N-substituted perfluoroalkylated pyrrolidines and process...

Details N-substituted perfluoroalkylated pyrrolidines and process... N-substituted perfluoroalkylated pyrrolidines and process...

2000-10-18

2002-08-20

Ramsuer, Robert W. (Department: 1626)

Paper making and fiber liberation

Processes and products

With coating after drying

C162S158000, C162S183000, C548S400000, C548S539000, C548S524000, C548S569000

Reexamination Certificate

active

06436235

ABSTRACT:

FIELD OF INVENTION
The present invention relates to N-substituted perfluoroalkylated pyrrolidines, reaction products thereof and the use of these reaction products as specialty surfactants, as oil- and grease-proofing agents for paper, textiles and hard surfaces such as masonry and wood.
BACKGROUND OF INVENTION
Perfluoroalkylated polymers which are used for treatment of textile and paper products to impart water, oil and grease repellency are almost exclusively derived from R
F
-substituted acrylates or methacrylates, where R
F
represents a perfluorinated alkyl or alkenyl moiety. Certain R
F
-acrylamide derivatives, although described in the literature, have not found a use in the market because of their uneconomical synthesis cost. A novel R
F
-acrylamide has now been found which is easily prepared in high yield from readily available starting materials, i.e. diallylamine, an R
F
-iodide and a difunctional acryloyl derivative, preferably 3-chloropropanoic acid chloride. Reaction products of this R
F
-acrylamide have diverse uses.
U.S. Pat. No. 3,535,381 describes the synthesis of R
F
-substituted amines and (meth)acryl-amides thereof by reaction of R
F
-ethylene with a primary amine with elimination of hydrofluoric acid, followed by reaction with methacroyl chloride. The yield of R
F
-amine based on the R
F
-iodide is about 60%. U.S. Pat. No. 3,996,281 describes the synthesis of R
F
-amines and derived (meth)acrylates from R
F
-epoxides or R
F
-chlorohydrins by reaction with primary or secondary amines. The necessity of preparing an R
F
-epoxide first makes this approach very impractical. Other previously described R
F
-acrylamides are described in JP 10139747 A2, for example R
F
-ethylacrylamide synthesized from acryloyl chloride and 1,1-dihydro-heptafluorobutylamine. EP-A 177122 describes an R
F
-substituted urethane derived from acryloyl isocyanate.
U.S. Pat. No. 3,996,281 describes N,N-di-R
F
-acrylamides derived from an R
F
-epoxide, an amine and acryloyl chloride. U.S. Pat. No. 3,763,225 describes an R
F
-acrylamide derived by reaction of R
F
-iodide with a primary amine and amidification with acyloyl chloride in pyridine. JP 03261749 describes an N-R
F
-ethyl-N-allyl diacrylamide prepared from R
F
-ethyl iodide by reaction with allylamine and acryloyl chloride.
The free radical-induced addition of perfluoroalkyl iodides to N,N-diallyl derivatives and subsequent formation of pyrrolidines by ring closure is well documented. Brace, in J. Polymer Science, Part A-1, 8, 2091 (1970) describes the synthesis of 3-(perfluoroalkyl)methyl-4-methylenepyrrolidine of the formula I
by addition of R
F
-iodide to diallylcyanamide and subsequent hydrolysis; large amounts of the corresponding pyrrolidine amide are formed as a by-product. In the case of diallylamine itself, Brace (J. Org. Chem. 36, 3187 (1971)) found that the intermediate R
F
-iodide adduct formed a polymeric R
F
-amino compound by substitution; the desired R
F
-pyrrolidine amine of the formula I was not obtained.
The N-benzoyl, N-acetyl and N-trifluoroacetyl, N-carbonitrile, N-propionitrile and N-carboxamide derivatives of 3-(perfluoroalkylmethyl)4-methylenepyrrolidine are known from Brace, J. Org. Chem. 36, 3187 (1971), and maleic acid amide copolymers are known from U.S. Pat. No. 5,427,859. Each of these products however is made by reacting the N-substituted diallylamine with R
F
-iodide, and it is often almost impossible to remove the eliminated iodide salts from the final product, especially if the product is water soluble.
