CA2230272A1 - Isomerization of bisphenols - Google Patents

Abstract

A catalyst useful for the condensation of an aldehyde or ketone starting material with a phenol was an insoluble mercaptosulfonic acid compound. The heterogeneous catalysts comprise catalytically-active species represented by formula (II). L was an optional linking group and - was a bond, which catalytically-active species was attached by the bond - to an insoluble organic or inorganic support; or a catalytically-active species represented by formula (III), wherein L' was an optional linking group, - was a bond and .theta.' and .theta." were residues of .theta., and a and b were independently selected from integers equal to or greater than 1. These catalysts isomerize o,p-bisphenols to p,p-bisphenols.

Description

CA 02230272 l998-02-24 2 PCT~US96/13683 ISOMERIZATION OF BlSrl IC~

This inv ntion r~latos to pr-paration o-f P~lYr~Aol Q~ more parl ;C~ A - ly to the preparation of poly~h~~l R frvm kQtonQs or ald-hya~s nd ~ 1A
A id catAlyzed c-~A_~tiAA~ of r~ ~ A With rla9hyd~s or kQton9 8 wa8 w~ll known Acid cataly8ts i~ acidic ion ~ J~ r~sin cataly~t~
rnd sol~hlo acia cataly~ts Sol~h~ acia catalysts can be, for - _le, Lv_ _ chloriao, sulfuric acid, hydrochloric acid, rh.-~h~-~ c acid, Ly~ v~ c rcid, nitric AAcid, dim9thyl ~ulfAte, sulfur ~;~Y;~ , 4-toltt~ lf-~;c acid, boron trifluoriae, ~ lf.-~;C acia8, boron trifluoriae A _l~ ~ and oth~r acid-acting r __ -n~ inClUaing C _ _ 'n wh~ch w_r~ hyarolyzod by wat-r to Form rAcids; for - _le, chlorid~, sulfonyl chloridQ and ~ho~ -A numb~r OAf __ ~R werO kn~wn to prvmote such _n acid-catalyzQd c '- --tion Th~s~ promotQrs ;~ ~tAAn groups that worc ~ither rro~ or bound to a r~in Alkyl - ~-A~tan~ and bis ~,A~Lo~t~A~l~ ~9 wor~ of reportQd yromoters It ha8 been ~l._oAr~ by Scri_bine et al , (U S Patent No 2,923,744) to produco ~;Qrh~~l A using sulfAuric acia, ~romotoa by ~_~LOA1~ fo~c ~cias or _alts or cv 9~ ;~ rulf~~-t - Qstors at a l vel of O 1 to 5 p~ . by weight of th~ ba8e char~e, to catalyze c~o~-~;~ of A~e-c ~ and ph~ln~ when uArQd in r of 0 1 to 5 _e ~ by woight bas-d on total char~ Sulfuric acid was usod in ~ r of 2 moles p~r ~ le of acotono ~A~ et al , (U S Pat~nt No 4,675,458) have ~ _-r-' making 9,9-bis-(4-Lyv ~y~ yl)fluor-nQ in the ~ ~- -- of sulfuric acid, pr~fA9rAbly __ _ 8ulfuric acid, and rA ~_~L_A~ p_rticA" 1 A ly 3-~_~Lo~ropi~;c acid, a~ a promot-r ~ io ~t al , (U S Pat-nt No 5,248,838) havo ~ lc~-~ th~ u8e of ~A _ ~At; ~ of ~fonic acid _nd a ~A~Lan/ ~_~to-lkA~~ic ncid for catalyzing thc c ~ ~ of rh~~~l~ with fl~oA~nv ~ ~i~h level~ of ~ h-~-F lf~~;c acid with L~ to the foed and the tan/ ~ ~_l ~A~; C acid, w~rQ us~d The reactions can b run in h - 1,~ t-' Ly~ ~olvsnts Bott-nbruch ~t al , (U S Patcnt No 4,996,373) havo ~l-_OcAF~ a ~lOC~ for proA~ g aih~ v~y~Aryl c __ ~~ from carbonyl ~ __ 'A Una WO 97/08122 PCTtUS96tl3683 rhe~ol~ under hi~h pr~ssure, in the ~ of various catalysts, including ~ulfonic Acid ro~ins CAtaly~ts c~r~t~ s sulfhydryl func~ l;ty, for ~xampl-, ion ~Y~-h~ns~rs tl ~te~ with - o~8O
c ~ , have boen A;~l08-a for this uso ~I-yor ~t al , (U S Patent No. 4,387,251) _AVO ~ ~ v ~a~ rl~ ~
for makinSr 4,4'-a~L~a ~ ;rh~yl AlkAr~ u8ing a ~ -t;c sulfonic acids as c~ a ~2eir~Sr aSJents ~ ~to groups wor~ ;~ lv~Aea7 within the d--finition of R3 and w-re charactorizod as b--ins~ in~rt Fro~ta~ ot al , (U 8 Pat-nt No 5,210,328) ~a~ ID~ usin~ t_o name tys~s of 8ulfonic ncid catnlyst_ for lO m~kin~ Cy~l~A~ aen~ h; ~?h~
;rans~n (U S Pat-nt rJo 2,468,982) has ~ ljc8~a~ vr~ParAtion of h; ~h~r ~ uging ~hydrous hy l _ chloride in ~ A1~ with n --~s,Lc~ Ar~ic acid, wh~Lc_ may be formed in situ by reaction of a ~~:.~ton with tho k~ton-, as C~ A~ ;n!J ag-nt I!Cnobel ~t al, (U S Pat--nt No 4,931,594) AiP-~ thQ us-- of laryo ~mounts of sulfonic acid resin, mix ~d with ~ d 3 ~ .... ~.topro~i~r;c acid, to cau~e the ~ ,a o_t,; ~ to occur It has b---n ~lC_ O~ a in Briti~h Patent No 1,185,223 to uno a mixtur-- of ~i~ l--resins, ono n~ a e~ l f~;c acid r--nin and tho othor n r-~in c~nt-;n;n~ - ~AA~to ~rou~s, for making bisrh~
p~nAo~h et al , (U S Patent No 5,212,206) a;Pc~08~ a cataly8t, mad- by ~o~t;n~ a sulfonatod i~n ~ o r-sin with a d~alky~ ~tan other rofe .~c A, ~ ~trt;ve of ro~ P on of sulfonic acid iv~ O r-sin~, ;nAl~e Wagn~r (U S
; 25 Pat-nt No 3,172,916) Mc~Att ~t al , (U S Pat-nt No 3,394,089), Fal-r ~t al , (~ S Pat nt Nos 4,455,409~ 4,294,995 and 4,396,728)~ l lch ~t al , (~ S Patont No 4,369,293)~ Bor~ ~t al , (~ S Patont No 5,302,774) ana Maki ~t al , (~ S Pat-nt No 4,423,252) Tho r~activ cataly~ts ~enorally ;nA-~ Ld- _ ~ ~A~to-f~n~t;~nn attached to a ~ulfonic acid ~rou~ in tbe for~L of a ~ul f~ - ~ or a, oniu~L sulfonate salt 8haw (U S Pat-nt No 4,859,803) disclo80s pr-~arin~ b;~ ln from ~h nol and a kotono in tho ~ ~ of an acidic (~ulfonic acid) ion-re d n and a ~_~Lan Tho --~AA~tan being adaed at ~art;c~ A -~oA~rti~n~ of a s~e~Aif;~va r-actor confi~Auration to ~l_v ~ the f~ An of cyclic di~Lers ~ i _a ~;AClAV8~d (U S Pat~nt No 4,825,010) ;q ~ 7-tion of L -~vd~cL~ of ~ A -~-to~ of ~ -~ and k-tones, using a catalytic ' .

CA 02230272 l998-02-24 amount Of acidic ~ulf~ te~ c-t;~ic-~Y~-h--~ge rosin ha~in~ sulfonic acid ~ites ;~n;C'11Y bonded to alkyl ~ Othor ~-t~ by Li (U S
Patont Nos 4,822,923 ana 5,001,281) further sug~ost the state Or tho art of usin~ ion --~ 7~ ~ rosins to ;- - ~ by~~ ~l~cts of bisph nol synth~-~08.
Powell et al , (U S Patent No 5,105,026) ~;~close using aciaic iv~ ~ r~sin~ to ;- z- ~ '--;-able proaucts Or bisphenol ~y~h~in to ~ ~lo products, for _le, to R;~h-~-l A Mor~an (~ S
Patent No 3,546,165) has ~;~clc~d c~ at;~ o~ ph-nol with variou~
10 kotones, ;~ ;~g fluo OnO~ ana ;-'-1~1'----~, using hi~h l~v018 of Lyl ochloric acid or L~ ~ chloriao, in th~ of minor ~ ~-o~ 3 - ~_~topropionic acid The products were used for the preparation of poly-st-r resins S~-~olcs (U 8 Pat-nt No~ 4,467,122 ana 4,503,266) ~ lor-D
~ ~;~g crud-~ proauct, c-~t~ ~g s~pF~ from a hyarochloric acia/~inc chlorido catalyzed ~ ~ , to remove HCl, ZnCl2 and cxcess phenol, prior to y~ l;~ from ~;~hlorooth_ne Bee also the abstract for DE
OLS 2,948,222 (~uly 30, 1981) ~orshak et al , (SU 172,775) ~ h;~ a mixture of phonol, ao B~PF and HCl with water, a~ter which ph~nol was l ~ ' by aist;lla~
The foll ~g refoL_~ces ~;--lc~ the v e~A -ti~~ o~ resins, c~t-;~;~g ~lf~;c acid funct;~Al;ty, introduced oither by copolymer~~-t~ or by sulfonation after polym-r;~-t~o~
U S Patent No 3,205,285 Turbak et al 25~ S Pat-nt No 3,366,711 MA~_O1;n; et al U S Patont No 3,426,104 Ma3son S Pat-nt No 4,587,304 Thaler et al ~ S Pat-nt No 4,764,557 ~;f~' -~ et al Traya~o (U S Patent No 3,706,707) ~;~cl~- the preparation of -~ tr _rom a polymHrizod cyclic ether and a sultone D-_n (U S Pat-nt No 4,568,724) was o~ 1A_ interest with .~o~_L to reaction ~.vd~cLs _rom nn EPD~ rubbor and _ nulton-Welch (U S Pat-nt No 3,029,221) and Niwa ~t al , (~ S Pat nt No 4,912,170) ~;o-laoa ~..o no~- for modifyin~ poly~Lyl~ne rosins It was an object o~ this invontion to provid- a ~. oer~ ~or the ~ i~ of ala-hyd 8 or k~ton-n with ~h~.- l ~, to A chi-v~ high yielas ~.

