METHOD FOR MANUFACTURING POLYALKOXYLATED POLYMERS

Abstract

The present invention relates to a method for the manufacture of polyalkoxylated polymers.

Claims

1. A process for the manufacture of an alkoxylated derivative of a hydrogenated or (per)halogenated polymer comprising at least one OH group [polymer (P.sub.ALK-OH)], said process comprising the steps of: (a) contacting at least one pre-catalyst C complying with formula (1)
E(Q).sub.t (1) wherein E is an element selected from IV-group metals, post-transition metals and silicon, Q is chlorine, bromine, iodine or an optionally fluorinated alkoxy or aryloxy group, and t is an integer corresponding to the valence of E; with (a-i) at least one polymer (P.sub.OH), wherein polymer (P.sub.OH) is a hydrogenated or (per)halogenated polymer comprising at least one OH group, thus providing a mixture (M.sub.a-1) comprising said polymer P.sub.OH and a product (CP.sub.OH) obtained by the reaction between said pre-catalyst C and said polymer (P.sub.OH), or (a-ii) at least one compound (I), wherein compound (I) is a source of iodine thus providing a mixture (M.sub.a-2) comprising said pre-catalyst C and said compound (I); (b) contacting said mixture (M.sub.a-1) with at least one compound (I), wherein compound (I) is a source of iodine or contacting said mixture (M.sub.a-2) with at least one polymer (P.sub.OH), thus obtaining mixture (M.sub.b) comprising said polymer (P.sub.OH), said product (CP.sub.OH) and said compound (I); (c) contacting said mixture (M.sub.b) with at least one alkylene oxide, thus obtaining polymer (P.sub.ALK-OH), optionally in admixture [mixture (M.sub.c)] with said polymer (P.sub.OH), said product (CP.sub.OH) and/or said compound (I).

2. The process according to claim 1, wherein E is an element selected from the group consisting of IV-group metals selected from titanium and zirconium; post-transitional metals selected from gallium, indium, tin and aluminium; and silicon.

3. The process according to claim 1, wherein Q is an optionally fluorinated alkoxy or aryloxy group.

4. The process according to claim 1, wherein said pre-catalyst C is selected from the group consisting of: titanium(IV) isopropoxide, titanium(IV) propoxide, titanium(IV) tert-butoxide, titanium(IV) methoxide, zirconium(IV) propoxide, aluminium isopropoxide, tin(IV) isopropoxide, tetraethyl orthosilicate, indium alkoxide and gallium alkoxide.

5. The process according to claim 1, wherein said pre-catalyst C is used in an amount in the range from 0.01 to 10% expressed as moles of pre-catalyst C per number of equivalents of OH groups in polymer (P.sub.OH).

6. The process according to claim 1, wherein said compound (I) is selected from the group consisting of: alkali metal or alkaline-earth metal iodides; ammonium and alkyl-ammonium iodides; elemental iodine; and combinations thereof.

7. The process according to claim 1, wherein said compound (I) is used in an amount in the range from 0.01 to 8% expressed as moles of the source of iodine per number of equivalents of OH groups in polymer (P.sub.OH).

8. The process according to claim 1, wherein said hydrogenated polymer (P.sub.OH) is selected from the group consisting of polymers of formula R.sub.HOH, wherein R.sub.H is a linear or branched alkyl chain comprising from 3 to 12 carbon atoms.

9. The process according to claim 1, wherein said (per)halogenated polymer (P.sub.OH) is selected from the group consisting of: polymers complying with general formula R.sub.FHCF.sub.2CH.sub.2CH.sub.2OH wherein R.sub.FH is a linear or branched alkyl chain comprising from 1 to 12 carbon atoms; and (per)fluoropolyether polymers (P.sub.OH-PFPE) comprising a partially or fully fluorinated, straight or branched, polyoxyalkylene chain (R.sub.f) having at least two chain ends, wherein at least one chain end comprises at least one group of formula CF.sub.2CH.sub.2O and at least one hydroxy group.

10. The process according to claim 9, wherein said polymer (P.sub.OH-PFPE) complies with formula (I):
A-O(R.sub.f)(CFX*).sub.z1-D*-O(R.sub.a).sub.z3H (I) wherein A is linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms or a group of formula H(R.sub.a).sub.z4O-D-(CFX.sup.#).sub.z2; z1 and z2, equal or different from each other, are equal to or higher than 1; z3 and z4, equal or different from each other, are 0 or 1; each of R.sub.a, equal to or different from each other, is a group of formula [CH.sub.2CH(J)O].sub.na[CH(J)CH.sub.2O].sub.na, wherein each of J is independently selected from hydrogen atom, straight or branched alkyl chain, or aryl group, and each of na and na is independently zero or an integer up to 15, with the proviso that na+na is from 1 to 15; X.sup.# and X*, equal or different from each other, are F or CF.sub.3, provided that when z1 and/or z2 are higher than 1, X.sup.# and X* are F; D and D*, equal or different from each other, are an alkylene chain comprising from 1 to 6 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms; (R.sub.f) comprises, repeating units R, said repeating units being independently selected from the group consisting of: (i) CFXO, wherein X is F or CF.sub.3; (ii) CFXCFXO, wherein X, equal or different at each occurrence, is F or CF.sub.3, with the proviso that at least one of X is F; (iii) CF.sub.2CF.sub.2CW.sub.2O, wherein each of W, equal or different from each other, are F, Cl, or H; (iv) CF.sub.2CF.sub.2CF.sub.2CF.sub.2O; (v) (CF.sub.2).sub.jCFZOwherein j is an integer from 0 to 3 and Z is a group of general formula OR(.sub.f-a-T, wherein R(.sub.f-a) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen from: CFXO, CF.sub.2CFXO, CF.sub.2CF.sub.2CF.sub.2O, and CF.sub.2CF.sub.2CF.sub.2CF.sub.2O, with each of X being independently F or CF.sub.3 and T being a C.sub.1-C.sub.3 perfluoroalkyl group.

