Chromophoric-moiety-containing, polymeric materials, containing at least one fluoroaliphatic radical, which are useful as dyes or colorants for fluorine-containing liquids, as coatings or components of coatings which are colored, light-absorbing, or fluorescing and characteristic properties of fluorocarbon polymers, e.g. chemical inertness and hydrophobicity; and a method of detecting leaks in normally sealed devices, e.g. electronic devices, using a coating which includes the polymeric material, and a bath of a fluorine-containing liquid in which the coating is soluble.

This invention relates to fluorine-containing polymers. In another aspect, 
it relates to the method of preparing such polymers. In a further aspect 
it relates to a method of dyeing fluorine-containing liquids. In still a 
further aspect, it relates to a method of making selectively soluble or 
chemically inert coatings of fluorine-containing polymers. In still a 
further aspect, it relates to a method of detecting leaks in normally 
sealed, fluid-containing devices such as electronic devices. 
Self-colored, polymeric compounds have been described in the art. In 
Asquith et al., Self-Coloured Polymers Based on Anthraquinone Residues, 
Journal of the Society of Dyers and Colourists, April 1977, 114, the 
author classifies these compounds into categories according to their 
method of synthesis. The categories include polymers formed by 
modification of an already synthesized polymer, polymers formed by 
addition polymerization of dye monomers through olefinic links in which 
subsequent polymers are generally straight chain or crosslinked structures 
with chromophore-containing, side-chain groupings, and condensation 
polymerization usually based on a polyamide or polyester structure in 
which the chromophore-containing monomer acts as the polyfunctional acid, 
base, or alcohol. The condensation polymers generally contain the 
chromophore as an integral part of the main chain. 
U.S. Pat. No. 4,619,990 (Elmasry) describeds a number of polymeric dyes 
known in the art and their uses, including dyes with polymeric backbones 
of polyester, polyurethane, polyamide, and vinyl polymers with pendent 
phthalocyanine chromophores, and polymeric dyes derived from acrylate or 
methacrylate monomers with pendent azo, anthraquinone, or triarylmethane 
dye moieties. Disclosed in Elmasry are thermoplastic, polymeric dyes 
derived from condensation polymerization or copolymerization of 
ethylenically unsaturated monomers, with pendent chromophore groups 
selected from azo, tricyanovinyl, anthraquinone, methine, and indoaniline 
groups. Various other polymeric dyes are disclosed in the art, see U.K. 
Pat. No. 1,036,700 (Tadao) homopolymeric pigments containing anthraquinone 
groups polymerized through ethylenically unsaturated olefinic, e.g. 
acrylate, linkages, U.S. Pat. No. 3,567,678 (Kalopissis) water soluble 
polymer with an acrylate or methylacrlate backbone, U.S. Pat. No. 
3,503,087 (Wolf) water-soluble copolymers consisting of ethylenically 
unsaturated azo or anthraquinone dye monomers and a water-soluble 
monomers, U.S. Pat. No. 2,371,052 (Kirby) azo polymeric dyes that are 
condensation products, where said condensation product is dispersed in a 
cellulose derivative and treated with a diazonium compound to produce an 
azo dye in the cellulosic material. 
The art also teaches the preparation of non-polymeric dyes with 
fluorine-containing substituents. U.S. Pat. No. 3,281,426 (Tiers) 
discloses a process of perfluoroalkylating aromatic compounds whereby one 
or more perfluoroalkyl chains become attached to an aromatic nucleus. Said 
process produces compounds which are soluble in some fluorinated solvents 
forming strongly blue solutions. U.S. Pat. No. 3,933,914 (Coles) discloses 
non-polymeric, organic dyes having fluoroaliphatic substituents. U.S. Pat. 
No. 4,585,460 (Schwander) discloses a bis-vinyl or substituted ethyl 
sulphenyl azo reactive dye. The dye may have substituents on its aromatic 
nucleus such as fluorine, or a C.sub.1 -C.sub.4 alkyl or alkoxy straight 
chain or branched radical which may be further substituted by halogen, and 
alkyl or alkyoxy straight chain or branched groups which may be further 
substituted with fluorine. The dye also has a radical of a coupling 
component, attached through an azo group, which may have substitutients as 
given above. There have also been a number of disclosures of non-polymeric 
dyes with F or CF.sub.3 substitutents, see U.S. Pat. No. 4,544,738 
(Baumann), U.S. Pat. No. 4,548,613 (Bode), U.S. Pat. No. 4,560,744 
(Baumann), U.S. Pat. No. 4,582,509 (Buhler). 
