NASA CASE NO.

PRINT FIG. /

The invention disclosed in this document resulted from research in aeronautical and

space activities performed under programs of the National Aeronautics and Space

Administration. The invention is owned by NASA and is, therefore, available for

licensing in accordance with the NASA Patent Licensing Regulation (14 Code of

Federal Regulations 1245.2).

To encourage commercial utilization of NASA-owned inventions, it is NASA policy to

grant licenses to commercial concerns. Although NASA encourages nonexclusive

licensing to promote competition and achieve the widest possible utilization, NASA

will provide the necessary incentive to the licensee to achieve early practical

application of the invention.

Address inquiries and all applications for license for this invention to NASA Patent

Counsel, Langley Research Center, Code 143, Hampton, Virginia 23681-0001.

Serial No.: 08/209,504

03/07/94 LaRC

(NASA-Case-LAR-15041-1)

POLY(ARYLENE ETHER)S CONTAINING

PENDENT ETHYNYL GROUPS Patent

Application (NASA. Langley

Research Center) 24 p

• H

N95-13838

Unclas

G3/27 0029865
AWARDS ABSTRACT 

POLY(ARYLENE ETHER)S CONTAINING PENDENT ETHYNYL GROUPS 

NASA Case No.: LAR 15041 -1 

Poly(arylene ether)s are condensation polymers that can be prepared by various 

routes. The most common route involves the reaction of an aromatic bisphenol with an 

activated aromatic dihalide to form the polymer. The synthesis and characterization of 

poly(arylene ether)s containing ethynyl groups has been known to those skilled in the 

art. Ethynyl and substituted ethynyl groups have been placed on the ends of oligomers 

and pendent along the backbone of polymers and thermally reacted to induce chain 

extension, rigidization, branching andlor crosslinking. In addition, a series of phenyl 

ethynyl terminated arylene ether oligomers having good melt stability were prepared 

and thermally reacted to yield polymers exhibiting excellent solvent resistance and high 

adhesive properties. 

By the present invention a series of novel bisphenols containing pendent ethynyl 

groups were synthesized. These bisphenols contain an ethynyl or substituted ethynyl 

group which undergoes a thermal reaction with other ethynyl groups at temperatures 

ranging from approximately 150°C to approximately 400°C. The bisphenols can react 

with activated dihalides or activated dinitro compounds to form arylene ethers, or react 

with acid chlorides to form esters. Since these bisphenols are difunctional, they can 

react with other difunctional compounds to form polymers. 

The novelty of the invention resides in the bisphenol structure which contains pendent 

ethynyl groups. Poly(ary1ene ether)s are prepared from the reaction of the ethynyl 

containing bisphenols with activated difluoro monomers. When heated, these polymers 

form a crosslinked structure which yields the unexpected properties of improved solvent 

resistance, glass transition temperature, and modulus. In addition these polymers are 

high molecular weight and form tough films before the ethynyl crosslinking reaction 

takes place. 

Inventors: Paul M. Hergenrother 

Address: 304 Old Dominion Road 

Yorktown, VA 23692 

Brian J. Jensen 

127 Branscome Blvd. 

Williamsbura, VA 231 85 

Employer: NASA LaRC 

Initial Evaluator: Terry L. St. Clair 

Serial No.: 08/209,504 

Filed: March 7, 1994 
LAR 1 5041-1 -1 - PATENT APPLICATION

POLY(ARYLENE ETI-IER)S CONTAINING PENDENT ETHYNYL GROUPS

Origin of the Invention

5 The invention described herein was made by employees of the United

States Government and may be manufactured and used by or for the Government

for governmental purposes without the payment of any royalties thereon or

therefor.

10 Background of the Invention

1. Field of the Invention

15

20

The present invention relates to a series of new bisphenols containing pendent

ethynyl groups and new poly(arylene ether)s containing pendent ethynyl groups.

These bisphenols are reacted with activated dihalide monomers to form

poly(arylene ether)s with pendent ethynyl groups. Upon heating, the pendent

ethynyl groups react to form crosslinked resins that are useful as adhesives,

composite matrices, moldings and f'dms.