11. The process according to claim 10, wherein said polymer (P.sub.OH-PFPE) complies with formula (I-A) here below:
A-O(R.sub.f)CF.sub.2CH.sub.2O(R.sub.a).sub.z3H (I-A) wherein: R.sub.f is as defined in claim 10; A is CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7, CF.sub.2Cl, CF.sub.2CF.sub.2Cl, C.sub.3F.sub.6Cl or a group of formula CF.sub.2CH.sub.2O(R.sub.a).sub.z4H; z3 and z4, equal or different from each other, are 0 or 1; each of (R.sub.a), equal or different from each other, is a group of formula [CH.sub.2CH(J)O].sub.na[CH(J)CH.sub.2O].sub.na, wherein each of J is independently hydrogen atom or methyl, and each of na and na is independently zero or an integer from 1 to 7, with the proviso that na+na is from 1 to 7.

12. The process according to claim 10, wherein said polymer (P.sub.OH-PFPE) complies with formula (I-B):
A-O(R.sub.f)13 CF.sub.2CH.sub.2OH (I-B) wherein R.sub.f is as defined in claim 10 and A is CF.sub.2CH.sub.2OH or a linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms, and wherein before said step (a-i), a step (a-i-0) is performed which comprises contacting polymer (P.sub.OH-PFPE) of formula (I-B) with a base, thus providing the corresponding alkoxide of polymer (P.sub.OH-PFPE)

13. The process according to claim 1, wherein said product (CP.sub.OH) complies with formula (II-A) or (II-B):
A.sup.II-O(R.sub.f)(CFX*).sub.z1-D*-O(R.sub.a).sub.z3-E(Z).sub.n (II-A)
A.sup.I-O(R.sub.f)CF.sub.2CH.sub.2O-E(Z).sub.n (II-B) wherein Rf, X*, D*, (R.sub.a), z1 and z3 are as defined above for polymer P.sub.OH; A.sup.II is a (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms or it is a group of formula (Z).sub.nE-(R.sub.a).sub.z4O-D-(CFX.sup.#).sub.z2 wherein X.sup.#, D, (R.sub.a), z2 and z4 are as defined above for polymer P.sub.OH; A.sup.I is a linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms or it is a group of formula (Z).sub.nE-(R.sub.a).sub.z4OCH.sub.2CF.sub.2 wherein (R.sub.a) and z4 are as defined in claim 10; E is an element selected from the group consisting of IV-group metals selected from titanium and zirconium; post-transitional metals selected from gallium, indium, tin and aluminium; and silicon; n is an integer corresponding to the valence of E; and Z independently is an optionally fluorinated alkoxy or aryloxy group, a group derived from the reaction with another polymer (P.sub.OH-PFPE), or a group of formula (Z-I) or (Z-II):
A.sup.II-O(R.sub.f)(CFX*).sub.z1-D*-O(R.sub.a).sub.z3(Z-I)
A.sup.I-O(R.sub.f)CF.sub.2CH.sub.2O(Z-II) wherein A.sup.I, A.sup.II, Rf, X*, D*, (R.sub.a), z1 and z3 are as defined above.

14. The process according to claim 1, wherein said step (c) is performed as follows: (c-i) by feeding two or more alkylene oxides at the same time to the reaction environment of step (c-i), thus obtaining polymer (P.sub.ALK-OH) comprising randomly arranged recurring units derived at least from said first and second alkylene oxide, wherein the first alkylene oxide and the second alkylene oxide have different chemical formulas; or (c-ii) by feeding a first alkylene oxide, finishing/stopping the feeding of the first alkylene oxide, feeding a second alkylene oxide having a chemical formula different from the first alkylene, finishing/stopping the feeding of the second alkylene oxide, optionally feeding a third alkylene oxide having a chemical formula different from the second alkylene oxide and repeating said steps until completion of the reaction, thus obtaining polymer (P.sub.ALK-OH) comprising recurring units derived at least from said first and second alkylene oxide arranged in blocks.

