The present invention relates to film and coating materials prepared from novel fluorinated poly(phenylene ether ketones). A fluorinated poly(phenylene ether ketone) is prepared by reacting a bisphenol with 1,1,1,3,3,3 hexafluoro-2,2-bis 4-(4-halobenzoyl) phenyl propane (wherein halo is fluoro or chloro), which is a novel monomer formed as the reaction product of halobenzene (wherein halo is fluoro or chloro) and 1,1,1,3,3,3 hexafluoro-2,2-bis (p-chloro formyl phenyl) propane. Especially beneficial results of this invention are that films and coating materials prepared from the novel fluorinated poly(phenylene ether ketone) are essentially optically transparent/colorless and have a lower dielectric constant than otherwise comparable, commercially available poly(phenylene ether ketones). Moreover, unlike the otherwise comparable commercially available materials, the novel fluorinated poly(phenylene ether ketones) of the present invention can be solution cast or sprayed to produce the films and coatings. Furthermore, the long term thermal stability of the polymers of the present invention is superior to that of the commercially available materials

Cassidy, Patrick E.

St.clair, Anne K.

Tullos, Gordon L.

English

NASA Technical Reports Server

United States Patent 
Cassidy et al. * 
[54] LOW D I E L E W C  FLUORINATED 
POLY(PHENYLENE ETHER KETONE) FILM 
AND COATING 
[75] Inventors: Patrick E. Cassidy, Austin; Gordon L. 
Tullos, Lake Jackson, both of Tex.; 
Anne I(. St. Clair, Poquoson, Va. 
represented by the Administrator of 
the National Aeronautics and Space 
Administration, Washington, D.C. 
[73] Assignee: The United States of America as 
[21] Appl. No.: 248,009 
[22] Filed: Sep. 23, 1988 
[51] Int:Cl.' ........................ CO8G 8/02; C08G 14/00 
[52] U.S. Cl. .................................... 528/125; 528/126; 
528/128; 528/219; 528/220 
[58] Field of Search ............... 528/125, 126, 128, 219, 
528/220 
[561 References Cited 
U.S. PATENT DOCUMENTS 
3,442,857 5/1969 Thornton ............................ 528/176 
Primary Examiner-John Kight 
Assistant Examiner-M. L. Moore 
Attorney, Agent, or Firm-George F. Helfrich; John R. 
Manning; Charles E. B. Glenn 
VI ABSTRACI' 
A fluorinated poly(pheny1ene ether ketone) having one 
of the following structural formulas 
[11] Patent Number: 4,902,769 
[45] Date of Patent: Feb, 20, 1990 
-continued 
1 
or 
wherein X is selected from the group consisting of aryl, 
SO;?, 0, CO, -C(CH3)2, and S, is prepared by reacting 
a bisphenol with 1,1,1,3,3,3-hexafluor0-2,2-bis[4-(4- 
halobenzoyl)phenyl]propane (wherein halo is fluoro or 
chloro), which is a novel monomer formed as the reac- 
tion product of halobenzene (wherein halo is fluoro or 
chloro) and 1, 1,1,3,3,3-hexafluoro-2,2-bis(p-chlorofor- 
mylpheny1)propane. 
9 Claims, No Drawings 
https://ntrs.nasa.gov/search.jsp?R=19910017906 2020-03-24T07:00:31+00:00Z
retain title. 
BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates generally to fluorinated 
poly(pheny1ene ether ketone). It relates particularly to a 
highly optically transparent, low dielectric fluorinated 
poly(pheny1ene ether ketone), and especially to films or 
coatings thereof. Both the precursor and the polymer 
itself are novel compositions of matter. 
2. Prior Art 
As a class, poly(pheny1ene ether ketones) are thermo- 
plastic matrix resins which are being considered for 
fiber-reinforced composite applications. However, 
these polymer systems have been difficult to produce in 
high molecular weight form, as has been the case for 
PEEK 8, a commercial poly(pheny1ene ether ether 
ketone) marked by ICI. (See J. P. Critchley et al, Heat 
Resistunt Polymers, Plenum Press, New York, p. 173). 
Poly(pheny1ene ether ketones) have not been materi- 
4,902,769 
1 2 
Another primary object of the present invention is to 
LOW DIELECTRIC FLUORINATED provide a highly optically transparent, fluorinated 
poly(pheny1ene ether ketone) film and coating material. 
Another object of the present invention is to provide 
5 a processable, soluble fluorinated poly(pheny1ene ether 
ketone) film and coating material. 
