Copolymers containing fluorine and their use for the water-repellent and oil-repellent treatment of various substrates

• US 4,366,299 A
• Filed: 01/27/1981
• Issued: 12/28/1982
• Est. Priority Date: 02/19/1980
• Status: Expired due to Fees

• Current Assignee: P C U K Produits Chimiques Ugine Kuhlmann
• Original Assignee: P C U K Produits Chimiques Ugine Kuhlmann
• Inventors: Dessaint, Andre L.
• Primary Examiner(s): Wong, Jr., Harry
• Application Number:
  US06/228,826
• Time in Patent Office: 700 Days
• Field of Search: 526/245, 526/246, 526/243, 525/329
• US Class Current: 526/243
• CPC Class Codes: C08F 220/24 containing perhaloalkyl radicals
• CPC Class Codes: D06M 15/277 containing fluorine
• CPC Class Codes: D21H 17/37 Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
• CPC Class Codes: D21H 21/16 Sizing or water-repelling agents
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated

Abstract

The invention relates to fluorinated copolymers and their application to the waterproofing and oil-resistance treatment of various substrates. These copolymers comprise by weight:

(a) 35 to 98% of a monomer or monomers of the formula: ##STR1## in which Rf is a perfluoro radical, Q is an oxygen or sulfur atom, B is a bivalent chain linked to Q by a carbon atom, one of the symbols R is a hydrogen atom and the other a hydrogen atom or an alkyl radical:

(b) 1 to 15% of a monomer or monomers of the formula: ##STR2## in which B'"'"' is an alkylene radical, R'"'"' is a hydrogen atom or an alkyl radical, R₁ is an alkyl, hydroxyethyl or benzyl radical, R₂ is a hydrogen atom or an alkyl, hydroxyethyl or benzyl radical or R₁ and R₂, together with the nitrogen atom, form a heterocyclic radical:

(c) 1 to 50% of a monomer or monomers of the formula: ##STR3## in which R₃, R'"'"'₃, R₄ and R₅ are hydrogen atoms or alkyl radicals; and possibly

(d) up to 10% of any other monomer.

These copolymers are particularly well adapted to the waterproofing and oil-proofing of paper and similar articles.

Claims

1. A fluorinated copolymer which comprises:

(a) 35 to 98% by weight of one or more polyfluorinated monomers of the formula;

##STR17## in which Rf represents perfluoroalkyl with a straight or branched chain containing 2 to 20 carbon atoms, Q represents oxygen or sulfur, B represents a bivalent chain selected from;

##STR18## --(CH₂)_p --, --(CH₂)_p --O--(CH₂)_r --,

--(CH₂)_p --S--(CH₂)_r --,

--(CH₂)_p --(OCH₂ CH₂)_r --,

--(CH₂)_p --SO₂ --(CH₂)_r --,

--CH═

CH--(CH₂)_p --, ##STR19## --COO--(CH₂)_p -- or ##STR20## in which p is a whole number from 1 to 20, q is a whole number from 1 to 4, r is a whole number from 1 to 20, R₆ is hydrogen, alkyl containing 1 to 10 carbon atoms, cycloalkyl containing 5 to 12 carbon atoms, hydroxyalkyl containing 2 to 4 carbon atoms, aryl or aryl substituted by alkyl containing 1 to 6 carbon atoms, R₇ is hydrogen or alkyl containing 1 to 4 carbon atoms, X, X'"'"', Y and Y'"'"' are the same or different and each represents hydrogen or alkyl containing 1 to 4 carbon atoms, one of the symbols R represents hydrogen and the other hydrogen or alkyl containing 1 to 4 carbon atoms;

(b) 1 to 15% by weight of one or more monomers of the formula;

##STR21## in which B'"'"' represents linear or branched alkylene containing 1 to 4 carbon atoms, R'"'"' represents hydrogen or alkyl containing 1 to 4 carbon atoms, R₁ represents alkyl containing 1 to 18 carbon atoms, hydroxyethyl or benzyl, R₂ represents hydrogen or alkyl containing 1 to 18 carbon atoms, hydroxyethyl or benzyl or R₁ and R₂ together with the nitrogen form morpholino, piperidino or pyrrolidinyl-1;

(c) 1 to 50% by weight of one or more pyrrolidone monomers of the formula;

##STR22## in which R₃, R'"'"'₃, R₄ and R₅ are the same or different and each represents hydrogen or alkyl containing 1 to 4 carbon atoms; and

(d) up to 10% by weight of a monomer other than the monomers of formulae (I), (II) and (III), which is copolymerizable with said monomers of formulae (I), (II) and (III), and, optionally, its salt form obtained by salifying with an acid having a dissociation constant or first dissociation constant greater than 10^-5, or its form obtained by quaternizing by means of a quaternizing agent.

2. A copolymer according to claim 1 comprising 69 to 93% by weight of one or more polyfluorinated monomers of formula (I), 5 to 11% by weight of one or more monomers of formula (II), 2 to 20% by weight of one or more monomers of formula (III), and 0 to 5% by weight of another monomer.

3. A copolymer according to claim 2 comprising 7 to 10% by weight of one or more monomers of formula (II).

4. A copolymer according to claim 1, 2 or 3 in which the monomer of formula (III) is N-vinyl-2-pyrrolidone.

5. A copolymer according to claim 4 in which the polyfluoro monomer or monomers have the formula:

##STR23## in which Rf and R have the same significance as in claim 1, p represents a whole number from 1 to 20, q represents a whole number from 1 to 4, R₆ represents hydrogen or alkyl containing 1 to 10 carbon atoms, cycloalkyl containing 5 to 12 carbon atoms, hydroxyalkyl containing 2 to 4 carbon atoms, aryl or aryl substituted by alkyl containing 1 to 6 carbon atoms, X, X'"'"', Y and Y'"'"' are the same or different and each represents hydrogen or alkyl containing 1 to 4 carbon atoms.

6. A copolymer according to claim 5 obtained from a mixture of monomers of formula (IV) having different Rf radicals.

7. A copolymer according to claim 6 in which the monomer of formula (II) is dimethylaminoethyl methacrylate.

8. A copolymer according to claim 5 in which the monomer of formula (II) is dimethylaminoethyl methacrylate.

9. A copolymer according to claim 4 in which the monomer of formula (II) is dimethylaminoethyl methacrylate.