2. Description of Related Art

25

Poly(arylene ether)s are condensation polymers that can be prepared by various

routes. The most popular route involves the reaction of an aromatic bisphenol

with an activated aromatic dihalide to form the polymer which has a repeat unit of

the general type
LAR 15041-1 -2- PATENT APPLICATION

5

--_--O--Ar --O--Ar' t

where Ar is a divalent aromatic radical, which can be as simple as 1,3- or 1,4-

disubstituted benzene, or it may be a bis-3 or 4-(diphenylene) having the general

structure

where X=nil, O, S, SO2, C=O, C(CH3)2, C(CF3)2, etc. Ar may be any other

appropriate divalent radical. Ar' is a divalent aromatic which contains an electron

1 5 withdrawing activating group para to the halide to be displaced. Ar' has the

general structure

20

where X= SO2, C=O, etc.

25 m ,

O O

II II

--C _C--

30

Synthesis and characterization of poly(arylene ether)s containing ethynyl

groups have been reported in the literature and summarized in two reviews [P. M.

Hergenrother, J. Macromol. Sci. Rev. Macromol. Chem., C19, 1 (1980) and P.
LAR 1

5

10

5041 - 1 -3- PATENT APPLICATION

M. Hergenrother, in H. Mark, ed., Encyclopedia of Polymer Science and

Engineering. 2nd ed., Vol. 1, John Wiley & Sons, Inc., New York, 61 (1985)].

Ethynyl and substituted ethynyl groups have been placed on the ends of oligomers

and pendent along the backbone of polymers and thermally reacted to induce chain

extension, rigidization, branching and/or crosslinking. More recently, a series of

phenylethynyl terminated arylene ether oligomers having good melt stability were

prepared and thermally reacted to yield polymers exhibiting excellent solvent

resistance and high adhesive properties [R. G. Bryant, B. J. Jensen and P. M.

Hergenrother, Polym. Prepr., 33(1), 910 (1992)].

Summary of Invention

15

20

According to the present invention, a series of novel bisphenols containing

pendent ethynyl groups were synthesized having the following general structure:

C-C-R

where R = H, n-C4H 9- , and C6I-I5- .

These bisphenols contain an ethynyl or substituted ethynyl group which undergoes

a thermal reaction with other ethynyl groups at temperatures from - 150"C to

25 -400"C, depending on the R group. In comparing the curing behavior of two

different materials, when R=H, differential scanning calorimetry at a heating rate

of 20 °C/minute indicates the reaction is initiated at - 225" C and is complete after

0.5h at 250"C; but if R= f, the reaction initiates at slightly less than 350"C and

is complete after a short period (< 1 h) at 350" C. Other R groups would be

30 expected to have different reaction initiation temperatures. The bisphenols can
LAR 1 5041-1 -4- PATENT APPLICATION

react with activated dihalides or activated dinitro compounds to form arylene

ethers, or react with acid chlorides to form esters. Since these bisphenols are

difunctional, they can react with other difunctional compounds to form polymers.

Poly(arylene ether)s are prepared from the reaction of the ethynyl containing

5 bisphenols with activated difluoro monomers. Upon heating these polymers at

elevated temperatures, the ethynyl groups react with one another to form a

crosslinked structure. The advantage of poly(arylene ether)s containing pendent

ethynyl groups compared to linear poly(arylene ether)s is the ability to react

forming a crosslinked structure which typically increases the solvent resistance,

10 glass transition temperature, and modulus. These properties are important for

various applications as films, moldings, adhesives and composites.

The advantage of poly(arylene ether)s containing pendent ethynyl groups

compared to acetylene-terminated arylene ether oligomers (ATAE) is that the

poly(arylene ether)s containing pendent ethynyl groups are high molecular weight

1 5 and form tough f'dms before the ethynyl crosslinking reaction takes place. The

ATAEs typically form brittle films. Furthermore, the crosslink density of the

cured resins from poly(arylene ether)s containing pendent ethynyl groups can be

controlled by copolymerizing bisphenol without ethynyl groups and bisphenol

containing the pendent ethynyl groups to form high molecular weight polymers.

20 With ATAEs the crosslink density can be varied only by changing the molecular

weight of the oligomer, which affects the ability to make f'dms and moldings.

An object of this invention is to provide a bisphenol containing a pendent

ethynyl group.

Another object of this invention is to provide a bisphenol containing a pendent

25 phenylethynyl group.