Another object of the present invention is to provide 
ether ketone) 
Another object of the present invention is to provide 
a fluorinated low dielectric poly(pheny1ene ether ke- 
tone) film and coating material having a dielectric con- 
stant near 2.4 which should find special utility in elec- 
tronic applications where high electrical insulation and 
Another object of the present invention is to provide 
a highly optically transparent fluorinated poly(pheny- 
lene ether ketone) film and coating material having high 
transparency at wavelengths in the visible region of the 
20 electromagnetic spectrum, such material being useful 
for transmitting solar energy as needed in such applica- 
tions as transmitting solar energy as needed in such 
applications as solar cell covers or second surface mir- 
ror coatings in thermal control coating systems. 
SUMMARY O F  THE INVENTION 
According to the present invention the foregoing 
objects are achieved by the provision of a fluorinated 
poly(pheny1ene ether ketone) having the following 
POLYG'HENYLENE ETHER KETONE) FILM AND 
COATING 
ORIGIN OF THE INVENTION 
The invention described herein was jointly made in 
an employee of the United States Government. In ac- 
cordace with 35 
the performane of work under a NASA Grant and by a highly fluorinated po1y(Phenylene 
202, the grantee elected to 10 
15 thermal stability are required. 
25 
30 structural formula: 
L 
40 
als of choice of thin film aDDlications. Thev are bv na- 
ture insoluble and cannot de'solution cast i h o  polimer 
films. The only known film form of the commercial 
product PEEK 8 must be extruded. The extruded film 
is difficult to produce and is pale to dark amber in color, 
depending on thickness. 
State-of-the-art polymer film and coating materials 
used as passivant insulators and interlevel dielectrics in 
the area of microelectronics range in dielectric constant 
from approximately 3.2 to 4.0, depending upon fre- 
quency and moisture content. Although the dielectric 
constant of commercial poly(pheny1ene ether ketone) is 
attractively low (2.8-2.9 at 10 GHz). it has not been 
useful in the field of electronics because of its inability 
to be processed. 
State-of-the-art optically transparent polymer film 
and coating materials used in thermal control coating 
systems and for other space applications have been 
traditionally the aromatic polyesters (such as Mylar 8) 
or fluorinated hydrocarbons (such as FEP-Teflon 8). 
Poly(pheny1ene ether ketones) have not been exploited 
for thin film applications in space because of their inabil- 
ity to be processed in the form of thin film materials and 
because they are not optically transparent enough to be 
effective at the required solar wavelength (500  nm). 
Accordingly, it is a primary object of the present 
invention to provide a low dielectric fluorinated poly(- 
phenylene ether ketone) film and coating material. 
45 
50 
55 
60 
65 
J n  
This polymer, which is denominated 12F-PEK, is pre- 
pared by reacting bisphenol AF, which is 
with 1, 1,1,3,3,3,-hexafluoro-2,2-bis[4-(4-halobenzoyl)- 
phenyl] propane, which is 
wherein X is F or C1. 
The 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-halobenzoyl)- 
phenyl] propane is a novel monomer, which is formed 
as the reaction product of halobenzene and 1,1,1,3,3,3- 
hexafluoro-2,2-bis(p-chloroformylphenyl) propane. 
By the present invention, a fluorinated poly(pheny- 
lene ether ketone) is provided which is essentially opti- 
cally transparent/colorless and has a lower dielectric 
constant than the commercial material PEEK 8. The 
material of the present invention is soluble in common 
organic solvents, unlike commercial poly(pheny1ene 
ether ether ketone), and can be solution cast or sprayed 
to produce thin films or coatings. The long term ther- 
4,902,769 
3 4 
mal stability of the fluorinated poly(pheny1ene ether The 12F-PEK polymer is produced by reacting the 
ketone) of the present invention is superior to that of 6FBFP with the appropriate potassium salt of a bisphe- 
PEEK 8. These improvements in dielectric properties, nol, the bisphenol A F  shown in Equation I having been 
optical transparency, solubility, processability, and used in the specific example of the present invention. 
thermal stability have been made without sacrificing 5 Polymerization of this fluorinated poly@henylene ether 
other polymer properties. ketone) was achieved by heating the 6FBFP with the 
potassium salt of bisphenol A F  in a solvent to 165" C. to 
DESCRIPTION O F  THE PREFERRED form a viscous, high molecular weight solution. The 
EMBODIMENTS resulting 12F-PEK polymer, which was precipitated in 
The highly optically transparent, low dielectric fluo- 10 water, had an inherent viscosity of 0.71 dl/g when mea- 
rinated poly(pheny1ene ether ketone) according to the sured at 35' C. in chloroform. 