W O 97/08122 PCT~US96/13683 of preforroa bis-(4-Lyd v~y~ryl) i- ~ ~ with low roaction time~ whilo avolain~ uso of strong inor~anic acids Furthor object~ of the invention ;~l~lAo th- dev~lopment o~
proc~ n ~or tho 8y~t~-ri~ o-f PolYrh~o' ~ charactoriz-d by hi~h yiolds 5 of high ~urity ~roducts undor roaction condition8, which w ro not corrosivQ to vossels in which the g~ ~A ~Be~ wore conductod In addition, ~voiding the us- of sulfuric acid, ~; ~At-- tho po~ ;ty of ~ido r-actions, ;~l~A;~ sulf~t;~ of rh~ n~
In ono a~p-ct, this invontion rolates to a ~ oc088 for thn c~A~ t;~ of an aldohydn or kotono startinq mat-rial with a ph-nol, un~ubstituted in at l-ast ono po~ition, cvmpri8ins r-actin~ th- ald-hyde or kotono starting mat-rial with the phenol in a re-~t;o~ mixture in tho pr-~OnCe of a solublo or insolublo -~tosulfonic acid _ __ ' under condition~ suffici-nt to br~n~ about f ~;~ of a _ ~Al b;~ ic 15 moioty at oach aldohydo or k-tono moiety in tho starting mat-rial;
provided that the sol~ e ~to~ l f~; C acid _ __ ' was charactorized by th- formula (HS),-~-(S03H)b whor-in ~ wa~ an alkylono, cyclc~l;ph~t;c, arylono, alkyl-noarylone, alkyl~ - y~lo~ hatic, al~ylon-aryl, h torocyclic or alkyl~ ~'-torocyclic r-sidue and a and b wore ;~ A~ ~ly seloctod from ;~tog ~ from 1 to 205 ana Tho insoluble c~Los~lfo~;c acid comprisos a catalyt;c~lly-active - - -m~ O~ ~rA -a by the f. 1~
(Hg)~-~ -(803H)b I

L

in which ~ was an alkyl-no, cy~l~-l;~h~t~c, aryl-no, alkylonoaryleno, ~lkyl-nocy~l~l;~h~t~c, alkyl~ ~~ yl, het~ ~y~lic or alkyl~ erocyclic rosiduos a and b w ro i ~ -'- ly seloctod from ;~e_ ~ from 1 to 205 L
wan an opti~l 1;~;~ group and - wa~ a bond, whieh eatalytieally-activo ~p-cio~ wa~ ~tt-~-' by tho bond - to an ;~ol hle organic or inorganie ~V~Ls or a eatalyticallY-activo 8pocio8 ~ a~ _e~ by the unit fc_ 1 (HS)A (8~3H)b \
( b ) r whnrei~ ~ wa3 an alkyl-ne, arylene, eyrloAl;~hA~;c, alkylenearylene, alkyl~ -_Y~-lo-l;rh~t~c, alkylon-aryl, heterocyclic or alkyl -~ torocyclic resiaue; a and b w_ro ;n~ ly soloctod frvm ;nt~ D from 1 to 20;
L' waD an optional l; nk; ng -~roup and - wa8 a bond ThiD invOntion furth r r-lateD to novel catalytically-activo poly~Ly _~ rosin~, charactOriz-d by boarin~ at least one of oach of a ~Lo-funetion and a sulfonie aeia funetion on 80me indiviaual 8Ly ~ne units of a polymer ehain In yot An~th~r as~Oct, thiD ;nvOntion rolatOs to ~ - s~-r for pr-~arin~ th- eatalytically-active poly~Ly ~nc resins Th-se ~~ rc-~preferably eompri80e stOp8 of (b) 8ulf--nAt;n~- a hAloAl~yl~oly~Ly. - to produce an ;nt-- -';Ate h vin~ ~ulfo 4unetional ~rours; (c) opt;~Ally av~vO Li~-~ tho sulfo 4~n-ti~n-~ -~rou~ to av ~ ~ A;n~ alkali metal ~alts~ (d) th;ol~At;ng the thu8-~rodueed sulfG~LylO~o ;nl F- -~;Ato by r aeting tho halo f n-l;~n with a r-activO th;olA~e to ~L l~c~ a co ~--y ~A;n~ -~to ~rour or ~_o_~ ~v th roof;(O) o~ti~n~lly hydrolyzi~g the thu~-t h; ol A~ ;n~ tc with an acid or ba~e when tho th;~lAt~ VrouP 80 requires and (f) opt;~ lly aeidifying (if 80 r~quired) to ~. ~_ce ~lf~n;c acid _unctional 5-vroups units Tho ~ - rP of th inv ntion ~ormit3 u80 of vory low lovol3 of a ~in-~lO acidic a~ A ---;n~ a-~ont Tho ~-c r5 ~Ormits ~; _l;f;-d ~ vd~cL
; ~1 A~; ~n ~ ~8, rOeyelo ~1._ ~D, and/or w_8to ~ Tho r~ aoos not ro~uire a 'rAl;7-ti~n Dtor to rOmov hydrochloric or ~ul_uric aeia ~nd aoo8 not ~roduca a wa~tO salt ~L ~ - Th acidic 25 e ~ ~;ng a~ent~ u~od in th~ ~, - rY of this i~v~ ;~n wer- r-adily v~d from th~ L. --t;~n mixtures and can be lecvv~ and rOeycled Tho ~ _ VJ of this invontion ro~ult~ in hi~h ~Qlt Livity toward proforred bi~-(4-Ly~ v~y~ryl) ;~ D and v ry fast r-action rates The ~ .~~ of thiD in~ention was partir~lA~ly useful for tho 30 ~ ~_~ ;~n of bi~(L~a_v_y~lyl) ~ , such as h;~ ~1 A and 9,9-bi~-(4-L~-~ v_y~ yl)fluor-ne, both of which wero u~-ful in th e~a ~tion of polyc-- h~-t~P and oth r ~ --~ ally ~ j~n;f;~nt polym r~
Tho ~ t~ cataly8ts ~;P-lo~-' herein advAn~-~-ou-ly woro moro rOactive than hot~L ~ - ~ catalysts ~ ntly u~od Th y 35 advAn~a~ ~ly allow using lowor t' _ - ~turo8 with co O~_ ~;n~ly gr~atOr ~ ctivity for a-~ired ~roduct than was ~ ~Lly ~xp-rionc-d Groator o ~ ;vity _ ~-r purif;c-~;~n ec q~- y to ~roduce a dosired or pr-sel-cted purity of product Thus~ for a ~ lly ~roducod bisphenol like b;~ph~~l A, a hetoL~,c~s catalyst disclosed herein can be adv_ntageously substituted in an existing c cial procQso, run with the same or hi~hor th ~L~L at a lower t _--~ture with le88 purific-ti~ to achiove at least ~quAlly ~ure product ~ etones or aldehydQs and ~ ~l;c c _ '~ (hereinafter phenol, rh~ phenol or ph~~~l;c startin~ material) useful in process of tho invcntion were known in tho art and were d-scribed in the lit-rAtur0, for ~nstnnce, Jannen '982, supra, Maki ~t _1 , '252, ~u~rA, ~organ '165, ~u~ra, and Rn-bol ot al , '594, ~u~ra Tho c~~ t;~ of this invention can be re~ by the ~quation for a L~.e8. IAt;ve c~~ ;~, that of phenol with 9-fluorenone z HO OH

The pL.~P~ for making ~;~rh~~~l A can be ~ ~ y the equation C~3cc~ 3 2 ~ ~O ~ ~ O~

Ph~nol ~tarting mat-rials wer- adv~taL _~ly any a ~ tic L~l ~y ~which have at loast one unsubstituted ~osition, and optio~A~ly have one or moro in~rt sub3tituent~, ~uch a~ hydrocar~yl or hAlo~n at the ono or moro r$ng positions An inort substituent was a ~ubstituent which ao-8 not ~nterrere ~o~ bly with thn c~ -ti~ of the ~henol and katone or _ldehydo and which was not, itself, catalytic Pr~ferably, the ~wero unsu~st~tut-d in tho position, par_ to the LYd~G~1 group Alkylcne (alk), alkyl, cy~lo~lirhAtic~ aryl, arylono (~r), alkyl-~ryl~no (~llkar), arylalkylono (ar~lk), alkylcy~ls~l;phAtic and alkylene-cyclo~li~hAtic were hyd v~rbyl function3, that was, functions c~tA;n;~g carbon and l.~dhvg~l~ atoms ThYo alkylene functions can be straig_t-chain or branchod-chain and ~aturatoa or ~-t~at~d, that wa~ alkylan~, alkonyl-ne, or alkynylono Cy~lsAl;phAtic Lyd v~--~~~ rs~ includo both satur_tod _nd ~ t~-ated cyclic ~o~iA~eo~ that was, cycloalkyl-ne and cy~o~ ~ylone Arylon- includ-s mono- and ~olycyclic a,~ tic r~FjA -~, ~or ~x~mplo, thoso of ~ -, bip_-nyl, biaryl, naphthyl, 10 ~h~A~ h enyl, anthracenyl or aryl ~roup8, i~ A;~ tho8e bridgod by an alkylone grou~ Alkaryl r~o-;A~eo ;~ll-A~ alkyl, alkenyl and ~lkynyl-xub3titut~d aromatic rings Aralkyl includos alkyl, alkonyl or alkynyl r~niA~--o, ~ubstitutod by ono or more ~. tic ~roups Alkyl ~roup8 ;~ A~ both 8trai~ht-chain and L~ched-ch_in ~
of methyl, ethyl, propyl, butyl, pentyl, hoxyl, hortyl, octyl, nonyl, decyl, undocyl, dodncyl, tridocyl, totradocyl, ~ -Aocyl, h~~A~ocyl, _~pt-docyl, ~-'-_~1 and eico_yl ~roups, A8 woll as th~ Cvl Y8~ A;~Y
unsaturated (alkenyl or alkynyl) groups, as well as hi~her ~- logue~
Pref-rably, the alkyl groups WQre of 1 to 20 carbon atoms, moro proferably of 1 to 5 car~on atoms, mo_t rrY-ferably tho~o of 1 to 3 carbon atoms Alkyl of 1 to 5 carbon atoms ;~ A-8 the various methyl, ethyl, propyl, butyl and p-ntyl ;~ ~ ~
Alkyl, aryl, alk_ryl and aralkyl substituonts wor- ~uitablo Lyllvc~rbyl substituonts on the phonol ~rct-~t Othor in-rt ~ubstituents on thQ ~r-l~ ~, but wero not limited to alkoxy, aryloxy or alkaryloxy, whorQin alkoxy incluaos methoxy, othoxy, propyloxy, butoxy, pentoxy, h xoxy, heptoxy, octyloxy, nonyloxy, decyloxy and polyoxy thylon-, ns w 11 as higher homologuos; aryloxy, ~- y~ b~ph~ y, naphthyloxy and alkaryloxy ~ '-8 alkyl, alk-nyl and _lkylnyl-substitutod ~ -lic~
Add~tional inort substituonta in ~h-~lo includY-s halo, ~uch as bromo, chloro or iodo Cyano and nitro substituents may deactivato tho rh~~~lo and aldohydo and carboxylic acid substituQnts may cause interferin~ reactions Additional L~alv~yl ~ubstitu-nts may be suitablo in somo cas-s Pr~f-rred substituents ;~luAs alkyl moietios c~~tA;n;~ from 1 to ~ 10 carbon atoms, more proferably, lowor alkyl ~ ieti-s, c~~1-;~;~ from 1 W O 97/08122 PCT~US96/13683 to 5 carbon atoms, most prQfQrably from 1 to 3 carbon Atoms Th~ alkyl substituents may be straiyht-chAin or branched-chain i8 r 1~-y rh -1~ ;n-~uAe~ but wer- not limit-d to, phenol, 2-cr-~ol, 3-cr-sol, 4-cr-sol, 2-chloro~h-nol, 3-chlororh~nol, 4-chloropho-nol, 2-t-rt-butylr - -1, 2,4-dim thylrh-n~l, 2-othyl-6-methyl~h~n~l, 2-bromophQnol, 2-fluo~v~h~ , 2-phonv~y~he~ol, 3-m tho~y~honol, 2,3,6-trimothylr'- -1, 2,3,5,6-tetramethyl~h~nsl, 2,6-xylenol, 2,6-A;~hl~ vL~- ~1, 3,5-diethylrh~n~l, 2-benzylrh~n~l~ 2,6-di-t~rtbutylphen~l, 2-phenylrh -1, 1-n~hthol, 2-narhlh~l Profcrred rh~n~ls ;n~lu~- ph~nol, 2- or 3-crosol, 2,6-dim~thylphenol, ~soL~lnol, ~A~h~h~l~, nnd mixtures th-r-o~ ~o~t prefQrably, the phenol wAs un~ubstitut-d Th- k~tones which were Advnntageously usoa includo any kotone having A ~in~le k-tone carbonyl (C=0) group or soveral ketono carbonyl groups, ana which were reactive und-r tho conditions used The ketoncs c~n be 3ubstituted with ~ubstituents, which were inert und-r the conditions us~d In-rt Qub~titu~nt~ werQ as ~et forth abo~- for th~ r-active rh~nolQ
The ketv~os w~re advanta~Qously selocted from ~lirhAtic~ aromatic, alicyclic or mixed aromatic-~l;~hat;c ketones, dik-tones or polyk-tones, of which ac-tone, methyl ~thyl ketone, diethyl ketono, bonzil, ~c-tylac-ton~, mothyl i5v~ vyvl k~tono, methyl isobutyl kotone, AcetoF~ -, ethyl phenyl k~tone, cy~l~h~ ~ ~, cyc~op~nt~
'~ ~, fluor-nono, ;nA~n~ns~ 3,3,5-trimethylcycl-~q- -, ~nth_Aquinon~ 4-Lyd V~yacotoP~ -, ac -rht~ -_~inon~, quinon~, bonzoyl~-t - And A~ yl w~re ~l~r~ -~t;v~ oxampl-s ~tono~ ha~in~ halo, nitrilo or nitro substitu-nts can also bo us~d;
~or . _~-, 1,3_A; ~hl ~ro~-t~~- or hexafluoroac-tonQ
~l~h-t;c ketono~ which w~r~ us~ful starting materials ;~_l--A~, but wer~ not l$mited to ac-tono, othyl mothyl k~tone, isobutyl methyl keton-, 1,3-A~hlo-oacetono, h-xafluoro~cot~n9 A pref-rrea ~l;ph~t;c ketono wa~
ac-tone, which c~nAen~e~ with phonol to ~ v~co 2,2-bis-(4-L~l v~y~__lyl)-~ ly known ~s b;~p~ --1 A ~nother preferroa ~l;rh-tic k~tone was h fl~~roaceton~, which roacts with two moles of phonol to .n~o Z~2-bi8-(4-_y~v~yp~ yl)~h~fl~ v~v~ane (~;q~rh~n~l AF) A pr-f-rred cla~s of l--t -8 has at least on- l.y~va~rbyl ~roup c~nt-~n;ng an aryl group, for _~ _lo, a ph~nyl, tolyl, naphthyl, xylyl or 4-Lyd~v~y~h_~yl group I

