Advances in Polycarbonates - ACS Publications - American Chemical

Chapter 11

Synthesis of 1,1-Dichloro-2,2-bis[4-(4'Hydroxyphenyl)phaenyl]ethene and Its Incorporation into Homo- and Heteropolycarbonates 1

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David A. Boyles , Tsvetanka S. Filipova , John T. Bendler , Maria J. Schroeder, Rachel Waltner , Guy Longbrake , and Josiah Reams 3

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Downloaded by STANFORD UNIV on February 18, 2015 | http://pubs.acs.org Publication Date: March 8, 2005 | doi: 10.1021/bk-2005-0898.ch011

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1

Department of Chemistry and Chemical Engineering, South Dakota School of Mines and Technology, Rapid City, SD 57701 Physics Department and Chemistry Department, U.S. Naval Academy, Annapolis, MD 21402 2

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Polycarbonates from 1,1-dichloro-2,2-bis-(4-hydroxyphenyl)ethylene (BPC) constitute a highly flame-resistant family of engineering thermoplastics. The preparation of polycarbonates from B P C was first reported in 1964 as a copolymer with bisphenol A (BPA). A new monomer analogue of B P C has been synthesized which has a higher aspect ratio than B P C . This monomer has been polymerized to polycarbonates with the goal of improved ductility and heat-resistance. A n efficient synthesis of the monomer 1,1-dichloro-2,2-bis[4'-(4hydroxyphenyl)phenyl]ethane (TABPC) is reported, as are the molecular weights and glass transition temperatures of homoand heteropolycarbonates of T A B P C .

© 2005 American Chemical Society

In Advances in Polycarbonates; Brunelle, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2005.

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134


Introduction Since first synthesized in 1898 by Einhorn,(i) polycarbonates have not only been commercialized but have continued to be actively investigated both by theoreticians as well by synthetic organic chemists. From a theoretical standpoint the origin of ductility in commercial polycarbonate remains yet unknown and new and ductile polycarbonates which can withstand higher temperatures than current materials are of interest in aircraft, automotive, electronic, and medical applications, as well as in military applications such as transparent armor. Bisphenol C polycarbonate (BPCPC) from the monomer l,l-dichloro-2,2bis(4-hydroxyphenyl)ethene (BPC) in Figure (I), was developed by Porèjko's group (2,3) at Warsaw Technical University. The patent on this material first appeared in 1964 with subsequent publication in 1968. The 1970's literature on the polymer focused primarily on the self-extinguishing properties of this material. (4-9) Rusanov (10) has written an extensive review on the polymers of B P C . As recently as 2000, Ramirez (11) proposed a mechanism for the exothermic decomposition of these materials which leads to char yields responsible for their self-extinguishing properties. As noted by Lyon,(72) General Electric was at one time interested in this polymer but downselected to the polyetherimide ( U L T E M ) polymer instead, due to the better fire and temperature-resistant properties of the latter. In spite of the retirement of the bisphenol C polycarbonate, bisphenol C itself continues to find many uses, and is derivatized to epoxies, cyanate esters, polyarylates, and other usual bisphenolderived materials. Interest in many of these materials has recently been shown by the Federal Aviation Agency (FAA)(72)owing to the fire-resistant properties and ability of these materials to meet property requirements for aircraft interiors. Our interest in this polymer involves the synthesis of bisphenol A analogues having high aspect ratio monomers such as the tetraarylbisphenol C (TABPC) compound also shown in Figure (i). Synthesis of this material and its polymers and copolymers may provide new additions to the already-extensive library of polycarbonate compounds and literature, as well as insights into dynamic mechanical processes of similar compounds.

Figure 1. Bisphenol C and target monomer tetraarylbisphenol C (TABPC).