This invention provides a new class of normally solid, fluorine-containing 
polymers which are inherently colored, light absorbing, or fluorescing and 
are preferably insoluble, at 20.degree. C., in water and common, 
non-fluorinated, organic solvents, e.g. toluene and acetone, and generally 
soluble, at 20.degree. C., in fluorinated liquids, e.g. 
1,1,2-trichloro-2,2,1-trifluoroethane sold as Freon.RTM. 113 or 
perfluorochemical liquids or mixtures of such liquids like 
perfluoroalkanes, e.g. perfluorooctane; perfluorotrialkylamines, e.g. 
perfluorotributylamine; perfluorodialkylether, e.g. perfluorodibutylether. 
Many of such liquids are commercially available such as Fluorinert.RTM. 
Electronic Fluids from 3M Company, Freon.RTM. E Series from DuPont De 
Nemours and Co., Flutec PP Series from ISC, Ltd., and Galden.TM. 
Perfluorinated Fluid from Montedison S.P.A. 
One class of the polymers of this invention are colored, light-absorbing, 
or fluorescing polymers which contain fluorine in the form of 
fluoroaliphatic radicals and comprise interpolymerized repeating units 
derived from: (A) partially- or non-fluorinated, 
non-chromophoric-moiety-containing monomer(s) and (B) partially- or 
non-fluorinated chromophoric-moiety-containing co-monomer(s), at least one 
of monomers (A) and (B) containing said fluoroaliphatic radicals. Said 
chromophoric moiety is a group of atoms that absorbs actinic radiation, 
such as visible light and ultra-violet radiation, and provides a colored, 
fluorescing or light absorbing molecule. The momomers (A) and (B) can be 
co-polymerized through chain-growth (i.e. addition) or step-growth (e.g. 
condensation) reactions, but a preferred class of polymers are made by 
chain-growth polymerizations. Step-growth monomers contain at least one, 
but preferably two, polymerizable groups such as hydroxyl, carboxyl, 
haloformic, isocyanato, and amino groups. Chain-growth monomers must have 
at least one, and preferably only one, ethylenically-unsaturated, 
polymerizable group such as acrylic, methacrylic, acrylamido, vinyl or 
allyl groups. 
Another class of polymers of this invention are fluorine-containing, 
colored, light-absorbing or fluorescing, graft polymers which contain 
fluorine in the form of fluoroaliphatic radicals and are comprised of (1) 
a polymeric backbone comprising interpolymerized repeating units derived 
from partially- or non-fluorinated, non-chromophoric-moiety-containing 
monomer(s) containing at least one polymerizable group, e.g. vinyl, at 
least one of which monomer(s) contains a reactive group which can be 
selected from hydroxyl, carboxyl, haloformic, isocyanato, amino, acrylic, 
methacrylic, vinyl and allyl groups, and (2) at least one pendent group on 
the polymer backbone, which is derived from partially- or non-fluorinated, 
chromophoric-moiety-containing, pendent-group-precursor compounds 
containing at least one reactive group which can be selected from the same 
class described for said monomer(s) from which the polymeric backbone is 
derived. The reactive group(s) on the polymer backbone will react with 
selected reactive group(s) on the pendent-group-precursor compound(s) to 
form linkages such as carbamato, ester, amide and carbon-carbon linkages, 
but the reactive groups on the monomers from which the polymeric backbone 
is derived and the pendent-group-precursor compound(s) must not react with 
the polymerizable groups on the monomers from which the backbone is 
derived that react in the polymerization reaction which forms the 
backbone. 
At least one monomer used in making the chain-growth and step-growth 
polymers, and at least one pendent group of the graft polymer or monomer 
making up the polymeric backbone of the graft polymer, contains a 
fluoroaliphatic radical, but preferably a plurality of fluoroaliphatic 
groups will be incorporated in the polymer and all or substantially all of 
the fluorine content of the polymer will reside in the plurality of 
fluoroaliphatic radicals incorporated into the polymer. The 
fluoroaliphatic radical is a fluorinated, stable, inert, non-polar, 
preferably saturated, monovalent or divalent moiety which is both 
oleophobic and hydrophobic. It can be straight chain, branched chain, and 
if sufficiently large, cyclic, or combinations thereof, such as 
alkylcycloaliphatic radicals. The skeletal chain can include catenary 
oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms, 
such hetero atoms providing stable linkages between fluorocarbon portions 
of the radical and not interfering with the inert character of the 
radical. The R.sub.f group can be a CF.sub.3 - group, but preferably it is 
larger and its terminal portion has at least three fully fluorinated 
carbon atoms, e.g., CF.sub.3 CF.sub.2 CF.sub.2 -, or (CF.sub.3).sub.2 CF- 
and the preferred compounds are those in which the R.sub.f group is fully 
or substantially completely fluorinated as in the case where R.sub.f is 
perfluoroalkyl, C.sub.n F.sub.2n+1. While the radical can have a large 
number of carbon atoms, generally the radical will have between 1 and 20 
carbon atoms, and 4 to 10 carbon atoms are preferred. The radicals can 
contain about 40 to 83 weight percent, but preferably about 50 to 78 
weight percent, fluorine. 