W 097/08122 PCT~US96~13~83 othor pr-~Qrrea kotonos ;n~AA those in which tho Iyd.~rbon rA~A; CAl R co~ecLed to th- carbonyl ~rou~s of tho ketone waO in a Cy~loAl; ~hAt; c group Ex_mplAs of ~e~;fic pr~iurrod keton~s ; n~l ~Ag 9 fluorcnon~, cy~l~h~ ~, 3,3,5-trimothylcy~o~ ~ o, ;nAAn~n9, ;~n~n_~ and Anthraguinono ~ ost ~referred ketones in~ 9-fluo e~o o, b~n-o~h~nA, A~-tAno, _ceto~ -, 4-hy~h~y~cetorh-~ - ana 4~4~-dihyd~y ~ Most ~r-for_bly, tho ~. _ -~ of this inv ntion was u80d to make bisFhenol A by roaction of phonol with acetone or to make 9,9-bis-(4-l.y~.~y~henyl)fluorene (BHPF) by roaction of p_enol with 9-fl~o~an~c The ~L._~F~ Or thi~ invention cnn ~I80 bo usod for tho c~n~Pn~-tiAn of ~ with aldohydos; for _ _le, with fc l~hvde, acotaldehyde, ~ropi~nAl~-hyde, butyraldohyd- or hi~hor ~ -lo~1~~ of thn f 1~A RC~0, wh-rein R w_s _lkyl of 1 to 20 c_rbon _tom~ Tho c~n~~~t;~ o- two molo~ o_ ~hanol with ona molo of f ~ ~ydo produc-~ bin-(4-l.yl ~y~honyl)methanA, _180 known a~ 8isphenol F
It will be ~ Lood that ~;Al~-hydos and kotoAl~~h~yos, for = _lo, ~lyoxal, phonyl~lyoxal or yyruvic _ldohydo, c~n al80 bo used Th~ product~ woro ~enerally ~ ~nA~ ~h~n~7 n~ th_t WaR~ R
ao having ono or moro Oin~le cArbon _toms to which wore attached nucloi of two ~h~n~l;c moi-ti-s This singlo carbon atom ~o. o~ An to tho c- h~n~l c_rbon of tho kotono or A ~ lo ro_ct_nt In tho c_so of ~t_rting m_tari_ls, conlA;n;n~ ~ ro th_n one aldehydo or kotone carbonyl, the ~roduct will c~nlA;n more th_n one ~ ~Al ~;~h~n~l;c moiety For 25_le, the ~ te from acetyl acotono and phonol waO 2,2,4,4-t-trakis-(h_dko~y~hc-yl)~ ~An~ _nd tho _ ~ ~-te from benzoylacetono was 2,2,4,4-t-trakis-(h"~l.~,y~b- yl)-4-phonylhutAno The ~ o~lfonic acia catalyst was any ~oci~, wh-ther sol~lo or ;n~ol~hle in tho reaction mixture, c~n~-;n;ng at loast ono thiol (8H) ~roup and at l-ast on- sulfonic _cid (S03H) ~roup, ;n~l~;n~ any ~roup which can be ~v_.Lod to a 8--1 f~n; c acid group undor tho roaction conaitions us-d In tho __~ ~;c-ti~n and claims, tho solublo ~ ~a~tosulfonic acid moi-ty wan ~ so-Lod by tho f~ 1 A
35(RS),-~-(S03H)~

~ .9_ W O 97/08122 PCT~US96/13683 wh~r-in ~ was an Hlkylene, cycloaliphatic, arylene, alkylonearylen~, alkyl-n-cycloaliphatic, alkylen-aryl, h-t-rocyclic or alkylen-hetcrocyclic rosiauo and ~ach of "An ana b" wa~ i A~ A ~ly ~n ;~t~__L from 1 to 20 n~olublo -~ -~to~ulfonic acia," a~ usea in the spe~;fi~t;on ana claim~, me~ns a - __ ' which hAs som~ solubility in the r-action mixture ana which can b- ~ from the mixture, at tho ena of tho reaction, by ~xtraction, ion ~ ~, ~ ritation, absor~tion "Inxoluble ~Losulfonic acid," ns usea in the c_~c;f;~at;~ and claims, means a matQrial, which was ;~ol~hle in the reaction mixturo Th~s~ material~ wore generally polym~ric or~anic resins, or catalytically-activ ~ , bond-a to an inor~anic ~/L
Whon ~ was alkyl-ne, the alkyl-n- can be of 2 to 20 carbon atoms, includin~ strai~ht and branched chain alkylene moietiQs, Col _L~A;n~
h-terochain moi~ties and alkylene substitut~a with inert substitu~nt~
Inort ubstituents ;~l~A-, for le, alkoxy, alkonyl, alkynyl, halo, nitro, aryl R~l~s l;v~ - ~Lo-l~A-~~ulfonic acias ;~l A~, but w~r~ not limit-d to, 2-morcapto-than-sulfonic acid, 3 ~a~Lo~ v~ ~__lfA~;c ac~ a, 4 ~L~h-ut~ ul fonic ncid, 4 ~tc~e ~ ~-_lfonic acid, 3 - ~to-2,2-dimethylprop~ -~ulfonic acid, 2,3-A;- ~toprop-~-~ul~onic acia, c~topropane-2,3-disulfonic acid, 2-benzyl-4 ~ ~t~hut~--L.lfonic ac~d, 5 -~c~op-~t -=_1 f~; c acia~ ~ost ~reforrea among this group of cataly~ts worQ 3 - ~yLopropanesulfonic acid nnd 4- -~a~hut~ lfonic ~cia~ .
~ho ty~es of ~ ~to~ _lf~;c acids which w r- u---hlo w ro _l;f~d by the followin~ _ __ '~ of r~_ la I

WO 97/08122 PCT/U596~13683 H8 ~ 803H Fo rmul~ I (a) HS ~ ~S03H Formul~ I (b) Q
SH
¦ Formula I (c) Q ~~ S03H

whorein Q was _n inert ~ubstituent and Y was an optional hetero~7~ , ~or Dxampl~ 0, N-Q or S Q was H, hyd~_~rbyl, halo, c~rboxy, ~ul~onyl, ~8 doscribod ~oovo ror inert substituonts on tho ~honol, koton~ or aldohyaQ starting matorials ~ore than ono Q may opt;~Ally be prQsQnt Th- Q substituent can be at any position on th- chain and more than on~ Q
can b- ~Le~ L As ~ot ~orth in tho gonor~l fr lA for th~ solublo catalysts, ~ ro th~n onu 8H or s~lf~;c ~cia f~ t;~ worQ o~ti~7~11y in th~ catalyst C ~ of r~ 1~ I(a) are ;~ within tho genoric f~
0 H8(CH2)yCH(Q) (CH2) ~503H
wheroin y was an into~r 4rom 0 to 20, z was an ;~1 3~ from 0 to 20, Q
wa8 an optional in~rt substituont and y I z 2 1, u~ to a ~ of 40 _ ~~ 0~ r~ 1A I(b) ar~ within the sQneric formula H8 (CH2)y~Y~ (CH2) s8~3H~
wL~ _ ~ on~ or ~ r~ inort substitu~nts, Q, can be nttach~d at any ~oint along tho carbon chain; whorein Y was a hetoro-lQmont, for ~ , -S-;
~ach of y and z was at l~nst 1 and y -I z 2 2, up to a - of 40 P f~ ~ ~ lin~ar - ~to-l~r --~ulfonic acias woro thos~ in which tho aistanco b_L~_ the ~ o and ~ulf~;c acid _unction~ wrre le88 than ao 20 atoms, ;~lu~;n~ both carbon and h~t-roat ~8 C __ a~ O~ F~- 1A
I(b) can al80 havo moro than one SH and/or mor~ th~n ono sulronic acid functi ~
C ~ of F~ 1 A I (C) are included within tho ~ormula CA 02230272 l998-02-24 WO 97/08122 PCTAUS96/l3683 HS
I

TH ( CH2 ) y t Z SOIH
Q
wher-in y and z wor~ as abova.
r~- ~Lo8ulfonic acid pr~_ ~Gl8 can al80 be usea as catalysts, by cv.... ...v~ ~ion to active ~Losulfonic acid catalyst8 in the roaction mixtures. For ~ _le, a pr~cursor alkali met~l sulfonate salt can b~
noutralizeA with a min-ral acid to produce a froQ sul~onic acia.
8ulfonat~ ~ster ~ ~__ dO18 ean be hydrolyzed by treA with a stron~
baxe, for ~ _le, soaium or ~o~r; l-y~ v~ide, and thus cv~vv.Lod to a co~ ~vnding alkali m~tal salt. A further ~ or of sulfonic acias for the practiee of this invention, was ~ sulfonyl haliae group, which ean roadily co..v~rLod to a co ~ 'A;~ sul~onic acid.
~ ~Losul~onie aeids can be ~ropared from co ~6~A;~g h-lo~lkA~-~_lfonic acids by reaction with an alkali metal - ~Lide; for ~x~l~, X-alk-803H + Na8H -~ HS-alk-803H + NaX
wh~r-in X was Cl, Br or I nnd alk was alkylono, ~enorally in accoraanco w~th Elli8 et al., "The Preparation and P v~Al Li-s o~ a Double 8eries of Aliphatic - ~pLans, n J Am. Chem. 80c., Volume 54 (1932), Pages 1674-1687.
Alt~-~At;v ly, tL~- of a h~l oAl 1- - - - S ~lfonic acid with an Alkali mHtal ~h;~-~-tat~, foll~d by hydrolysis, can be usea to preparo to~ -r~l fonic acias .
Anoth-r route to ~Los~lf~;c acids was by co~v~ Lin~ h~l;~ to a cv ~ thiouronium salt, which was hydrolyz~d with ~ stron~ base, a~ ~ollow~:
X-alk-803H + ~, ~ ) HN=C-8-alk-80 H
I

~ NaOH

H8-alk-803H

~-norally according to 8chramm ot al., "The 8ynt~ of ~ c~LQ-lkA~-r~lfonie Acias," J. Am. Chem. Soc., Volume 77 (1955), Pagos 40 6231-6233.

