Esters of anhydride aromatic polycarboxylic acids with perfluoroalkyl alcohols

This invention describes new perfluoroalkyl substituted esters, diesters and polyesters which contain at least one cyclic 5-membered anhydride group or two carboxy groups, as well as half amides and half esters thereof; their synthesis and their use as surface-active reactants in polycondensate resin systems. The anhydrides are synthesized by reaction of perfluoroalkyl substituted alcohols or diols with dianhydrides or an anhydrides-acid chloride and have the general structure ##STR1## wherein: Q is the tetra-radical rest of a tri- or tetracarboxylic acid, which contains at least one 1,2-dicarboxy grouping, PA1 X is hydrogen or COOH, PA1 R.sub.f is a perfluoroalkyl or perfluoroalkoxy-perfluoroalkyl group of 4 to 18 carbon atoms, PA1 a is 1 or 2, PA1 A is hydrogen or ##STR2## wherein: M IS AN INTEGER FROM 0 TO 5, AND PA1 R.sup.3 is the residue of a R.sub.f substituted alcohol or diol.

BACKGROUND OF THE INVENTION 
Perfluoroalkyl substituted compounds are widely used in a large number of 
applications where the unique ability of perfluoroalkyl groups to lower 
the surface energy of solids, or organic or aqueous solutions, is of 
decisive importance. In polymers, the presence of perfluoroalkyl groups 
reduces the polymer surface-free energy to below 15 dynes/cm, and such 
polymers are used by the textile industry to make fabrics not only water 
repellent, but also oil repellent. 
R.sub.f -surfactants which are otherwise like their hydrocarbon analogues 
in that they are either anionic, cationic, nonionic or amphoteric, but 
which contain perfluoroalkyl groups reduce the surface tension of aqueous 
or organic liquids to extremely low levels, down to 15 dynes/cm, as 
compared to 25-30 dynes/cm obtainable with conventional surfactants. Such 
low surface tensions allow these liquids, which may be molten polymers to 
polymer solutions or emulsions, to wet substrates which are otherwise 
impossible to wet. Therefore properties which depend on good wetting are 
often substantially improved, such as adhesion and surface smoothness, and 
such coating deficiencies as crawling, "fisheyes," "orange peel," etc. are 
largely eliminated. Numerous R.sub.f -surfactants have been described in 
U.S. Pat. Nos. 2,915,554; 3,274,244; 3,621,059; 3,668,233; and German 
Offenlegungsschift No. 2,215,388. 
R.sub.f -surfactants of the prior art cited above are used for coating 
systems to help in wetting and to prevent crawling and other side effects 
of poor coatings. These R.sub.f -surfactants are nonionic in nature 
because ionic compounds are poorly compatible with resins. All the R.sub.f 
-surfactants described are non-reactive. 
DETAILED DISCLOSURE 
This invention pertains to new perfluoroalkyl substituted esters, diesters 
and polyesters which contain at least one cyclic 5-membered anhydride 
group or two carboxy groups as well as half amides and half esters derived 
therefrom and the processes to prepare said compounds. 
The compounds of this invention are useful as surface-active reactants in 
polycondensation resin systems. The compounds of this invention contain 
chemical groups which can co-react with curable resin systems during the 
curing cycle. This assures optimum compatibility of the compounds of this 
invention as additives with the curable resin throughout the curing cycle. 
The perfluoroalkyl compounds may by themselves have minimal surface 
activity properties, but form surface active derivatives during cure of 
the resin in situ. Besides the optimal compatibility and effectiveness 
achieved, the perfluoroalkylated compounds of this invention are tightly 
built into the resin network and remain an integral part of it. They 
cannot bleed out, like other surfactants. This is an important and 
requisite property for coatings coming in contact with food. Additionally, 
the surface appearance of the coating is improved and often its surface 
free energy is reduced. 
In specific detail, the compounds of this invention comprise perfluoroalkyl 
substituted esters of the formula I 
##STR3## 
wherein Q is the tetraradical rest of a tricarboxylic or tetracarboxylic 
acid which contains at least one 1,2-dicarboxy grouping, 
X is hydrogen or carboxy, 
R.sub.f is perfluoroalkyl of 4 to 18 carbon atoms or 
perfluoroalkoxyperfluoroalkyl of 4 to 18 carbon atoms, 
a is 1 or 2, 
A is hydrogen or the group II 
##STR4## 
m is an integer from 0 to 5, Q.sub.1 is the same as Q or is a different 
tetraradical rest of the definition given for Q, and 
R.sup.3 is the residue of a R.sub.f substituted, branched or straight 
chain, aliphatic alcohol or diol of 1 to 12 carbon atoms which may contain 
1 to 5 non-terminal oxygen, sulfur or nitrogen atoms, the third 
substituent on the nitrogen atoms being independently hydrogen, alkyl of 1 
to 6 carbon atoms or hydroxyalkyl of 2 to 6 carbon atoms. 
The preferred compounds of this invention are those of formula I wherein Q 
is the tetraradical rest of a tricarboxylic or tetracarboxylic acid 
selected from the group consisting of trimellitic acid, 
3,3',4,4'-benzophenonetetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic 
acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid and 
##STR5## 
X is hydrogen or carboxy; R.sub.f is perfluoroalkyl of 6 to 18 carbon 
atoms; 
a is 1 or 2; 
A is hydrogen or Group II 
##STR6## 
m is an integer from 0 to 2; Q.sub.1 is the same as Q; and 
R.sup.3 is the residue of a R.sub.f substituted, aliphatic alcohol or diol 
of the structure 
##STR7## 
where R.sup.1 is a branched or straight chain alkylene of 1 to 12 carbon 
atoms, alkylenethioalkylene of 4 to 12 carbon atoms, alkyleneoxyalkylene 
of 4 to 12 carbon atoms or alkyleneiminoalkylene of 4 to 12 carbon atoms 
where the nitrogen atom contains as the third substituent hydrogen or 
alkyl of 1 to 6 carbon atoms; and 
R.sup.2 is a straight or branched chain alkylene of 1 to 12 carbon atoms or 
an alkylenepolyoxyalkylene of the formula C.sub.n H.sub.2n (OC.sub.k 
H.sub.2k).sub.r where n is 1 to 12, k is 2 to 6 and r is 1 to 40. 
Especially preferred compounds of this invention are those of formula I 
wherein Q is the tetraradical rest of tetracarboxylic acid selected from 
the group consisting of 2,3,4,5-tetrahydrofurantetracarboxylic acid and 
3,3',4,4'-benzophenonetetracarboxylic acid; X is carboxy; R.sub.f is 
perfluoroalkyl of 6 to 18 carbon atoms; a is 1 or 2; A is group II 
##STR8## 
m is 0; Q.sub.1 is the same as Q; and R.sup.3 is the residue of an R.sub.f 
substituted aliphatic alcohol or diol of the structure 
##STR9## 
where R.sup.1 is a branched or straight chain alkylene of 1 to 4 carbon 
atoms; and 
R.sup.2 is a branched or straight chain alkylene of 1 to 4 carbon atoms or 
alkylenepolyoxyalkylene of the formula C.sub.n H.sub.2n (OC.sub.k 
H.sub.2k).sub.r where n is 1 to 4, k is 2 to 4 and r is 1 to 20. 