In the interest of brevity, said monomer(s) (A), and co-monomer(s) (B) are 
respectively referred to, hereinafter on occasion as "non-dye monomers" 
and "dye monomers". The amount of dye and non-dye monomer(s) used to make 
the step-growth and chain-growth polymers, and the amounts of polymeric 
backbone and pendent groups comprising the graft polymer can vary 
depending on the intensity of color, light absorption or fluorescing 
properties desired in the polymer, but generally the non-dye monomer(s) or 
polymeric backbone is a major component of the polymer. Preferably, in the 
case of step-growth and chain-growth polymers, such polymers can be 
prepared by polymerizing 90 to 99.9 percent of non-dye monomer(s) with 10 
to 0.1 percent of dye monomer(s) on the basis of total monomer weight. In 
the case of graft polymers, such polymers can be prepared by reacting 90 
to 99.9 percent of polymeric backbone, via its reactive groups, with 10 to 
0.1 percent pendent-group-precursor compound(s) on the basis of total 
backbone and pendent group weight. 
Some of the polymers of this invention are useful as colored, light 
absorbing, or fluorescing additives or colorants to impart color, light 
absorbing or fluorescing properties to fluorine-containing, normally 
colorless liquid such as perfluorochemical liquids or mixtures of such 
liquids. Dissolving the polymer in the liquid imparts color, or changes 
the light absorbing or fluorescing properties, of said fluorinated 
liquids, aiding in visually distinguishing one liquid from another. 
Generally, these polymers will be more soluble in the liquid if all or 
substantially all of their fluorine content resides in fluoroaliphatic 
radicals incorporated into the polymer and if the polarity of the polymer 
is similar to that of the liquids into which it is dissolved. Preferably, 
the fluorine content of the polymer will be about 40 to 70% based on total 
polymer weight. The polymers can also aid detection of leaks of 
fluorinated liquids from normally sealed devices, used for the purpose of 
heat transfer. Where used in the detection of leaks in heating and cooling 
equipment, a solution of the polymer in the fluorine-containing, heat 
transfer liquid is substituted for normally colorless, heat-transfer 
liquid, thereby making detection of the leaking liquid easier. The 
polymers can enhance detection of leaks into normally sealed systems, such 
as semiconductors, or other hermetically sealed electronic devices, using 
procedures like those described in MIL-STD-883C, Method 1014.8 or 
MIL-STD-750A, Method 1071. Where used in the detection of leaks in 
normally sealed systems, the polymer can be dissolved in one of the 
fluorochemical liquids specified in MIL-STD-883C, Method 1014,8, 
"Fluorocarbon Gross Leak Test", or MIL-STD-750A, Method 1071, 
"Fluorocarbon Gross Leak Test", and the procedure is carried out according 
to the steps specified. The polymer imparts color to or changes the light 
absorption or fluorescing properties of the bath described in such 
procedure, making bubbles escaping from the device into the bath easier to 
detect. 
This invention also provides a new method of electronic device leak 
testing, in which some portion of the surfaces of the internal cavity of a 
normally sealed device are coated with a film containing at least one of 
the chromophore-containing polymers and said coating is soluble in a 
fluorine-containing liquid or mixture of liquids such as those described 
above. Preferably, the coating is comprised of a film-forming 
chromophoric-moiety-containing polymer. However, it can be comprised of a 
mixture of one or more chromophoric-moiety-containing polymer(s) and one 
or more, non-chromophoric-moiety-containing, film-forming polymers which 
are compatible; that is, the polymer must remain intimately mixed with the 
other polymer(s) comprising the mixture without macrophase separation when 
the mixture is in the solid state. The compatibility of a mixture of 
polymers is generally determined by trial and error, however, polar 
polymers, i.e. those containing a plurality of polar moieties such as 
oxygen atoms, will be more compatible with other polar polymers, e.g. 