=

CA 02230272 l998-02-24 W O 97/08122 PCT~US96/13683 ~yd~yAl~A~ lfonic acids can also bo c~v~Lod to tho corro~p~n~;~ morcapto-~l -n~lfonic acid by r-action with t_iourea and HBr/HCl to produce a thiouronium salt, which was hydrolyzod usin~ a _trong ba~o. S~e, Frank et al., "The Preparation of - ~a~Lans 4rom Alcohols,"
J. Am. Ch m. Soc., Volumo 67 (1946), Pa~es 2103-2104.
High-r - ~to~ r-L lfonic acias can be pre2arod from high~r olsf;n~ulfonic acids, _or examplo, oleyl sulfonic acid, by aading h~ ~J'-r~lf;~ across tho ol~4inic bond. Alt~-~At;vely, tho olofinic bond o~ an ol~fin;c sulfonic acid can be h~lo~ e~, for example, chlorinat~a, and the h_l o~n moiety re~laced by a - ~-~Lo _unction, as abov~.
~ erc-pto-l~an~sulfonic acias c~n also be made from correnpnn~;n~
sultones, for example, 1,4-hut---A~ultone, in accordance with Chem. Abs., 90:86742m (1979); R. Fischer, "Prop~ ~~ultone,~ Ind. ~n~. Chem., Volumo 56 (1964), Pa~es 41-457 or A. ~ustafa, ~Tho Chomistry of SultonQs ana 8ultams," Chemical Review~, Volume 54 (1954), Pa~es 195-223.
When -~- was arylene, th- sulfonic acid and - ~to moieti~s worQ
attached airoctly to an aromatic rin~. Reprosont~tive al. t;c _~tosul~onic acids include 2-mercaptobon~ nulfonic acid, 3--~-~to~ -- -s~lfonic acid, 4 -~-~tobenz~no~lfonic acid, 2---~a~t~rhth-l~~sulfonic acia. Tho aromatic .s;~o8 can bo ~ub~titutod with substituent~, for oxam~le, H, alkyl, alkenyl, alkynyl, aryl, halo, alkoxy, aryloxy (Q, ahove), which w~re inert unaer the reaction conditions. Tho active catalysts can cAn~-;n moro than one SH
and/or moro than ono sul40nic acid function in each molecule.
Cycloaliphatic resi~leO- ;n~1-~9 thoQe o$ cyrlohoY-~o, cycloFont~no and cyclohe~tan-; the aliphatic rin~ of indane, Tetralin or benzocycloheptano. Ro~ C8 -tivo cyrloAl;~h-t;c - ~Losul40nic acids include, but wero not limited to, a ~a~tocy~lo~-- -~ulfonic acid, 2-- ~-~Locyclc~ fonic acid, 3 --c-ptocy.~l ~h~ esul40nic acid, and 3- ~Locyclo~nt~no~ulfonic acid. The cycloaliphatic rin~s can also be ~ubstitutQd with inort _ubstituents and can cnnt-;n ~ re than one S~ ~roup and/or more than one sul40nic acid ~rou~.
R~r-~-nt-tive alkylen~cyrlo-l;rh-tic - ~Losul4onic acid can be r-pre~ e~ by the followin~ fr 1_Q:

CzH2~SO3H CZH2z8o3H
CzH2zSO3H

u ~ c y il 2 y e CyH2ySH CyH2ySH

Q ~ CyH2ySH

C~cH2zSO3H

whor-in y ana z wRro i~tY~ of 0 to 20; Q wa8 an oytional inort ~ubstituent soloetad from alkyl, aryl, hAlo, ~lkoxy or aryloxy and y + z >
1. Typical c ~ includo ( --~Lomothyl)cy~ lfonic Aeid and ( --c~Lomothyl)(sulfomothyl)eyr~ Y~~.
Typienl ~lkylanoAryl morea~tosulfonie aeids ean bo a~ ~e~t~ by tho f~

Q

HSCyH2y / ~CzH2zSO3H
Q CzH2zSO3H
~ Q ~J
CyH2y8H
¦ CyH2ySH
CzH~zSO3H

Q ~ CyH2ySH

CzH2zSO3H

-WO 97~08122 PCT/[~S96/13683 whorQin x, y ~na Q woro a8 abovo ana x ~ y 2 1 A typical - __ ' of thi~ group, (mercaptomethyl)~ sulfonic acid, can be preparea from a co 7~y~ ;~ chlorom thyl- or bromo-mothylh ~ f~;c acid 0~ from vinylsulfonic acid can provide soluble matQrials, c~t~;~;ng large '- ~ of -~ Lo and sl~lf~n;c acid groups This typo of soluble c~talyst can be prepar~a from oligom~rs c~nt~;n;n~
vi~yln lfosic acid units, h~lf of which c~n b- cv.vO Loa to chlorosul f~yl unita and ~ to ~ ~a~to units in acco~ c~ with the foll r.. n~
reaction schome --~--CH2--CH--CH2--CH--CH2--CH--CH2--CH--]--l l -t-CH2-CH-CH2-CH-CH2-CH-CH2-CH-]-l l S03H S02Cl S03H so2cl --[--CH2--CH--CH2--CH--CH2--CH--CH2--CE~--]--Another type of oligomeric catalysts, c~n~;n;n~ a multi~licity of -~Lo and ~ulfon;c acia units, can be ~ ~ a from ~ ._ - ~ltono P ~ -~ ltono WA8 propar-a as ao~cribod by G -8~9 ~t al , Chom Abs 53 2083c (1959), Helborger et al , DE 1,146,870 and Ch m Abs 59 11259 (1963) The sultono ring of the polymor can be _ -d, g-norally a8 abovO, to furni~h ~Lo~lf~;c acia ol;~ s, co~n;n~ a plurality of 7~Lo nnd ~ f~n;c acid units In addition, oli~ c~nt~;n;ng a plurality of ~Losulfonic acid functions can be pr-parea from ol;~ - 5 of 4-allyl-1,4-h~t~ lton- Tho - was preparoa ns a-scribea for 4-bonzyl-1,4-~t-n- ,ltono, using allyl chlorido inst~ad of benzyl c~loriao 4,4-Diallyl-1,4-but~ tono can be proparea by addition of a ~econd allyl group othor catnlytically activo --~a~Losulfonic acid ol;L L can be pre~ar-d from allyl vinylsulfonat~ (C~ C020ru~u~ which was polymer-ize~ to form a cvl ~ ~;ng sultono-c~nt~;n;n~ polymer in accordanco with Goethal~, ~8ynlh-~is and Polymor;-~ti~n of Allyl Vinyl Sul_onato,~

-, CA 02230272 l998-02-24 Polymer Lottors, Volume 4 (1966), Pa~s 691-693 T_o rosulting polymor, co~t-;~;~ ~ultono groups was treated with a reacti~e th;ol~te to open tho ultono rin~ and Droduco ~toalkyl sulfonate Folymers The co.v~l~ions can be roprs~ d by the oquation _ SO2 ~ SO2 ~ SO3H
~ - n - SH

~; ' 1 A~ catalytically-active ~olid ol;~ 8 can be prepared from oligom~rs of allyl allyl~ulf~te (CH2-~rU~-~O2or~r~-~u~)~ which can bo polymcrizod in acco d~ece with E Go-t-als et ~l , "Polymer; 7~ti~ and Copolymor;~1;o~ of Allyl Sulfonate," J Macromol Sci - Chnm , Volume A5 (1971), Pagos 63-72 The oligomers were cv~v~lLed to mercaptosulfonic acid functional material~ by a correspA~;n~ rin~ op~;~ reaction The con~er~ion can be L ~ ~ by th~ equation O o - S O2 - n - SH S03H

~ot-rocyclic re~ ad~ g~ nly ;~I ~A cyclic rAq;15 ~~~ ~g N, O, or S T_ese will g-nerally corr-spond to aromatic , for - lo, a~ es from pyridine, th;o~' -, q~;~ol;
~idine, a~ well as the COL e~_ ~;n~ partially or fully Alkyl; - torocyclic r~-i~--~ ot_~rwise corro~pond to ~romatic r~ of tho ~ame configuration, a8 do alkyl h~t~ o~y~lic l_riA~ , n~ well as cv ~-~~A;~ fully or partially l~a~v91~~t--d , _ --n, Pr-ferr-d nol~l ~A~tosulAfonic acids were _ ~ in which t_~
c~pLan nd ~ulfonic acid functions wer~Q ~e~aratud by A chain of 2 to lO
atoms, whother the chain or linkor arm was in an alkylone group or i~col~o~At~d in nn a ~ -tic, cyclo~l;ph-t;c or heterocyclic ring, whether or not thu chain includes hot_ oJ :, and ~hsth~ or not t_e -r~_~Lo W 0 97~0f~122 PCT/US96/1368;~

and _ulA4Onic acid functions wor- attached directly or indirectly to the rin~ structurAs Prcferrea 80luble cataly#ts for the practice of this invontion werQ morca;A,tosulfonic acids in which ~ and b w~ro ;A~7p~ y ~ from 1 to 4 ~orc pr-A4~rably, a and b werc ;-- ; 'AAtly 1 or 2 Most 5 preforred were - ~_~tosulfonic acid8, contAAiniAg mercapto and sul~onic _cid ~unction8 in a 1 1 molar ratio, that wa8 a and b wero ~ach 1, more rticularly 3 - __~tv~Av~An~_ulfonic acid and 4 -~,A~L~but~ ulfon;c acid When the c~to8ulfonic acid wa8 ;n~ol~hle, the heteLv~ Y~o 10 catalyst comprises a catalyticAAlly-active -L cAie~ r-jA,r~ by r- 1 II
(H5)~-~ -(SO3H)b F~ lA II

in which ~ach of a and b was ;A~ tly an integer from 1 to 20, ~ waAA
an alkylcne, cyclo-l;;AhAtic, arylon~, alkylonoarylono, nlkylono-cycloA~l;~hAti~A~, alkylonearyl, hetorocyclic or alkylenehcterocyclic ~i ~, L wa_ an o~tional ~ grouj, and wa8 a bond, whiCh catalytically-active sp-ciQs was attach-d by the bond - to an ;A~ol ~e or~A~ic or inor~anic ~o L; or a catalytically-active ~peci~
-s~ l~' by J 1A III
(HS) A ( 803H)~ (F~ 1A III) \ /
_[
wheroin ~ was an alkyl-no, arylen-, cy~lo-l;rhAtic, alkyl-noarylono, alky~ - y~lOAli~hAt;c~ alkylenoaryl, hoterocyclic or alkyl~h~t--ocyclic r-siduo; a and b wero ;- ~ ' ly sol-ctea from i~1~ ~ from 1 to 20;
L' was an optional 1;~; n~ grou~ and - W_8 a bond Catalytically-active material~ of F~ 1A~ II were generally derivQd ~rom ~olymers of ethylenic ~, whor-in the ;~ol~l- organic ~v.L
w_~ tho main chain of a rosulting ~olymor and -L- was a coval-nt bond or a 1; n~; ng group This ty~o of ~olymer will ; n~ ~e unit structure8 ~ 8 F 1 by th~ ~ -~ 1 f~- 1A
-~CH2CH~-I

(HS),-~-(SO3H)~

, Pr--f--rably, th- catalytically-activ materials will i~~lude those ha~ring from 1 to 4 of oach of -- capLo and sulfonic acid groups por More preforably, the catalytically-acti~ro materials will ;r~ those havinsr 1 or 2 of ~ach of ~a~.to and sulfonic acid groups Ror ~ ~ Most 5 pr--f--rably,tho catalytically-acti~r-- matorislls c~t~; ~ 1 1 ratio3 of ,Lo and sul fo; c acid function~; ~nd will correapond to tho gon--ral formula - lCH2CH] -I

L
HS-~ ~ -SO3H
r - 1A y ~?olymers, made from othyl~ lly ~ t ~ted --L~ and which can be used as carriers for the catalytically-active Fl~--cios, 15 includo, but woro not limit-d to L ~ ---(8) -phenyl ~L~ _ -CH2- ~honyl ally~
-O- ~henyl phenyl ~rinyl oth-r -COO- ~lkyl, aryl acrylic osters -OCO- alkyl, aryl ~rinyl osters ~(C~2)r~ alk-nyl a,o3-~;olefi.. o r ~ 4-20 -N}~- alkyl, aryl ~riny~ r -CON~I- alkyl, aryl acryl '~
-NHCOO- alkyl, aryl vinylurothane~

- alkylphonyl ~rinyltol~ ~
- ph-nyl a-mothylsLy ~n~
-8- ph-nyl ~h nyl ~inyl et~-r -8O2- aryl vinyl aryl ~u~ f -~
-80- aryl vinyl aryl ~u~ f~
-NSO2- aryl aryl ~ulf- ~e The l~.l.i.~5J grou~s, -L-, accordinlJly can includo alkylone, a co~al--nt bon~l, oxycarbonyl, carbonyloxy, oxy, uroido, amido, amino, thio 20 (~ ulfur), sulfono or sulfoxo Preferr d l;~k;~ rroups ; ~1~ io a covalont -WO 97J08122 PCT/US96~13683 bond, methylenO, sulfur or oxygen, more ~_rtie~lA~ly a eoval~nt bond joining a phonyl ring to a carbon h,~h~e in ~ol~L~ _ - or ~oly~Ly-~o dorivativos, o~ch e~~ A;~;~ SH An~ S03H functions in sin~lo c units of ~oly~Ly ~o One type of novel eatalytieAlly-acti~e poly~Lyl~ne resin~ lu~
unit struetures o~ ~8~ ~ by F~ IV