15. The process according to claim 1, wherein said polymer (P.sub.ALK-OH) complies with the following formula (IV):
A.sup.IV-O(R.sub.f)(CFX*).sub.z1-D*-O(R.sub.a-IV)H (IV) wherein z1 is equal to or higher than 1; X* is F or CF.sub.3, D* is an alkylene chain comprising from 1 to 6 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms; (R.sub.f) comprises repeating units R, said repeating units being independently selected from the group consisting of: (i) CFXO, wherein X is F or CF.sub.3; (ii) CFXCFXO, wherein X, equal or different at each occurrence, is F or CF.sub.3, with the proviso that at least one of X is F; (iii) CF.sub.2CF.sub.2CW.sub.2O, wherein each of W, equal or different from each other, are F, Cl or H; (iv) CF.sub.2CF.sub.2CF.sub.2CF.sub.2O; (v) (CF.sub.2).sub.jCFZO wherein j is an integer from 0 to 3 and Z is a group of general formula OR.sub.(f-a)-T, wherein R.sub.(f-a) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen from: CFXO, CF.sub.2CFXO, CF.sub.2CF.sub.2CF.sub.2O, and CF.sub.2CF.sub.2CF.sub.2CF.sub.2O, with each of X being independently F or CF.sub.3 and T being a C.sub.1-C.sub.3 perfluoroalkyl group; A.sup.IV is a linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms or a group of formula H(R.sub.a-IV*)O-D-(CFX.sup.190 ).sub.z2wherein z2 is equal to or higher than 1 and X# is F or CF.sub.3, and D is an alkylene chain comprising from 1 to 6 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms; and each of (R.sub.a-IV) and (R.sub.a-IV*) is independently selected from group of formula [CH.sub.2CH(J)O].sub.na*[CH(J)CH.sub.2O].sub.a#, wherein each of J is independently hydrogen atom or methyl, and each of na* and na# is independently zero or an integer from 1 to 100, with the proviso that at least one of na* and na# is in integer having a value higher than the value of na and na, respectively, in polymer (P.sub.OH).

16. A product (CP.sub.OH) obtained by the reaction between element E of pre-catalyst C as defined claim 1 and the at least one OH group of polymer P.sub.OH as defined in claim 1.

17. A mixture (M.sub.c comprising polymer (P.sub.ALK-OH) as defined in claim 1, polymer (P.sub.OH) as defined in claim 1, and optionally product (CP.sub.OH) as defined in claim 1 and/or compound (I), wherein compound (I) is selected from the group consisting of: alkali metal or alkaline-earth metal iodides; ammonium and alkyl-ammonium iodides; elemental iodine; and combinations thereof.

18. The process according to claim 3, wherein Q is an optionally fluorinated alkoxy or aryloxy group of formula O-T, wherein T is a linear or branched alkyl chain having from 1 to 12 carbon atoms, said alkyl chain being optionally substituted with one or more fluorine atoms, or a 5- or 6-membered optionally fluorinated aryl group.

19. The process according to claim 10, wherein D and D*, equal or different from each other, are an alkylene chain comprising 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. The process according to claim 10, wherein D and D*, equal or different from each other, are an alkylene chain comprising 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.

20. The process according to claim 15, wherein D and D*, equal or different from each other, are an alkylene chain comprising from 1 to 3 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atom

Description

DESCRIPTION OF EMBODIMENTS

[0022] For the purpose of the present description and of the following claims: [0023] 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 number from the rest of the text and, hence, said parenthesis can also be omitted; [0024] the acronym PFPE stands for (per)fluoropolyether and, when used as substantive, is intended to mean either the singular or the plural form, depending on the context; [0025] the term (per)fluoropolyether is intended to indicate fully or partially fluorinated polyether polymer; [0026] the term pre-catalyst is intended to indicate a compound that is converted into a catalytic species during the course of the catalyzed reaction; [0027] then expression catalytic species is used as synonym of catalyst.

[0028] Preferably, E is an element selected in the group comprising, more preferably consisting of, IV-group metals selected from the group comprising, more preferably consisting of, titanium and zirconium; post-transitional metals, selected from the group comprising, more preferably consisting of, gallium, indium, tin and aluminium; and silicon.

[0029] Preferably, Q is an optionally fluorinated alkoxy or aryloxy group. More preferably Q complies with formula O-T, wherein T is a linear or branched alkyl chain having from 1 to 12 carbon atoms, said alkyl chain being optionally substituted with one or more fluorine atoms, or a 5- or 6-membered optionally fluorinated aryl group. Even more preferably, Q is a group of formula O-T wherein T is a linear or branched alkyl chain having 1 to 6 carbon atoms or C.sub.6H.sub.5.

[0030] Even more preferably, said pre-catalyst C is selected in the group comprising: titanium(IV) isopropoxide, titanium(IV) propoxide, titanium(IV) tert-butoxide, titanium(IV) methoxide, zirconium(IV) propoxide, aluminium isopropoxide, tin(IV) isopropoxide, tetraethyl orthosilicate, indium alkoxide and gallium alkoxide.

[0031] Titanium(IV) isopropoxide, titanium(IV) propoxide, titanium(IV) tert-butoxide, titanium(IV) methoxide and zirconium(IV) propoxide are particularly preferred.

[0032] Preferably, pre-catalyst C is used in a catalytic amount, more preferably in the range from 0.01 to 10%, more preferably from 0.1 to 5%, expressed as moles of pre-catalyst C per number of equivalents of OH groups in polymer (P.sub.OH).

[0033] Compound (I) is preferably selected in the group comprising: alkali metal or alkaline-earth metal iodides, such as for example NaI, KI, CaI.sub.2; ammonium and alkyl-ammonium iodides, such as NH.sub.4I and (R).sub.4NI wherein each R is a linear or branched alkyl chain comprising from 1 to 6 carbon atoms; elemental iodine; and combinations thereof. Good results have been obtained using KI.

[0034] Compound (I) is advantageously used in a catalytic amount. Preferably, compound (I) is used in an amount in the range from 0.01 to 8%, more preferably from 0.5 to 2.5%, expressed as moles of the source of iodine per number of equivalents of OH groups in polymer (P.sub.OH).