135


Structural Considerations Several notable structure-property comparisons can be made from the brief list of polycarbonates shown in Figure (2). The phenyl rings of bisphenol A polycarbonate (BPAPC) undergo 180° phenyl ring flips in the glassy state at an activation energy similar to that of the mechanical γ process which occurs at 100° C.13) Ring flips for this material have also been observed by solution NMR.(14,15) That the polymeric material remains ductile down to - 40° C has evoked speculation that the ring flip process, the γ process, and ductility are correlated with each other. Yee, for example, has indicated that the gamma peak is "related to motions of the phenylene ring" although he concludes that "On the whole...it appears likely that the γ dispersion arises from motions involving the displacement of the entire monomer unit."(/6) While each of the polycarbonates in the list exhibits a γ process, unlike the others, the spirobiindane analogue is locked into rigid conformation and is therefore unable to undergo phenyl ring flipping. T

Bisphenol A

g

°C

y Transition °C

150

-100

225

-105

245

-100

Phenolphthalein

280

-95

Bisphenol C

160

-105

275

-100

1

"lO^tO"' "'''^

Spirobiindane

Isophorone

^C^CX,,.,.^

Q-p Fluorenone

^JCt^J-^

Figure 2: Comparison ofT and /transition data for known polycarbonates. g

B P A P C and B P C P C show center groups of similar size, the latter compound having an sp center in its aryl bridging dichlorovinylidene unit compared to the sp center of the isopropylidene unit in bisphenol A . This difference has a relatively minor effect on the properties of these corresponding polycarbonates: it is generally recognized that BPCPC is similar to B P A P C in terms of both 2

3



136 dynamic N M R studies as well as mechanical results.(/7) The two materials thu exhibit remarkably similar properties in terms of glass transition temperature (150 °C versus 168 °C), flexural modulus (336 ksi versus 376 ksi), flexura strength (16,300 psi versus 16,200 psi), tensile yield strain (10% versus 11%) and amorphous character. Also, the glass transition temperatures of B P A P C am B P C P C are close, and B P C P C is the only polycarbonate with a ductility nea that of B P A P C . On the other hand, B P C P C has been shown by solution N M R t( have phenylene rings that have a relaxation time twice that of the BPA-PC.(/S) Unlike the polymers depicted in Figure (2), polycarbonates exist whicl differ structurally from those having bulky center group substitution Polycarbonates of the 2,2-bis[4-(4-hydroxyphenyl)phenyl]alkanes in particulai have glass transition temperatures which are 30-40°C higher than those ο BPAPC,(/9,20) as do many of the polycarbonates in Figure (2). Among these ii a polycarbonate containing the bisphenol monomer tetraarylbisphenol A ( T A B P A P C ) first reported by Bendler and Schmidhauser (19,20) (Figure (3)) While retaining the increased molecular mass of repeat units having spherica center groups, tetraarylbisphenol A polycarbonate (TABPAPC) is distinguishec from them by its higher aspect-ratio repeat units which effectively distribute the molecular weight outwardly in the direction of the para position of the aryl ring, resulting in linearly rigid but rotatable biphenyl units. Thus, the monomer centerof-mass distance is small and the aspect ratio large. Such linear profiles are characteristic of mesogenic units found in liquid crystalline materials as well as in liquid crystalline homo- and copolycarbonates.(27 ) >

Figure 3: A polycarbonate with high aspect-ratio tetraaryl repeat units: tetraarylbisphenol A polycarbonate (TABPAPC).

The striking ductility and higher glass transition temperatures resulting from the incorporation of these high aspect-ratio repeat units into polycarbonates may bear out the observations of Vincent (22) over 40 years ago that polymer chain cross-sectional area is inversely proportional to brittle toughness, and that the latter property may be enhanced upon an increase of intermolecular cohesive attractions. Clearly, the easiest way to increase cross-sectional area is to increase molecular mass not by structural modifications which tend toward sphericity of repeat units as has been commonly the case, but by modifications which tend toward monomer elongation. Synthetically, this means introducing potentially rotatable rigid rod elements in the form of biphenyl units. Such mesogenic units are similarly found in liquid crystalline materials, including various copolymer


137


polycarbonates containing 4,4'-biphenol as reviewed by Schmidhauser and Sybert.(2i) It was with these considerations that we sought to synthesize polycarbonates from B P C which had additional phenyl rings with the goal of understanding whether the properties of polycarbonates prepared from such monomers would parallel those of the tetraarylbisphenol A polycarbonate (TABPAPC). Rings furthest removed from the repeat unit center may undergo lower energy threshold ring rotation because of less steric inhibition. Conceivably, this could afford a molecular dissipation mechanism by which impact energy could be converted into phenyl ring rotation, perhaps enhancing ductility and polymer toughness, and in resisting fracture upon impact.

