(Co) polymerization process of fluoro-containing monomers for obtaining hydrogen containing polymers

• US 6,103,843 A
• Filed: 10/29/1996
• Issued: 08/15/2000
• Est. Priority Date: 10/31/1995
• Status: Expired due to Fees

• Current Assignee: Ausimont, S.p.A.
• Original Assignee: Ausimont, S.p.A.
• Inventors: Abusleme, Julio A., Chittofrati, Alba
• Primary Examiner(s): Lipman, Fred
• Application Number:
  US08/740,406
• Time in Patent Office: 1,386 Days
• Field of Search: 526/209, 526/255
• US Class Current: 526/209
• CPC Class Codes: C08F 14/18 Monomers containing fluorine
• CPC Class Codes: Y10S 526/911 Emulsifying agents

Abstract

Polymerization process of unsaturated pefluoromonomers, fluoro-containing monomers and optionally in the presence of hydrogen containing olefins, for obtaining polymers contaning hydrogen and fluorine, which utilizes a microemulsion comprising the following components:

(a) water;

(b) a fluoropolyoxyalkylene having hydrogen-containing end groups and/or hydrogen-containing repeating units;

(c) a fluorine-free organic radicalic initiator for the polymerization of fluoro-containing monomers, soluble in component (B);

(d) a fluoro-containing surfactant.

Claims

1. A process for polymerizing unsaturated perfluoromonomers and fluoro-containing monomers, optionally in the presence of hydrogen-containing olefins for obtaining polymers containing hydrogen and fluorine, said process utilizing a previously prepared microemulsion consisting of the following components:

(a) water;

(b) a fluoropolyoxyalkylene having hydrogen-containing end groups and/or hydroqen-containing repeating units;

(c) a fluorine-free organic radicalic initiator for the polymerization of fluoro-containinq monomers, soluble in component (b), said component c) is optionally dissolved in an hydrocarbon C₁ -C₂₀, of aliphatic, cycloaliphatic, aromatic or mixtures thereof, creating a mixture, optionally the hydrocarbon can contain halogen atoms, said mixture is soluble in component b); and

(d) a fluoro-containing surfactant.

2. Polymerization process according to claim 1, wherein the fluoropolyoxyalkylenes having hydrogen-containing end groups and/or hydrogen-containing repeating units of component b) are constituted by repeating units, randomly distributed along the chain, selected from:

--CFZO--, --CF₂ CFZO--, ##STR9## where Z is H or F, R_f is CF₃, C₂ F₅, or C₃ F₇ ;

and by hydrogen-containing end groups selected from --CF₂ H, --CF₂ CF₂ H, --CFH--CF₃, and --CFH--OR_f, wherein R_f is defined as above, or perfluorinated end groups selected from --CF₃, --C₂ F₅ and --C₃ F₇, at least one of the end groups containing hydrogen, the perfluorinated end group can also contain a chlorine atom, for instance of the type CF₂ Cl, CF₃ --CFCl--CF₂, ##STR10##

3. Polymerization process according to claims 1 and 2, wherein the average molecular weight of component b) is generally comprised between 200 and 4000, and the hydrogen content of component b) is generally greater than 10 ppm.

4. Polymerization process according to claim 1, wherein fluoropolyoxyalkylenes containing hydrogen can be selected from the following classes:

wherein;

T₁ and T₂, equal to or different from each other, are hydrogen-containing groups --CF₂ H, --CFH--CF₃, or perfluorinated groups --CF₃, --C₂ F₅, --C₃ F₇, wherein at least one of the end groups contains hydrogen;

X is --F or --CF₃ ;

a, b being integers such that the molecular weight is comprised in the above range, a/b being comprised between 5 and 15;

space="preserve" listing-type="equation">T.sub.3 --O(CF.sub.2 CF.sub.2 O).sub.c (CF.sub.2 O).sub.d --T.sub.4( )

wherein;

T₃ and T₄, equal to or different from each other, are hydrogen-containing groups --CF₂ H or --CF₂ --CF₂ H, or perfluorinated groups --CF₃, --C₂ F₅ ;

wherein at least one of the end groups contains hydrogeng;

c, d being integers such that the molecular weight is comprised in the above range, c/d is comprised between 0.3 and 5;

##STR11## wherein;

T₅ and T₆, equal to or different from each other, are hydrogen-containing groups --CF₂ H, --CF₂ CF₂ H, or --CFH--CF₃, or perfluorinated groups --CF₃, --C₂ F₅, --C₃ F₇, wherein at least one of the end groups contains hydrogen;

