even more preferably from 100℃ to 180℃.
Preferably, said step (a0) is performed under pressure, more preferably at a pressure from about 1.5 to 3 atm.
Preferably, said step (a0) is performed under inert atmosphere, more preferably using argon, nitrogen gas or a mixture thereof.
Preferably, said compound (C) is used in an amount higherthan 0.01 wt. ％based on the total weight of said polymer (POH) , more preferably from 0.05 to 10 wt. ％, and even more preferably from 0.1 to 1.0 wt. ％
Preferably, step (a) is performed by reacting at least one polymer (POH) as defined above, with at least one compound of formula HNR1R2, wherein each of R1 and R2, identical or different from each other, is selected from hydrogen atom or linear of branched alkyl chain comprising from 1 to 3 carbon atoms, with the proviso that at least one of R1 and R2 is hydrogen atom. According to a preferred embodiment, both R1 and R2are hydrogen atoms.
Preferably, step (a) is performed under heating, more preferably at a temperature of from 60℃ to 210℃, even more preferably from 110℃ to 190℃.
The invention will be herein after illustrated in greater detail by means of the Examples contained in the following Experimental Section； the Examples are merely illustrative and are by no means to be interpreted as limiting the scope of the invention.
Experimental section
________________________________________________________________________
Materials and Methods:
Polymer (I) -Poly (ethoxy) perfluoropolyether complying with formula:
HO (CH2CH2O) j1CH2CF2O (CF2CF2O) a1 (CF2O) a2CF2CH2 (OCH2CH2) j1OH wherein j1＝5, a1/a2～1, average number molecular weight (Mn) 2, 200 and F＝1.8 was manufactured according to the procedure disclosed in WO 2014/090649.
Polymer (II) -
Figure PCTCN2017071476-appb-000006
E10H PFPE complying with formula:
HO(CH2CH2O) j1CH2CF2O (CF2CF2O) a1 (CF2O) a2CF2CH2O (CH2CH2O) j1H having j1＝1.79, a1/a2＝1.2, average molecular weight (Mn) 1, 765 and equivalent weight (Ew) 962.
Example 1–Amination of polymer (I)
Under an argon atmosphere, 0.024 g (0.025 mmol) of carbonylchlorohydrotris (triphenylphosphine) ruthenium (II) (CAS number: 16971-33-8) , 0.017 g (0.030 mmol) of xantphos (CAS number: 161265-03-8) and 8 mL of 2-methyl-2-butanol as solvent were placed in a 30 mL stainless steel autoclave (internal diameter 2.0 cm) . The autoclave was then evacuated with a vacuum pump, and then pressurized with a 2 bar of argon. The autoclave was then heated at 140℃, while stirring for 1 hour. After cooling to room temperature, the autoclave was opened and 2 ml (3.0 g) of polymer (I) were added under an argon atmosphere. The autoclave was closed and again evacuated with a vacuum pump. Then 1.0 g of NH3 was condensed into the autoclave from a gas cylinder while cooling the autoclave in iced water. The mixture was then heated under stirring at 160℃ and maintained at the same temperature for 12 hours. After cooling to room temperature, the autoclave was vented slowly, the reaction mixture was evaporated under reduced pressure on a rotary evaporatorto remove the solvent. The remaining liquid was filtered and analysed with 13C-NMR.
The analysis showed a conversion of the hydroxyl chain ends of 100％and selectivity to the primary amine of 95％ (the remaining was the secondary  amine as side-product) .
Example 2–Amination of polymer (II)
The same procedure described in Example 1 was repeated starting from polymer (II) .
The analysis by 13C-NMR showed a conversion of the hydroxyl chain ends of 92％and selectivity to the primary amine of 93％ (the remaining was the secondary amine as side-product) .
Example 3–Amination of polymer (I)
The same procedure described in Example 1 was repeated starting from polymer (I) and using 0.012 g (0.0125 mmol) of CAS 16971-33-8 and 0.0087 g (0.015 mmol) of CAS 161265-03-8.
The analysis by 13C-NMR showed a conversion of the hydroxyl chain ends of 70％and selectivity to the primary amine of 94％ (the remaining was the secondary amine as side-product) .