Synthesis Synthesis of Monomeric Bisphenols Our group has previously demonstrated the synthesis of several high aspect ratio bisphenols using a Suzuki reaction sequence (Figure (4)).(23-26)

Effle f, Metfiylfna, qntj ?ulfone fafrflafVt AnatoflMea

Bis[4-(4'-hydroxyphenyl)phenyl]methane

HO-^^HQ-I-^HQ-OH Bis{4-(4'-hydroxyphenyl)phenyl)sulfone Tetraar vltormal Analogues

Blsanlline Ρ apcj Bis^i|ipa M Tatraaryls

bis[4-(1.(4'^ydroxy henyl)-1-methyi thyl)phenyloxylmethan P

e

e

1 > b

is[l.(4^hyd ^^ r o

Figure 4: Tetmarylbisphenols synthesized by the Suzuki reaction.


138 In addition to the synthesis of these tetraarylbisphenolic systems, the utility of the Suzuki reaction has been demonstrated by the synthesis of unsymmetrical triaryl systems, namely, the synthesis of a bisphenol A analogue which has a single additional aryl ring, 2-(4'-hydroxyphenyl)-2-[4'-(4-hydroxyphenyl)phenyl]-propane 9 shown in Scheme (1). Tetrakis(triphenylphosphine)palladium(O) was used in this reaction due to the lower reactivity of the triflate substrate compared to that of aryl iodides.(27) The monomer has since been polymerized to afford a polycarbonate of M 57,010 and M 26,070, which had a glass transition temperature of 150° C.(28) w

n


Scheme 1: Suzuki synthesis of asymmetric bisphenol A analogue.

h

°-o4Y~y O H ^ — > \

//

CH3 I \

/

benzyl chbride 72%

3

'

CH

argon, reflux 92%

V

Bno-oTrv °*

(CFjSO^O

pyridhe 100%

\

/

CH3 Τ \

/

CH3

W

3

9

New Synthesis of Tetraarylbisphenol A (TABPA) Also, whereas the patented synthesis (79,20) of T A B P A relies on the use of a ligand-mediated Stille coupling sequence of a tri-n-butylorganostannane and the ditriflate of bisphenol A , we successfully synthesized T A B P A by a less expensive, ligandless Suzuki reaction procedure. As depicted in Scheme (2), 2,2bis(4-iodophenyl)propane 7 was synthesized from commercially available 2,2diphenylpropane. The diiodo product was reacted in aqueous acetone with palladium acetate under ligandless conditions as described by Goodson, et al., (29) providing 2,2-bis[4-(4-methoxy-phenyl)phenyl]propane 8. Demethylation was accomplished in high yield using pyridinium hydrochloride under melt conditions to afford T A B P A 4.

Synthesis of Tetraarylbisphenol C (TABPC) It was thus that we turned our attention to the synthesis of the desired bisphenol C tetraaryl analogue, the l,l-dichloro-2,2-bis[4-(4 -hydroxyphenyl)phenyljethene (TABPC). Since the Suzuki reaction most reliably required either ,


139 Scheme 2: Ligandless Suzuki coupling using aryl iodide with polymerization of monomer.

Cyr/Λ

CO,

2

11 pyridhiu m hydrochio ride 215-220^ 96%

12 In this manner the complementary set of the isomeric ortho meta, and paraT A B P A analogues was also synthesized, as was that of the isomeric ortho, meta, and para-TABPC analogues indicated in Figure (6).(52) t

1.1-dJchloro-2,2-bis[4-(2-hydroxyphenyl)phenyl^lhene ,

i,i-dichloro-22-bi8f4-(3'-hydroxyphenyl)phenylJethene 1

1.1-dichloro-22-bi8[4-(4-hydroxyphenyl)phenyiefhene t

,

Figure 6: Positional isomers synthesized. 33

For polycarbonate synthesis we used the triphosgene method of Sun, et al., with pyridine to dissolve the difficultly-soluble T A B P C . Likewise we prepared several copolymers including those of bisphenol A (BPA), bisphenol C (BPC), 4,4'-(hexafluoroisopropylidene)diphenol (HFBPA) and 4,4 -sulfonylbiphenol (SBPA) as indicated in Table (I). The molecular weights are dependent on stoichiometry as shown, and although the polydispersities are narrow, the degree of polymerization is also low. In subsequent polymerizations we have utilized ,


141 phosgene gas to produce materials having superior molecular weights. For example, we have synthesized the 75/25 copolymer of bisphenol A with tetraarylbisphenol C using /?ara-i-butylphenol as end-cap, obtaining M =84,380, M =50,930 and polydispersity of 1.66. The Tg of the copolymer was 181.58 ° C . We continue to optimize the syntheses of the polymers in Table 1 to obtain higher molecular weights. w

n

Table 1: Stoichiometry and molecular weight data for polymers synthesized.