[~
B
I

F~ 1 A CnH~n IV

CIIR SH

wherQin B was a bridging grou~, R _nd R1 werQ ;~ ly soloetod from H, Alkyl or aryl, -CnH2n- wa~ str_i~ht or b~ ' chain alkylene _nd n was an int-~er from O to 20 Tho briaging group B, can bo n~leeto~ ~rom _lkylone, generally a8 above Alkyl and aryl arQ Aof; -~ above Yol~Ly.~ - rosins of F~ 1 A IV enn b~ m~de by tho st-ps of (_) raacting _ hAlo-l~y~Ly~O~c ~olymer with _ lith;At~ sultone, (b) t -t;~g a reO~ultin~ sultone-~unct;~ ' ~olymer with a reActiv~ 1h;~1Ate and (c) acidifying th~ rosulting ;~- ';At- to ~roduc- A yolymer e~~t-;~;ng ( ~ to~ lfoAl~yl)~y~ o units ~ -~oAlkyl~Ly.~c ~olymers ;~ , but wer- not limited to poly(chloromethyl~Ly~- ~), ~oly(L. - - hyl~Ly ~ -), ~oly(L _ ~yl~Ly e-~o)~ yoly(L ~ Ly~ ~
Ineludin~ ~ lym rs _nd eopolymers, whether m_de by ~olymer;~A~t;~~ of h-lo-l~ylsLy.~6 --8 or hAlo-l~ylation of ~oly~Ly eno rosins RG~ tiVQ starting materi~ls can be made by co~olymerization of - vinylbonzyl chlorido or vinylbenzyl b ~ with styr-no Eithor startin~

~ -19-material can be crog~l;nke~l with divinylbenzene or Q,; ~1A CrO881;n1~;nSr ~ ~ The pol-ymers can c~ntain other ~ , for oxample, styrcne, ~-mQthyl~Ly onQ~ acrylonitrile, l~uta~;rr~ maleic anhydridc, ethylono or propyl-no The h-loalkylated polymer~ will adv~nta~reouQly c~nt~in ~rom 0 5 m~g/g to 10 meq/g of h~ thyl ~rroups ~alomethylated or h-loAlkylated polymers -- lly compriso mixtureQ Or ~olymers, substitutQd in the ortho, m ~ta- and par~-po_itions Poly(chloromethyl~Ly-e o), con1-a;r~ ~ 2 to 5 meq/g of chlorine, wa a preferred ntartin~ mat-rial Tho r--action s--quonce described above can be performed ut;l;~tr~SJ a variety of chloromethylated or Ll~ thylated ~Ly . e ~olymQrs or co~olym~ r In particular, crorslin'~~d hAl~ ~thylatod ~Ly -/divinyl~ co~?olymers in various formQ, for Dxam;ple, mi_ v~,, v~s or ma~v~OL~,~s boads, powdors, can be ~uncti~nal;~d to provid the Cvl ~" Ain5J ~apto~ulfonic acid polymers In the ca~o of all tho polymer-basod cataly~ts u1;l;~ t;~n of tho funcl;~n~ Ly _~ ~ or othor ~olymer_ in bead form may advanta5~--ously ~; _1;fy workup ~Loced~ 8 during pr--~aration and provide for more facil--i _~ in cataly~t A~l;cAti~n- 8eads WQrQ suitably of any size throuSJh which Hff--ctive flow and contact was achieved Physical forms ;n~l ~;n~ ~c 1~ ~, bQads, ~xtruded ~hapes, maclo~v v~8 and mi~ v~oro~,s con~iguration w re; '- _v~r, suitably u~ed in the ~ractice of tho inv ntion 3n g-n~ral ller size ~?rovid 8 mor~ ~urface nr--a for c~nt~ct, but larger ~iz-- permit- ~r--at~ r flow throuS~h a bed Opti z;ng th----- factor~ was within tho Xill of th~ art R--activ-- tl~iolAt6~r advAnt-~ aly ;n 1~ but wero not limit--d to, ~odium ~h~-cetat--, pot-~ri fh;Q-c tat~ 1 hioAcnt~te ana lithium 4h;cl~-rt~to and the corres~~n~;nSr L~ _ lfjA8a Of the~o, lithium, ~oaium or pot-o~; thi~ tato wa ~ yr--forred Wh-n co ~,~ Dion to a -v~,to f nnlj~n was dono throuSJh a thiourea int~ t~ the thioureas w re advanta" ~_~ly sol--ct--d from thiouroa, N-mothylthiourea, N- ~thylthiour--a, N ~ ylthiourea In another alt~~-n-t ;ve odium thiosulfate can be u~ed A pr--ferrod speci--s of cntalytically-active PO1YDLY ~.e r--sin was mad-- by r--acting poly(chloromethyl)~ly - with li~ h;~ted 1,4-;

W 0 97/08~22 PCT~US96/~3683 b~l ~~ulton~ to produce an int~ ';ate sultone, ~lan~n~A by the -L ~L~ ~1 unit formula \~/

[ ~

I

(CH2)2CH2 Tho re~ulting polymsr contA;~-d (~ -~Lo-~--sulfo~entyl)~L
units, that was, n in F~- 1 A IV wn~ 2 ana B wa~ -CH2 ~ ost pr-~erably, this ty~e of r-8in w~8 mado from a 81ightly cro8~1~ks~ poly~Ly~ ; th~3 rQsultin~ catalytically active matQri~l w~
~ignAt-~ as P~BSA-~ER
Anoth-r typ~ o~ cat-lyticnlly-acti~e poly~Lyl ~ rosin8 can b~3 20 ~l_p~._' by tho ~tops of (a) alkylating a PO1YDLY1~-- with an alkenyl haliao of tho f 1 RC(Rl)3C(R~)C~2~CH(R3)X, wLc _;n nach of R, R , R and R was H, alkyl or ~ryl; m wa~ 0 to 20 ana X was F, Cl, Br or I to produc3 a hAloAl~yl ~oly~Ly -;
(b) fu~fonAI;~g thQ r-~ulting h~~sA~yl~oly~Ly ~ ~ to produce an ;nt ~ t~ ha~ing sul~o-_~n~ti~Al groups;
(c) opt;o~Ally c~v~Ling tho ~ulfo-functional groups to a 80dium or ~ot~Q~i ~ulf~n-~- _unction;
(d) th;olAt;~ the thu~-~roduc-d ~ulfG~Ly ~ ;nt- -';At0 by roacting tho halo function with a r-activo 1h;olAte to ~ ~c~ a c~ __~ ~;ng ~ Lo ~unction or ~1~ ~OL thereof, and (-) opti~-lly hydroly~ing the thu~-t~;olAted ;n0~ -';At~ with an acid or basQ wh~n the th~lAte~ ~roup 80 requir-s; nnd (f) opt;~n-lly aciaifying (i_ ~o r-quired) to proauco tho sulf~n;c acid function Thi8 ~ r~ can be l~La~ od broadly by the reaction soqu~nc~3 ~ .

,~

[~ + R ( R ) C=C ( R ) CmH2mCH ( R ) X

[~ or [~
R --C--R Rl--C--CR(R ) H

H-- C ( R ) CmH2mCH ( R ) X

CmH2mCH ( R ) X

~ul f onation /~f ~ /' 803H ~ 803H

R -C-R or R -C-CR(R ) H

2) H CmH2mCH ( R ) X

C~H~CH( R ) X

WO 97/08122 PCT/US96/l3683 to produc~ ;~t~ -a;~<te haloAlkyl ~ f~r~At~!d styrenQ polymsrs, of which h~llo functionE~ were Cv~-v~l L-d to ~ Lo-functions to ~roduco th foll r n~ typ~Js o~ products of F 1~ V

HO3S R-C_Rl SO3~ R2-C-CR (R ) H

C ( R ) H CmH2mCH (R ) SH

CmX2mCH ( R ) SH

Alkonyl hnl;~ 3 o~t~ Ally c~ A;~- ~ryl and ~lkyl sub~titu~nts, A8 ~fi -~ abov~ R~ tivo ~lk~nyl ~ ;cl~, u~cful for pr--p lrinSJ the catalyt~cally-activ polym~rs, include, but worc not limitod to, ~llyl chlorido, allyl L ~ ae, allyl iodide, methallyl chloride, m~th~llyl Ll '~'-, crotyl chloriae, crotyl b ~A, 4-bromo-1-but-n~, 5-br~o-1-butano, 6-bromo-1-h~xono or hiçrhor chloro or L ~ lr- -7, tho alk--nyl ~ )3 wer ~llylic hAl;~a~~t, repre~e~tecl by the formula RC(Rl)~C(R2)CH(R3)X Most prel~arably, th~ alkonyl h~lid~ wa~ 5-bro~-1-pe~t--~, 11-bromo-1-ll~a-- - or ~llyl L 'd~
A ~rt;clll~-ly ~r--~~rrod product thuE~ mad-- can bH charactoriz~d by 15 tho fc_ 1 A, in thQ Ca8Q of a ~,,Lvl cL from 5-brvmo-l-p~r~

5~ [~SO3H

--~ SO3H

SH

or, whon th halido was allyl L ~ ~is or allyl chloride, by the fc- 1 CH~ SH

R--activo th;~ t--~ wore as ~efi -' above Mo~3t preforably, tho 25 roactiv~ thiolate was ~ alkali metal th;o~~~tate or Lyl -_lf;~~, 8y varyin~ tho choice of ~tartin~ L ~ --lkA~e (or oth~r hAlo-llrA~9) us--d in th ~ allcylation ~tep of~ the proce ~8, tho basic ~ doscribea bov can also bo us-d to propar- a vari-ty of catalystl~ with varying chain l-ngth~ ~ ~t the ~O~tan nnd ~ l fo~ acid moioti-s A num}~or 30 of cat~ly~t~ with di_for nt I ~ ~ o4 ~ LOYUl f~'~; C ~-cid ~ite~, sr upon tho d--gr--e of functi~ tion in tho alkylation and PUlfc~tior~ ~t--ps in the ~ r~rs~ and structural r~ t;~ h;~ L~_- tho Lan ana ~ulfonic acia xit--s, ~ 1 ';~r u~on tho choice of bromo- or chloroalkyl~tinsJ aSrent, can ~ccordingly be mado P ~f-- 1 ~ catalytically-activo specios of F~ V wero those derivea from poly~Ly _ ~3, tr-atud with 5-bromo-1-p -~9, ll-bromo-l-c~~e or an allylic halido of the _- 1 A RCH--~-u~/~U~ wher--in R wa~ R
or alkyl of 1 to 5 caroon atom~

-WO 97/08122 PCT/US96~136~3 In anoth-r aspoct, this invention relatos to novel ~ ~Loalkyl)(sulfo)phonyl~lkyl aulfonated ~oly~Ly ~ne eAt~lyst~, mado by a procQss com~rising thQ stops of (~) ~lkylating ~ ~ lkyl~tod ~oly ~Ly _~e with ~ haloalkylarylone ~ to produco an ;~t~ te hAlo~lkyl~oly~Ly~.ne h_ving (h~ 1 OA 1 kyl ) phonylalkYl ntyrone unitss (b) sulf~t;~g tho thu~-proauc~d h~loAlkylpoly~Ly ~ ~
';ate to pro~uco an ;~t- -~;at~ having sulfo-funetional groups;
(c) oP1; ~Al ly Cv~-vG' Ling tho sulfo function~l groups to corro~p~n~;~ alkali metal salts;
(d) th;ol~t;~ tho thus-~roduced sulfG~Ly ono ;~te ~;Ate by re~ctin~ tho halo ~unction with a r~aetive th;~l~to to p~vd~ce a corre~p~n~;~g --~to function or ~l~C~O~ thereof and (Q) Opl ;~nlly hydrolyzing tho thus-~h;olAtn~ ;~t~- ';~t~ with an aci~ or b~so wh~n tho I h; ol -te~ ~roup 80 rocuir-~; and (f) opti~lly Aci~;fying (if uo required) to ~ od~ce tho ~ulfonic ~cid f~l~ti~
This ~.e~e~ produeos polymor~ having ._--t;~ units o~ tho ~SO3H ~SO3H