Most preferably the compounds of this invention are those where R.sub.f is 
perfluoroalkyl of 6 to 18 carbon atoms, R.sup.1 is ethylene; and R.sup.2 
is methylene or methyleneoxyalkylene of the formula CH.sub.2 (OC.sub.k 
H.sub.2k).sub.r where k is 2 and r is 1 to 20. 
The perfluoroalkyl substituted alcohols or diols useful in this invention 
have the general structure 
##STR10## 
where Z is hydrogen or hydroxy. When Z is hydrogen in formula III, A in 
Formula I is also hydrogen. When Z is hydroxy, A in formula I has the 
structure of group II. R.sup.3, a, and R.sub.f are as previously defined. 
When Z is hydrogen and a is 1, other perfluoroalkyl alcohols contemplated 
to be of value in this invention include 
##STR11## 
Where Z is hydroxy and a is 1, other perfluoroalkyl diols contemplated to 
be of value in this invention have the structures below 
##STR12## 
The perfluoroalkyl alcohols and diols can also contain two R.sub.f groups 
as seen in the compounds illustrated below, where a is 2. 
##STR13## 
Formula III thus also describes di-R.sub.f -substituted alcohols and diols. 
In all the above structures, 
R.sup.4 is a branched or straight chain alkyl of 1 to 6 carbon atoms, 
R.sup.5 is hydrogen or methyl, and 
R.sup.1 and R.sup.2 are as previously defined. 
R.sub.f -alcohols and diols are described in U.S. Pat. Nos.: 2,803,615; 
3,079,214; 3,207,730; 3,256,230; 3,332,902; 3,282,905; 3,304,198; 
3,304,278; 3,361,685; 3,378,609; 3,498,946; 3,384,627; 3,384,628; 
3,407,183; 3,424,285; 3,510,455; 3,547,894; 3,686,283; 3,728,151; 
3,736,360; 3,759,874; 3,794,623; 3,872,858; and 3,883,596; in British Pat. 
Nos.: 1,101,049; and 1,130,822; and in German Offenlengungsschrift No. 
2,342,888. 
A particularly preferred class of perfluoroalkyl substituted compounds 
contain the residue of an R.sub.f -glycol characterized by the presence of 
one or two perfluoroalkylthio groups on adjacent carbon atoms. The R.sub.f 
-glycols have the structure 
##STR14## 
wherein R.sub.f is perfluoroalkyl of 6 to 18 carbon atoms; 
R.sup.1 is straight or branched chain alkylene of 1 to 4 carbon atoms; 
R.sup.2 is a straight or branched chain alkylene of 1 to 4 carbon atoms or 
CH.sub.2 (OC.sub.k H.sub.2k).sub.r 
wherein 
m is 1 to 4 
k is 2 to 4 
r is 1 to 20 
The R.sub.f -glycol can be obtained by addition of 2.0 moles of a mercaptan 
of formula R.sub.f --R.sup.1 --SH to one mole of an acetylenic diol of 
formula HOR.sup.2 --C C--R.sup.2 OH or 1 mole of mercaptan to one mole of 
a diol of the formula HOR.sup.2 CH.dbd.CHR.sup.2 OH wherein R.sup.1, 
R.sup.2, and R.sub.f are as described above, in the presence of an azo 
type free radical catalyst such as azobisisobutyronitrile at a temperature 
of 60.degree. to 80.degree. C, in bulk or in the presence of a C.sub.6 
-C.sub.10 alkane solvent. 
A preferred class of mercaptans is disclosed in U.S. Pat. No. 3,544,663 and 
can be obtained by reacting a perfluoroalkyl alkyl iodide with thiourea, 
followed by hydrolysis. 
Preferred are the compounds of this invention which contain the residue of 
an R.sub.f -glycol, 
wherein 
R.sub.f is perfluoroalkyl of 6 to 12 carbon atoms; 
R.sup.1 is ethylene, 
R.sup.2 is methylene, 
obtained by adding two moles 2-(perfluoroalkyl)ethyl mercaptan to one mole 
2-butyn-1,4-diol or one mole of said mercaptan to one mole of 
2-buten-1,4-diol. 
The tetraradical rest Q (or Q.sub.1) is derived from a tetracarboxylic acid 
or tetracarboxylic dianhydride of formula IV or a tricarboxylic acid 
anhydride acid chloride of formula V. 
##STR15## 
The dianhydrides of formula IV can be aliphatic, alicyclic, aromatic, or 
heterocyclic in general structure. 
A list of suitable dianhydrides of structure IV is given below. 
Generally dianhydrides of tetracarboxylic acids in which the four carboxy 
groups are attached in pairs to two adjacent carbon atoms have the 
structure of two 5-membered cyclic anhydride groups in one molecule. 
1,2,4,5-benzenetetracarboxylic dianhydride 
1,2,3,4-benzenetetracarboxylic dianhydride 
2,3,6,7-naphthalenetetracarboxylic dianhydride 
3,3',4,4'-diphenyltetracarboxylic dianhydride 
1,2,5,6-naphthalenetetracarboxylic dianhydride 
2,2',3,3'-diphenyltetracarboxylic dianhydride 
3,3',4,4'-azobenzenetetracarboxylic dianhydride 
2,3,4,5-tetrahydrofurantetracarboxylic dianhydride 
2-phenyl-4,6-bis(3',4'-dicarboxyphenyl)-s-triazine dianhydride 
2-diphenylamino-4,6-bis(3',4'-dicarboxyphenyl)-s-triazine dianhydride 
2,2-bis-(3,4-dicarboxyphenyl)propane dianhydride 
bis-(3,4-dicarboxyphenyl)sulfone dianhydride 
3,4,9,10-perylenetetracarboxylic dianhydride 
bis-(3,4-dicarboxyphenyl)ether dianhydride 
1,1,2,2-ethylenetetracarboxylic dianhydride 
1,2,4,5-naphthalenetetracarboxylic dianhydride 
1,4,5,8-naphthalenetetracarboxylic dianhydride 
decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride 
4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic 
dianhydride 
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride 
2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride 
2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride 
1,8,9,10-phenanthrenetetracarboxylic dianhydride 
1,2,3,4-cyclopentanetetracarboxylic dianhydride 
2,3,4,5-pyrrolidinetetracarboxylic dianhydride 
2,3,5,6-pyrazinetetracarboxylic dianhydride 
2,2-bis-(2,5-dicarboxyphenyl)propane dianhydride 
1,1-bis-(2,3-dicarboxyphenyl)ethane dianhydride 
bis-(2,3-dicarboxyphenyl)methane dianhydride 
bis-(3,4-dicarboxyphenyl)methane dianhydride 
bis-(3,4-dicarboxyphenyl)sulfone dianhydride 
1,2,3,4-butanetetracarboxylic dianhydride 
2,3,4,5-thiophenetetracarboxylic dianhydride 
3,3',4,4'-diphenyltetracarboxylic dianhydride 
3,3',4,4'-benzophenonetetracarboxylic dianhydride 
Other dianhydrides contemplated to be of use in this invention are 
synthesized by the base catalyzed addition of a dithiol to two moles of 
maleic anhydride or by the free radical addition of a dithiol to 
tetrahydrophthalic anhydride, norbornane anhydride or methylnorbornane 
anhydride. Such dianhydrides have the structures below: 
##STR16## 
In these structures, R.sub.6 is a linear or branched alkylene chain of 2 
to 20 carbon atoms, which may also contain an ether oxygen or ester 
groups. 