polyester. Non-polar polymers, e.g. those which are predominantly 
hydrocarbon, will generally be more compatible with other non-polar 
polymers, e.g. vinyl polymers. Where the coating is comprised of a mixture 
of polymers, the amounts of each polymer in the mixture can vary widely 
depending upon the color-imparting or tinctorial strength of the 
chromophoric-moiety-containing polymer(s), the color, light absorption or 
fluorescing properties of the coating required, and any effect the 
chromophoric-moiety-containing polymer(s) may have on reducing the film 
forming properties of the mixture. In general, the major component of the 
mixture would be comprised of non-chromophoric-moiety-containing 
polymer(s), and preferably, chromophoric-moiety-containing polymer(s) can 
be present at levels of about 0.1-20% based on total mixture weight. The 
coating can be applied to the surfaces of the normally sealed device from 
solvent solution by known methods such as spraying, brushing, wire 
coating, knife coating, curtain coating or gravure coating. The device can 
then be immersed in a colorless liquid bath comprised of 
fluorine-containing liquid or a mixture of such liquids, the bath and 
device may be subjected to the pressurization step described in the 
fluorocarbon gross leak tests cited above, and the bath is monitored for a 
change in color, light absorption properties or fluorescing properties 
caused by the coating dissolving in the liquid that has leaked into the 
devices' internal cavity, and the subsequent migration of the dissolved, 
chromophoric-moiety-containing polymer from the internal cavity back into 
the bath. A change in the bath color, light absorption or fluorescing 
properties indicates a defective device. 
Some of the polymers of this invention are also useful as colored, light 
absorbing or fluorescing coatings or components of such coatings, that 
provide the characteristic properties of fluoropolymer coatings, e.g. 
chemical inertness, electrical non-conductivity, hydrophobicity, 
oleophobicity, and repellency to silicone oils. Preferably, the coatings 
are comprised of a film-forming, chromophoric-moiety-containing polymer, 
however, the coatings may be comprised of a mixture of one or more 
chromophoric-moiety-containing polymer(s) and one or more compatible, 
film-forming, non-chromophoric-moiety-containing polymer(s). Where the 
coating is comprised of a mixture of polymers, the amounts of each polymer 
in the mixture can vary widely depending upon the desired coating color, 
fluorescing or light absorption properties, the film-forming properties of 
the mixture of polymers comprising the coating, and other desired coating 
physical properties, e.g. chemical inertness. In general, the major 
component of the mixture is comprised of 
non-chromophoric-moiety-containing polymer(s). Preferably, the 
chromophoric-moiety-containing polymer or polymers can be present at 
levels of about 0.1-20% based on total mixture weight, and the fluorine 
content of the coating should be at least about 30%. Some examples of such 
coatings are UV-absorbing, protective coatings for billboards, oil 
repellent, fluorescing, antimigration coatings for the inside of 
oil-filled devices, e.g. rocket gyroscopes, to prevent oil leakage from 
the device and allow visual inspection of the coated surface to ensure it 
is covered with the coating, electrically non-conducting, chemically 
inert, protective, copolymer coatings for electronic devices like circuit 
boards, release coatings, and selectively soluble coatings used as 
selectively soluble photo resists for imaging systems and electronic chip 
etching. 
The invention permits the adjustment of color, color intensity, and light 
absorbing or fluorescing properties of the polymer by controlling the 
selection and amount of the polymerizable dye monomer(s), or 
pendent-group-precursor compound(s) incorporated in the polymer. The use 
of the polymers of this invention as a photo resist in the production of 
electronic chips offers advantages over currently used photo resists, for 
example, the non-wetting character of coatings made from the polymers may 
provide sharper, clearer painted patterns on the chip substrate, and the 
solvents used to wash the coating off the chip substrate are generally 
less toxic and less flammable than currently used solvents. 
Some of the polymers of this invention can be made by step-growth or 
chain-growth polymerization reactions, others by graft polymerization, but 
a preferred class of polymers are made by chain-growth reactions. 
Step-growth polymers can be derived from mono- or di-functional, or 
mixtures of mono- and di-functional, non-dye monomer(s), and mono- or 
di-functional, or mixtures of mono- and di-functional, dye monomer(s). 