PC

1 2 3 4 5 6 7 8 9 10 11 12 13

Diol 1-Diol 2

p-TABPC p-TABPC-BPC p-TABPC-BPC p-TABPC-BPC p-TABPC-BPC p-TABPC-BPA p-TABPC-BPA /7-TABPC-HFBPA f?-TABPC-SBPA m-TABPC* m-TABPC-BPA 0-TABPC* 0-TABPC-BPA

Mol Ratio Diol 1Diol2 100 50/50 25/75 50/50 75/25 50/50 50/50 50/50 50/50 100 25/75 100 25/75

TP*

Yie Id

mol 0.60 0.32 0.42 0.42 0.42 0.37 0.42 0.42 0.42 0.37 0.34 0.37 0.34

% 88 60 95 96 91 88 85 91 93 99 97 99 98

M

w

M„

PD I

°c

g/mol

g/mol

20,083 6,250 10,100 7,900 3,786 6,500 7,143 7,713 4,126 7,474 -

6,305 3,547 6,458

4,009 -

3.1 1.5 1.6 1.4 1.3 1.3 1.4 1.4 1.4 1.9 -

10,590

5,144

2.1

5,436 2,883 4,771 4,948 5,644 3,050 -

Tg

138.94 139.22 157.82 152.09 146.36 148.56 154.40 158.98 156.79 135.94 149.18 137.94 151.37

'Triphosgene; H F B P A = hexafluorobisphenol A , S B P A = bisphenol S; (* not all dissolved, cloudy solution).

Experimental Section Materials. A l l reagents were of commercial quality and were purchased from the Aldrich Chemical Co. 4-Methoxyphenylboronic acid was purchased from Optima Chemical Group, L L C . Chloral was obtained upon dehydration of chloral hydrate by mixing with twice its weight of sulfuric acid and subsequent separation. Solvents were dried and purified by standard procedures.


142 Instrumentation. IR spectra were determined on a B I O - R A D FT-40 spectrophotometer, using K B r pellets. H N M R spectra were recorded with a GE-QE300 operating at 300 MHz. Ή chemical shift were reported as δ values (ppm) relative to the used solvent CDC1 (7.24) or D M S O - d (2.49). Molecular weights, relative to narrow polystyrene standards, were measured using a Shimadzu H P L C - G P C system consisting of a LC-10AD pump, SIL-10AF autosampler and Wyatt Mini D A W N light scattering detector. The measurements were taken with T H F as mobile phase on two PLgel 5μιη M I X E D - D columns with flow rate of lmLmin" . Samples were also run using a Waters 510 Pump and Controller, HPLC-grade T H F , filtered, flow rate: 1.0 mL/min with a Styragel H M W 6 E and Phenogel 5 100A column using a Waters 410 Refractive Index Detector. Millennium software was used for data analysis. EasiCal polystyrene standards were used for calibration. Elemental analyses were performed by Midwest Microlab, L L C , 7212 N.Shadeland Avenue, Suite 110, Indianapolis, IN 46250. !

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Synthesis of2,2-bis(4-iodophenyl)-lJJ-trichloroethane, I-DDT. Chloral (16.2 g, 0.11 mol) was mixed with iodobenzene (40.8 g, 0.20 mol), and the mixture was stirred and cooled to 5°C. Chlorosulfonic acid (12 mL, 0.18 mol) was added at a rate of a few mL every 10 min and the temperature was maintained at 5 °C. The reaction mixture was allowed to warm and after reaching room temperature, then stirred for 2 h. The dark purple mixture was poured over ice, whereupon it formed pink crystals. The crystals were filtered and washed with water (3x150 mL), then taken into ethyl acetate, washed with dilute sodium bisulfite solution (150 mL) and then with brine (150 mL). The organic layer was dried (Na S0 ) and concentrated. The residue was recrystallized from ethanol to afford the title compound I-DDT (26.9 g, 50%) as white needles, mp 179-180°C. Ή N M R (300 M H z , CDC1 ) δ 7.65-7-70 (d, 7=8.5 Hz, 4H, ArH), 7.28-7.33 (d, 7=8.5 Hz, 4H, ArH), 4.95 (s, 1H, CH). Anal. Calcd for C H C l l 2 : C, 31.29; H , 1.69; C l , I, 47.23. Found: C, 31.22; H , 1.68; I, 47.41. 2