Another object of this invention is to provide bisphenols containing pendent

substituted ethynyl groups.

Another object is to provide bisphenols containing pendent ethynyl groups

which undergo a crosslinking reaction at temperatures from - 150"C to -400 °C.

30 Another object is to provide poly(arylene ether)s with pendent ethynyl or
LAR 15041-1 -5- PATENT APPLICATION

substituted ethynyl groups from the reaction of these bisphenols with activated

dihalide monomers.

Another object is to provide poly(arylene ether)s containing pendent ethynyl

groups which crosslink to form a network structure by heating at elevated

5 temperatures.

Another object is to provide copolymers containing pendent ethynyl groups

which crosslink to form a network structure by heating at elevated temperatures.

10

15

20

Brief Description of the Drawings

FIG. 1 is an equation showing the synthesis of 4-bromotrifluoroacetophenone

and 1,1-bis(4-hydroxyphenyl)-l-(4 bromophenyl)-2,2,2-trifluoroethane according to

the present invention;

FIG. 2 is an equation showing the synthesis of l,l-bis(4-hydroxyphenyl)-l-

(4 ethynylphenyl)-2,2,2-trifluoroethane, 1,1 -bis(4-hydroxyphenyl)- 1-

(4 phenylethynylphenyl)-2,2,2-trifluoroethane and 1,1-bis(4-hydroxyphenyl)-l-(4-

hexynylphenyl)-2,2,2-trifluoroethane according to the present invention;

FIG. 3 is an equation showing the synthesis of polyarylene ethers according to

the present invention; and

FIG. 4 is an equation showing the synthesis of arylene ether copolymers

containing pendent ethynyl or substituted ethynyl groups according to the present

invention.

25

30

Description of the Preferred Embodiments

A series of novel bisphenols containing pendent ethynyl or substituted ethynyl

groups were synthesized. These bisphenols have been reacted with various

activated dihalide monomers to provide poly(arylene ether)s containing pendent

ethynyl groups. Copoly(arylene ether)s of these bisphenols and other bisphenols

have also been prepared. The poly(arylene ether)s and copoly(arylene ether)s
LAR 1

5

5041-1 -6- PATENT APPLICATION

have been characterized and mechanical properties determined on films. The

polymers containing pendent ethynyl groups react to form insoluble films when

heated above - 200" C. These crosslinked films also have high modulus and high

temperature use properties due to the reaction of the ethynyl groups. Specific

examples follow.

Example 1

10

Synthesis of 4-bromotrifluoroacetophenone (FIG. 1)

Into a flame-dried three-necked round bottomed flask, fitted with a pressure

equalizing addition funnel and under nitrogen was added 1,4-dibromobenzene

(20.04 g, 84.00 mmol). Using a syringe, 150 mL of anhydrous ether was added

into the flask. Some of the 1,4-dibromobenzene dropped out of solution when the

1 5 solution was cooled to -78"C in a dry-ice/acetone bath.

n-Butyl lithium(n-BuLi)(1.6M in hexane, 55 mL; 88 mmol) was introduced into

the addition funnel with a syringe and the funnel was adjusted for dropwise

addition of the n-BuLi solution into the reaction flask. The addition was

completed in 30 min and the resulting white suspension was stirred at -78"C for

20 2h. After the two hours, the reaction vessel was removed from the bath and

allowed to warm to 0*C to ensure complete metal-halogen exchange. The reaction

mixture changed from a suspension to a solution on wanning. On recooling to -

78"C, the suspension reappeared. To this white suspension was added dropwise,

through the addition funnel, 13.47 g(95.00 mmol) of ethyl trifluoroacetate. The

25 suspension became a solution before complete addition of the ester and the solution

was left to warm to room temperature in about 12 h.