HO3S (CH2)n SH

whoroin n was prof~rably an ;~t~__. from 0 to lO, moro proforably 2 or 3 A ~L ~e~ ~tivo mQmbor of this ~-rios of polym~rs, dosignatod a8 DP~SA-XE3C was mAde ~rom chlo-~ --hylstyreno polymor and 3-25 L.. _ ~yl~ -, in accordance with the followin~ roaction ~e_~-~ce -E~

Cl alkyl at i on Lewis acid ~ CH2 CH2 CH, Br )~ ~ B r -W 097/OXl22 PCT~US96~13683 8~11 fonation 1) ClS03H
2) NaHCO3 NaO3S{~ [~SO3Na ~ Br Na~S

thiolation 1) Na thioac~tat~
~ 2) aCid hYdrO1Y8i~

HO3S ~ ~ S03H

~ "~ ~SH

Tho h~lo~l~vl poly~Ly O~e ~tartin~ m t-rials can ~dvantngOou~ly be s-l-cL~ from c_loromethylat-a poly~Ly~ -~, b ~ ~thylat--d poly~Ly ~-c~, C_1OrO~thY1at-a PO1YDLY1O -~, iodo-t~ylat-d poly~Ly -8, gen-rally as abov~, ~rO~Orably tho halomethyl~t~d poly~Ly . -8 Those skillOd in th-art 5-~ ;7O that sel-ctivity dOcr~a~s with h~lo~l~yl grou~s on aryl rin~s which ~roup~ havc ~ L-1 ectivity T_o h~lo~l~ylary-nQ c __ ' can conv~i~~tly bo s-lOct~d ~rom chlG~ , (chloromethyl)hq -, (chloroethyl)b~
(chlo v~ ~yl)~-~~ -, (chlG ~Lyl)~~~ -, ~8 woll ~g tho ~ ~ -A;~
~luoro, bromo and iodo analo~uos R-~ t;ve _1~ e (2--CA 02230272 l998-02-24 WO 97/08122 PCT~US96/l3683 chloroothyl)b~~~r~, (2-bL~ ~thyl)h~~~, (2-iodoQthyl)~-~, 1-chloro-3-phenyl~ ~o, 1-bromo-3-phonylpropane, and 1-iodo-3-; phenylpropano Th~ bromo ~ ds wor~ proferr_a Th~ alkylation wrAs convoni~ntlY carri~d out in tho ~,~ e of J
5 Fri - d~l-CrrA4t8 crAtaly~t, of which aluminum trichlorido, aluminum b ~
boron trifluor$d~, Lyd ~_, fluorido, phosphoric aeid, zinc ehlorid~, titanium ehloride, othylrAluminum ~;rhlo id- and 3t~nnic chloride wQrQ
r-pr-r~ ;ve A prOferrQd catrAlyst was ~1 chlorido in nitromothane or nitro~ - -, as di8closoa by A WrAr~~hawsky ot al , "FunctiA~-~; 7~tir~ of Poly~Lyl ~, I Alkylation with Sub8titutôd B~nzyl Halid~ And B-nzyl ~lc~h~l C _ ~n, J Org Chem , Volume 43 (1978), Pay--s 3151-3157 Conv~~;~~~tly, ~ft~r nlkylation, unrQactod h~lo-lkyl~ , solvOnt and catrAlyst in th_ -~ Ytu-o w-ro l v ~ Afrom the alkylatOd poly~Ly _.o by m~an~ within th~ art Auch a3 filtration Adv~ ly, tho -~ Yt~o wa~ r~cyclod for roaction with ~dditional h~lo~l~yl poly~Ly~ o Th~
~lkylat~d poly,Ly ~no was optio~lly wa8hod with a solvont such as dichloromothano and op~ ly dried The re~ultiny- nlkylat-d ~oly"Ly ,~o was sulfonatod usin~
chloror~lf~~;c aeid, oloum or othor known sulf~~ a~onts Prior to _ ~ion of tho halo mOiQty to thô ~ o moiety, $t wa8 eonvoni~nt to cv~v_ L th~ gulfo moi0tios to cO~ ;ng alkali motal salts ChlG 7f~~;c acid, ~ulfurie acid or sulfur trioxide was conv~~;~t~y u~-d in an amount ~ff;ri~ to achi-ve a ~rodot~ or desirable do~rO- of ~ulf~-ti~, adv~t~L l~y to avoid e~r8- y worku~, in an mount not in lar~o ~xe-8s of thô ~uffici~nt amount whieh vari~s with oaeh r-~in but Wa8 ~t- -' without unauo ~x~or~ -tio~ Tho adv~ r of low~r reaetion t~ _ ~tur-s woro y _~t~r with ehloro~lf~~;e aeid Tho th;ol~t;~g ~S ~ wore eonv~niOntly s-loetOd from tho~o ~;-cl~-~ abovO 8Odium th; ~--~tato was pro_orroa Exc-~3 soaium L~ ~ lf;~ w~ opt~ ly usad for th;ol~t;~~ Hydrolysis was thon ~c-~r--y ~inco a thio group rathor than a ~h;o~cOtat~ wa8 formed Th~
~t 'i~te thi~lAt~' __ ' was, if n-c~ssary, acidifioa with a strong acid to cv~v. L rulf~to salt moi~tie~ to COL e~ ~;ng sulfonic acid moietiO~ Ad~antag-ou~ly, a minOral acid was us~d, as abovo In an alt~ t~ '-~~; , tho ~lOC~88 co~prise8 WO 97/08122 PC~/US96~136X3 (~) alkylating ~ PO1YDLY OU~e resin with a hAl~ thyl h~ lo~lkvlarylene c _ _ ' to produae an int~- -';ate h~vin~
(haloAlkyl)3;~hnnyl~1kyl ~-y _ Q unit~;
- (b) sulfonating the thus-proauced int~ te to produco an ~nt~ to having 8ul~0-functional groups;
(c) o~ ly cc VOlLing tho sulfo functions to COl O~ ;ng alkali motal s~lts;
(a) th; ol~t;ng the thus-produced sulfG~ Ly n~ ;nl ~ te by r~-acting the halo function with a r--active 1 h; ol AtC to produco a 10 corre81y~n~; nsJ ~ ~ ~LO function or ~ t o theroof ~Ind (~) ol?ti~ Ally hydrolyzinS~ the t_us-th;olAte~'l ;n1-r- ~';~te with an acid or b~se wh~n tho ~h;ol~tn~ sJrouP 80 requirod; and op~ lly ~lciairying (if 80 roquirod) to ~ ~ l~co tho sulfonic ~cid function Illustrntive of this reaction was tho followinSr s-quQnco (~ "A', (~ "S~

~3 Lev~isAud ~3 1)CI503H ~SO N 1)NaSAc [~S03H
T ~ 2)Acid Hydrol 1' D~ \~3Na \ \~

Br ao Tho alkylatin~ 3tep was ~>orformoa as in the preco~;nçr process opticn~lly $n a ~olvent such a~ chlo of,~ , 1,2-dichloroethan--, ~irhloromethano~ 1~2-~irhl~ .~a~a, prefer~bly ~I solvent which swells poly~yl~o (for exam;plO, ~Lylono/divinylh~n~ - copolymOr boads) The alkylatinq aSIont was any h-l~ -thyl h~lo~ ylarylenQ prefQrably whOrein tho alkyl Srroup has from 0 to 10 carbon atoms Tho arylone group prefHrably has from 6 to 14 carbon atoms -., It wa3 within tho skill of the art to select halomethyl h~loAlkylarylones in which the hAlo~lk~rl and hJ~l~ thyl ~roups havQ

activiti--s E~ufficiQntly differ--nt to achiove th- d~8iroa result R--~?r--sl~nl ~tiv~ hAl thyl hAlo~lkylarylenQ = _ _ " ;n~ lu~9 5 (2-b ~ :Lhyl)b0nzylchl0riae ana (3-~ v~yl)benzylchlorid~.
Chloromethyl h~loAlkylarlenes were conveniQntly proparea by moans within the Dkill of tho art ~uch a8 d--Dcribea by gelva et al, Syn~ ~-ri~, l99l, 1003-1004, wher--in hAlo~lkylarylen0s were reacted with f l~ehyaQ in acia (for - _~e, sulruric or hyl o-hloric) in the ~L--- -= of a 10 quaternary ~ ; l?ha~ tran~for catalyst Chloromethylation can also b~ ~erformea usinSr zinc chloride ana ~araf~ 1~ hyae in accoLd-~lce with the m~ thod doscrib0d by Daren in U S Pat0nt No 4,967,026.
Alt--rnativoly, chloromethyl ethQrs were usea to chloromQthylat0 a h-loAll~yl arylene by methods ~ to that tau~rht by Ral y in U S
Pat--nt No 3,311,602, by Shinka, et al, J Poly Sci Polym Lott Ed 14(1), 1-3 (1976), ana by Shis~--o, et al, Chem Abstr 72:32290 (1970), or by oth--r m ans within the skill of th0 art In ~nother aD~oct, hydr~l Alo~_ -;nS~ aSronts~ such a8, I~Br wero adaea to alk--nyl aryl--nos, such as, ~yl e undor radical forminSI conaitions such a~ tauSJht by Martan in U S Patent No 4,228,106 or Plesmia in U S
Pat--nt No 3,321,536. In an ~ n of theD~ works, vinylbenzyl chloriae w~s hydroL ~ 'nAteA by this method The s~lf~n~ion ana th;olAtio" ste~s were as aescribea for the prov~ OU8 p . " ~ 8 ~ .
In .~a~ tion to tho m thoas ~;~cl~o~-' abov~, a vari ty of othor methoas w r alDo avA;~ le for ~ ;n~ the h~lo~lkyl-funct;~n-l;~
~oly"Ly _, e ro~ins which were pL ~ V16 to tho merca~tos~lf~n;c acid polymer cataly~ts Ro~ r -t;ve a~roachQs for ~reparinsJ the h-lo~ ylat--a poly~l_y~ nQ r--Dins include (but wore not limited to) tho de~crib~d or ~ ~' by a) P C R eves and M S Chile~, "Pha~
Tran8fer Catalysts Anc1c,~ ' to PO1YD~-Y~nO~ " Tetrah--dron Letters (1979), P~--s 3367-33705 b) M Tomoi, ot al , ~NOVQ1 Syn~h-s;~ of S~acer-~ ;fl-~ Polymer S~po~L~ and Activity of PhasQ ~ fer Cataly8ts Derivea from tho Polym~r 8up~orts," J. Poly-mer. Sci. Polymer Chem. Ed., Volume 20 (1982), Pa~oD 3015-3019; c) M. J. Farrall and ~. N. J. F~;-~-t, -t~ and Lith; At; ~n: Two Important Ste~8 in the Functi~ ation of Poly~Ly~ - Resins", J. Or~. Chem., Volume 41 (1976), Pa~Qs 3877-3882;