[0035] Preferably, said hydrogenated polymers (P.sub.OH) used as starting materials are selected polymers of formula R.sub.HOH, wherein R.sub.H is a linear or branched alkyl chain comprising from 3 to 12 carbon atoms.

[0036] Preferably, said (per)halogenated polymers (P.sub.OH) used as starting materials are selected from: [0037] polymers complying with general formula R.sub.FHCF.sub.2CH.sub.2CH.sub.2OH wherein R.sub.FH is a linear or branched alkyl chain comprising from 1 to 12 carbon atoms, and [0038] (per)fluoropolyether polymer [polymer (P.sub.OH-PFPE)] comprising a partially or fully fluorinated, straight or branched, polyoxyalkylene chain [chain (R.sub.f)] having at least two chain ends, wherein at least one chain end comprises at least one group of formula CF.sub.2CH.sub.2O and at least one hydroxy group.

[0039] Preferably, said polymer (P.sub.OH-PFPE) complies with the following formula (I):

A-O(R.sub.f)(CFX*).sub.z1-D*O(R.sub.a).sub.z3H(I) (I)

wherein
A is linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms or a group of formula H(R.sub.a).sub.z4OD(CFX.sup.#).sub.z2-;
z1 and z2, equal or different from each other, are equal to or higher than 1;
z3 and z4, equal or different from each other, are 0 or 1;
each of (R.sub.a), equal or different from each other, is a group of formula [CH.sub.2CH(J)O].sub.na[CH(J)CH.sub.2O].sub.na, wherein each of J is independently selected from hydrogen atom, straight or branched alkyl chain, or aryl group, and each of na and na is independently zero or an integer up to 15, with the proviso that na+na is from 1 to 15;
X.sup.# and X*, equal or different from each other, are F or CF.sub.3, provided that when z1 and/or z2 are higher than 1, X.sup.# 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;
(R.sub.f) 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 CF.sub.3;
(ii) CFXCFXO, wherein X, equal or different at each occurrence, is F or CF.sub.3, with the proviso that at least one of X is F;
(iii) CF.sub.2CF.sub.2CW.sub.2O, wherein each of W, equal or different from each other, are F, Cl, H;
(iv) CF.sub.2CF.sub.2CF.sub.2CF.sub.2O;
(v) (CF.sub.2).sub.jCFZO wherein j is an integer from 0 to 3 and Z is a group of general formula OR.sub.(f-a)-T, wherein R(.sub.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, CF.sub.2CFXO, CF.sub.2CF.sub.2CF.sub.2O, CF.sub.2CF.sub.2CF.sub.2CF.sub.2O, with each of X being independently F or CF.sub.3 and T being a C.sub.1-C.sub.3 perfluoroalkyl group.

[0040] Preferably, said linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms is selected from CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7, CF.sub.2Cl, CF.sub.2CF.sub.2Cl and C.sub.3F.sub.6Cl.

[0041] Preferably, z1 and z2, equal or different from each other, are from 1 to 10, more preferably from 1 to 6 and even more preferably from 1 to 3.

[0042] Preferably, J is hydrogen atom, methyl, ethyl or phenyl.

[0043] Preferably, each of na and na is zero or an integer from 1 to 12, more preferably from 2 to 12, even more preferably from 2 to 10.

[0044] More preferably, each (R.sub.a) comprises ethoxylated and/or propoxylated recurring unit(s). Even more preferably each (R.sub.a) complies with one of the following formulae (R.sub.a-I) to (R.sub.a-III):

(CH.sub.2CH.sub.2O).sub.j1(R.sub.a-I)

[CH.sub.2CH(CH.sub.3)O].sub.j2(R.sub.a-II)

[(CH.sub.2CH.sub.2O).sub.j3(CH.sub.2CH(CH.sub.3)O).sub.j4].sub.j(x)(R.sub.a-III)

wherein
j1 and j2, each independently, are an integer from 1 to 15, preferably 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;
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.

[0045] More preferably, D and D*, equal or different from each other, are a chain of formula CH.sub.2or CH(CF.sub.3).

[0046] Preferably, chain (R.sub.f) complies with the following formula:

[(CFX.sup.1O).sub.g1(CFX.sup.2CFX.sup.3O).sub.g2(CF.sub.2CF.sub.2CF.sub.2O).sub.g3(CF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.g4](R.sub.f-I)

wherein [0047] X.sup.1 is independently selected from F and CF.sub.3, [0048] X.sup.2, X.sup.3, equal or different from each other and at each occurrence, are independently F, CF.sub.3, with the proviso that at least one of X is F; [0049] 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.