Typical examples for R.sub.6 are: 
##STR17## 
R.sub.7 is hydrogen or methyl. 
The anhydride acid chlorides of formula V are best exemplified by 
trimellitic acid anhydride acid chloride (commercially available) 
##STR18## 
The preferred dianhydrides useful in this invention are 
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 
1,2,4,5-benzentetracarboxylic acid dianhydride, 
##STR19## 
2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride. 
The most preferred dianhydrides are 
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride and 
2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride. 
The anhydrides of formula IV are generally items of commerce. They can also 
be prepared by conventional procedures from the corresponding acids using 
an acid chloride and pyridine or in the aromatic or heterocyclic series by 
oxidation of the corresponding tetramethyl compounds. 
The compounds of this invention having structure I are prepared by reacting 
a mono-R.sub.f or a di-R.sub.f substituted alcohol of formula III with a 
dianhydride of formula IV or anhydride acid chloride of formula V in a 
suitable organic solvent at slightly elevated temperatures. The mol ratios 
of the reactants are selected so that at least one anhydride group is 
present in the product. This anhydride group can subsequently easily be 
opened up with water, alcohols or amines to give diacids, diacid salts, 
acid-esters, and acid-amides (amic-acids). 
In like manner the compounds of this invention having structure I where A 
is group II are prepared by the same reaction described above, but using a 
mono-R.sub.f or a di-R.sub.f substituted diol of formula III. 
The synthesis of a compound of formula I is carried out in an organic 
solvent which will dissolve both the R.sub.f -alcohol or R.sub.f -diol and 
the dianhydride or anhydride acid chloride at the reaction temperature. 
Useful solvents include ethers such as dioxane, tetrahydrofuran, ethylene 
glycol dimethyl ether; esters such as ethyl acetate or ethyl cellosolve 
acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide, 
N-methylpyrrolidone; pyridine; ketones such as acetone, methyl ethyl 
ketone or methyl isobutyl ketone and the like. Generally any aprotic 
solvent or mixture of aprotic solvents which will dissolve both reactants 
will suffice. The reaction is carried out preferably at slightly elevated 
temperatures, namely between 50.degree. and 100.degree. C. The reaction 
rate is greatly influenced by the nature of the reactants, with the 
di-R.sub.f -diols and aromatic dianhydrides reacting slower than the 
mono-R.sub.f -diols and aliphatic anhydrides. However, in the presence of 
basic catalyst, such as tertiary or quaternary amines, all reactions 
proceed rapidly and smoothly. Preferred catalysts are quaternary ammonium 
compounds such as tetramethylammonium hydroxide or tetramethylammonium 
chloride. The product is obtained as a 10-70% solution which is a most 
desirable form for applications where a small amount of the compound is to 
be added to large volumes of resins or resin solutions. 
Since there novel anhydrides are usually insoluble in resins or resin 
solutions unless one of the aforementioned solvents it present, the 
compounds of this invention usually are first reacted with the --OH or 
--NH groups of the resin or are otherwise transformed into a soluble or 
compatible state. For incorporation into polyurethane foams, for instance, 
the anhydride or dianhydride is first reacted with part of the polyol 
component, as described in Example 22 before mixing into the final 
formulation; for incorporation into aqueous resin solutions, the compounds 
are reacted with water solubilizing alcohols or amines such as 
polyethylene oxide, bis-amino propyl ether of polyethylene oxide, or 
N,N-dialkylaminealcohols, or N,N-dialkylaminoalkyl diamines. Preferred 
reactants are N,N-dimethylaminoethanol and 
N,N-dimethylaminopropane-1,3-diamine. This reaction leads to formation of 
amphoteric groups and easy water dispersibility at high and low pH. If 
only solubility in basic medium is required the dicarboxylate derivative 
of the anhydride is sufficient, for instance the ammonium salt. 
Since the water soluble forms of the novel compounds are not especially 
good surface-active agents for water, or the water-resin solutions as 
such, it is often useful to add another surfactant to aqueous systems, one 
which is especially designed to reduce the surface tension of water. In 
this way good wetting of the aqueous phase is initially achieved 
whereafter the polyfunctional R.sub.f -compounds of this invention become 
effective after the water has been evaporated. Especially useful 
cosurfactants for water-based coatings are ionic, cationic and amphoteric, 
R.sub.f -surfactants, which will reduce the surface tension of water to 
below 20 dynes/cm. 
Thus, combination of the novel compounds of this invention with 
conventional, ionic R.sub.f -surfactants for use in aqueous resin systems 
is another embodiment of this invention. The unique usefulness of these 
novel compounds is demonstrated in detail in the examples. 
Thus, the compounds of this invention are useful in the development of a 
"dual wetting" system for water based coatings for hard-to-wet surfaces. 
Such a system comprises two parts. One is based on a perfluoroalkyl 
(R.sub.f) ionic surfactant, effective in reducing the surface tension of 
the water phase, and the second part derived from the perfluoroalkyl 
dianhydrides of this invention, effective in the resin phase. Use of this 
dual system can provide complete (100%) coverage of hard-to-wet 
substrates, for instance industrial grade electrolytic tin plate when 
coated by an aqueous epoxy resin coating system.

It is understood that the scope of the invention is not limited by the 
following postulations nor that the effectiveness of the dianhydrides of 
this invention necessarily results from the proposed explanations thereof. 
The following postulations appear to offer a plausible mechanism by which 
the "dual wetting" system may operate in order to effect its efficacious 
activity during the coating of aqueous based resin systems on 
hard-to-wet-surfaces. 
When a polymeric thermosetting resin coating, such as a water based epoxy 
resin, is applied to a hard-to-wet substrate, the following stages appear 
to occur: 
1. The surface is first wetted by the aqueous phase of the coating system. 
A surfactant which can reduce the interfacial tension between the water 
and the substrate will be beneficial. Ionic perfluoroalkyl compounds are 
particularly useful in this stage. 
2. As the applied coating system is then heated, the water present 
evaporates. The resin component viscosity will be initially low, dependent 
on temperature and cure rate, and as the water evaporates, the surface 
tension of the resin phase itself will determine wetting. If it is high, 
the resin may then retract from the surface, bead up and cause an 
imperfect coating of the substrate to occur. 
This state of affairs can be avoided if the surfactant effective in the 
aqueous phase has also sufficient compatibility within the resin to be 
effective in preventing the undesirable beading up of the resin. 
Generally, ionic type surfactants are poorly compatible with resins, while 
non-ionic types, which are more compatible, are not as good surfactants 
for the water phase. 
However, the presence of a second surfactant compound tailored for optimum 
compatibility in the resin phase will overcome the problem of beading up 
and poor surface wetting noted above. This second surfactant causes the 
surface tension of the resin phase to remain low, prevents bead up of the 
resin and assures complete coverage of the substrate with the resin. This 
will allow the resin to cover the surface as completely in the absence of 
water as did the original aqueous resin solution. 
3. Continued heating effects complete resin cure with complete coverage of 
the substrate surface by the cured resin. 