4

3

14

9

3

Synthesis of I, I, l-trichloro-2 2-bis[4'-(4-methoxyphenyl)-phenyl]ethane, pTADDT. l,l,l-trichloro-2,2-bis(4-iodophenyl)ethane (26.9 g, 0.05 mol) and 4methoxyphenylboronic acid (16.7 g, 0.11 mol) were dissolved in acetone (90 mL). A solution of potassium carbonate (34.6 g, 0.25 mol) in water (90 mL) was then added and reaction mixture was stirred 5 min to gentle reflux. After evacuation and flushing with argon, palladium(II)acetate (10 mg) was added and the suspension was then heated for 10 h under reflux and a positive argon pressure. It was then cooled to room temperature and extracted with ethyl acetate (4x200 mL), washed with water (2x100 mL) and brine (1x150 mL). The combined organic layers were dried (Na S0 ) and concentrated under reduced t

2

4


143 pressure. The residue was recrystallized from ethanol to afford the title compound (23.4 g, 94%) as white crystals, mp 148-150 °C. IR (KBr, cm" ): 3065, 3026, 2973, 2909, 2836, 1608, 1581, 1525, 1498, 1462, 1441, 1249, 1179, 1041, 824. H N M R (300 M H z , CDC1 ): δ 7.68-7.70 (d, 7=8.0 Hz, 4H, Ar//), 7.50-7.53 (m, 8H, Ar//), 6.95-6.98 (d, 7=8.1 Hz, 4H, Ar#), 5.13 (s, 1H, C//), 3.84 (s, 3H, O C / / ) . C N M R (75 M H z , CDC1 ) δ: 159.3 (C-OCH ), 140.4 (ArCquat.), 136.6 (ArCquat.), 132.9 (ArCquat.), 130.5 (ArCH), 128.2 (ArCH), 126.6 (ArCH), 114.3 (ArCH), 101.8 (C-C1 ), 70.6 (CH), 55.4 (OCH ). Anal. Calcd for C 6 H C 1 0 : C, 67.55; H , 4.66; CI, 21.36. Found: C, 67.07; H , 4.71; CI, 21.43. 1

]

3

, 3

3

3

3

3


2

23

3

3

2

Synthesis of l,l-dichloro~2,2~bis[4'-(4-hydroxyphenyl)phenyl] ethene, p-TΑ ΒΡΟ. l,l-dichloro-2,2-bist4-(4 -methoxyphenyl)-phenyl]ethene (10.00 g, 0.020 mol) and pyridine hydrochloride (16.73 g, 0.138 mol) were placed in a beaker and slowly heated with stirring to 215-220 °C. Three additional 10 g portions of pyridine hydrochloride were added over the course of the reaction. The temperature was held at 215-220 °C for 30 min. Then the viscous, dark, redbrown liquid obtained was poured with stirring into 500 mL of water. The solid was collected by filtration and recrystallized from ethanol/water. The final product T A - B P C (8.34 g, 96%) was fine light yellow crystals, mp 220 °C. IR (KBr, cm" ): 3520, 3300-2600, 3034, 1609, 1595, 1527, 1497, 1252, 1171, 1110, 960, 861, 823, 509. *H N M R (300 M H z , DMSO-d ): δ 9.59 (br s, 2H, exchangeable with D 0 , OH), 7.56-7.59 (d, 7=8.6 Hz, 4H, Ar//), 7.45-7.49 (d, 7=8.4 Hz, 4H, Ar//), 7.30-7.34 (d, 7=8.7 Hz, 4H, Ar//), 6.80-6.82 (d, 7=8.2 Hz, 4H, Ar//). C N M R (75 M H z , DMSO-d ): δ 157.9 (C-OH), 140.9 (C=CC1 ), 140.4 (ArCquat.), 137.4 (ArCquat.), 130.5 (ArCquat.), 129.9 (ArCH), 128.3 (ArCH), 126.4 (ArCH), 118.3 (C=CC1 ), 116.3 (ArCH). Anal. Calcd for C H , C 1 0 : C, 72.07; H , 4.19; CI, 16.36. Found: C, 70.89; H , 4.64; CI, 15.61. ,