To quench the reaction, the solution was cooled to between -30" and -20°C

and then 40 mL of aqueous saturated ammonium chloride (NH,C1) was added

dropwise through the addition funnel. To ensure complete hydrolysis, 40 mL of

30 1N hydrochloric acid(HC1) was added and the mixture was allowed to warm to
LAR 1

5

10

5041-1 -7- PATENT APPLICATION

room temperature. The reaction mixture was transferred to a separatory funnel

and the aqueous layer was removed. The ether solution was washed carefully with

saturated aqueous sodium bicarbonate(NaHCO3), until all the acid was neutralized

(no effervescence on adding fresh amounts of the aqueous bicarbonate). The ether

solution was transferred to a flask and dried over anhydrous magnesium

sulfate(MgSO4). Suction fdtration, followed by rotary evaporation of the solvent,

left a yellow-colored, slightly lachrirnatory liquid which was vacuum distilled (0.2

Torr, 80"C) to obtain 19.75 g (88%) of 4-bromotrifluoroacetophenone as a dense,

colorless liquid. The liquid solidified on storing in the refrigerator. 'H NMR: an

AB quartet centered at 7.66 ppm.

4-Iodotrifluoroacetophenone was prepared by a similar procedure in 81% yield

from p-diiodobenzene. 'H NMR: an AB quartet centered at 7.65 ppm.

15

Example 2

Synthesis of 1,1-bis(4-hydroxyphenyl)-l-(4-bromophenyl)-2,2,2-trifluoroethane

(BBP)fFIG. 1)

4-Bromotrifluoroacetophenone (3.00 g, 12 mmol) and phenol (18.6 g, 20

20 mmol), trifluoromethanesulfonic acid (0.04 g, 2 mol %) and a magnetic stirrer

were placed in a 250 mL single-neck round bottom flask equipped with a

condensing column. The reaction mixture was heated to 100"C and maintained at

reflux for 48 h becoming a deep brown color. The reaction was steam distilled

and the product formed a dark brown solid which was dissolved in warm

25 methylene chloride. Addition of MgSO4 and Norit-A with stirring and f'tltration

provided a light orange solution. The solution was concentrated to about 65 % of

the original volume on a rotary evaporator and cooled in an ice bath. White

crystals formed which were f'lltered and dried in a vacuum. A total of 4.0 g

(80%) of product was collected: m.p. 187-189°C. tH NMR (acetone-d6): 6.6-7.0
LAR 15041-1

5

10

-8- PATENT APPLICATION

(m, 8H); 7.3 (d, 4H); 8.3 (s, 2H); Mass Spectrum m/e (relative intensity) 422

(M +, 20), 424 (20), 353 (100), 355 (100); Calc'd for C_-I,,BrF302: C, 56.76%;

H, 3.33%; Found: C, 57.12%; H, 3.24%.

1,1-Bis(4-hydroxyphenyl)- 1-(4-iodophenyl)-2,2,2-trifluoroethane (IBP) was

prepared in a similar manner in 77 % yield from 4-iodotrifluoroacetophenone: m.p.

210-212*C (after vacuum heat-drying). 'H NMR (acetone-h): 6.6 (s, 10H), 7.3-

7.6 (d, 2H), 8.0 (br s, 2H); Mass Spectrum, m/e (relative intensity) 470 (M +, 11),

401 (100); Calc'd for C_oI-I,,IF302: C, 51.09%; H, 3.00%; I, 26.99%; Found: C

,50.84%; H, 2.98%; I, 27.16%.

Example 3

15

Synthesis of 1,1-bis(4-hydroxyphenyl)-l-(4-ethynylphenyl)-2,2,2-trifluoroethane

(EBP)fFIG. 2)

Into a 50 mL single-neck round bottom flask were added 1,1-bis(4-

hydroxyphenyl)-l-(4-bromophenyl)-2,2,2-trifluoroethane (3.00 g, 7.1 mmol),

triethylamine (40 mL), copper(I)iodide (CuI, 0.054 g, 0.28 mmol, 4 mol%),

tetrakis(triphenylphosphine)palladium(0) (0.33 g, 0.28 mmol, 4 mol %) and

20 trimethylsilylacetylene (1.39 g, 14.2 mmol). The solution was sealed in the flask

with a rubber septum and the magnetically stirred mixture was heated at 80" C. A

dark precipitate formed (the amine hydrobromide sal0, which increased in quantity

with time. After 48 h, the solvent mixture was filtered to remove the salt and

transferred to a 250 mL flask whereby the triethylamine was removed on a rotary

25 evaporator. The product was desilylated by stirring in methanol (80 mL) in the

presence of Na2CO3 (2.12 g, 20 mmol) overnight at room temperature (RT). The

reaction was filtered, the methanol removed on a rotary evaporator and 100 mL of

1N HC1 was added to the flask. The acid solution was extracted with ether, dried

over MgSO,, then ether was removed to provide a solid which was purified by

30 column chromatography using silica gel and a mixture of 80 % benzene and 20 %
LAR 1