X is --F or --CF₃ ; and

e, f, g are integers such that the molecular weight is comprised in the above range, e/(f+g) being comprised between 1 and 10, f/g being comprised between 1 and 10;

##STR12## wherein;

T₇ and T₈ are hydrogen-containing groups --CFH--CF₃, or perfluorinated groups --C₂ F₅, --C₃ F₇, wherein at least one of the end groups contains hydrogen;

h being an integer such that the molecular weight is comprised in the above range;

space="preserve" listing-type="equation">T.sub.9 --O(CZ.sub.2 CF.sub.2 CF.sub.2 O).sub.i --T.sub.10 ( e)

wherein;

Z₂ is F or H;

T₉ and T₁₀, equal to or different from each other, are groups --CF₂ H or --CF₂ --CF₂ H, or perfluorinated groups --CF₃, --C₂ F₅, --C₃ F₇₁ wherein at least one of the end groups contains hydrogen;

i being an integer such that the molecular weight is comprised in the above range;

##STR13## wherein;

R_f is --CF₃, --C₂ F₅, or --C₃ F₇ ;

T₁₁ and T₁₂, equal to or different from each other, are groups --CF₂ H, --CF₂ CF₂ H, --CFH--OR_f, or perfluorinated groups --CF₃, --C₂ F₅, --C₃ F₇, wherein at least one of the end groups contains hydrogen;

j, k, l being integers such that the molecular weight is comprised in the range indicated above, k+l and j+k+l are at least equal to 2, k/(j+l) is comprised between 10^-2 and 10³, l/j is comprised between 10^-2 and 10² ;

##STR14## wherein;

T₁₃ and T₁₄, equal to or different from each other, are hydrogen-containing groups --CF₂ H, --CFH--CF₃, or perfluorinated groups --CF₃, --C₂ F₅, --C₃ F₇, wherein at least one of the end groups contains hydrogen;

X is --F or --CF₃ ;

m, n, o, p being integers such that the molecular weight is comprised in the range indicated above, m/n is comprised between 5 and 40, m/(o+p) is comprised between 2 and 50, o+p is at least 3, o is lower than p;

space="preserve" listing-type="equation">T.sub.15,--O(CF.sub.2 CF.sub.2 O).sub.q (CF.sub.2 O).sub.r (CFHO).sub.s (CF.sub.2 CFHO).sub.t --T.sub.16 ( h)

wherein;

T₁₅ and T₁₆, equal to or different from each other, are hydrogen-containing groups --CF₂ H, --CF₂ --CF₂ H, or perfluorinated groups --CF₃, --C₂ F₅, wherein at least one of the end groups contains hydrogen;

q, r, s, t are integers such that the molecular weight is comprised in the range indicated above, q/r is comprised between 0.5 and 2, (q+r)/(s+t) is comprised between 3 and 40, s+t is at least 3, s is lower than t;

##STR15## wherein;

T₁₇ and T₁₈, equal or different from each other, are hydrogen-containing groups --CF₂ H, --CF₂ CF₂ H, --CFH--CF₃, or perfluorinated groups --CF₃, --C₂ F₅, --C₃ F₇, wherein at least one of the end groups contains hydrogen;

X is --F or --CF₃ ;

u, v, w, x, y are integers such that the molecular weight is comprised in the range indicated above, (u+v)/w is comprised between 5 and 40, (u+v)/(x+y) is comprised between 2 and 50, x+y is at least 3, x is lower than y.

5. Polymerization process according to claim 1, wherein component c) is selected from alkylperoxides, alkylperoxydicarbonates.

6. Polymerization process according to claim 5, wherein the solvent for the peroxide is a branched hydrocarbon with C₆ -C₁₄ carbon atoms, with a ratio between number of methyl groups and number of carbon atoms higher than 0.5.

7. Polymerization process according to claim 1, wherein component d) is of both ionic and non-ionic type.

8. Polymerization process according to claim 7, wherein the fluoro-containing surfactant is selected from the anionic ones of formula:

space="preserve" listing-type="equation">R.sub.fb --(CH.sub.2)n.sub.b --X.sup.- M.sup.+

wherein;

n_b is an integer from 0 to 6;

R_fb is a (per)fluoroalkylic chain C₅ -C₁₆ or a (per)fluoropolyoxyalkylenic chain as defined above, X^- is --COO^- or --SO₃^-, M⁺ is selected from;

H⁺, NH₄⁺, alkali metal ion, the R_fb chain can contain one or more anionic groups described above and the end group R_fb can contain chlorine atoms.

9. Polymerization process according to claim 1, wherein the amount of radicalic initiator component c) in the microemulsion is comprised between 0.003% and 5% by weight with respect to the total amount of (co)polymerized monomers.