Process for fluorinating cellulosic materials and...

Details Process for fluorinating cellulosic materials and... Process for fluorinating cellulosic materials and...

1998-09-29

2001-09-25

Kopec, Mark (Department: 1751)

Bleaching and dyeing; fluid treatment and chemical modification

Chemical modification of textiles or fibers or products thereof

Cellulose fibers

C008S115680, C162S009000, C162S158000, C106S164010, C106S287280, C536S056000, C536S057000, C536S058000, C536S072000, C536S075000

Reexamination Certificate

active

06293972

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a method for fluorinating cellulosic material, and a fluorinated cellulosic material.
RELATED ART
A method of obtaining a fluorine-containing cellulose derivative by using a solvent-soluble cellulose derivative has been known (cf. Japanese Patent Kokai Publication No. 171702/1986). This method can not be applied for treating normal wood, cotton cloth, paper and the like. Furthermore, it is not practical because of difficulty in removing HF as by-products generated during the reaction. It has also been known that cellulose is directly reacted with a fluorine-containing compound such as trifluoroacetic acid to obtain a cellulose derivative (cf. Cellulose Chemistry and Technology, 16(6), 615, (1982)). However, according to this reaction, the performance expected by induction of fluorine is not sufficiently exhibited, although a derivative having high substitution degree is obtained.
Wood is a typical lignocellulose material. As the method of imparting water repellency to the wood to enhance the stain proof property, for example, a method of impregnating wood with a fluorine-containing monomer such as heptadecafluoro-decyl acrylate and heating the wood to polymerize the monomer (cf. Japanese Patent Kokai Publication No. 86972/1986), and a method of impregnating wood with a compound having a highly fluorine-containing organic group and heating the wood (cf. Japanese Patent Kokai Publication No. 120705/1986) have been known. However, in any case, since the fluorine-containing compound is expensive and uneconomical and is also a polymer, only the surface of wood is modified and internal modification is not achieved. On the other hand, a method such as a method for surface treatment using a fluorine-containing gas plasma such as tetrafluoromethane (cf. Japanese Mokuzai Gakkai-Shi, Vol. 38, No. 1, pp.73-80, January 1992) has also known. According to this method, the internal modification was slightly achieved, but the fluorine content is poor and the treatment efficiency is inferior.
Also, with respect to cotton cloth, paper or the like as typical cellulose and/or lignocellulose materials, there has well been known an attempt to modify the surface by applying a water- and oil-repellency agent of a polymer of a compound such as acrylate or methacrylate ester having a perfluoroalkyl group, or a copolymer of the above compound and other polymerizable compound such as acrylate ester, maleic anhydride, chloroprene, butadiene, methyl vinyl ketone on the surface of cotton cloth, paper or the like is well known, but internal modification has stilled to be accomplished.
SUMMARY OF THE INVENTION
An object of the present invention is to modify not only the surface but also the inside of cellulose and/or lignocellulose materials, thereby realizing high performance of cellulose and/or lignocellulose materials.
The present invention provides a method for fluorinating a cellulosic material, which comprises reacting the cellulosic material selected from the group consisting of a cellulose material and a lignocellulose material with at least one fluorine-containing compound selected from the group consisting of a fluorine-containing olefin compound, a fluorine-containing acrylate compound and a fluorine-containing methacrylate compound in an organic solvent in the presence of a catalyst.
The present invention also provides a fluorinated cellulosic material obtained by said method for fluorination.
DETAILED DESCRIPTION OF THE INVENTION
The reaction between the cellulose material and/or lignocellulose materials and the fluorine-containing compound is preferably an ionic reaction. In general, an OH group of the cellulose material or lignocellulose material reacts with the fluorine-containing compound. A fluorocarbon group (R
f
group or R
f
′ group in the formulas described hereinafter) is introduced into the cellulosic material by the reaction.