5

5041 - 1 -9- PATENT APPLICATION

diethyl ether. After drying under vacuum, 2.2 g (73 %) of product was recovered:

m.p. 158-160°C. 'H NMR (acetone-d_): 1.00 (or s, 3 I-I), 1.57 (or s, 4 H), 2.33

(or s, 2 H), 5.00 (or s, 2 IT), 6.66 - 7.33 (m, 12 H), 8.33 (or s, 2H); 'H NMR

(CDC13): 1.00 (or s, 3 H), 1.57 (or s, 4 H), 2.33 (or s, 2 H), 5.00 (or s, 2 H),

6.57 - 7.3 (m, 12 H); Mass Spectrum, m/e (relative intensity): 368 (M ÷, 23), 299

(100); Calc'd for CzJ-L_F302: C , 71.73%; H, 4.10%; Found: C , 71.43%; H ,

4.09%.

10

Example 4

Synthesis of 1,1-bis(4-hydroxyphenyl)-l-(4-phenylethynylphenyl)-2.2.2-

trifluoroethane (PEBP)fFIG. 2)

Into a 50 mL single-neck round bottom flask were added 1,1-bis(4-

1 5 hydroxyphenyl)-l-(4-iodophenyl)-2,2,2-trifluoroethane (3.50 g, 7.40 mmol),

phenylacetylene (1.51 g, 14.80 mmol, 100% excess), bis(triphenylphosphine)-

palladium(H) chloride (0.208 g, 0.300 mmol, 4 mol%), CuI (0.056 g, 0.300

mmol; 4 mol%) and triethylamine (30 mL). The solution was sealed in the flask

with a rubber septum and the magnetically stirred mixture was heated at 80"C. A

20 precipitate formed (the amine hydroiodide salt), which increased in quantity with

time. After 48 h, the solvent mixture was f'dtered to remove the salt and

transferred to a 250 mL flask whereby the triethylamine was removed on a rotary

evaporator. The product was dissolved in diethyl ether and washed with 1N HC1

followed by extraction with aqueous NaOH. The product was regenerated by the

25 dropwise addition of HCI to the neutralization point, Filtered, then redissolved in

diethyl ether. After drying over MgSO,, the ether was removed and the product

was purified by column chromatography using silica gel and a mixture of 80 %

benzene and 20% diethyl ether. After drying under vacuum at 80"C for lh, 2.7 g

(82%) of product was recovered: m.p. 205-207"C. 'H NMR acetone-d6:6.3 -

30 7.6 (m, 17 I-I), 8.3 (or s 21-1); Mass Spectrum, m/e (relative intensity): 444 (M ÷,
LAR 1 5041-1 -10- PATENT APPLICATION

30), 375 (100); Calc'd for C=H,_F302: C , 75.67%; H, 4.31%; found: C,

75.56%; H, 4.42%.

5

Example 5

Synthesis of 1,1-Bis(4-hydroxyphenyl)-l-(4-hexynylphenyl)-2,2,2-trifluoroethane

fflBP)(FIG. 2)

This compound was prepared from 1,1-(4-hydroxyphenyl)-l-(4-bromophenyl)-

10 2,2,2-trifluoroethane and 1-hexyne by the same procedure as for the

phenylethynylphenyl analog. After drying under vacuum at 80°C for lh, 2.2 g

(73%) of product was recovered: m.p. 142-144°C. 1H NMR (acetone-d_): 3.6 (s,

1 I-I), 6.6-7.39 (m, 12 H), 8.3 (br s, 2 H); 'H NMR (CDC13): 3.15 (s, 1 H), 5.0

(br s, 2 H); 6.6-7.6 (m, 12 H); Mass Spectrum, m/e (relative intensity) 424 (M+,

15 20), 355 (100); Calc'd for C_I-Iz, F302: C , 73.57%; H, 5.46%. Found: C,

73.88%; H, 5.38%.