1

6

2

1 3

6

2

2

26

8

2

2

Synthesis of homopolycarbonate (TABPCPC) Homopolycarbonate (PC T A B P C ) was synthesized in accordance with the literature method.(35) T A B P C (0.217 g, 0.5 mmol) was dissolved in 5.8 mL of pyridine and the solution was cooled to 0 °C. A solution of triphosgene (0.062 g, 0.21 mmol) in methylene chloride (2 mL) was added dropwise and the reaction mixture was vigorously stirred at 0-5 °C for 15 min. The solution became viscous and saturated with pyridine-hydrochloride after this time and was subsequently warmed to room temperature. The suspension was then stirred for an additional 4 hours. A 5% aqueous hydrochloric acid (10 mL) was used to neutralize the reaction mixture. The polymer was extracted with methylene chloride (3x20mL), washed with water (3x20mL), and the combined organic layers were dried (MgS04) and concentrated. The viscous residue was poured


144 into methanol. The precipitated polymer was filtered, washed with methanol and dried at 40 °C under vacuum for 24 h (0.20 g, 88% yield). IR (KBr) 3032, 1771, 1610, 1590, 1494, 1225, 1185, 1161, 1005, 974, 860, 821, 514 cm" . *H N M R (300 M H z , CDC1 ) δ 7.35-7.41 (m, 8H, ArH), 7.55-7.58 (d, J=7 Hz, 4 H , ArH), 7.62-7.65 (m, J=7.6 Hz, 4H, ArH). 1


3

Synthesis of copolycarbonates Bisphenol A (BPA), bisphenol C (BPC), 4,4'(hexafluoroisopropylidene)diphenol (HFBPA) and 4,4'-sulfonylbiphenol (SBPA) were used as co-monomers. A l l copolymers (PC T A B P C - B P A , P C T A B P C - B P C , P C T A B P C - H F B P A and PC T A B P C - S B P A ) were prepared using triphosgene similar to the above method for the synthesis of the homopolymer. The copolycarbonates were characterized by IR, Ή N M R and H P L C - G P C using laser light scattering for molecular weight determination.

Conclusions More than 40 years after the synthesis of the polycarbonate of B P C by Porejko we have synthesized a novel tetraarylbisphenol-l,l-dichloro-2,2-bis[4(4'-hydroxyphenyl)phenyl]ethene (TABPC). The title monomer T A B P C is an analogue of the 2,2-bis[4-(4-hydroxyphenyl)phenyl]propane ( T A B P A ) of Bendler and Schmidhauser. The unique, high aspect ratio profile of these monomers makes them a separate category of computationally-designed bisphenols for polycarbonate. The synthetic conditions for the title compound and its positional isomers involved a mild, ligandless Suzuki procedure using an aryl iodide substrate which is easily accessible. Structure has been confirmed by IR, and 300 M H z proton and carbon-13 nuclear magnetic resonance spectroscopy. Solution polymerization was performed using triphosgene to give both homopolymer and heteropolymers. In spite of the lower molecular weights of the products the T ' s are relatively high; Flory-Fox calculations as well as polymerization of the monomers with phosgene to obtain high molecular weight polymers continue. Dynamic N M R studies of these materials are in progress, as are dynamic mechanical analyses to ascertain thermal properties and scale-up for mechanical testing of the new polymers. Since bisphenol A finds use in a variety of resins (epoxies and cyanate resins, for example) the synthetic strategies outlined herein additionally provide the possibility for not only interesting polycarbonate materials, but for a wide range of useful materials. Work continues in these areas. g


145

Acknowledgements


We gratefully acknowledge the financial support of the National Science Foundation (Grant No. DMR-98-15957)Department of Defense-Army Research Office (Grant No. DAAD19-01-1-0482), the Army Research Laboratory (Grant No. DAAD19-02-2-0011),NSF (ILI Grant No. USE-9052345 for the N M R used in this work). This material is also based in part upon work supported by the National Science Foundation/EPSCoR Grant #EPS-0091948 and by the State of South Dakota.

References 1. 3. 4. 5.

6. 7. 8. 9. 10. 11.

12.

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