Example 4–Amination of polymer (II)
Under an argon atmosphere, 0.024 g (0.025 mmol) of CAS 16971-33-8, 0.017 g (0.030 mmol) of CAS 161265-03-8, 2 ml (3.0 g) of polymer (II) and 8 mL of 2-methyl-2-butanol as solvent were placed in a 30 mL stainless steel autoclave, which was closed and evacuated with a vacuum pump. Then 1.0 g of NH3 was condensed into the autoclave from a gas cylinder while cooling the autoclave in iced water. The mixture was then heated under stirring at 160℃ and maintained at the same temperature for 12 hours. After cooling to room temperature, the autoclave was vented slowly, the reaction mixture was evaporated under reduced pressure on a rotary evaporatorto remove the solvent. The remaining liquid was filtered and analysed with 13C-NMR.
The analysis showed a conversion of the hydroxyl chain ends of 85％and selectivity to the primary amine of 92％ (the remaining was the secondary amine as side-product) .
Comparative example 1–Amination of polymer (II) without solvent
The same procedure described in Example 2 was repeated but without adding 2-methyl-2-butanol as the solvent.
The analysis by 13C-NMR showed a conversion of the hydroxyl chain ends of 42％and selectivity to the primary amine of 77％ (the remaining was the secondary amine as side-product) .

Claims (15)

  1. A process for the synthesis of a (poly) alkoxylated (per) fluoropolyether polymer [polymer (PN) ] comprising a (per) fluoropolyether chain [chain (Rpf) ] having two chain ends, wherein at least one chain end bears a chain [chain (RN) ] complying with the following formula:
    -CH (J1) CH (J2) -NR1R2
    wherein
    each of J1 and J2 is independently selected from hydrogen atom； linear or branched alkyl chain comprising from 1 to 3 carbon atoms, preferably methyl； or aryl group, preferably phenyl； with the proviso that at least one of J1 and J2 is hydrogen atom； and
    each of R1 and R2 is independently selected from hydrogen atom or linear or branched alkyl chain comprising from 1 to 6 carbon atoms；
    and wherein said chain (Rpf) and said chain (RN) are linked together via a (poly) alkoxylated chain [chain (RO) ] ；
    said process comprising the following step:
    (a) reacting at least one (per) fluoropolyether polymer [polymer (POH) ] comprising a (per) fluoropolyether chain [chain (Rpf) ] having two chain ends, wherein at least one chain end bears a chain [chain (ROH) ] complying with one of the following formulae:
    (ROH-I) - [CH2CH2O] j1-H,
    (ROH-II) - [CH2CH (J) O] j2-H or
    (ROH-III) - [CH (J) CH2O] j3-H,
    wherein
    J is independently straight or branched alkyl or aryl, preferably methyl, ethyl or phenyl, and
    each of j1, j2 and j3 is, independently, an integer from 1 to 50；
    with at least one compound of formula HNR1R2, wherein each of R1 and R2, identical or different from each other, is selected from hydrogen atom or linear or branched alkyl chain comprising from 1 to 6 carbon atoms；
    in the presence of:
    (i) at least one catalyst [compound (C) ] based on at least one element  belonging to Group 8 or 9 of the Periodic Table of the Elements；
    (ii) at least one organo-phosphorous compound [compound (P) ] and
    (iii) at least one solvent.
  2. The process according to claim 1, wherein said chain (Rpf) is a chain complying with formula:
    -O-D- (CFX) z1-O (Rf) (CFX’) z2-D*-O-
    wherein
    z1 and z2, equal or different from each other, are equal to or higher than 1；
    X and X', equal or different from each other, are-F or-CF3,
    provided that when z1 and/or z2 are higher than 1, X and X’are-F；
    D and D*, equal or different from each other, are an alkylene chain comprising from 1 to 6 and even more preferably from 1 to 3 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms；
    (Rf) comprises, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of:
    (i) -CFXO-, wherein X is F or CF3；
    (ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is F or CF3, with the proviso that at least one of X is–F；
    (iii) -CF2CF2CW2O-, wherein each of W, equal or different from each other, are F, Cl, H；
    (iv) -CF2CF2CF2CF2O-；
    (v) - (CF2) j-CFZ-O-wherein j is an integerfrom 0 to 3 and Z is a group of general formula-O-R(f-a)-T, wherein R(f-a)is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen among the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, with each of each of X being independently F or CF3 and T being a C1-C3 perfluoroalkyl group.