Synthesis of Polymers

20 The poly(arylene ether)s (PAE) were synthesized as shown in FIG. 3 by the

nucleophilic substitution of DFB with a bisphenol using potassium carbonate in

DMAc at 155°C. Toluene was added at the beginning of the reaction to form an

azeotropic mixture with any water present in the reaction and maintain an

anhydrous environment by collection in a Dean-Stark trap. Table 1 shows

25 inherent viscosities (_._ of the PAE homopolymers. Specific examples of these

polymers follow.

Example 6

30 The following example illustrates the synthesis of PAE with pendent bromo
LAR 1

5

10

5041-1 -1 1- PATENT APPLICATION

groups. BBP ( 0.8465 g, 2.00 mmol), DFB (0.4364 g, 2.00 mmol), potassium

carbonate (0.61 g, 4.40 mmol), toluene (12 mL) and DMAc (12 g) were added to

a three-neck flask equipped with a stirring motor, nitrogen purge and Dean-Stark

trap with a condenser. The reaction was heated to - 155"C during 5h and

maintained at this temperature for 16h. The reaction was filtered, neutraJized with

acetic acid and poured into water to form a white precipitate. The precipitate was

washed in water and boiling methanol and dried at 100"C overnight to provide a

near-quantitative yeild of polymer with inherent viscosity (_/_ of 1.15 dL/g. The

polymer was dissolved in chloroform (15 % solids) and this solution was cast onto

plate glass and cured in air for 1 h each at 100, 200 and 350°C to form a film

with a T s of 162"C by differential scanning calorimetry (DSC) at a heating rate of

20°C/min. This f'dm was completely soluble in DMAc or chloroform.

15

Example 7

The following example illustrates the synthesis of PAE with pendent ethynyl

groups. EBP ( 1.8418 g, 5.00 mmol), DFB (1.0910 g, 5.00 mmol), potassium

carbonate (1.52 g, 11.0 mmol), toluene (20 mL) and DMAc (22 g) were added to

a three-neck flask equipped with a stirring motor, nitrogen purge and Dean-Stark

20 trap with a condenser. The reaction was heated to - 150"C during 4h, held for

lh when the reaction appeared to gel. After diluting with DMAc (20 g), the

reaction was held at - 150 for 16h in an unsuccessful effort to dissipate the gel,

indicating a reaction of the ethynyl groups during synthesis. Therefore, both

reaction time and temperature were reduced in a effort to prepare high molecular

25 weight, soluble polymers containing pendent ethynyl groups. When the reaction

was held at or below - 145 *C for up to 4h, high molecular weight polymer was

not obtained. If the reaction temperature was allowed to increase even a few

degrees (to -148°C), a gel would form within -2h. Several other attempts

using different conditions were also unsuccessful in producing high molecular

30 weight polymer.
LAR 15041-1 -12-

Example 8

PATENT APPLICATION

The following example illustrates the synthesis of PAE with pendent hexynyl

groups. HBP ( 2.1224 g, 5.00 mmol), DFB (1.0910 g, 5.00 mmol), potassium

5 carbonate (1.52 g, 11.0 mmol), toluene (20 mL) and DMAc (18 g) were added to

a three-neck flask equipped with a stirring motor, nitrogen purge and Dean-Stark

trap with a condenser. The reaction was heated to - 150"C during 4h, held for

l h when the reaction appeared to gel. After diluting with DMAc (20 g), the

reaction was held at - 150 for 16h in an unsuccessful effort to dissipate the gel,

10 indicating a reaction of the hexynyl groups during synthesis. Therefore, both

reaction time and temperature were reduced in a effort to prepare high molecular

weight, soluble polymers containing pendent hexynyl groups. When the reaction

was held at or below - 145°C for up to 4h, high molecular weight polymer was

not obtained. If the reaction temperature was allowed to increase even a few

1 5 degrees (to - 148"C), a gel would form within -2h. Several other attempts

using different conditions were also unsuccessful in producing high molecular

weight polymer.

2O

Example 9

The following example illustrates the synthesis of PAE with pendent

phenylethynyl groups. PEBP ( 2.2223 g, 5.00 mmol), DFB (1.0910 g, 5.00

mmol), potassium carbonate (1.52 g, 11.0 mmol), toluene (30 mL) and DMAc

(21.7 g) were added to a three-neck flask equipped with a stirring motor, nitrogen

25 purge and Dean-Stark trap with a condenser. The reaction was heated to - 155°C

during 5h and maintained at this temperature for 16h. The reaction was filtered,

neutralized with acetic acid and poured into water to form a white precipitate.