The "dual wetting" system of this invention provides for 
a. the best surfactant available for the initial wetting out the aqueous 
phase of the aqueous resin coating system; and 
b. the best surfactant available for the subsequent reducing of the surface 
tension of the resin phase during the critical precuring step as the water 
is evaporated from the applied aqueous coating system. 
The advantages of the instant invention are thus that optimal performance 
is achieved throughout the entire coating operation and a greater range of 
aqueous resin coating systems can be successfully used. 
In the "dual wetting" system the surfactant to be effective in the aqueous 
phase can be the ionic type surfactants normally incompatible in most 
resins. The second surfactant of the dual system is preferably a 
multifunctional compound, such as the dianhydrides of this invention, 
capable of coreacting with the curable resin, thus preventing any loss of 
surfactant by bleedout. 
Attempts to use one surfactant active in both the aqueous and the resin 
phases where a water soluble structure provides some compatibility of the 
surfactant in the resin is exemplified in the prior art as seen with 
commercial products which are R.sub.f non-ionic surfactants. This approach 
represents a compromise and a significant loss in coverage of the 
substrate occurs during the curing step. 
In the instant invention, an effective R.sub.f -amphoteric, anionic or 
cationic surfactant is combined with an R.sub.f -dianhydride compound or 
its derivatives of this invention. 
A preferred surfactant combination consists of an R.sub.f -amphoteric 
surfactant 
##STR20## 
Lodyne S-100, (as described in Ser. No. 538,432, incorporated herein by 
reference), which is effective in the aqueous phase of the water-based 
resin coating system, with a reactive water soluble derivative of an 
R.sub.f -dianhydride as described earlier in this application. 
The effectiveness of the use of any one surfactant on effecting coverage of 
an industrial grade electrolytic tin substrate, wet or after cure, is seen 
on Table A. Only the R.sub.f -amphoteric surfactant Lodyne S-100 gave 100% 
wet coverage, but after cure only 45% coverage remained. With other 
commercial products such as FC-430 or even the derivative of an instant 
dianhydride (Example 14a) when used alone, a compromise in coverage was 
attained, but none achieved the desired and necessary 100% coverage both 
wet and after cure. However, the instant derivative of (Example 14a) was 
able to prevent shrinkage of the initially wetted substrate coating during 
cure. 
It is noted on Table A from the surface tension measurements of the water 
solutions shown that the critical property which determines wetting of a 
surface is not surface tension per se, but more likely interfacial 
tension. 
Table A 
__________________________________________________________________________ 
Aqueous Epoxy (of Ex. 17): Wetting of Electrolytic Tin using Various 
Additives 
(#7 wire rod; 200.degree. C/10 min) 
% 
Sample % % F 
.gamma.s 
Coverage of Tin 
No. Additive Type in solids 
[dyne/cm] 
wet 
after cure 
__________________________________________________________________________ 
1 Pluronic L-72 (polyox derivative).sup.1 
0.5 
-- 80 50 
2 Pluronic L-72 (polyox derivative).sup.1 
1.0 
-- 35.8 80 50 
3 BYK 301 (silicone).sup.2 
0.5 
-- 70 60 
4 BYK 301 (silicone).sup.2 
1.0 
-- 33.4 85 75 
5 FC-430 (R.sub.f -surfactant nonionic).sup.3 
0.5 
0.067 75 65 
6 FC-430 (R.sub.f -surfactant nonionic).sup.3 
1.0 
0.134 
20.7 75 60 
7 Example 14a (R.sub.f -dianhydride) 
0.18 
0.067 65 65 
derivative 
8 Example 14a (R.sub.f -dianhydride 
0.36 
0.134 
33.8 85 85 
derivative 
9 Lodyne S-100 (R.sub.f -surfactant 
0.15 
0.067 
17.1 100 
45 
amphoteric).sup.4 
10 Control -- -- 40.1 50 30 
__________________________________________________________________________ 
.sup.1 BASF Wyandotte 
.sup.2 Mallinckrodt 
.sup.3 3M Company 
.sup.4 CIBA-GEIGY 
The effectiveness of the "dual surfactant" system of the present invention 
is explicitly illustrated on Table B. Clearly the R.sub.f amphoteric 
surfactant Lodyne S-100 is most effective in giving essentially 100% wet 
coverage regardless of what second surfactant was present in the system. 
None of the second surfactants tested, including FC-430, an R.sub.f 
non-ionic type, were effective in giving after cure coverage of the tin 
substrate save Example 14a the derivative of the instant R.sub.f 
dianhydride of Example 1b, where excellent coverage (up to 100%) depending 
on the specific ratios of surfactants used after cure was attained. The 
combination of both Lodyne S-100B and Example 14a was the only dual 
surfactant system to prevent shrinkage (bead up) of the initially (100%) 
wetted substrate coating during cure as seen on Table B. The compounds of 
this invention can, of course, be combined with other R.sub.f ionic 
(amphoteric, cationic and anionic) surfactants to achieve the above 
described effect. 
Table B 
__________________________________________________________________________ 
Aqueous Epoxy (of Ex. 17): Wetting of Electrolytic Tin using Additive 
Combination 
(#7 wire rod; 200.degree. C/10 min) 
Lodyne S-100 % 
R.sub.f surfactant % F (solids).sup.1 
Coverage of Tin 
Sample No. 
% by Wt. 
Other Surfactant 
% by Wt. 
s r wet after cure 
__________________________________________________________________________ 
1 0.15 PL-72 (Pluronic).sup.2 
0.5 0.067 
-- 100 10 
2 0.07 BYK 301 (Silicone).sup.3 
0.25 0.038 
-- 90 60 
3 0.15 BYK 301 0.5 0.067 
-- 100 10 
4 0.07 FC-430 (R.sub.f -type).sup. 4 
0.25 0.134 
-- 95 65 
5 0.15 FC-430 0.5 0.268 
-- 98+ 
15 
6 0.047 Example 14a 
0.12 0.022 
0.044 
80 80 
7 0.07 Example 14a 
0.09 0.033 
0.033 
95 95 
8 0.105 Example 14a 
0.046 0.050 
0.017 
90 40 
9 0.15 Example 14a 
0.18 0.067 
0.067 
100 100 
__________________________________________________________________________ 
.sup.1 surfactant type: s 
reactant type: r 
.sup.2 BASF Wyandotte 
.sup.3 Mallinckrodt 
.sup.4 3M Company 
One example of a particularly preferred R.sub.f dianhydride of this 
invention is the compound of Example 1. 
##STR21## 
Although the anhydrides and dianhydrides of this invention are insoluble in 
polyhydric resins, such as polyols or polyamines, they can be solubilized 
by ring opening reaction with these compounds. For instance, in order to 
incorporate the novel R.sub.f -moieties into a polypropylene oxide diol, 5 
g of a 33% solution of the new R.sub.f -anhydride compound are heated with 
5-20 g of the polyol until a clear product is obtained; the solvent can be 
evaporated and the remaining R.sub.f -modified resin, which contains 1-10% 
fluorine, can be further diluted with unmodified resin to the desired 
fluorine level usually between 0.001% and 0.5%. 