[0050] More preferably, chain (R.sub.f) is selected from chains of formula:

[(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2](R.sub.f-IIA)

wherein: [0051] a1 and a2 are independently integers 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 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;

[(CF.sub.2CF.sub.2O).sub.b1(CF.sub.2O).sub.b2(CF(CF.sub.3)O).sub.b3(CF.sub.2CF(CF.sub.3)O).sub.b4](R.sub.f-IIB)

wherein:
b1, b2, b3, b4, are independently integers 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably b1 is 0, b2, b3, b4 are >0, with the ratio b4/(b2+b3) being 1;

[(CF.sub.2CF.sub.2O).sub.c1(CF.sub.2O).sub.c2(CF.sub.2(CF.sub.2).sub.cwCF.sub.2O).sub.c3](R.sub.f-IIC)

wherein:
cw=1 or 2;
c1, c2, and c3 are independently integers 0 chosen so that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably c1, c2 and c3 are all >0, with the ratio c3/(c1+c2) being generally lower than 0.2;

[(CF.sub.2CF(CF.sub.3)O).sub.d](R.sub.f-IID)

wherein:
d is an integer >0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000;

[(CF.sub.2CF.sub.2C(Hal*).sub.2O).sub.e1(CF.sub.2CF.sub.2CH.sub.2O).sub.e2(CF.sub.2CF.sub.2CH(Hal*)O).sub.e3](R.sub.f-IIE)

wherein: [0052] Hal*, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom; [0053] 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.

[0054] Still more preferably, chain (R.sub.f) complies with formula (R.sub.f-III) here below:

[(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2](R.sub.f-III)

wherein: [0055] a1, and a2 are integers >0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000, with the ratio a1/a2 being generally comprised between 0.1 and 10, more preferably between 0.2 and 5.

[0056] When in polymer P.sub.OH-PFPE, one chain end bears one hydroxyl group and one chain end bears a neutral group selected from CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7, CF.sub.2Cl, CF.sub.2CF.sub.2Cl and C.sub.3F.sub.6Cl, polymer P.sub.OH-PFPE is also referred to as monofunctional PFPE alcohol.

[0057] When in polymer P.sub.OH-PFPE, both chain ends bear one hydroxyl group, polymer P.sub.OH-PFPE is also referred to as bifunctional PFPE alcohol and PFPE-diol.

[0058] More preferably, polymer P.sub.OH-PFPE complies with formula (I-A) here below:

AO(R.sub.f)CF.sub.2CH.sub.2O(R.sub.a).sub.z3H (I-A)

wherein: [0059] R.sub.f is as defined above and preferably complies with formula (R.sub.f-III) above; [0060] A is selected from CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7, CF.sub.2Cl, CF.sub.2CF.sub.2Cl, C.sub.3F.sub.6Cl or a group of formula CF.sub.2CH.sub.2O(R.sub.a).sub.z4H; [0061] z3 and z4, equal or different from each other, are 0 or 1; [0062] each of (R.sub.a), equal or different from each other, is a group of formula [CH.sub.2CH(J)O].sub.na[CH(J)CH.sub.2O].sub.na, wherein each of J is independently selected from hydrogen atom or methyl, and each of na and na is independently zero or an integer up to 7, with the proviso that na+na is from 1 to 7.

[0063] Even more preferably, each of na and na is independently zero or an integer up to 3, with the proviso that na+na is from 1 to 3.

[0064] Bi-functional polymers (P.sub.OH-PFPE) wherein A is a group of formula CF.sub.2CH.sub.2O(R.sub.a).sub.z4H wherein (R.sub.a) and z4 are as defined above are particularly preferred.

[0065] Preferred polymers P.sub.OH-PFPE according to formula (I) or formula (I-A) above 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.sub.4, or by catalytic hydrogenation, as disclosed, for example, in U.S. Pat. No. 6,509,509 (AUSIMONT S.P.A.) 5 Jul. 2001, U.S. Pat. No. 6,573,411 (AUSIMONT SPA) 21 Nov. 2002, WO 2008/122639 (SOLVAY SOLEXIS SPA) 16 Oct. 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 U.S. Pat. No. 3,847,978 (MONTEDISON SPA) 12 Nov. 1974, U.S. Pat. No. 3,766,251 (MONTEDISON SPA) 16 Oct. 1973, U.S. Pat. No. 3,715,378 (MONTEDISON SPA) 6 Feb. 1973, U.S. Pat. No. 3,665,041 (MONTEDISON SPA) 23 May 1972, U.S. Pat. No. 4,647,413 (MINNESOTA MINING & MFG) 3 Mar. 1987, EP 151877 A (MINNESOTA MINING & MFG) 21 Aug. 1985, U.S. Pat. No. 3,442,942 (MONTEDISON SPA) 6 May 1969, U.S. Pat. No. 577,291 (AUSIMONT SPA) 7 Jul. 1998, U.S. Pat. No 5,258,110 (AUSIMONT SRL) 2 Nov. 1993 or U.S. Pat. No. 7,132,574 B (SOLVAY SOLEXIS SPA) 7 Nov. 2006.

[0066] 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 Fluorolink.

[0067] Preferably, step (a-i) is performed under heating, for example at a temperature from about 50 C. to about 150 C.

[0068] Preferably, step (a-i) is performed under vacuum.

[0069] According to one embodiment, when said polymer (P.sub.OH-PFPE) complies with the following formula (I-B):

A-O(R.sub.f)CF.sub.2CH.sub.2OH (I-B)

wherein [0070] R.sub.f is as defined above and [0071] A is CF.sub.2CH.sub.2OH or a linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms, before said step (a-i), a step (a-i-0) is performed which comprises contacting polymer (P.sub.OH-PFPE) of formula (I-B) with a base, thus providing the corresponding alkoxide of polymer (P.sub.OH-PFPE).

[0072] As a consequence, according to this embodiment, step (a-i) comprises contacting said pre-catalyst C with the alkoxide of polymer (P.sub.OH-PFPE) of formula(I-B)

[0073] Preferably, said base is selected from NaH, NaOH, KOH.