present invention is designated hereinafter as 12F-PEK. Films or coatings of the I2F-PEK polymer are pre- 
It is prepared according to the reaction route shown pared by spray-coating, painting, or spreading the poly- 
below: mer in a solvent onto glass or other substrate, and re- 
6FDCA 
6FDAC 
I 
Bisphenol AF 6FBFP 
L 
I2F-PEK 
The first step in preparing the 12F-PEK polymer of 
the present invention involves synthesis of the novel 
monomer 1, 1,1,3,3,3-hexafluoro-2,2-bis[4-(4-fluoroben- 
zoy1)phenyllpropane (designated 6FBFP in Reaction 
Equation I above). Preparation involves reaction of 50 
1,1,1,3,3,3-hexafluoro-2,2-bis(p-carboxyphenyl)propane 
(6FDCA) with thionyl chloride to produce the mono- 
mer precursor 1,1,1,3,3,3-hexafluor0-2,2-bis(p- 
chloroformylpheny1)propane (6FDAC). The 6FDAC 
is then reacted with fluorobenzene in the presence of 55 
aluminum chloride to produce the 6FBFP monomer. 
J n  
moving the solvent by either air drying or heating in a 
vacuum or forced air oven. Films and coatings that are 
optically transparent/colorless, flexible and tough are 
thus produced. 
Although the bisphenol used in the specific example 
of the present invention was the bisphenol A F  (struc- 
ture shown in Equation I), any all-aromatic bisphenol 
compound could be reacted with the 6F-bis-fluorophe- 
nyl monomer 6FBFP to produce a fluorinated poly(- 
phenylene ether ketone) as shown below in Reaction 
Equation 11. 
- EQUATION I1 
4,902,769 
6 
-continued - 
where X = aryl, SOL 0, CO, -C(CHj)z, or S. 
EXAMPLES 
EXAMPLE I 
Preparation of (6F-bis-fluorophenyl monomer 
A 50 ml, round-bottom flask was charged with 1.18 g 
(3 mmol) of 1,1,1,3,3,3-hexafluoro-2,2-bis(p-carboxy- 
pheny1)propane (designated above as 6FDCA) and 
25 thionyl chloride ( 5  ml, 69 mmol). The mixture was 
stirred at reflux for two hours, at which time the reac- 
tion mixture was clear and almost colorless. The reac- 
tion flask was allowed to cool, and unreacted thionyl 
has also been used to produce 12F-PEK pobmer. The chloride was removed by distillation. A vacuum pump 
6FBFP. however, is preferable. 30 was further used to remove any remaining thionyl chlo- 
A comparison of properties of the fluorinated poly(- ride. The resulting residue, 1,1,1,3,3,3-hexafluoro-2,2- 
phenylene ether ketone) 12F-PEK of the present inven- bis(p-chloroformylpheny1)propane (6FDAC), was a 
tion with those of the commercially available poly(phe- clear, beige viscous liquid (1.3 g, 100% yield), which 
nylene ether ether ketone) PEEK @ are shown in Table formed white needle crystals from hexane and had a 
I below. The 12F-PEK has a higher glass transition 35 melting point of 96" C.-97" C. 
temperature as determined by differential scanning cal- In addition to the above preparation, 8 ml of fluoro- 
orimetry. The dielectric constant of the fluorinated benzene and 4 g (30 mmol) of aluminum chloride were 
polymer of the present invention is decidedly lower placed in a 100 ml three-neck, round-bottom flask. The 
than that of the commercial material. Although the mixture was stirred and heated to reflux (85" C.) under 
dynamic thermogravimetric analysis (TGA) data show 40 argon gas. A solution of 6FDAC (5.51 g, 12.8 mmol) 
the two polymers to have relatively the same behavior, prepared as stated above in 6 ml of fluorobenzene was 
upon isothermal aging in air at 350" C. the 12F-PEK added dropwise to the reaction flask containing fluoro- 
showed superior long-term thermal stability. The 12F- benzene/aluminum chloride over a 30 minute period. 