Many reactive polymers of prepolymers can be treated and modified with this 
method: polyethylene oxide diols, polypropylene oxide diols, 
bis-2-aminopropyl ethers of polyalkylene oxides, poly-n-butylene oxide 
diols; polyester diols from dibasic acids and diols, as they are used in 
polyurethane chemistry; polyamines used as epoxy curing agents; siloxane 
diols; isocyanate terminated prepolymers; methylolated resins, such as 
methylolated melamines and ureas; hydroxy terminated polybutadienes; other 
hydroxy bearing polymers, such as hydroxy ethyl cellulose, hydroxy alkyl 
acrylates -- and methacrylates polymers and copolymers and polyvinyl 
alcohol. 
Thus the novel R.sub.f -anhydrides of this invention are the precursors for 
a large group of resin-compatible wetting agents. Derivatives produced 
from them impart excellent wetting abilities to polycondensate resin 
systems. In many cases, they act as adhesion promoters. 
Experimentally these compounds have been found to improve adhesion of a 
thermoset acrylic resin to aluminum (from failing to passing a cross-out 
adhesion test), and of a polysulfide sealant to concrete. 
In certain other cases, dependent on polymer and substrate, they can also 
act as mold release agents. 
These water-soluble derivatives are compounds of high reactivity and of 
unique structure. During the curing process they co-react with the resin. 
Thus, they are prevented from bleeding out, and a low surface tension, 
that is good wetting, is maintained throughout the cure cycle. 
A particularly preferred derivative of the dianhydride of Example 1 
illustrated above is prepared by reaction of one mole of the dianhydride 
with two moles of an N,N-substituted aminoalcohol or diamine such as 
N,N-dimethylethanolamine or N,N-dimethylpropane-1,3-diamine. One such 
derivative has the structure below: 
##STR22## 
This derivative of an (R.sub.f).sub.2 -dianhydride is especially designed 
for incorporation into aqueous and highly polar resin systems. 
It is soluble or dispersible in aqueous or polar organic resin solutions, 
as well as in resins themselves. However, its solubility sometimes is 
limited to low molecular weight and polar components of resin systems 
(amine-hardeners; alkyd resins; low molecular weight polyols; methendic 
anhydride). If it is used with water-based coatings, such as aqueous 
epoxies, it is preferably used in combination with an ionic R.sub.f 
-surfactant designed to reduce the surface tension of water. 
Dependent on resin systems and substrates, the compounds of this invention 
behave either as mold release agents or as adhesion promoters. 
a. With a thermosetting acrylic resin, the anhydrides of this invention 
acted as adhesion promoters for coatings of such resins on aluminum 
substrates. 
b. With polysulfide sealants, the dianhydrides of this invention perform as 
internal mold release agents when the substrates were smooth surfaces such 
as glass or aluminum, but acted as excellent adhesion promoters when the 
polysulfide sealant was bonded to a "rough" concrete surface. 
The R.sub.f -anhydrides of this invention also possess valuable utility as 
a control agent in the preparation of polyurethane foams which have lower 
densities and a larger plurality of very small uniform bubbles than in 
normal polyurethane foams. These R.sub.f -dianhydrides also act as mold 
release agents with the polyurethane foams, 
The preparation and unique usefulness of the novel compounds of this 
invention are demonstrated in detail in the following examples. The 
examples are meant to illustrate the invention without introducing any 
limitation thereby whatsoever. 
In the following examples, R.sub.f refers to a mixture of perfluoroalkyl 
groups in the following weight ratio unless otherwise indicated: 
EQU C.sub.6 F.sub.13 /C.sub.8 F.sub.17 /C.sub.10 F.sub.21 = essentially 1/2/1 
but may also contain a small quantity of C.sub.12 F.sub.25. 
Examples 1 to 9 illustrate the preparation of synthesis of compounds of 
this invention. 
It must be pointed out that the amounts of the compounds of this invention 
necessary to achieve the aforementioned effects such as surfactant, mold 
release, adhesion promotion, polyurethane foam control, etc., in a system 
will vary from 0.003 to 2.0% by weight of said compounds to give a 
fluorine concentration in the polymer system of 0.001 to 0.5% fluorine. 
It must be further pointed out that the perfluoroalkyl substituted 
anhydrides of this invention are normally prepared as a mixture of formula 
isomers. While the pure isomers can be separated by standard organic 
laboratory techniques such as chromatography, vacuum distillation, 
selective fractionation and the like, it is quite unnecessary and not 
economic to do so since the valuable surface tension properties of these 
materials reside essentially equally with all formula isomers. 
The mixture of formula isomers is caused by the asymmetry of most of the 
starting intermediates which are reacted with the R.sub.f alcohol or diol 
usually through the opening of an anhydride five-membered ring. This 
reaction of the alcohol or diol with the anhydride can result in a 
carboxyl group on one carbon atom and an ester group on an adjacent carbon 
atom, but there is no particular selection as to which carbon atom will 
bear which group. If the overall molecule were otherwise symmetrical, it 
would result in one isomer. However, in most of the instant cases, 
mixtures of isomers are obtained. 
When in Example 1, one mole of the R.sub.f diol (A) reacts with two moles 
of benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride (BTDA) a 
mixture of three formula isomers are formed. 
##STR23## 
These three structures may be combined into one structure which 
definitively describes the mixture of the three formula isomers above as 
seen below: 
##STR24## 
In like manner, when the anhydride groups at the left of the above 
structure are opened as seen in Example 14 with N,N-dimethylaminoethanol 
or a like tertiary amine containing compound a plurality of additional 
formula isomers are possible as the remaining anhydride groups are opened. 
The structure below where the exact position of the center carbonyl group 
--CO-- is floating between the two sets of adjacent carbon atoms properly 
describes such mixtures of formula isomers produced. 
##STR25## 
Again there is no need to separate the various isomers which are all 
water-soluble or water-dispersible as seen in Example 14. 
EXAMPLE 1 
##STR26## 
a. An (R.sub.f).sub.2 -diol of structure A 
##STR27## 
20.44 g (0.02 mole) and 67 g glyme (ethylene glycol dimethyl ether) were 
heated to 60.degree. C under nitrogen. 
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), 14.17 g 
(0.044 mole) and 0.4 g triethylamine were added and the reaction mixture 
stirred at 60.degree. C for 10 hours, at which time IR analysis indicated 
completeness of the reaction. 
The solution was filtered to remove unreacted BTDA and the residue was 
evaporated to dryness on rotary evaporator. The resulting brittle solid 
was ground and dried under high vacuum for 8 hours. 33.2 g of a light tan 
powder (99.8% yield) was obtained. MP: 127.degree.-133.degree. C. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
833 855 
acid equiv. wt. 833 730 
fluorine, % 39.0 39.4 
______________________________________ 
b. A dianhydride of the same formula structure as in Example 1a was also be 
prepared using an (R.sub.f).sub.2 -diol of structure A 
##STR28## 
were R.sub.f refers to a mixture of perfluoroalkyl groups in the following 
weight ratio: 
EQU C.sub.6 F.sub.13 /C.sub.8 F.sub.17 /C.sub.10 F.sub.21 = essentially 1/2/1. 
The product is a light tan powder having a m.p. of 110.degree.-116.degree. 
C. 