CA 02230272 l998-02-24 d) S p r~ and R D Olin~er, "RQactions of Cyclic ~alonium Ions ana Alkylene D;hAl~AQ8 with Polystyryllithium PrQ~Aration of ~Alc-1kylatod Poly~Ly.~ Q~, J or~ Chom , Volume 45 (1980), Pa~os 2717-27195 e) M
~r_tnke, ~t al "Sorption of E' ol~ on Anion-~ o Resins Havinu omega -~v~-lkvl or ome~_ -~yd O~y~lkyl Spacor," An~lytic~l g~i~n~s, - Volume 4 (1988), P~on 591-594; f) ~ aauthi~r and A ~;~ - n~
"Alkylatoa SLy.~no I~ with Variable Len~th Spac-r8 I Syn~h~si~,"
J Polymer Sci PArt A Polymer Chem , Volume 28 (1990), Pag~s 1549-1568;
~) P Tundo, "Ea~y and ~--- cAl 8yn~ of Wia~ly Porous RosiAs; Vory ~ffi~;~nt Su~port~ for T ~; 1 t - - ~ ph~ ~sfor C_talysts," Sy~hA~i8 (1978), P~-~ 315-316; h) T~hik~w-~ ot al , "rl~c~8 for the Production of SilAn~", (U S Pat-nt No 4,725,420); i) G Zhon~, ~t A1 , nSye~h~r;~
of ~l --lky1at-d Cro~rl; nk~ Poly~Ly ~na", Xinan 8hifan Daxue Xu-bao, zir~n ~~~t~An, Volume Z (1986) Pa~s 68-70; j) ~ ~ ~llen~lobon, "Preparation of Poly(p-( omo~a -lithiumalkyl)~Lyl -a) and Their Us~ as Polymer MetAlAt;n~ A~Qnts", An~ow M_kromol Chem , Volum~ 31 (1973), Pa~es 147-159; k) F Do~ ~ ot ~1 , ~8yn~h-~i~ of Sulfoalkylatod SLy e_c Divinyl~ ~ Co~olymers", Makromol Chem , Rapid Commun , Volume 1 (1980), Pa~os 297-302 It was to bo ~d_ ~Looa that a h_loalkylat~d poly~L~_~o re~in ~repared in _ mannor ~uch as that d-scribQd in tho abovo ref- e;-er could b~ further f n~li~nA~ ~ by thQ 8~lf~nAti~n and th;olA~;An ~ ,-- ~8 pr-viously describQd to provide a ~~Los~lf~n;c acid polymer catalyst Ot_er ~L ~ -~iVQ roforoncos on methods for ~olymer '~f;c-ti~~
or for us-n of functional ~olymQrs ;n~ Ak-lah ot al , n~r~l;~Atinn of Functi~n~ a~ Polymers in Or~anic Syn~~~;~n, Chom RQ~ , VO1U~Q 81 (1981), Pa~es 557-587; ~ ch~t ~t al , nFunct;~nAl;--t;~n of Cro~l;n~-A
Poly~Ly ~ Ro~ins by Ch~mical ~;f;~r1 i~n A R~viow in "Ch~mistry and P ~_ Li-~ of Cro9~ ;nl a Polymors", 8 ~aban_, od , ~ d- c Pros~, New York (1977), Pa~-s 59-83; and Maréchal, n~ 1 r ';f;CAt;~ of 8ynthotic Polymersn, in "C _ ehc ~iv~ Polymer Scionc~", Volumo 6, All-n, ~a., P~L Pro~, New York, Pag~s 1-47 Catalysts deri~od from poly~Ly.v~e8 will advAn~AgeJ~ly c~ntA;n from 0 2 to 5 meq of I -~tosu~f~n;c acid ~unct;~nAl;ty por ~, most ~refQrably from 2 to 4 moq/g It will bo una-rstooa th_t polymers, c~n1A;n;ng lar~ of _ ~ ~a~Lo~lf~n;c acid functi~nAlity on a ~i~en carrior, p~naA~t from a l y l ~ chain, can be preparod by graftin~ vinylsulfonic acid, propA~ ultone, to th~ p~ t carricr function, and c, v LLing the gr~ft--d polym~r to matorials _avin~ .;c ~Lo/~ulfonic acid functi~ nl;ty Catalytically-activo ~olymers in which - was an ionic bond can ~ advantagoouxly be pr~p~r~d 4rom ion-~Y~h~r~SrCI rQsin~ and r~activo c~ t~ 5J both -- .a~ o and sulfonic acid functions For ~ _ le, a ~trongly ba~ic ion _- -hA~ ge renin 8uch as poly(vinylbenzyl amin~) can be reacted with a c __ ' such a~ 4 ~ c pLo-1,2-h~lt~ ulfonic ~cid to ~roduc-- catalytically-activ-- matorial a8 cp - e~l by th~ equation 1 HSCH2CH2CH ( SO3H ) CH2SO3H

+_ CH2NH3 03scH2cH ( SO3H ) CH2CH2SH

R.p r ~1 ;ve strons~ly ba~ic ion-~Y~h~-gn re~ins ;~ ~9 DOWEXTM
lX2-400, from T_-- Dow ~ r~l Campany, Amberlyst~M A-21 from Rohm nnd Haas, DOW35XTM WGR-1, DOWEXTM WGR-2 and DOWEXTM MSA-1, from T_o Dow r~ c~
r _ y Tho WGR re~in~ were ~oly~ropyl~~ conv~ ly obtained 15 by c ~ ti~ of ~pic_lo-~ hy l-in with ~
Catnlytically-active mat. rials can also adv~r~tr;r _~ly b~ prepar-d Erom an acidic ion - ' __ resin, for _ 1~ l~ulfonated poly~ ne by ..-cti~ with an ~ '-- - A~to~ulf~ ;c acid, for ~ _ le, a ~ o-4-r~ ~ ~ R~lf~ ;c acid, a8 .~ e~ l~y tho ~quation CA 02230272 l998-02-24 W O 97/08122 PCT~US96/13683 ,~L~