PEK, as opposed to PEEK @, can be dissolved in a The reaction mixture was stirred an additional ten min- 
solvent such as chloroform, methylene chloride, or 45 utes and cooled to room temperature. The reaction 
methyl ethyl ketone, and applied as a film or coating to mixture was slowly poured into 200 ml of rapidly stir- 
a desired substrate. It can also be solution cast to pro- ring water. The reaction flask was rinsed with 3-50 ml 
duce a self-supporting polymer film, as opposed to ex- portions of benzene and these washes were also poured 
truding which is the method used to produce commer- into the water. After stirring for ten minutes, the or- 
cia1 film from PEEK @. The 12F-PEK polymer of the 50 ganic layer was separated and washed with 200 ml of 
present invention is more colorless or optically trans- fresh water. The organic layer was again separated and 
parent in the 400-500 nm range of the electromagnetic dried over anhydrous magnesium sulfate. The dry or- 
spectrum, as compared with the amber-colored com- ganic layer was then decanted and concentrated to an 
mercial material PEEK @. oily residue. Isopropyl alcohol (30 ml) was added to the 
55 residue and stirred to yield white crystals of the desired TABLE I 
product 1,1,1,3,3,3-hexafluoro-2,2,-bis[4-(4-fluoroben- 
OF ETHER zoyl)phenyl]propane (6FBFP). Crystals of this polymer 
IZF-PEK PEEK @ precursor were filtered and recrystallized from isopro- 
180' C. 143' C. pyl alcohol to* yield white plate needles (4.0 g, 56% 
343'c 60 yield) with a melting point of 142" C.-143" C. The 
537' C. 540' C. structure of the 6FBFP (6F-bisfluorophenyl monomer) 
is: 
Although 6F-bis-fluorophenyl monomer (6FBFP, 
Equation I) was used in the specific examples to prepare 2o 
the 12F-PEK polymer of the present invention, the 
6F-bis-chlorophenyl monomer shown below 
i0T&iOCl c+--c 0 c 0 c 0 
CF3 
PROPERTY 
Glass Transition Temperature 
Melt Temperature (a) 
Dynamic TGA. 10% wt. loss in air at 
Isothermal TGA. % wt. loss 
Optically Soluble Common Transparent Organic at 400-500 Solvents nm Ye3 s N O  65 F+!-&&!-Q-F. 
(a) Semicry\iallinr \iruciure from x-ray dilfraciion hut no ohurvrblr: melt 
Dielectnc Constant at IO GHz 2.40 2.85 
after 100 hours at 350' C. 14% 34% 
200 hours at 350' C. 20% 96% 
Film Former (from Cast Solution) YeS NO 
CFi 
4,902,769 
7 8 
The above examples are considered illustrative of the 
invention, and there may be modifications and varia- 
tions therein that will be apparent to those skilled in the 
art without departing from the spirit and scope of the 
EXAMPLE I1 
Preparation of Fluorinated Poly(pheny1ene ether 
ketone) (I2F-PEK) 
A ml, round-bottom flask was 5 invention 
charged with 0.6167 g (1.823 mmol) of bisphenol A F  
6 ml dimethylacetamide (DMAc) and 3 ml of toluene. 1o Of: 
The reaction flask was then fitted with a Deansstark 
trap which was filled with toluene and topped with a 
reflux condenser. The contents of the flask were heated 
under argon for one hour at reflux (120' C.). Water was 
azeotroped off with toluene as the potassium sale of 
bisphenol A F  formed. When water evolution ceased, 
the Dean-Stark trap was drained, and the excess toluene 
in the reaction flask was allowed to distill until a tem- 
perature of 163" C. was obtained. The flask was then 
allowed to cool and the Dean-Stark trap was replaced 2o 
with the reflux condenser. At this time, 1.oooO g (1.823 
mmol) of 6F-bis-fluorophenyl monomer 6FBFP (struc- 
ture shown and preparation described in Example 1 
above) was added to the reaction flask in crystal form. 
The reaction mixture was heated to reflux at 160" 25 
C.-165" C. and stirred for 15 minutes, at which time the 
contents of the flask became noticeably viscous. The 
reaction mixture was diluted with 3 ml of DMAc and 
stirred at reflux for 45 minutes. The flask was allowed to 
cool and the contents were further diluted with 40 ml 3o 
DMAc. The DMAc solution was solowly poured into 
400 ml of rapidly stirred water to precipitate the poly- 
mer. This reaction precipitate was white and flaky and 
was allowed to stir for one and one-half hours in water. 
solved in 30 ml of chloroform. The chloroform solution 
was slowly dripped into rapidly stirring methanol (200 
ml) to yield a stringy white precipitate. The mixture 
was filtered and the resulting precipita was dried in 
poly(pheny1ene ether ketone) 12F-PEK (as shown in 
Equation I). By the above preparation the yield was 
1.17 g at 76%. The inherent viscosity of the 12F-PEK 
polymer was 0.71 dl/g, indicating a high molecular 
weight product. The polymer was soluble in common 45 
organic solvents. 
as defined in the hereto appended claims. 