EXAMPLE 2 
##STR29## 
Following the same procedure as in Example 1, an (R.sub.f).sub.2 -diol of 
structure B 
##STR30## 
21 g (0.02 mole) was reacted with 14.17 g (0.044 mole) BTDA. 33.5 g of a 
light tan powder was obtained representing 98% yield. MP: 
105.degree.-108.degree. C. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
800 741 
fluorine, % 32.9 31.9 
______________________________________ 
EXAMPLE 3 
##STR31## 
Trimellitic anhydride acid chloride 33.7 g (0.160 mole) was dissolved in 
200 ml dry "glyme" (ethylene glycol dimethyl ether) and placed in an 
addition funnel on top of a 500 ml 3-necked flask equipped with stirrer, 
nitrogen-inlet and drying tube. In the flask 77.77 g (0.075 mole) 
(R.sub.f).sub.2 -diol of structure (A) (Example 1) and 12.65 g (0.160 
mole) pyridine were dissolved in 100 ml dry "glyme." The solution was 
stirred at room temperature under nitrogen while the anhydride/acid 
chloride solution was added over 45 minutes. A white precipitate formed 
and the exothermic reaction raised the temperature of the mixture to 
34.degree. C. After stirring another 15 minutes hydrochloride was filtered 
off and the glyme solution evaporated to near dryness. The residue was 
stirred with 500 ml anhydrous ethyl ether, filtered and evaporated to 
dryness. 82.4 g of a brittle material was collected (79.3% yield). MP: 
66.degree.-72.degree. C. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
685 746 
fluorine, % 46.0 47.6 
______________________________________ 
EXAMPLE 4 
##STR32## 
Following the procedure of Example 1, 20.44 g (0.02 mole) of 
(R.sub.f).sub.2 -diol of structure (A) and 8.72 g (0.040 mole) 
1,2,4,5-benzenetetracarboxylic acid dianhydride (pyromellitic dianhydride) 
were reacted in the presence of 0.05 g. tetramethylammonium chloride. 
After filtration and drying, a brittle tan powder was obtained in 96% 
yield; MP: 97.degree.-115.degree. C. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
588 610 
fluorine % 40.5 42.1 
______________________________________ 
EXAMPLE 5 
##STR33## 
Following the procedure of Example 1, 20.44 g (0.02 mole) of 
(R.sub.f).sub.2 -diol of structure (A) and 22.64 g (0.040 mole) of the 
dianhydride obtained by free-radical addition of 1 mole of ethylene 
bis-mercaptoacetate to 2 moles of 5-norbornene-2,3-dicarboxylic acid 
anhydride (nadic anhydride) were reacted in the presence of 0.4 g 
triethylamine. After filtration and drying, the product was obtained as a 
light yellow powder in 94% yield. MP: 65.degree.-70.degree. C. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
1053 1111 
fluorine, % 27.3 28.6 
______________________________________ 
EXAMPLE 6 
##STR34## 
a. Using the procedure of Example 1, 5.68 g (0.01 mole) of the diol of 
structure C 
##STR35## 
and 6.44 g (0.02 mole) of 3,3',4,4'-benzophenonetetracarboxylic acid 
dianhydride (BTDA) were heated in the presence of 0.4 g of triethylamine. 
After removal of the solvent, the product was obtained as a brittle 
yellowish solid; MP: 116.degree.-121.degree. C in 95% yield. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
606 595 
fluorine, % 26.6 23.3 
______________________________________ 
b. A dianhydride of the same formula structure as shown above may also be 
prepared using the R.sub.f -diol of the structure 
##STR36## 
using the procedure described above. 
EXAMPLE 7 
##STR37## 
Following the procedure of Example 1 20.44 g (0.02 mole) of 
(R.sub.f).sub.2 -diol of structure (A) and 8.48 g (0.04 mole) of 
2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride were heated in the 
presence of 0.044 g of tetramethylammonium chloride. After removal of 
solvent, the product was obtained as a brown solid in 98% yield. MP: 
155.degree.-160.degree. C 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
763 833 
fluorine, % 42.4 40.5 
______________________________________ 
EXAMPLE 8 
##STR38## 
Using the procedure of Example 1, 10.75 g (0.02 mole) of 
6-perfluoroalkyl-4-thiahexane-1-ol and 6.44 g (0.02 mole) of BTDA were 
heated in the presence of 0.022 g of tetramethylammonium chloride. The 
solvent was removed on a rotary evaporator leaving a yellowish brittle 
solid. MP: 123.degree.-132.degree. C 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
860 1026 
fluorine, % 37.6 35.3 
______________________________________ 
EXAMPLE 9 
##STR39## 
Following the procedure of Example 1, 15.24 g (0.015 mole) of 
2,3-di-(1,1,2,2-tetrahydroperfluoroalkylthio)propanol-1 and 4.83 g (0.015 
mole) of BTDA were heated in the presence of 0.20 g of triethylamine. The 
solvent was stripped off on a rotary evaporator leaving a yellowish 
brittle solid. MP: 80.degree.-90.degree. C, in 95% yield. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
1338 1307 
fluorine, % 48.3 47.0 
______________________________________ 
EXAMPLE 10 
##STR40## 
Following the procedure of Example 1, 10.76 g (0.02 mole) of 
6-perfluoroalkyl-4-thiahexane-1-ol and 4.24 g (0.02 mole) of 
tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride were heated in 
the presence of 0.02 g of tetramethyl ammonium chloride. After removal of 
solvent, the product was obtained as a tan glass-like solid, m.p. 
150.degree.-160.degree. C. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
750 889 
fluorine, % 43.1 40.0 
______________________________________ 
EXAMPLE 11 
##STR41## 
Following the procedure of Example 1, 15.24 g (0.015 mole) of 
2,3-di(1,1,2,2-tetrahydrofluoroalkylthio)propane-1-ol and 3.18 g (0.015 
mole) of tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride were 
heated in the presence of 0.02 g of tetramethyl ammonium chloride. After 
removal of solvent, the product was obtained as a tan glass-like solid. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
1228 1042 
fluorine, % 52.6 51.47 
______________________________________ 
EXAMPLE 12 
##STR42## 
Following the procedure of Example 1, 8.52 g (0.015 mole) of 
2-(1,1,2,2-tetrahydroperfluoroalkylthio)-butane-1,4-diol and 6.36 g (0.03 
mole) of tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride were 
heated in the presence of 0.033 g of tetramethylammonium chloride. After 
removal of solvent, the product was obtained as a tan brittle solid, m.p. 
123.degree.-126.degree. C. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
496 623 
fluorine, % 32.5 31.07 
______________________________________ 
EXAMPLE 12a 
##STR43## 
4.30 g (0.050 mole) of 2-butyne-1,4 diol, 7.32 g (0.050 mole) of octyl 
mercaptan, 24.03 g (0.050 mole) of 
1,1,2,2-tetrahydroperfluorodecylmercaptan and 1.64 g (0.010 mole) of 
azobisisobutyronitrile were mixed together and sealed, under nitrogen, in 
an ampol. The reactants were heated at 75.degree. C for 20 hours in a 
shaker bath. On cooling, a soft semisolid was obtained, which by GC 
analysis was observed to be a mixture of 3 products, 
##STR44## 
EXAMPLE 12b 
##STR45## 
4.30 g (0.050 mole) of 2-butyne-1,4-diol, 7.32 g (0.050 mole) of 
octylmercaptan, 23.52 g (0.050 mole) of 
1,1,2,2-tetrahydroperfluoroalkylmercaptan and 1.64 g (0.010 mole) of 
azobisisbutyronitrile were sealed, under nitrogen, in 75.degree. C for 16 
hours in a shaker bath. On cooling, the product was obtained as a soft 
semi-solid, bearing the same distribution of diols as in Example 12a. 