It is an object of the present invention to provide a convenient high yield synthesis of 3-(perfluoroalkyl)methyl4-methylenepyrrolidine. It is a further object of the present invention to provide fluorinated derivatives thereof, such as amides, ureas, ethers and urethanes, by reaction of 3-(perfluoroalkyl)methylmethylenepyrrolidine with amino-reactive compounds such as carboxylic acids, acid chlorides, anhydrides, oxiranes, isocyanates, halo-alkanes, ureas and (meth)acrylates or other vinyl compounds, which fluorinated derivatives are substantially free of iodide salts and which are useful as specialty surfactants and as oil proofing agents for paper and textiles.
It is a further object of the present invention to provide a novel monomer, 1-(meth)acryloyl-3-(perfluoroalkyl)methyl4-methylenepyrrolidine of the formula II
wherein R is hydrogen or methyl and R
F
is a perfluorinated alkyl or alkenyl moiety and a method for its synthesis from diallylamine, R
F
-iodide and a (meth)acryloyl derivative using a novel process for the addition of the R
F
-iodide to the allylic double bond.
It is a further object of the present invention to provide polymers derived from 1-(meth)acryloyl-3-(perfluoroalkyl)methyl-4-methylenepyrrolidine which are useful to impart water, oil and grease repellency to substrates such as wood, paper, textiles, metal, glass or masonry.
The inventive R
F
-(meth)acrylamides can readily be copolymerized with other vinyl monomers, such as (meth)acrylates, (meth)acrylamides, styrene or vinyl ethers or -esters. The hydrolytic stability of polymers based on tertiary acrylamides gives them a special advantage over the more commonly used (meth)acrylates, because it allows the synthesis of anionic water-dispersible polymers which need to be stable at alkaline pH.
DETAILED DISCLOSURE
The present invention relates to novel R
F
-pyrrolidines of the formula III
in which
R
F
is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
B is a direct bond, —C(═O)— or —C(═O)—N—,
q is an integer from 1 to 10 in which,
when q is 1,
Q is a monovalent organic radical with 2 to 200 carbon atoms and which can contain one or more unsaturated groups and is optionally interrupted by one or more —O— or —S— linkages or tert. amino groups, and which is unsubstituted or substituted by one or more hydroxyl, tert. amino, amide, R
F
, —P(═O)(OH)
2
, —SO
3
H or —COOH groups, or is also NH
2
if B is —C(═O)—, and, when q is greater than 1,
Q is a di- or polyvalent organic radical with 2 to 200 carbon atoms which can be interrupted by one or more —O— or —S— linkages, amide or tert. amino groups, and which is unsubstituted or substituted by one or more hydroxyl, tert. amino, amide or carboxyl groups; —C(═O)— or a di- or triradical derived from cyanuric chloride,
with the proviso that if Q is —C(═O)—, B is a direct bond,
and wherein any amino groups are optionally partially or fully salinized, quatemized or in the form of the corresponding N-oxides.
Preferably R
F
is saturated and contains 4-12 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group; most preferably R
F
is saturated and contains 6-10 fully fluorinated carbon atoms.
Preferably q is 1 or 2.
Preferred are compounds of the formula III wherein q is 1 and B-Q is —(CH
2
)
1-3
COOH; —CH
2
—C(═O)NH
2
; —C(═O)—CR═CH
2
; —C(═O)—COOH; —C(═O)—(CH
2
)
2-3
—COOH; —C(═O)—CH═CH—COOH; —C(═O)—C(═CH
2
)—CH
2
—COOH and —C(═O)—CH
2
—C(═CH
2
)—COOH; —C(═O)—(C
6
H
4
)—COOH; —C(═O)—(C
6
H
8
)—COOH; —C(═O)—(C
6
H
5
R
F
)—COOH; —C(═O)—(C
7
H
6
)—COOH; —C(═O)—(C
8
H
8
)—COOH; —C(═O)(CH
2
)
8
CH═CH
2
; —CH
2
—CHOH—CH
2
—O—CH
2
—CH═CH
2
; —C(═O)CH
3
; —CH
2
CH
2
N(CH
3
)
2
; —C—CH
2
CH
2
CH
2
N(CH
3
)
2
; —CH
2
—CH(OH)—CH
2
—N(CH
3
)
3
+
; —CH
2
—CHOH—CH
2
—O—(CH
2
CHR—O)
m
R
1
; —P(═O)(OH)
2
or —SO
3
H, in which R is hydrogen or methyl, m is a number from 1 to 20 and R
1
is hydrogen, an alkyl group with 1 to 20 carbon atoms, or a phenyl group substituted by p-octyl- or p-nonyl, or SO
3
H.
R and R
1
are preferably hydrogen. Preferably m is a number from 1 to 10.
Most preferred are compounds of the formula III wherein q is 1 and B-Q is —C(═O)—CR═CH
2
; —CH
2
—COOH; —C(═O)—(CH
2
)
2
—COOH; —C(═O)—(C
6
H
4
)—COOH; —C(═O)—(C
6
H
5
R
F
)—COOH or —C(═O)—(C
6
H
8
)—COOH wherein R is hydrogen or methyl. E

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