[0074] Preferably, said base is used in a sub-stoichiometric amount compared to polymer (P.sub.OH-PFPE)

[0075] Preferably, the ratio between the base and the pre-catalyst C is higher than 1, more preferably between 1 and 2.

[0076] Product (CP.sub.OH) complies with the following formula (II-A) or (II-B):

A.sup.II-O(R.sub.f)(CFX*).sub.z1-D*-O(R.sub.a).sub.z3-E(Z).sub.n (II-A)

A.sup.I-O(R.sub.f)CF.sub.2CH.sub.2O-E(Z).sub.n (II-B)

wherein
Rf, X*, D*, (R.sub.a), z1 and z3 are as defined above for polymer P.sub.OH;
A.sup.II is a linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms as defined above for A or it is a group of formula (Z).sub.nE-(R.sub.a).sub.z4O-D-(CFX.sup.#).sub.z2 wherein
X.sup.#, D, (R.sub.a), z2 and z4 are as defined above for polymer P.sub.OH;
A.sup.I is a linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms as defined above for A or it is a group of formula (Z).sub.nE-(R.sub.a).sub.z4OCH.sub.2CF.sub.2 wherein
(R.sub.a) and z4 are as defined above for polymer P.sub.OH;
E is as defined above for pre-catalyst C;
n is an integer corresponding to the valence of E; and
Z independently is group Q as defined above for pre-catalyst C or a group deriving from the reaction with another polymer (P.sub.OH-PFPE), i.e. a group of formula (Z-I) or (Z-II):

A.sup.II-O(R.sub.f)(CFX*).sub.z1-D*-O(R.sub.a).sub.z3(Z-I)

A.sub.I-O(R.sub.f)CF.sub.2CH.sub.2O(Z-II)

wherein A.sub.I, A.sup.II, Rf, X*, D*, (R.sub.a), z1 and z3 are as defined above.

[0077] Preferably, Z is a group of formula (Z-I) in formula (II-A) and a group of formula (Z-II) in formula (II-B).

[0078] Preferably, step (a-ii) is performed at room temperature of under heating, for example at a temperature from about 50 C. to about 150 C.

[0079] Preferably, step (a-ii) is performed under vacuum.

[0080] Preferably, step (b) is performed by mixing together mixture (M.sub.a-1) obtained in step (a-i) and said compound (I) or by mixing together mixture (M.sub.a-2) obtained in step (a-ii) and said polymer (P.sub.OH).

[0081] Preferably, said at least one alkylene oxide is selected from those of formula (III) below:

##STR00001##

wherein R1, R2, R3 and R4, identical or different each other, are selected from hydrogen, straight or branched alkyl chain comprising from 1 to 4 carbon atoms.

[0082] Preferably, said alkylene oxide is selected from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.

[0083] According to an embodiment, step (c) is performed once by feeding one alkylene oxide.

[0084] According to an alternative embodiment, step (c) is performed by feeding two or more alkylene oxides having different formula within the same process.

[0085] In this case, step (c) can comprise the following steps:

(c-i) feeding two or more alkylene oxides at the same time, i.e. at least a first alkylene oxide and a second alkylene oxide having a chemical formula different from the first alkylene oxide are fed at the same time to the reaction environment of step (c-i), thus obtaining polymer (P.sub.ALK-OH) comprising randomly arranged recurring units deriving at least from said first and second alkylene oxide;
(c-ii) feeding a first alkylene oxide, finishing/stopping the feeding of the first alkylene oxide, feeding a second alkylene oxide having a chemical formula different from the first alkylene, finishing/stopping the feeding of the second alkylene oxide, optionally feeding a third alkylene oxide having a chemical formula different from the second alkylene oxide and repeating said steps until completion of the reaction, thus obtaining polymer (P.sub.ALK-OH) comprising recurring units deriving at least from said first and second alkylene oxide arranged in blocks.

[0086] Preferably, the amount of the alkylene oxide(s) to be fed in step (c) can be easily calculated depending on the final alkoxylation degree desired in the final polymer (P.sub.ALK-OH) and on the equivalent number of OH groups in the starting polymer (P.sub.OH).

[0087] Preferably, step (c) is performed by monitoring the consumption of the alkylene oxide(s) and/or the formation of the alkoxylated polymer. Typically, the reaction is monitored by checking the pressure of the alkylene oxide(s) within the reactor wherein step (c) is performed.

[0088] When ethylene oxide is used as the alkylene oxide, step (c) is preferably carried out by maintaining a pressure of from about 0.1 to 6 atm, preferably from about 1 to 5 atm.

[0089] According to a preferred embodiment, polymer (P.sub.ALK-OH) complies with the following formula (IV)

A.sup.IV-O(R.sub.f)(CFX*).sub.z1-D*-O(R.sub.a-IV)H (IV)

wherein
Rf, X*, D*, (R.sub.a) and z1 are as defined above for polymer P.sub.OH,
A.sup.IV is a linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms or a group of formula H(R.sub.a-IV*)O-D-(CFX.sup.#).sub.z2 wherein (R.sub.a), and z2 are as defined above for polymer P.sub.OH, and each of (R.sub.a-IV) and (R.sub.a-IV*) is independently selected from group of formula [CH.sub.2CH(J)O].sub.na*[CH(J)CH.sub.2O].sub.na#, wherein each of J is independently hydrogen atom or methyl, and each of na* and na# is independently zero or an integer from 1 to 100, with the proviso that at least one of na* and na# is in integer having a value higher than the value of na and na, respectively, in polymer (P.sub.OH).