  3. The process according to claim 2, wherein said chain (Rf) complies with the following formula:
    (Rf-I)
    -[ (CFX1O) g1 (CFX2CFX3O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4] -
    wherein
    -X1 is independently selected from-F and-CF3,
    -X2, X3, equal or different from each other and at each occurrence, are independently-F, -CF3, with the proviso that at least one of X is-F；
    -g1, g2, g3, and g4, equal or different from each other, are independently integers≥0, such that g1+g2+g3+g4 is in the range from 2 to 300, preferably from 2 to 100； should at least two of g1, g2, g3 and g4 be different from zero, the different recurring units are generally statistically distributed along the chain.
  4. The process according to any one of claims 2 or 3, wherein said chain (Rf) is selected from the following formulae:
    (Rf-IIA) - [ (CF2CF2O) a1 (CF2O) a2] -
    wherein:
    -a1 and a2 are independently integers≥0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000； both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably comprised between 0.1 and 10；
    (Rf-IIB) - [ (CF2CF2O) b1 (CF2O) b2 (CF (CF3) O) b3 (CF2CF (CF3) O) b4] -
    wherein:
    b1, b2, b3, b4, are independently integers≥0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000； preferably b1 is 0, b2, b3, b4 are>0, with the ratio b4/ (b2+b3) being≥1；
    (Rf-IIC) - [ (CF2CF2O) c1 (CF2O) c2 (CF2 (CF2) cwCF2O) c3] -
    wherein:
    cw＝1 or 2；
    c1, c2, and c3 are independently integers≥0 chosen so that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000； preferably c1, c2 and c3 are all>0, with the ratio c3/ (c1+c2) being generally lower than 0.2；
    (Rf-IID) - [ (CF2CF (CF3) O) d] -
    wherein:
    d is an integer>0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000；
    (Rf-IIE) - [ (CF2CF2C (Hal*) 2O) e1- (CF2CF2CH2O) e2- (CF2CF2CH (Hal*) O) e3] -
    wherein:
    -Hal*, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom；
    -e1, e2, and e3, equal to or different from each other, are independently integers≥0 such that the (e1+e2+e3) sum is comprised between 2 and 300.
  5. The process according to any one of claim 2 to 4, wherein said chain (Rf) complies with formula (Rf-III) here below:
    (Rf-III) - [ (CF2CF2O) a1 (CF2O) a2] -
    wherein:
    -a1, and a2 are integers>0 such that the number average molecular weight is between 900 and 10,000, preferably between 900 and 5,000, with the ratio a1/a2 being generally comprised between 0.1 and 10, more preferably between 0.2 and 5.
  6. The process according to claim 1, wherein said chain (RN) complies with one of the following formulae (RN-I*) to (RN-III*) :
    (RN-I*) -CH2CH2-NR1R2
    (RN-II*) -CH2CH (CH3) -NR1R2
    (RN-III*) -CH (CH3) CH2-NR1R2
    wherein
    each of R1 and R2 is independently selected from hydrogen atom or linear or branched alkyl chain comprising from 1 to 6 carbon atoms.
  7. The process according to claim 1, wherein said chain (RO) complies with the following formula:
    -[ (CH (J) CH (J*) O] j-
    wherein
    j is an integer from 1 to 50, more preferably from 1 to 20, even more preferably from 1 to 10, still more preferably from 1 to 8；
    each of J and J*is independently selected from hydrogen atom； linear or branched alkyl chain comprising from 1 to 3 carbon atoms, more preferably methyl； or aryl group, more preferably phenyl；
    with the proviso that at least one of J and J*is hydrogen atom.
  8. The process according to claim 1, wherein said chain (ROH) complies with one of the following formulae (ROH-I*) to (ROH-III*) :
    (ROH-I*) - (CH2CH2O) j1-H
    (ROH-II*) - [CH2CH (CH3) O] j2-H
    (ROH-III*) - [ (CH2CH2O) j3- (CH2CH (CH3) O) j4] j(x)-H
    wherein
    j1 and j2, each independently, are an integer from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, and still more preferably from 1 to 6；
    j3, j4 and j (x) are integers higher than 1, such that the sum of j3 and j4 is from 2 to 15, more preferably from 3 to 15, even more preferably from 4 to 15, and still more preferably from 4 to 10； and
    each of R1 and R2 is independently selected from hydrogen atom or linear or branched alkyl chain comprising from 1 to 6 carbon atoms.
  9. The process according to claim 1, wherein said compound (C) is based on at least one element selected in the group comprising, preferably consisting of iron, cobalt, ruthenium, rhodium, osmium and iridium.