The precipitate was washed in water and boiling methanol and dried at 100°C

overnight to provide a polymer with inherent viscosity (_/m) of 0.38 dL/g. The

30 polymer was dissolved in chloroform (15 % solids) and this solution was cast onto
LAR 1 5041-1 -13- PATENT APPLICATION

plate glass and cured in air for 1 h each at 100, 200 and 350"C to form a yellow

film with no Tg detected by differential scanning calorimetry (DSC) at a heating

rate of 20°C/min. This film was completely insoluble in DMAc or chloroform.

5 Synthesis of Copolymers

Arylene ether copolymers containing pendent ethynyl or substituted ethynyl

groups were prepared as shown in FIG. 4 using 10 or 30 mole % of the bisphenol

containing a pendent ethynyl group and 90 or 70 mole %, respectively, of BPAF

10 (a bisphenol without a pendent ethynyl group), although any ratio of these

bisphenols could be used. Table 2 gives the _/_ and the original and f'mal T,s of

these PAE copolymers. Table 3 gives data on the thermal stability and film

properties (tensile strength, modulus and elongation) of the same copolymers. For

reference, the homopolymer of BPAF and DFB is included and is soluble in

1 5 DMAc and CHC13. When cured at 250-350*C, the ethynyl groups react and the

copolymers become insoluble in DMAc and CHCI3. Specific examples of these

copolymers follow.

20

Example 10

The following example illustrates the synthesis of an PAE copolymer where

one out of ten repeat units contains a pendent bromo group. BBP (0.4232 g, 1.00

mmol), BPAF (3.0262 g, 9.00 mmol), DFB (2.1821 g, 10.00 mmol), potassium

carbonate (3.04 g, 22 mmol), toluene (30 mL) and DMAc (30 g) were added to a

25 three-neck flask equipped with a stirring motor, nitrogen purge and Dean-Stark

trap with a condenser. The reaction was heated to - 155°C during 5h and

maintained at this temperature for 16h. The reaction was f'dtered, neutralized with

acetic acid and poured into water to form a white precipitate. The precipitate was

washed in water and boiling methanol and dried at 100"C overnight to provide a

30 polymer with _/_ of 1.4 dL/g. The polymer was dissolved in chloroform (15 %
LAR 1

5

5041-1 -14- PATENT APPLICATION

solids) and this solution was cast onto plate glass and cured in air for 1 h each at

100, 200 and 350"C to form a light yellow film with a Tg of 170"C by differential

scanning calorimetry (DSC) at a heating rate of 20"C/min. This film was

completely soluble in DMAc or chloroform.

Example 11

The following example illustrates the synthesis of an PAE copolymer where

one out of ten repeat units contains a pendent phenylethynyl group. PEBP (0.8889

10 g, 2.00 mmol), BPAF (6.0523 g, 18.00 mmol), DFB (4.3641 g, 20.00 mmol),

potassium carbonate (6.08 g, 44 mmol), toluene (40 mL) and DMAc (40 g) were

added to a three-neck flask equipped with a stirring motor, nitrogen purge and

Dean-Stark trap with a condenser. The reaction was heated to - 155"C during 5h

and maintained at this temperature for 16h. The reaction was f'dtered, neutralized

1 5 with acetic acid and poured into water to form a white precipitate. The precipitate

was washed in water and boiling methanol and dried at 100°C overnight to

provide a polymer with _/mhof 0.92 dL/g. The polymer was dissolved in

chloroform (15 % solids) and this solution was cast onto plate glass and cured in

air for 1 h each at 100, 200 and 350"C to form a light yellow film with a Tg of

20 179°C by differential scanning calorimetry (DSC) at a heating rate of 20"C/min.

This f'dm was completely insoluble in DMAc or chloroform but did swell.