______________________________________ 
Analytical Data Theory Found 
______________________________________ 
% Fluorine 43.97 42.5 
Equivalent wt., OH 
702 768 
______________________________________ 
EXAMPLE 13 
##STR46## 
Following the procedure of Example 1, 7.78 g (0.01 mole) of the diol 
mixture prepared in Example 12b and 6.44 g (0.02 mole) of 
benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride were heated in the 
presence of 0.040 of triethylamine. After evaporation of the solvent, the 
product was obtained as a yellow waxy solid, containing 50% of the above 
compound. 
______________________________________ 
Analytical Data Calculated Found 
______________________________________ 
anhydride equiv. wt. 
706 766 
fluorine, % 23.9 22.5 
______________________________________ 
EXAMPLE 14 
a. 10 g of the compound of Example 1b were dissolved in 20 g 
N,N-dimethylformamide and heated to 80.degree. C for 20 minutes with 1.5 
g, or three times the molar amount of N,N-dimethylaminoethanol. A water 
soluble product was obtained which has the following structure: 
##STR47## 
Using the same procedure as in Example 14a, the anhydrides of Examples 6-12 
were also reacted with N,N-dimethylaminoethanol to give water soluble 
products having the corresponding structures. 
______________________________________ 
Reaction Product of 
N,N-dimethylaminoethanol 
and R.sub.f -anhydride example 
Sample Number 
number R.sub.f -Anhydride 
______________________________________ 
14b 6a 
14c 7 
14d 8 
14e 9 
14f 10 
14g 11 
14h 12 
14i 13 
______________________________________ 
EXAMPLE 15 
Following the procedure of Example 14, the compound of Example 1b was 
reacted with three times the molar amount of the following compounds: 
N,N-dimethyl-propane-1,3-diamine; N-methyl-diethanolamine; 
N-methyl-di-(3-aminopropyl)-amine; 1,4-bis(3-aminopropyl)piperazine; 
N,N-diethylpropane-1,3-diamine; N-dimethylamino-2-propanol; 
N-dimethylamino-1-propanol; N,N,N'-trimethyl-1,2-ethylenediamine; 
N,N-bis[2-hydroxypropyl]aniline; N-(3-aminopropyl)morpholine. In all cases 
water-soluble half ester or half amide products were obtained. These 
stayed dissolved in water under both basic and acidic conditions. 
The compounds of Example 2-13 could also be reacted with 
N,N-dimethylaminoethanol or with any of the above listed compounds to give 
the corresponding water-soluble half ester or half amide products. 
EXAMPLE 16 
5 g of samples of the di-anhydride of Example 1 (33% in glyme) were mixed 
with 20 g of the following compounds: 
polyethylene oxide diol of MW: 600 
polyethylene oxide diol of MW: 2000 
polypropylene oxide diol of MW: 1010 
polytetramethylene diol oxide of MW: 1000 
bis-(2-aminopropyl ether of polyethylene oxide of MW: 600 Jeffamine ED 
(Jefferson Chemical Co.) 
bis-(2-aminopropyl ether of polyethylene oxide of MW: 900 Jeffamine ED 
(Jefferson Chemical Co.) 
bis-(2-aminopropyl ether of polypropylene oxide of MW: 400 Jeffamine D 
(Jefferson Chemical Co.) 
bis-(2-aminopropyl ether of polypropylene oxide of MW: 1000 Jeffamine D 
(Jefferson Chemical Co.) 
bis-(2-aminopropyl ether of polypropylene oxide of MW: 2000 polyester diol 
from adipic acid and 
diethylene glycol of MW: 1000 (Fomrez F18-62; Witco Chemical Co.) 
The samples were slowly heated to 90.degree. C until all glyme had 
evaporated, then heated to 150.degree. C for 2 hours; they formed clear, 
homogeneous solutions which could be further diluted with the original 
unmodified resin. 
These resins modified by the R.sub.f -dianhydride can be used in a myriad 
of applications where surface tension modification is an important 
consideration. The following examples show the usefulness of the novel 
compounds. 
EXAMPLE 17 
A water based coating formulation was mixed together, consisting of 28.6 
parts of water soluble, cross-linkable resin, containing polyethylene 
oxide segments as water solubilizing units and being derived from 
diepoxides, 15.4 parts of a crosslinking melamine resin (Uformite, MM-83 
from American Cyanamid) and 56 parts water. This aqueous resin was applied 
with a No. 6 wound wire rod to electrolytic tin plate, which has a 
remaining layer of a hydrocarbon-type oily impurity from processing and is 
especially difficult to wet. The samples were cured in a circulating air 
oven at 200.degree. C for 10 minutes. 
Surface active compounds were incorporated into the formulation to improve 
wetting, which was judged visually and expressed in percent covered 
surface area. The results are tabulated below. 
______________________________________ 
Coverage 
% 
Ex Additive % of before after 
17 Chemical Type Solids % F cure Difference 
______________________________________ 
a Pluronic L-72 0.5 -- 80 50 -30 
(Wyandotte Chem Co) 
nonionic hydro- 
carbon 
aa 1.0 -- 80 50 -30 
b BYK-301 (Mallin- 
0.5 -- 70 60 -10 
krodt Co) 
silicone type 
bb 1.0 -- 85 75 -10 
c FC-430 (3M Company) 
0.5 0.067 
75 65 -10 
nonionic fluorinated 
cc 1.0 0.134 
75 60 -15 
d LODYNE.RTM. S-100 
0.15 0.067 
100 45 -55 
(CIBA-GEIGY) 
amphoteric fluori- 
nated 
e Compound of 0.18 0.067 
65 65 0 
Example 14a 
ee Compound of 0.36 0.134 
85 85 0 
Example 14a 
f None -- -- 50 30 -20 
g Compound of 0.2 0.05 80 77 -3 
Example 14b 
______________________________________ 
Only the novel compounds of this invention (e,ee, g) essentially prevent a 
reduction of covered surface area during curing; only the ionic 
fluorinated compound of Example (d) gives a 100% wetting of the substrate 
by the aqueous phase. 
EXAMPLE 18 
The water based coating formulation of Example 17 was applied with 
different additives in combination with the amphoteric fluorinated 
surfactant LODYNE.RTM. S-100. Application and evaluation was done as in 
Example 17. 
__________________________________________________________________________ 
Coverage 
% 
Ex LODYNE.RTM. S-100 
Other % of before after 
18 % Additive Solids 
cure Difference 
__________________________________________________________________________ 
a 0.15 Pluronic L-72 
0.5 100 10 -90 
b 0.15 BYK-301 0.5 100 10 -90 
c 0.15 FC-430 0.5 100 15 -85 
d 0.15 Compd of Ex 14a 
0.18 100 100 0 
e 0.10 Compd of Ex 14a 
0.05 90 40 -50 
f 0.07 Compd of Ex 14a 
0.09 95 95 0 
g 0.05 Compd of Ex 14a 
0.12 80 80 0 
h 0.10 Compd of Ex 14b 
0.10 100 100 0 
__________________________________________________________________________ 
Using the novel compounds of Examples 14a and 14b at a level above 0.05% 
(of solids) the original good coverage of the substrate resulting from the 
use of amphoteric LODYNE.RTM. S-100 is retained during the curing step. 