Mono- and di-functional monomers have, respectively, one or two 
polymerizable groups, that can be selected from hydroxyl, carboxyl, 
haloformic, isocyanato, or amino groups. Preferably, dye and non-dye 
monomer(s) are difunctional and the polymerizable groups on all dye 
monomer(s) are capable of polymerizing through step-growth polymerization 
reactions with the polymerizable groups on all non-dye monomers. Examples 
of step-growth polymers are polymers derived from non-dye monomer(s) 
selected from diacid, dihaloformate, diisocyanate, and diacid halide 
non-dye monomers, and dye monomer(s) selected from diol and diamino 
monomers. An example of a graft polymer is one in which the polymeric 
backbone is derived from monomers with polymerizable acrylic groups, and 
at least one of the monomers incorporated in the backbone has a reactive 
group, e.g. hydroxyl, which will not participate in the polymerization 
reaction, but will react with the reactive group on the 
pendent-group-precursor compound, e.g. isocyanato. The 
pendent-group-precursor compound must not contain any group, including its 
reactive group, that will react with the polymerizable groups on the 
monomer(s) comprising the polymeric backbone. Chain-growth polymers may be 
derived from dye and non-dye monomer(s) with ethylenically unsaturated, 
polymerizable groups, such as acrylic, methacrylic, acrylamido, vinyl, or 
allyl. Said groups on dye and non-dye monomer(s) need not be identical, 
and said monomer(s) can have one or more ethylenically unsaturated 
polymerizable group(s) which need not be identical. However preferably, 
each monomer will have only one polymerizable group. Some chain-growth 
polymers will be comprised of interpolymerized units having the general 
formulas I and II given below: 
##STR1## 
Wherein R and R' are H or CH.sub.3, and Q and Q' are linking groups. Q' 
can be a valence bond, for example, where a carbon atom of the 
chromophoric-moiety is bonded or linked directly to the oxygen moiety. Q 
can also be a valence bond as long as the fluoroaliphatic radical is 
bonded to the oxygen moiety through a --CHR" group where R" is H or alkyl. 
Q and Q' each can also comprise one or more linking groups such as 
polyvalent aliphatic moieties, e.g. --CH.sub.2 CH.sub.2 -- and --CH.sub.2 
CH(CH.sub.2 --).sub.2, polyvalent aromatic moieties, e.g. 
##STR2## 
oxy, thio, carboxyl, sulfone, sulfoxy, phosphoxy, --P(O)OH--, amine, e.g. 
--NH-- and --N(C.sub.2 H.sub.5)--, or combinations thereof, such as 
oxyalkylene, iminoalkylene, iminoarylene, sulfonamido, carbonamido, 
sulfonamido alkylene, carbonamido alkylene, carbamato. R.sub.f is a 
fluoroaliphatic group, n is 1. All type I units incorporated in the 
polymer need not have the same R, R" or R.sub.f groups. R.sub.c is an 
organic radical containing a chromophoric moiety and m is a number greater 
than or equal to 1. All type II units in the polymer need not have the 
same R.sub.c or R' groups, but preferably, all R.sub.c groups will be the 
same and m will be equal to 1. Type I and II units may be randomly 
distributed in the polymer. A preferred class of polymers derived from 
monomers yielding interpolymerized units having general formulas (I) and 
(II) can be prepared by the chain-growth polymerization of highly 
fluorinated acrylates and non- or partially-fluorinated, dye acrylates or 
acrylamides, and optionally, small amounts of other non-dye monomers, such 
as alkyl acrylates, acrylic acid, vinyl chloride, vinylidene chloride and 
the like. The molar ratio of dye to non-dye monomer(s) can depend on the 
intensity of light absorption desired in the final polymer, and on the 
solubility of the monomers in the reaction solvents (e.g. Freon.RTM. 113, 
2,3,3-trichloroheptafluorobutane, or combinations of these solvents with 
non-fluorinated solvents such as ethyl acetate). 
Dye monomers and pendent groups used in the invention can be inherently 
light-absorbing, colored, fluorescent or UV-absorbing and may be 
partially- or non-fluorinated. Said monomers and pendent groups must have 
one or more chromophoric moieties of the same or different type, but 
preferably, only one chromophoric moiety is contained in each monomer or 
pendent group. Said chromophoric moieties can be selected from the 
following types as described in D. W. Bannister, A. D. Olin, H. A. Stinge, 
"Dyes and Dye Intermediates", Kirk-Othmer Encyclopedia of Chemical 
Technology 3rd Ed., 8, 159-212 (1979): 
##STR3## 
where X is O or N, 
##STR4## 
where X is O or N, moieties with C.dbd.N--OH ortho to C.dbd.O, 
##STR5## 
moieties containing an aromatic ring with a nitro group ortho or para to 
an amino, hydroxyl or ether group, 
##STR6## 
moieties containing a tetrabenzoporphyrazine group, moieties with a 
C.dbd.C--OH group and a C.dbd.C--C.dbd.O group, 
##STR7## 
and moieties with both 
##STR8## 
group and 
##STR9## 
group. 