What is is: 
(the structure ofbisphenol A F  was shown previously in 
Equation I), 0.5040 g (3.65 mmol) potassium carbonate, 
A fluorinated poly@henylene ether ketone) having 
a from the s o u p  
The precipitate was collected by filtration and dis- 35 and 
vacuum at 80' C. for three hours to yiel 2 the fluorinated 4o 
EXAMPLE 111 
Preparation of Fluorinated Poly(pheny1ene ether 
ketone) 12F-PEK Films/Coatings 
The fluorinated poly(pheny1ene ether ketone) 12F- 
PEK polymer as prepared in ~~~~~l~ 11 above was 
dissolved in a mixture of 70.0 methylene chlo,+je/. 
wherein X is selected from the group consisting of aryl, 
2. A soluble, high temperature stable, highly optically 
transparent. low dielectric fluorinated poly(pheny1ene 
ether ketone) formed by the reaction in a solvent of 
5o SOz,O, CO, -C(CH3)2, and S. 
chloroform at a concentration of 10% solids by weight. 
Polymer films were prepared by casting the cold 12F- 55 halobenzoyl)phenyllpropane~ wherein 
bisphenol AF with 1,1,1,3.3,3-hexafluoro-2,2-bis[4-(4- 
is 
PEK polymer solution onto glass plates in an enclosed 
dust-free chamber at a relative humidity of 10%. Solu- 
were set to ensure final film thicknesses of 1 mil and 0.5 
from the group consisting Of and chloro. 
3. A soluble, high temperature stable, highly optically 
ether ketone) formed as the reaction product Of 
tions were spread with a doctor blade, and blade gaps transparent, low dielectric, fluorinated poly(phenylene 
mil. m e  films were dried overnight at room tempera- 60 ~~~,1,~,~,3-he~~fluoro-2,2-bis[4-4-(halobenzoy~)pheny~]- 
ture and heated in a vacuum Oven for one hour at 150" propane, wherein hato is selected from the group con- 
C. 
Films were removed from glass substrates by immers- 
ing in a water bath. The resulting I2F-PEK polymer 
films were colorless/optically transparent, having ultra- 65 
violet films were transmission also flexible cut-offs and in had the a range glass of transition 360 nm. tem- The H O G O H  and 
perature of 180" C. 
sisting of fluoro and chloro, with a bisphenol selected 
from the group consisting Of 
9 
4,902,769 
10 
7. The high temperature stable, highly optically trans- 
parent, low dielectric film or coating of claim 5, which 
is produced by dissolving the fluorinated poly(pheny- 
lene ether ketone) in a solvent and spreading or spray- 
OH, 5 ing the resulting solution on a substrate to form the film 
or coating. 
8. A monomeric material having the following struc- 
tural formula 
-continued 
. O e X a - -  
wherein X is selected from the group consisting of aryb 
S02,0, CO, -C(CH3)2, and S. 
parent, low dielectric film or coating formed from the 
fluorinated poly(pheny1ene ether ketone) of claim 2. 
5. A high temperature stable, highly optically trans- 
10 
4. A high temperature stable, highly optically trans- 
x uiur&ie 0 c 0 c 0 c 0 x, 
CF3 
parent, low dielectric film or coating formed from the 15 wherein X is selected from the group consisting of fluo- 
fluorinated poly@henylene ether ketone) of claim 3. rine and chlorine. 
6. The high temperature stable, highly optically trans- 9. 1,1,1,3,3,3-Hexafluoro-2,2-bis[4-(4-halobenzoyl)- 
parent, low dielectric film or coating Of claim 4, which phenyllpropane formed as the reaction product of 
is produced by dissolving the fluorinated poly(pheny- 1,1,1,3,3,3-hexafluoro-2,2-bis(p-chloroformylphenyl)- 
lene ether ketone) in a solvent and spreading or spray- 20 propane and halobenzene, wherein halo is selected from 
ing the resulting solution on a substrate to form the film the group consisting of fluoro and chloro. 
or coating. * * * * *  
25 
30 
35 
40 
45 . 
50 
5 5  
60 
65 


Low dielectric fluorinated poly(phenylene ether ketone) film and coating

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