[0090] More preferably, each of (R.sub.a-IV) and (R.sub.a-IV*) is independently selected from ethoxylated, propoxylated, butoxylated recurring units. Even more preferably, each of (R.sub.a-IV) and (R.sub.a-IV*) complies with one of the following formulae (R.sub.a-I) to (R.sub.a-III):

(CH.sub.2CH.sub.2O).sub.j1*(R.sub.a-I)

[CH.sub.2CH(CH.sub.3)O].sub.j2*(R.sub.a-II)

[(CH.sub.2CH.sub.2O).sub.j3*(CH.sub.2CH(CH.sub.3)O ).sub.j4*].sub.j(x)*(R.sub.a-III)

wherein j1*, j2*, j3*, j4* and j(x)*, each independently, is an integer higher than 2, even more preferably from 2 to 100, such that the value of each of j1*, j2*, j3*, j4* and j(x)* is higher than the value of respectivelyj1, j2, j3, j4 and j(x) in starting polymer (P.sub.OH).

[0091] According to a preferred embodiment, both (R.sub.a-IV) and (R.sub.a-IV*) are recurring units of formula (R.sub.a-I) above.

[0092] According to another preferred embodiment, (R.sub.a-IV) and (R.sub.a-IV*) each independently comprise randomly arranged recurring units complying with at least two of formulae (R.sub.a-I), (R.sub.a-II) and (R.sub.a-III).

[0093] According to still another embodiment, (R.sub.a-IV) and (R.sub.a-IV*) each independently comprise blocks of recurring units complying with at least two of formulae (R.sub.a-I), (R.sub.a-II) and (R.sub.a-III).

[0094] Polymer (P.sub.ALK-OH) is obtained at the end of step (c).

[0095] Preferably, steps (a), (b) and (c) are performed under conditions such that the conversion rate of polymer (P.sub.OH) into polymer (P.sub.ALK-OH) is of at least 90%, more preferably at least 95% and even more preferably at least 97%.

[0096] According to a preferred embodiment of the process according to the present invention, at the end of step (c), polymer (P.sub.ALK-OH) is obtained with a conversion rate higher than 98%, i.e. at least 98% of the starting polymer (P.sub.OH) is transformed into polymer (P.sub.ALK-OH).

[0097] However, embodiments wherein polymer (P.sub.ALK-OH) is obtained with a conversion rate of less than 99% are also encompassed by the present invention.

[0098] According to this embodiment, polymer (P.sub.ALK-OH) is obtained at the end of step (c) in admixture with unreacted polymer (P.sub.OH), and optionally with un-reacted product (CP.sub.OH) and/or unreacted compound (I).

[0099] Accordingly, mixture (M.sub.c) comprises at least 90% by weight, preferably at least 95% by weight and more preferably at least 97% by weight of polymer (P.sub.ALK-OH) based on the total weight of said mixture (M.sub.c), the remaining percent by weight to 100% comprising unreacted polymer (P.sub.OH) and optionally un-reacted product (CP.sub.OH) and/or unreacted compound (I).

[0100] Preferably after step (c), step (d) of contacting said mixture (M.sub.c) with a solvent in order to extract or purify polymer (P.sub.ALK-OH) is performed.

[0101] Preferably, said solvent is water or a water-alcohol mixture, preferably a mixture between water and an alcohol selected from ethanol, i-propanol and i-butanol, wherein the alcohol is in an amount of less than 10 wt. % based on the total weight of the water-alcohol mixture.

[0102] Thus, the process according to the present invention provides the great advantage that the final polymer (P.sub.ALK-OH) is easily recovered using a solvent free from the traditional organic solvents used in the processes known from the prior art. The use of water or of the water-alcohol mixture provides for environmental advantages in terms of reduction of organic solvents and wastewaters.

[0103] Preferably, after step (d), step (e) of separating the aqueous layer and the organic layer comprising the final polymer (P.sub.ALK-OH) is performed according to methods known in the art.

[0104] Preferably, after step (e), step (f) of filtering the organic layer obtained from step (e) is performed.

[0105] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0106] The invention will be illustrated in greater detail in the experimental section and non-limiting examples reported below.

Experimental Part

Materials and Methods

[0107] The following were obtained from Solvay Specialty Polymers Italy S.p.A.: [0108] Fluorolink E10H PFPE [PFPE-1] of formula HO(CH2CH2O).sub.pCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.n(CF.sub.2O).sub.mCF.sub.2CH.sub.2O(CH2CH2O).sub.pH having m/n=1.2, p=1.79, average molecular weight M.sub.n=1.765 and equivalent weight Ew=962; [0109] bi-functional PFPE diol [PFPE-2] of formula HOCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.n(CF.sub.2O).sub.mCF.sub.2CH.sub.2OH having m/n=1.2, average molecular weight M.sub.n=1.550 and equivalent weight Ew=861

[0110] The other reagents and solvents were purchased from Sigma-Aldrich and used as received.

[0111] .sup.1H-NMR, .sup.13C-NMR and .sup.19F-NMR spectra were recorded on a Agilent System 500 operating at 499.86 MHz for .sup.1H, 125.70 MHz for .sup.12C and 470.30 MHz for .sup.19F.