The selection of chromophoric moiety or moieties can determine the color or 
light absorbing or fluorescing properties of the polymer. The dye 
monomer(s) for step-growth polymers may be mono- or di-functional, with 
polymerizable groups that will react with polymerizable groups on at least 
one of the non-dye monomer(s) or other dye monomer(s), where mixtures of 
dye monomers are used to derive the polymer, to form linkages through 
step-growth polymerization reactions. Preferably, said dye monomer(s) will 
be difunctional and said polymerizable groups will be identical, e.g. 
dihydroxyl or dicarboxyl. The dye monomer(s) for chain-growth polymers 
must have at least one ethylenically unsaturated, polymerizable group, and 
only one such group is preferred, but they may have more than one 
ethylenically unsaturated group and said groups need not be identical. 
Said groups can polymerize with ethylenically unsaturated groups on 
non-dye monomer(s) or dye monomer(s) to form linkages between said 
monomers through chain-growth polymerization reactions. Preferably, all 
polymerizable groups on dye monomer(s) will be terminal groups. The 
pendent-group-precursor compound used to prepare graft polymers will have 
at least one reactive group chosen, for example, from hydroxyl, carboxyl, 
haloformic, isocyanato, amino, acrylic, methacrylic, acrylamido, vinyl, or 
allyl, and this group will not react with polymerizable groups on the 
non-dye monomers making up the polymeric backbone. 
Commercially available dyes like Disperse Red 17 (color index No. 11210), a 
diol, available from Crompton and Knowles Corporation, can be used as a 
dye monomer in step-growth polymerization reactions. A preferred class of 
dye monomers used in chain-growth polymerization reactions can be prepared 
from dyes containing hydroxy or amino groups, by reaction with acrylic or 
methacrylic acid chlorides via the reaction 
##STR10## 
Where A is a chromophore-containing group, such as Ar--N.dbd.N--Ar--, Ar 
is a substituted or unsubstituted aryl (e.g. phenyl, naphthyl, etc.), X is 
O or NH, and R is H or CH.sub.3. The following is a list of representative 
dye monomers useful in this invention: 
##STR11## 
where R is H or CH.sub.3, and R.sup.1 is H or CN. 
##STR12## 
where X is O or NH, Ar is a substituted or unsubstituted aryl (e.g. 
phenyl, napthyl, etc.), and R is H or CH.sub.3. 
##STR13## 
where Y and Z, which may be the same or different, are selected from 
--NO.sub.2, --OR'", --NHR'", alkyl, aryl, and R'" is aryl or C.sub.1 to 
C.sub.8 alkyl, X is O or NH, and R is H or CH.sub.3. 
Non-dye monomer(s) used in chain-growth and step-growth polymers as well as 
the polymeric backbone of graft polymers can be partially-, or 
non-fluorinated, but preferably, non-dye monomer(s) are fluorinated and 
contain fluoroaliphatic groups. In step-growth polymers, the non-dye 
monomer(s) can be mono- or di-functional and the polymerizable groups can 
react with polymerizable groups on dye or other non-dye monomer(s), where 
mixtures of non-dye monomers are used to derive the polymer, to form 
linkages through step-growth polymerization reactions. Preferably said 
monomer(s) are di-functional, and their polymerizable groups are 
identical. In chain-growth polymers, the non-dye monomer(s) can have one 
or more ethylenically unsaturated groups, but preferably only one, which 
can react with ethylenically unsaturated groups on other non-dye or dye 
monomer(s) to form linkages between monomers through chain-growth 
polymerization reactions. If a monomer has more than one ethylenically 
unsaturated group, the groups need not be identical and the groups on 
other non-dye monomer(s) need not be identical. Non-dye monomers used to 
make the polymeric back bone in graft polymers are similar to those used 
in either step-growth or chain-growth polymers, but at least one of the 
monomer units comprising said backbone, must contain a reactive group, 
e.g. hydroxyl, carboxyl, haloformic, isocyanato, amino, acrylic, 
methacrylic, acrylamido, vinyl and allyl, that will react with the 
reactive group on the pendent-group-precursor compound(s) to form a 
linkage, and will not participate in the polymerization reaction used to 
make the polymeric backbone. Preferably, all polymerizable groups on 
non-dye monomer(s) will be terminal groups. A preferred class of non-dye 
monomers are fluorchemical acrylates which can be prepared by the 
condensation of suitable fluorochemical alcohols, amines or acrylamides 
with acrylic or methacrylic acid chlorides via the following reaction: 
##STR14## 
Where R.sub.f is a fluoroaliphatic group, X is O or NH, and R is H or 
CH.sub.3. 