EXAMPLE 19 
To an aqueous can coating formulation of an epoxy resin modified with 
polyethylene oxide to form a water emulsifiable adduct (70 grams) and an 
aminoplast melamine-formaldehyde (30 grams), available commercially as 
"Uformite MM-83" in 100 grams of water, were added selected reactive 
R.sub.f additives as seen in Example 17. 
The anhydrides were reacted with N,N-dimethylaminoethanol to achieve water 
solubility as seen in Example 14 and the resin was applied to electrolytic 
tin plate as described in Example 17. This resin formulation gave 100% 
wetting of the aqueous phase. Therefore, an additional ionic R.sub.f 
surfactant was not needed. 
The results are tabulated below: 
______________________________________ 
Mol Ratio of 
Ex Additive = Compound 
% of Coverage 
COOH/R.sub.f 
19 of Example Solids after cure 
in Additive 
______________________________________ 
a 14a 0.03 65 2 
b 14b 0.03 100 4 
c 14d 0.03 98 2 
d 14c 0.03 65 2 
e 14h 0.03 98 4 
f 14f 0.03 80 2 
g 14e 0.03 50 1 
h 14g 0.03 40 1 
i 14i 0.03 90 4 
k FC-430 0.03 60 -- 
1 Control -- 10 -- 
______________________________________ 
These results demonstrate the superior performance of the novel R.sub.f 
-additives, with the best results obtained with a high ratio of 
carboxy/R.sub.f groups. 
EXAMPLE 20 
A solution of a thermosetting acrylic resin (Rohm & Haas Co.) (50% in 
xylene) was heated for 10 minutes with 2% (based on total solids) of the 
compound of Example 1 until a clear solution was obtained. Several films 
were cast on aluminum panels, dried, and cured 200.degree. C for 10 
minutes, A fluorine-free control sample was also prepared. All samples 
formed smooth, glossy coatings. Cross-cut adhesion was tested by cutting 5 
close lines into the coating with a razor blade, pressing an adhesive tape 
on the cut and pulling the tape off. If adhesion is unsatisfactory, the 
coating will strip off. None of the coatings containing the compound of 
Example 1 failed the test, even when the resin was further diluted to 0.5% 
additive based on solids. 
Control applications, containing no additive, all failed badly. 
EXAMPLE 21 
453.6 grams of LP-32 polysulfide resin, commercially available from 
Thiokol, was modified with 6.5 grams (1.4% based on resin) of the 
dianhydride of Example 1. Samples of modified (T-816F) and unmodified 
(T-816) LP-32 sealant formulations.sup.1) were coated on glass, aluminum 
and concrete and allowed to cure for several days at room temperature. The 
samples were then cured for an additional 7 days at 70.degree. C and cut 
into one inch strips for testing. The samples were then immersed in 
distilled water at room temperature for 7 days, dried and tested by 
Instron Testing Apparatus for peel strength. Results are given on Table C. 
______________________________________ 
1) 100 Parts LP-32 
25 Parts CaCO.sub.3 Filler 
41.5 Parts clay 
10 Parts titanium oxide Part A 
8 Parts thixotropic agent 
0.1 Part sulfur 
23.5 Parts plasticizer 
7.5 Parts lead dioxide 
0.5 Part lead stearate 
Part B 
4.4 Parts plasticizer 
______________________________________ 
Parts A and B are mixed together on a roller mill. 
Table C 
______________________________________ 
Adhesion of Modified and Unmodified T-816 Polysulfide Sealant 
to Glass, Aluminum and Concrete 
Average Type of Failure 
Formulation 
Peel Value Adhesive 
Cohesive 
Substrate 
Test Sample 
lbs. % % 
______________________________________ 
Aluminum 
T-816 a 21.1 20 80 
b 17.7 70 30 
c 19.0 30 70 
d 20.0 50 50 
T-816F a 4.0 100 0 
b 5.0 100 0 
c 3.0 100 0 
d 2.9 100 0 
Glass T-816 a 23.0 0 100 
b 21.4 3 97 
c 22.0 0 100 
d 20.2 0 100 
T-816F a 13.4 100 0 
b 12.5 100 0 
c 1.5 100 0 
d 2.0 100 0 
Concrete 
T-816 a 0.4 100 0 
b -- 100 0 
c 0.7 100 0 
d 0.4 100 0 
T-816F a 4.0 100 0 
b 5.5 97 3 
c 2.7 100 0 
d 2.5 100 0 
______________________________________ 
On smooth surfaces, such as glass and aluminum, the modified T-816F 
formulation performs considerably worse than the control. The R.sub.f 
-dianhydride additive acts in fact as an internal mold release agent. 
However, on concrete, T816F is considerably better than the the control in 
peel stength values. 
EXAMPLE 22 
5 g of the dianhydride of Example 1 (33% in ethylene glycol dimethyl ether, 
glyme) was mixed with 15 g Thanol-TE 3000, a polypropylene oxide (MW: 
2000) from Jefferson Chemical Corporation and reacted as described in 
Example 15. The glyme was evaporated in vacuo at 70.degree. C. This 
resulting flourine containing prepolymer was used to modify the following 
two polyurethane foam formulations with varying amounts of fluorine. 
______________________________________ 
Polyurethane Foam Formulations 
Parts by Weight 
Components A B 
______________________________________ 
Thanol TE-300 300 300 
1,4-butanediol 38 48 
trimethylolpropane 15 -- 
water 0.6 -- 
T-12 (tin catalyst) 0.1 0.1 
Freon 11B -- 4.2 
Isonate 143 L (diisocyanate) 
21 19.8 
______________________________________ 
The following table shows that very small amounts of fluorine incorporated 
in this manner greatly reduce the foam density: 
______________________________________ 
% by 
Ex. Density 
Weight Compound 
Number Formulation 
% F [g/cm.sup.3 ] 
Example 1 in foam 
______________________________________ 
1 A -- 0.39 0 
2 A 0.0021 0.29 0.00534 
3 A 0.0042 0.24 0.01068 
4 A 0.0084 0.22 0.02136 
5 A 0.0168 0.23 0.04272 
6 B 0 0.48 0 
7 B 0.002 0.39 0.0051 
8 B 0.004 0.34 0.0102 
9 B 0.008 0.31 0.0204 
10 B 0.016 0.28 0.0408 
______________________________________ 
EXAMPLE 23 
5 g of the dianhydride of Example 1 (33% in glyme) was mixed with 15 g of 
two different siloxane diols of the following structures: 
##STR48## 
R is a lower alkylene of up to 6 carbons. 
The mixtures are heated to 100.degree. C and stirred for 20 minutes, after 
which time clear solutions were obtained, which consisted of the siloxane 
-- diesters with the novel dianhydride, dissolved in excess siloxane diol. 
Solutions of Silicone DC-20 (Dow Corning Corporation), 6% in 
1,1,1,-trichloroethane, a mold release agent used in polyurethane 
manufacture, were modified by small amounts of the above prepared 
derivatives to give 0.4% F on solids and tested for their wetting behavior 
on aluminum sheet by spreading a thin film with a Nr. 20 wire rod. 
Excellent wetting was achieved with both additives, while the control 
sample beaded up. In addition, the sample derived from Q4-3557 showed very 
little foaming.