  10. The process according to claim 1, wherein said compound (P) complies with the following formula (P-I) :
    Figure PCTCN2017071476-appb-100001
    wherein
    n is zero or 1；
    each of R1, R2, R3, R4, R5 and R6 is independently selected from linear or branched alkyl chain comprising from 1 to 10 carbon atoms, alkyl-diphenyl-phosphine wherein the alkyl chain comprises from 1 to 4 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 3-to 10-membered heterocyclyl group comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryl group optionally comprising at least one heteroatom selected from N, O and S； the above groups being optionally substituted with one substituent [group (S) ] selected from fluorine atom, chlorine atom, bromine atom, hydroxy group, cyano group, -NH2 and linear or branched alkyl chain comprising from 1 to 10 carbon atoms；
    Y1, Y2 and Y3 are, each independently, a sigma bond or an alkylene group selected from methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, said alkylene group being optionally substituted with one or more group (S) as defined above；
    A is a group selected from optionally substituted N, O, P, C1-C6 alkyl, C3-C10 cycloalkyl optionally comprising one heteroatom selected from N, O and S, C5-C14 aromatic group optionally comprising one heteroatom selected from N, O and S, or a group complying with one of the following formulae (A-I) and (A-II) : (A-I)
    Figure PCTCN2017071476-appb-100002
    wherein
    m and q are, each independently, zero or an integer from 1 to 4,
    R8 and R9 are, each independently, selected from the group comprising liner or branched alkyl chain comprising from 1 to 10 carbon atoms, fluorine atom, chlorine atom, bromine atom, -OR7 group or-N (R7*) 2 group wherein R7 and R7* are each independently selected from hydrogen atom, linear or branched alkyl chain comprising from 1 to 10 carbon atoms and aryl group comprising 5 to 10 members；
    X1 and X2 are, each independently, selected from NH, O and S；
    X3 is a sigma bond or a divalent group selected from: -N (R10) -, -O-, -S-, -C (R11) (R12) -wherein R10 is linear or branched alkyl chain comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 3-to 10-membered heterocyclyl group comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryl group optionally comprising at least  one heteroatom selected from N, O and S； the above groups being optionally substituted with one or more group (S) as defined above；
    R11 and R12 are, each independently, selected from linear or branched alkyl group comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 3-to 10-membered cycloalkoxy, 3-to 10-membered heterocyclyl comprising at least one heteroatom selected from N, O and S, 5-to 14-membered aryloxy group optionally comprising at least one heteroatom selected from N, O and S； the above groups being optionally substituted with one or more groups (S) as defined above.
  11. The process according to claim 10, wherein said compound (P) complies with the formula (P-I)
    Figure PCTCN2017071476-appb-100003
    wherein:
    n is zero or 1；
    each of R1, R2, R3, R4, R5 and R6 is independently selected from linear or branched alkyl chain comprising from 1 to 10 carbon atoms, cycloalkyl group comprising from 3 to 10 members, 5-to 14-membered aryl group；
    Y1, Y2 and Y3 are, each independently, asigma bond or an alkylene group selected from methylene, ethylene and trimethylene；
    A is C1-C6 alkyl, C3-C10 cycloalkyl or a divalent or trivalent group of formula:
    (A-II*)
    Figure PCTCN2017071476-appb-100004
    wherein
    X2 is O；
    X3 is a sigma bond or a divalent group of formula-C (R11) (R12) -wherein R11 and R12 are, each independently, selected from linear or branched alkyl group comprising from 1 to 10 carbon atoms.
  12. According to a particularly preferred embodiment, step (a) of the process according to the present invention is performed in the presence of a complex between said compound (C) and said compound (P) .
  13. The process according to claim 1, wherein said solvent is a polar protic solvent.
  14. The process according to claim 1, wherein before performing step (a) , step (a0) is performed, which comprises mixing together said at least one compound (C) , said at least one compound (P) and said solvent to provide a mixture [mixture (CP) ] and then contacting in step (a) said mixture (CP) with said at least one polymer (POH) and said compound of formula HNR1R2 as defined in any one of the above claims 1 to 13.
  15. The process according to claim 1, wherein said compound (C) is in an amount higher than 0.01 wt. ％ based on the total weight of said polymer (POH) .
PCT/CN2017/071476 2017-01-18 2017-01-18 Process for the synthesis of (per) fluoropolyether-amino derivatives WO2018132960A1 (en)

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