The following is a representative list of fluorochemical acrylates useful 
in this invention: 
##STR15## 
Further description of the preparation of graft, step-growth and 
chain-growth polymers will be omitted in the interest of brevity since in 
most cases they follow classical methods such as described, for example, 
in W. R. Sorenson and T. W. Campbell, Preparative Methods of Polymer 
Chemistry 57-234 (1961), and H. A. J. Battaerd and G. W. Treyear, Graft 
Copolymers (1967).

The following specific but nonlimiting examples will serve to illustrate 
the present invention. 
EXAMPLE 1 
1-acryloxy-4-(p-tolylamino)anthraquinone, an acrylate dye monomer, was 
prepared by dissolving 2.0 g (0.0061 mole) of 
1-hydroxy-4-(p-tolyamino)anthraquinone in 100 mL of chloroform. Said 
solution was heated to reflux and treated with 0.85 mL (0.61 g) of 
triethylamine. To this solution was added 0.49 mL (0.0061 mole) of 
acryloyl chloride dropwise over 15 minutes. The reaction was monitored by 
thin layer chromatography. After 3 hours, some product had appeared, and 
the reaction mixture was treated with additional triethylamine and 
acryloyl chloride. After a total of 6 hours, thin layer chromatography 
showed some remaining starting material. The mixture was cooled, washed 
with water and dried over sodium sulfate. After solvent removal, a 
blue-violet solid remained which was purified by column chromatography, 
using silica gel and chloroform, to give the pure acrylate with a melting 
point of 164.5.degree.-166.degree. C. The product was recrystallized from 
hexane as fine, blue-violet needles which gave a red solution when 
dissolved in organic solvents like chloroform. 
A copolymer of 
##STR16## 
(prepared by reacting methacrylol chloride with 
1,1-dihydroperfluorooctanol according to the method described in U.S. Pat. 
No. 2,642,416) and 1-acryloxy-4-(p-tolyamino)anthraquinone was prepared by 
dissolving 10 g of the fluorochemical methacrylate, 0.862 g of the 
anthraquinone acrylate and 0.06 g of azobis(isobutyronitrile) (i.e. AIBN) 
in 60 g of 2,3,3-trichloroheptafluorobutane. The reactants were mixed in a 
115 mL glass bottle then degassed by successive evacuations by an 
aspirator followed by flushing the bottle with nitrogen gas. After 
degassing, nitrogen gas was bubbled through the solution for 10 minutes. 
The bottle was then tightly sealed with a screw cap and placed in a 
Launder-O-Meter.TM. with the water bath set at 65.degree. C. The reaction 
bottle was agitated in the water bath for 16 hours after which it was 
cooled and opened. The polymeric product, which formed a red solution, was 
filtered and the solvent was removed under reduced pressure. The solid, 
polymer product was soluble in Freon.RTM. 113, Fluorinert.RTM. liquid, 
FC-75, and was insoluble in and did not impart color to toluene or acetone 
which means that the product contained no free dye monomer, nor did it 
contain any homopolymer of the dye monomer since these would both be 
soluble in and would impart color to acetone or toluene. 
EXAMPLES 2-9 
Examples 2-9 were prepared according to procedure of Example 1; however, 
different dye monomers, quantities of dye monomers, non-dye monomers, 
AIBN, Freon.RTM. 113, and in some cases, various quantities of a 
co-solvent, ethyl acetate were used. The dye monomer and quantities of 
each reactant used are summarized in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Monomer Dye Non-dye Ethyl 
structure monomer 
monomer 
AIBN 
Freon .RTM. 113 
acetate 
Example 
(color) (g) (g) (g) (g) (g) 
__________________________________________________________________________ 
##STR17## 0.2 20 0.12 
120 0 
3 " 1.0 20 0.12 
120 0 
4 
##STR18## 0.0195 
10 0.06 
60 1 
5 " 0.058 
10 0.06 
60 2.1 
6 
##STR19## 0.02 10 0.06 
60 1.5 
7 " 0.0485 
10 0.06 
60 2.5 
8 
##STR20## 0.0215 
10 0.06 
60 1 
9 
##STR21## 0.0215 
10 0.06 
60 1 
__________________________________________________________________________ 
EXAMPLE 10-12 
Examples 10-12 were prepared according to the procedure of Example 1; 
however, different, novel, dye monomers (the preparation of which are 
described below), and different quantities of dye monomer, non-dye 
monomer, AIBN, and Freon.RTM. 113 were used, and in some cases, various 
quantities of a co-solvent, ethyl acetate, was used. The dye monomer, and 
the quantities of each reactant used are summarized in Table 2. 