Examples of the cellulose material mainly include natural cellulose such as cotton and hemp; regenerated cellulose such as viscose rayon and cuprammonium rayon. Additional examples of the cellulose material include an ester of an acid having 1 to 20 carbon atoms, such as cellulose acetate and cellulose butyrate; an alkyl ether which may have a substituent having 1 to 6 carbon atoms, such as methyl cellulose, ethyl cellulose and hydroxypropyl cellulose; a cellulose derivative such as nitrocellulose, which is cheap and easily available.
Examples of lignocellulose material mainly include wood, pulp and paper, and any material can be used as a raw material regardless of shape and species of tree.
As the form of wood for the raw material, a wood plate, a thin wood sheet, a lumber, a cylindrical material, a block material, a plywood obtained by processing them, a laminated veneers, a fibrous board, a fibrous mat, a thinning board (wood chip) and a wood flour (particle) can be used.
As the pulp for the raw material, any of mechanical pulp, chemical pulp and semi-chemical pulp can be used. The chemical pulp may be bleached or unbleached one. The shape of the pulp may any shape such as chip, flake, sheet, pulp molding and block, and is not specifically limited.
The paper can also be treated in the shape of a sheet. A cotton-mixed fabric (a woven fabric and a non-woven fabric) or clothing can be used as a raw material of other cellulose material and/or lignocellulose material
An organic solvent is preferably an aprotic polar organic solvent. Examples of the organic solvent include acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphoamide, monoglyme, diglyme, triglyme and tetraglyme. Acetonitrile, dimethylformamide and dimethyl sulfoxide are particularly preferable. The amount of the organic solvent may be from 1 to 500 times, e.g. 5 to 200 times the weight of the cellulosic material.
A catalyst is preferably a basic catalyst, particularly a catalyst having no nucleophilicity. An electrophilic catalyst is preferable. The catalyst is preferably a fluoride salt of an alkali metal or alkaline earth metal. Among them, KF, NaF and CsF are exemplified in view of no decomposition and coloring of the cellulose and/or lignocellulose materials. It is particularly preferred to use KF. The catalyst is preferably a dried catalyst having high activity. The amount of the catalyst is preferably from 0.5 to 20 equivalents, particularly from 1 to 5 equivalents, based on 1 equivalent of the —OH group of the cellulose material and/or lignocellulose material.
The fluorine-containing olefin compound includes R
f
CF═CF
2
, R
f
CF═CC1F, R
f
CF═CH
2
, R
f
CH═CH
2
, R
f2
C═CF
2
and R
f2
C═CH
2
and the fluorine-containing acrylate compound includes R
f
OCOCH═CH
2
and, furthermore, the fluorine-containing methacrylate compound includes R
f
OCOC(CH
3
)═CH
2
wherein R
f
is F, Cl, a C
1-30
polyfluoroalkyl group, a C
1-30
polyfluoroalkenyl group, a C
1-30
polyfluoroalkoxy group, or a C
2-300
polyfluoropolyether group.
R
f
may be, for example, a perfluoroalkyl group, a perfluoroalkenyl group, a perfluoroalkoxy group or a perfluoropolyether group.
Specific examples of R
f
include the followings:
F—,
Cl—,
CF
3
—,
(CF
3
)
2
CF(CF
2
CF
2
)
x
—,
CF
3
CF
2
(CF
2
CF
2
)
x
—,
CF
3
O—,
(CF
3
)
2
CF(CF
2
CF
2
)
x
O—,
CF
3
CF
2
(CF
2
CF
2
)
x
O—,
H(CF
2
CF
2
)
y
CH
2
O—
wherein x is an integer of 0 to 10, and y is an integer of 1 to 10,
(CF
3
)
2
CF(CF
2
CF
2
)
m
CH
2
CH
2
OCH
2
CH(OH)CH
2
—,
CF
3
CF
2
(CF
2
CF
2
)
m
CH
2
CH
2
OCH
2
CH(OH)CH
2
—,
H(CF
2
CF
2
)
1
CH
2
CH
2
OCH
2
CH(OH)CH
2
—,
(CF
3
)
2
CF(CF
2
CF
2
)
m
CH
2
CH(OH)CH
2
—,
CF
3
CF
2
(CF
2
CF
2
)
m
CH
2
CH(OH)CH
2
—,
(CF
3
)
2
CF(CF
2
CF
2
)
m
CH
2
CH
2
—,
CF
3
CF
2
(CF
2
CF
2
)
m
CH
2
CH
2
—,
H(CF
2
CF
2
)
1
CH
2
—
wherein m is an integer of 0 to 10, and 1 is an integer of 1 to 10,
(CF
3
)
2
CF(CF
2
CF
2
)
m
CH
2
CH
2
OCH
2
CH(OH)CH
2
O—,
CF
3
CF
2
(CF
2
CF
2
)
m
CH
2
CH
2
OCH
2
CH(OH)CH
2
O—,
H (CF
2
CF
2
)
1
CH
2
CH
2
OCH
2
CH(OH)CH
2
O—,
(CF
3
)
2
CF(CF
2
CF
2
)
m
CH
2
CH(OH)CH
2
O—,
CF
3
CF
2
(CF

Affiliated with

Also associated with

Rating

Process for fluorinating cellulosic materials and... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for fluorinating cellulosic materials and..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for fluorinating cellulosic materials and... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2479039