[0112] Inductively Coupled Plasma (ICP) analyses were carried out with a Perkin Elmer ICP-OES spectrometer, model Optima 4300 DV.

Example 1

Step 1Synthesis of Ethoxylated PFPE Diol

[0113] 2.9 kg of PFPE-1 were charged in 2 L-reactor, equipped with a mechanical stirrer, a mechanical vacuum pump and a cold trap before the pump.

[0114] 16.65 g (58.6 mmoles) of titanium(IV) propoxide was added and the resulting mixture was stirred and heated at 100 C. with an oil bath, then vacuum was applied to the reactor, keeping the pressure at about 10 mbar; all solids in the mixture disappeared and a clear solution was obtained (about 1 hour). The amount of normal propyl alcohol in the cold trap was consistent with that expected by the reaction of titanium(IV) propoxide with PFPE-1 to form the corresponding titanium ester (about 14 grams).

[0115] The obtained solution was charged into a 10 L reactor and 10.5 g dried potassium iodide were added. The resulting mixture was heated at 100 C. under stirring and stripped with a nitrogen flow to remove water traces. The temperature was raised to 140 C. and the reactor evacuated.

[0116] Ethylene oxide (EO) was fed in the reactor up to a pressure of 3.5 atm and consumption of EO was readily observed by the pressure decrease. EO was continuously fed in order to maintain the pressure between 3 and 3.5 atm.

[0117] After 1.5 hours about 368.5 g EO were fed. EO feeding was stopped and within 50 minutes the pressure inside the reactor decreased from 3.5 atm down to 1 atm. The reaction mixture was cooled, stripped with nitrogen to eliminate dissolved residual EO and about 3,250 g of the product were recovered.

Step 2Purification and Analysis of the Ethoxylated PFPE Diol

[0118] 100 g of the product obtained in Step 1 were fed on a water solution of isobutylic alcohol (8% w/w) and vigorously stirred at reflux temperature 1 hour. The lower organic layer was collected and submitted to distillation in order to remove the solvents (water, isobutanol).

[0119] The solid product was filtered by using a 0.45 m PTFE membrane in order to remove precipitated titanium dioxide and the residue that consisted of 97 g of a clear pale yellow liquid was submitted to NMR analyses.

[0120] .sup.1H-NMR (solution in A113/CD.sub.3OD) and .sup.19F-NMR analyses confirmed the following structure:

HO(CH.sub.2CH.sub.2O).sub.pCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.n(CF.sub.2O).sub.mCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH

with an average ethoxylation degree (p) of 4.6 and content of bi-functional PFPE-1 of about 0.3% (conversion exceeding 99%).

[0121] .sup.13C-NMR spectroscopy confirmed the ethoxylation degree value obtained by .sup.1H-NMR.

[0122] Inductively Coupled Plasma (ICP) analysis revealed a negligible content of titanium (5 ppm).

Example 2

Step 1Synthesis of Ethoxylated PFPE Diol

[0123] 3.8 kg of PFPE-2 were charged in 10 L-reactor and added with 60.0 g of a 30% aqueous solution of KOH (325 mmoles of KOH). The mixture was stirred and heated at 80 C. under vacuum (from 50 mbar down to 10 mbar) till complete elimination of water.

[0124] The reactor was cooled down at 60 C. Then, 46.0 g of titanium(IV) propoxide (162 mmoles) were added and the mixture was stirred for half an hour under a slight nitrogen overpressure (0.2 bar). Then vacuum was applied to the reactor and temperature was raised again at 80 C. until complete elimination of the propyl alcohol.

[0125] 17.2 g of KI dispersed in slurry with 200 g of the starting PFPE were added to the mixture and the reactor was stripped with a nitrogen flow for 15 minutes.

[0126] Temperature was raised to about 110 C. and the reactor evacuated. EO was fed up to a pressure of 3.4 atm (about 270 g) and a consumption of the ethylene oxide was readily observed by the pressure decrease. EO was continuously fed in order to maintain pressure between 3 and 3.5 atm, using an automatic pressure control.

[0127] After 1.5 hours about 310 g of EO (theoretical average ethoxylation degree p=1.69) were fed to the reactor, but then the consumption rate slowed down and after one hour no further feeding of EO was observed.

[0128] The temperature was then increased to 140 C. in about half an hour and consumption of EO was again observed. The consumption rate became faster and after about 6 hours, overall 613 g of EO (13.9 moles) (theoretical average ethoxylation degree p=3) had been fed to the reactor. The feeding was stopped and within 45 minutes the pressure inside the reactor decreased from 3.5 atm down to 1 atm. The reaction mixture was cooled, stripped with nitrogen to eliminate residual dissolved EO and about 4620 g of product were discharged from the reactor.

Step 2Purification and Analysis of the Ethoxylated PFPE Diol

[0129] A portion of the polymer obtained in Step 1 above was treated according to the procedure of Example 1 in order to have it purified from the catalyst and analyzed.

[0130] The .sup.1H-NMR (solution in A113/CD.sub.3OD) and .sup.19F-NMR analyses confirmed the following structure:

HO(CH.sub.2CH.sub.2O).sub.pCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.n(CF.sub.2O).sub.mCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH

with an average ethoxylation degree (p) of 3.1 and a content of residual ZDOL chain ends close to 1.0% (conversion 99%).