Example 12

25 The following example illustrates the synthesis of an PAE copolymer where

one out of ten repeat units contains a pendent ethynyl group. EBP (0.1842 g,

0.500 mmol), BPAF (1.5131 g, 4.500 mmol), DFB (1.0910 g, 5.000 mmol),

potassium carbonate (1.52 g, 11 mmol), toluene (20 mL) and DMAc (22 g) were

added to a three-neck flask equipped with a stirring motor, nitrogen purge and

30 Dean-Stark trap with a condenser. The reaction was heated to - 150°C during 5h
LAR 15041-1 -1 5- PATENT APPLICATION

and maintained at this temperature for 2.5h. The reaction was filtered, neutralized

with acetic acid and poured into water to form a white precipitate. The precipitate

was washed in water and boiling methanol and dried at 100"C overnight to

provide a polymer with _/_ of 0.89 dL/g. The polymer was dissolved in

5 chloroform (15 % solids) and this solution was cast onto plate glass and cured in

air for 1 h each at 100, 200 and 3500C to form a light yellow film with a T z of

185°C by differential scanning calorimetry (DSC) at a heating rate of 20°C/min.

This film was completely insoluble in DMAc or chloroform but did swell.

10 Example 13

The following example illustrates the synthesis of an PAE copolymer where

three out of ten repeat units contains a pendent phenylethynyl group. PEBP

(2.0001 g, 4.500 mmol), BPAF (3.5305 g, 10.5 mmol), DFB (3.2731 g, 15.00

1 5 mmol), potassium carbonate (4.56 g, 33 mmol), toluene (40 mL) and DMAc (35

g) were added to a three-neck flask equipped with a stirring motor, nitrogen purge

and Dean-Stark trap with a condenser. The reaction was heated to - 155°C

during 5h and maintained at this temperature for 16h. The reaction was f'tltered,

neutralized with acetic acid and poured into water to form a white precipitate.

20 The precipitate was washed in water and boiling methanol and dried at 100"C

overnight to provide a polymer with _m of 0.52 dL/g. The polymer was

dissolved in chloroform (15 % solids) and this solution was cast onto plate glass

and cured in air for 1 h each at 100, 200 and 350°C to form a light yellow film

with a T_ of 184°C by differential scanning calorimetry (DSC) at a heating rate of

25 20°C/min. This film was completely insoluble in DMAc or chloroform and

showed only slight swelling.
LAR 15041-1 -16- PATENT APPLICATION

5

10

TABLE 1. INHERENT VISCOSITY OF

POLY(ARYLENE ETHER)S

Bisphenol

BBP

EBP

HBP

PEBP

Bisfluoro monomer

DFB

DFB

DFB

DFB

'r/i,a, dL/g

1.15

insoluble

Insoluble

0.38

15

20

25

TABLE 2. CHARACTERIZATION OF DFB/BPAF BASED

COPOLYMERS

Bisphenol

with BPAF

_, dL/g

0.35

) 350"C for lh.

DSC Tg, "C

Initial Final'

10% BBP 1.4 170 170

10% EBP 0.89 172 185

10% PEBP 0.92 165 179

30% PEBP 0.52 162 184

100% BPAF 168 168

"After heating t,
LAR 15041-1

TABLE 3.

-1 7- PATENT APPLICATION

THERMAL STABILITY AND THIN FILM PROPERTIF.S OF

POLYMERS AND COPOLYMERS

5 Bisphenol

Components

10

15

10 %BBP,

90% BPAF

10% EBP,

90% BPAF

10% PEBP,

90% BPAF

30% PEBP,

70% BPAF

100% BPAF

Temperature of

5 % Wt. Loss by

TGA "C

Air

484 490

461 484

455 487

452 484

476 493

23" C Tensile Properties (150" C)

Strength, ksi Modulus,ksi Elongation, %

7.9 (4.2) 261 (229) 60 (76)

10.3 (4.9)" 342 (260) 6.1 (9.1)

lO.O (4.9)

9.5 (4.5)

9.5 (4.0)

284 (214)

341 (232)

325 (198)

96 (180)

4.8 (76)

9.9 (1.3)
LAR 15041-1 PATENT APPLICATION

POLY(ARYLENE ETHER)S CONTAINING PENDENT ETHYNYL GROUPS

Abstract of the Disclosure

5 Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl

groups and poly(arylene ether) copolymers containing pendent ethynyl and

substituted ethynyl groups are readily prepared from bisphenols containing

ethynyl and substituted ethynyl groups. The resulting polymers are cured up to

350°C to provide crosslinked poly(arylene ether)s with good solvent resistance,

10 high strength and modulus.
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