The dye monomer used in Examples 10 and 11 was prepared by dissolving 3 g 
of 7-hydroxy-4-methylcoumarin in a solution of 0.68 g sodium hydroxide and 
30 mL of water. A 1.37 g quantity of 2-chloroethanol was added to the 
solution and the mixture was refluxed for 5 hours. The crude product, 
which precipitated when the mixture was cooled to room temperature, was 
isolated by suction filtration and recrystallized from ethanol as white 
crystals, with a melting point of 144.degree.-146.degree. C. A solution 
was prepared by dissolving 1.5 g of the white, crystalline product and 
1.38 g of triethylamine in 30 mL of chloroform. This solution was refluxed 
while 1.23 g of acryloyl chloride was added dropwise. The solution was 
then stirred and refluxed for 3 hours, and analysis by thin layer 
chromatography indicated complete reaction. The mixture was cooled to room 
temperature, and the solvent removed under vacuum. The crude product was 
recrystallized from ethanol to yield 1.27 g of the product, 
##STR22## 
which had a melting point of 90.degree.-92.degree. C., and a proton NMR 
spectrum consistent with the assigned structure. 
The dye monomer used in Example 12 was prepared by dissolving 1 g of 
3-pyrenemethanol (prepared according to the procedure of Yoshimoto, et 
al., 46 Bulletin of the Chemistry Society of Japan 358, (1973)) in 60 mL 
of chloroform, and adding 0.88 g of triethylamine to the solution followed 
by 0.78 g of acryloyl chloride. The solution was then refluxed for 6 
hours. After the solvent was removed, a yellow solid remained. The yellow 
solid was recrystallized from petroleum ether to yield 0.714 g of the 
white, crystalline, acrylate, product 
##STR23## 
which had a melting point of 70.degree.-72.degree. C. and a proton NMR 
spectrum consistent with the assigned structure. 
TABLE 2 
__________________________________________________________________________ 
Monomer Dye Non-dye Ethyl 
structure monomer 
monomer 
AIBN 
Freon .RTM. 113 
acetate 
Example 
(color) (g) (g) (g) (g) (g) 
__________________________________________________________________________ 
10 
##STR24## .125 10 .06 60 5 
11 " .257 10 .06 60 10 
12 
##STR25## .1 10 .06 60 0 
__________________________________________________________________________ 
EXAMPLE 13 
A fluorochemical, polycarbonate compound was prepared by a step-growth 
polymerization of a dye monomer and a bischloroformate monomer derived 
from a fluorochemical diol. The bischloroformate monomer, ClCOOCH.sub.2 
(CF.sub.2).sub.3 OCF(CF.sub.3)CH.sub.2 OCOCl, was prepared by reducing 
FCO(CF.sub.2).sub.3 OCF(CF.sub.3)COF (the 1:1 adduct of FCOCF.sub.2 
CF.sub.2 COF and 
##STR26## 
made by the method described in U.S. Pat. No. 3,250,807 (Fritz)) with 
sodium borohydride, yielding HOCH.sub.2 (CF.sub.2).sub.3 
OCF(CF.sub.3)CH.sub.2 OH. Some of the diol was then reacted with phosgene 
to form the bischloroformate monomer. The dye monomer was 
##STR27## 
Disperse Red 17 (color index No. 11210), available from Crompton and 
Knowles Corporation. 3.09 g of the bischloroformate monomer and 30 mL of 
tetrahydrofuran were placed in a reaction flask containing a magnetic 
stirring bar. A solution of 0.78 g of the dye monomer and 0.48 g of 
triethylamine was prepared in 15 mL of tetrahydrofuran and added dropwise 
to the stirred solution of the bischloroformate monomer. A fine solid of 
triethylamine hydrochloride formed during the addition. To this reaction 
mixture, an additional 0.78 g of the bischloroformate monomer and 0.48 g 
of triethylamine were added. After the addition, the reaction mixture was 
washed with water to remove the triethylamine hydrochloride salt 
by-product. The structure of the polycarbonate product, which formed a red 
solution in the tetrahydrofuran reaction solvent, was confirmed by IR and 
H-NMR spectral analysis. The polymer, isolated by removal of solvent, was 
a viscous red liquid soluble in acetone and benzotrifluoride and slightly 
soluble in Freon.RTM. 113. One drop of the above prepared polycarbonate 
dye was dissolved in 5 mL of a 30% by weight butyl acetate solution of a 
commerical fluorocarbon copolymer used as a conformal coating for 
electronic circuitry. The resulting polymer solution was coated on a clear 
plastic film using a #32 wire wound rod to give a solid, orange coating 
upon evaporation of the solvent. 
Various modifications and alterations of this invention will become 
apparent to these skilled in the art without departing from the scope of 
this invention.