- ~ S O3H

H~N ~ S O3H

~ SO3 H3N ~ ~ S 03H

S H

Re~ ~L ~tivo 8trongly acidic cation~ h-nge rosins ;n~lu~s DOWEX~
50X2-400, A~berlyst~ A-21, frvm Rohm and ~as, nnd DOWE~M MSC-l, from Tho Dow ~- ~l ~ y~
In a~dition to tho u~o of ~olym rs from othyl-nically ~ t~ated - ~, including copolym-rs, as i~oll~le D~O ~D for tho catalytically-active ~_~c;~, the cat~lytically-active s~oc;e~ can bo ~ttachod to an inor~anic ~v L, for ex~mpl- a min-ral, ~uch as silica, alumina, al~ ;c~t-~ or ~la~s, throu~h tho l;~;n~ ~roup -~- A
~ ~= ativo ca~- was that whoroin the ~;~;~ group was -osio- or --O--P (=O)--O--, mo~t pr-forably, -OSiO-Catalytically-nctivA __-Ci~Q of F~ III will convA~;~tly be inco ~t-d~ in tho b~k~o~ of c~ tion polymers; for ~ _le, poly st-rs, poly ~-~, polyc~ tes, polyurothanos, polysil~
~oly --, polyother~, ~olykotonos, ~olysulfonos and polysulfoxidos Tho dival-nt 1 i~ki ~ ~roup, -~'-, can bo seloctod from such structuros a~
~olyoxy(alk-di-yl), ~olyoxy(~r-di-yl), dioxy(alkar-di-yl), ~olyoxy(nralk-W O 97/08122 PCTnJS96/13683 di-yl), polythio(alk-di-yl), polythio(aralk-di-yl), polythio(ar-di-yl), polythio(alkar-di-yl), polythio(aralk- ai -yl ), polyamido(alk-di-yl)~
poly~mido(ar-di-yl), polyAmido-(aralk-di-yl)~ polyc~rbonyloxy(alk-di-yl)~
polyc~-honyloxy(ar-di-yl), polycarbonyloxy(alkar-di-yl), polycarbonyloxy-(aralk-d$-yl), polycarbonyldioxy(alk-di-Yl)~ polya~rbonyldioxy(ar-di-yl)~
polycarbonyldioxy(_lkar-di-yl), polycarbonyldioxy(aralk-di-yl), polyamino(alk-di-yl), polyamino(ar-di-yl), polyamino(alkar-di-yl), polyamino(aralk-di-yl), PO1YCYA 1; ' ~ ( ar-di-yl), polycy~7; ~~(alkar-di-yl), polycy~l; ~~(aralk-di-yl), polycarbonyl(alk-di-yl), poly~--h~r~vl(Ar-di-yl), polycarbonyl(alkar-di-yl), polycarbonyl(aralk-di-yl), ~olyimido-(alk-di-yl), polyimido(ar-di-yl), polyimido(alkar-di-yl), polyimido(aralk-di-yl), polyur-ylone(alk-di-yl), polyuroylone(ar-di-yl), polyuroyl-~no(ar_lk-di-yl), polyur~yl~ne alkar-di-yl), PO1YCA~ y(alk-di-yl), polyc ~y(ar di yl), P~lyc Y(alkar di yl)~
polyc~ y(alkar-di-yl), polyc- ~ ~o~v(aralk-di-Yl), ar-di-yl, alkaryl-di-yl, aralkyl-di-yl and A1 ~~ic-di-yl PrQA-rr-d dival-nt l~k;~ ~roups, -D'-, includo di(cArbonyloxy)l~a ~AArbylone, siloxy, dirA~ a~v~;_rbyl-ne~ di(oxycarbonyl)hyarv~arbylone, dithiohy~.ocarbylQne, and Lya v~_rbylono ~roups c~~tA;n;n~ a ~ t;c rinAys Durin~ batch ~roc~c;~v~ th~ ~tosulfonic Acid c_talyst wa~
~uitably ~ --~t in an amount r~ff;ci~t to ~nable c~ -~t;~n of th-phonol with the kotone/ald-hyde in a ro-~AhlQ tim~ Proforably, tho mount of ~tosul~onic acid rAn~os from O Ol o~uivalonts to 2 0 ~quival-nt~ of catalyst per l OO o~uivalHnts of tho koton-/aldehydo Moro prof-rably, tho amount of -- ~A~tC=_l f~; c acid catalyst was from 0 02 to l O equival-nt of r~o~ l f~; C acid por ~quivalents of ald-hyd-/k-tono Most pr-f-rably, th- roaction mixtur- will C~1A;~ from 0 03 to l O equiv_l-nt of -~to~ulf~;c acia per oquivnlonts of ald-hyao or kotone und-r batch p .ce~rin~
Wh-n k-tono/Al~-~~~ wa_ _dd-d ovor th~ cour~- of a ._~At;~~ (for ~ _lo, a c~ ou~ l~-Atj~) tho pr-viously ~t_tod ~reforr~a r-for to total cataly_t ana roactant~ add-d rath-r than catalyst ~ os~nt in a reaction mixturo _t a giv~n mom nt Those ~ 1 ~d in th- art th~t wh-n a r~act~nt w_s addoa in. ~ Ally or c~~t;~ou~]Y, ther- w_~ oft-n a largQ ~xc-ss of catalyst Tho ratio of cataly_t to koton-/~ld-hyde in tho r-action mixturo was advA~tA~ ly ~r~at-r than one, conv~ ~lly on tho ordor of 20 oquiv_lents to 1 oquivalont WO g7/08~22 PCT/US96/13683 Du~ to th~ high nctivity o4 tho - ~Lo8~l f~; C acia catalysts, ~oOa roaction ratos and high s~l-ctivity can bo obtained at t~ _ ~ture~
below tho melting ~oint of phenol The phonol reactant can advantageously be ke~t in the liquid state by addition of 801vents, for examrlQ, wator, methylene chlorid~, ~;rh- _,lm~thane Low t~ _- ~t~ ~ r~actions w-re o4ten - ~art;cul~ly advantaaeous, bec~n- the ~roduct dirh~n~l;c _ __ a~
crystalli7e in the reaction mixture and bec~ e lower reaction t~ _~ ~tures 4avor hi~her selectivity toward 4,4-h;~rh~~ol;c rroducts The r~action t- _ ~turo will accordin~ly adv~t~ ly b- ~elected 10 in the ran~o ~rom 0~C to 100~C, ~re~erably from 15~C to 60~C ~ _~ ~ture range3 can b~ chosen by routine exper; ~t;~, ~a~er~n~;~ upon thQ
k~tono/aldehyd~ and ~henol _Q-ds Wh~n oxcess r~~~; c _ ~ wa~ us-d a8 301v nt, th~ t~ _ t~e ~or the .- a~~e-ti~ was adv~ta~ ly selected 80 that the phenol was in the liquid 3tate In the case of high-melting ~h~ , for _le, thos~
m~lting abov~ 180~C, the us- o4 an inQrt ~olv~nt wa8 ~rQ4errQd Di~h~nylm~than- has b-~n 4ound to bo par~;cul~-ly us-4ul ~or this ~u _o~e Other useable inort ~olvents include, but were not limited to, the xyl~nes, mesitylQne, the d~ . rr, ~1UG ~ -7-~~, toluene, cy~-~-Y~~, chlorob-~7- -, halo~ ;r~tiC h_dL~.--~n and alkyl~h1h~le~--having low melting points I4 a sol~ent/~ t wa~ used, the amount used conv~ tly ranges 4rom 5 mL to 1 L per mole o4 ketone or aldahydQ Pre4~rably, _rom 200 mh to 400 mL were usQd per mole o_ k-ton- or aldehyd ~he addition o4 wat-r, ~-n-rally in an amount u~ to a o 5 n~ by wei~ht ot total _-ed, was c~ red hi~hly de~irable in ~roc~rs~P _or the pr-yaration o4 b; ~h~ A, bec~ e water low~rs th~
reezing ~oint o_ ph-nol and addition o4 wAtor ~0 - ~; ts th- c~~~-ti~
to be run at low~r t~ ~tures ~ost ~referably, the amount of addQd water was from 1 ~--c~nt by weight to 5 r~-cen~ by weight of tot~l f--d The r-action can adv~}a~ _~ly be carri~d out by stirring th~
k-tono or aldehyde and ~ ~tos~lf~;c acid into ~ lten ph~nol in such a way that the t~ _~ t~-e in th~ reaction ve~sel will not ri~e above 150~C
Th- molar ratio of rh~~ol;c roactant to k~tone or ald~hyde wa8 ~dv~t-g_ _~ly nelect~d 50 that at least two molos of ~henol will CA~o with the kQtone to ~roduce a c~ ~_ ';~g b;~h~~l or higher ro~~~ts _ Therofore, molar ratios of 2 1 or higher will advantageously be sel~ctod WO 97/08122 PCT/US96/l3683 It was preforred to carry out tho reactions u~inç~ lar~er ~~~r~es of r~ ; c rez~ctant, up to a~ much ~ 50 molos of phenol per mol-- of ketone or ald-hyao It will be ~dG ,Lood that tho oxc088 phonol acts as a ~olvent or ~ ~nt, as well as a reactant Iower ratios of phenol to ketone/ala--hyae wQre 5Jen--rally ~r: ;~A
by An increa~- in th-- amount of by-products formed In tho preparation of polyph~r~ol~, it has been found that molar ratios from 2 1 to 30 1 of phonol to ald-hydo/ketone wer proforred Mor- prefQrably, the reaction n xtur-s will cnnt-;~ from 4 1 to 25 1 molar ratios of l?h--nol to aldehyac/ketone Mo~t ~r-forably, th-- molar ratio was from 6 1 to 25 8inco the cn~e~ tinr~ roaction was cxothormic, tho r--actant~, inst-ad of beinsl mixea to~ether all at onco, w r~ o~1 inT~ ly ~v~ assively mixed tosrother at a spoea ~ep~ r u~on th~ ity of tho cool;n~r ~mployed to ;r~t~ th-- temporaturo of the r--action moaium within tho optimum limits Aftor the mixin~ of the reactants, th-y werc preferably l--ft in contact for 80me timo in order to complot th-- c~r~--r n~t; ~ The duration of th~ introauction of the reactants durinSr a batch p v~P8 conv--~;~r~tly varios from 15 ~u~ to 1 hour In batch proco~ s, the -~t~ and the catalyst were ~roforably tho v ~Lly ntirr1 d - -r~;c-~ly to a~sure b--tter mixinS~, and h~nce an ; __ov_d ~paco-time yi--ld Wh--n tho ~-e~s of this invention was conducted batch wi~e, the reaction time was aavanta~_ nly in tho ranSro of O l to 20 hours ~
on tho reaction conditions ;r~ 5r tho amount of the cataly8t u~ea, the roaction t-- _ ~turo, and _ ~clfic r--actants, solvQnts and ~l ,hcL~
The ~ - ~B of thi6 inv ntion can al~o be run in a c~~ modo, mor- pr-forably by u~e of a ~-ri~ of c~~t;~ stirr ~d tank reactor~, tho u ~- of which ~ 8 plug flow reaction conditions It was pr--forr--d to carry out the J?LOC-~8 of thi~ invnntion under c~~ ~u~
reaction conditions The pro~ure in th~ roaction zone wa3 not critical, but ~r--forably ranSI-s from O OOl to lO bar (0 1 to lO00 kPa), and moro ]?artiC~ ly from 0 5 to 3 bar (50 to 300 kPa) In many ca~os, it will be pref~rred to carry out the r--actions under ~ t pre~ure, that was, 1 bar (lOO kPa) DurinSr the r--action, one mole of wat~r wa8 ovolvea for oach mole of kotono/aldohydo undergoing the c ~A~ tion with phenol It ha~ beQn found that adaing wator to tho roaction mixture~ can be adv~ta~ _o,n for WO 97/08122 PCTAUS96~13683 docrQas$ng th~ moltin~ point of ph~nol Tho w~tor ovolvod during tho roactions n-~d not bo v_~ by distillation/ontr~; with an inert ~olvont in order to attain hi~h roaction ratQs In sQme casQs, ~ _v~r, it will be proferrod to entrain and remove water from the reaction mixturo, in ordor to incro~- reaction rato~
- It has bo~n found that tho solublo ~ ~Los~lf~ic acid catalystscan advantagoously bo ~ v_a from tho crude product by extraction with water Tho aqueous Qxtracts can be c ~ trated and _c~v~L~a - ~tosulfonic acid c~t~ly~t can b~ opti~lly recyclod to s~sc_~.L
run~ When tho ph~~lic starting matorial was phenol, a ~olutiQn o_ the ~ Losulfonic acid in phenol was conv~~~ ly l_cov~l~d and was op~ lly recycl-d without furth-r purific~
ThQ acid c~ t ~tion can b- ~ --~ bQlow tho limits of d - tQCtio and probably below 1 ppm by wei~ht of acid, by repe~ted extractions with wat-r Tho _acile removal of eatalyst from the roaction mixturos wa~ a s;~;fic-~t ~dv~nt~o ov~r tho prior ~rt, usin~ mixturos of C- '~
a~ont~ It was within th~ ~ractic~ of this invention to removQ the Losulfonic acid by C~ti~ C0~191~ ..L extraction The time for phasQ ~eparation durin~ extraetion of the acid catalyst was on the order of 10 to 15 ~ t~F under batch condition~, without a drag layor Stirring s~-od during tho ~xtraction in a mixor/settler wa~
adjusted 80 as to avoid ~ A~ f__ ; A~, Th- ~ol~l~ - ~Losulfonic acid cataly~ts can al~o b~ __ v ~ from reaction mixtur-s by c~L aoLion w~th a uolu~i~ of an alkali motal Ly l~id-, c~bQ~tn or bic-~ to In addition, the ~ol~le --c~Lo~ulfonic acid eataly~ts ean be _ v ~ from rc-~ti~ mixtur-n by F-~;~g the r action mixturo through column of anion-oY~h~n~o resin or amino rHsin, such as DOWEX~ WGR, from The Dow ~ e~l C _ y A wat-r pur~e from the p .~ will c~t~i~ phenol plus catalyst This purge was adv~t-L_~_~ly t ~-t-d to romovo phenol by oxtraction with mothyl isobutyl keton- boforo boing sont to a bio-pond for ~i~pos-l For ;PO1~;A~ of B~PF from r-action mixtures, made usin~ a ~ol~o catalyst, a phonol/wator mixtur~ was pr-fQrably distillod from the water-wa~h~a mixturo until thQ wQight ratio of phQnol B~PF was bolow 1 5 1 Most pr-farably, phunol was 1 ~d until th~ phQnol BHPF woight ratio was from 1 5 1 to 0 5 1 It has b~Qn found par~;c~ ly advantag-ou~ to i di~olve th- rosultin~ mat-rial in hot methylene chloride and cool the r- ulting solution to obt~in cryst~l~;~ BEPF
Vory highly purified BHPF accorainsly can b- obtained by a process wh-roin a ro~ultin~ crude yroduct was waBh-d with water to romove (ES),-~-(S03H)b; the r-sultin~ ~cid-free mixture wa8 di8till~d to remove phenol and water until tho phonol 9,9-bis-(4-1~-1 v~y~h-~.yl)fluoren- woight ratio was le~s than 1 5; th- r-sulting mixture wa~ takon uy in hot methylone chlorido and th- r-sulting solution was cool~d to yroduco cryst-ll;~e 9,9-i bis-(4-hyd v~y~hQnyl)fluorene BEPF purif~ed in this way can be usQd to m~ko ultr~hi~h quality polyc~ h~te rosins Exc-~s phonol can also be r mov-d by boilin~ the r~action mixturo t-'ly with wator, optionally with th~ u~e of a wateL- ~c;hl~ organic 301v~nt such au mothanol The nquoous solution was ~e~aratQd oach timo ana th0 product, then practically yure, wa~ driod Another orfoctiv~
mothoa of r moving ~xcess phonol was by stoam dist;ll~t;~n The r-action product solution was opt;on~lly then c ~A~t~ted by _v~Gl~tion and ~ t~ly extractod with boil;n~ wator for the r~moval of ~xc-~8 phonol The product 80 obtain-d was opt;~nAlly thon ~_ ~dL~ll; -' for furthor purification BEPF can be isolat-d from tho roaction mixturos in sevoral additional ways Th- m thod sol-ctod will dopond on the dogroo of purific-tion d-sir-d, a~ wull as th- ~ ition of the roaction mixturo, and th~ de~ired production rato When -~te~ive ~urific~tion was n~-~;-ablo or i~ v~ i~te, tho mixture, aftor b-ing t_ ~ted to remove cat~lyst, can be troated with a volume d hot water suffici-nt to dilute th- mixture and brin~
proc~itation of BEPF Alt--n~tiv-ly, the reaction mixtur- c n be addod to hot watHr nd the ph-nol ~ ~_ a in the form of a water/ph nol ~ t ~Q until the phenol c~nto~t- wa~ lo~ ~d suff;ciont7y to pormit p..-lp~tation of BEPF from th- mixturo Th- B~PF solids can b- coll-ct-d and dri-d boforQ use or can be u~od in th- form of a slurry Whon ~ ro ~ ive purjf~c~t~ of BEPF wa8 d-~ired, the solids can b- purifiod by pl~v~tation from a ~olvent, for ~xample, ~ ylmethano or methylenQ chloride Anothcr mcthod for isolatin~ BEPF compri8es adding to tho reaction mixturo, at tho ~nd of tho reaction, a solv-nt, bo;l;n~ at a highor t ~ than phenol, ~nd removing phenol from the phonol/BEPF/~olvont mixture until BHPF cry8tallizR8 or precipitate3 fr ~ the mixturo This method can be carriod out by ~ddin~ ~;p~ ylmethanQ or triis~ ~yl~n~-to A r~ction mixturo, from which c~talyst hoG be-n oxtractod or 1~ v_d, prior to distill;ng the mixture Alternatively, the 801vents can be added to the initial rcaction mixture 80 that the reaction8 wer- run in the - p ~ -n of tho solvont ~he roAction mixturo wa~ workod u~, by extrAction, to romove c~talyst and then by di8~ ati~n to romove 801vent and phenol, until BHPF cryrtAll;~A~ion occurs BHPF can also be i801ated by adding to a r-action mixtur- ~ solvent, which boils at a higher t- _~ ~turo th~n ph-nol nnd dissolvos sufficiont BHPF, in the ~ -e o~ phenol, that romoving phenol from the ph-nol/BHPF/801vent mixture provide8 a ~~ ~ oll~ti~n, cool;ng of which cau~e3 crystA~ -t;~n of BHPF 801v-nt~ ~-;n~ tho~e roqui include ~;ph~nylmethane, diphenyl ether, do~oc-n~, ~arhfhAl~g, I~opar~
(hyaroc~on mixture commercially avA;l~h70 from Exxon Cor~~rati~n) and trii~l~lh9n7 -, Further purif;c~t;~n can al~o be A~ h~, aftor removing c~talyst _rom th_ r-action mixture, by dist;ll;ng to romove phonol to n 1OVQ1 at which BHPF cry8t-71;~~r _rom tho phenol/B8PF mixture The B8PF
~Olia~ obtained can be ;~ol~to~ by c~v-~ti~nAl means and thon further t ~-t~, for ; _lo, by ~ ~h;ng with water to remove phenol An alt~rnative method for obt-;n;n~ hi~h purity B8PF compri8-s removing catalyst from the r~action mixturQ, disl;ll;ng ~henol from tho reaction mixturo to a ph-nol/BHPF lovel ~uch thAt ~;lu1;~n of the dis~;llat;~n residue with a ~olvont ;n~l~_~ cry~t-7l;7a1i~n of the B~PF
~rom the phonol/BHPF/~olvont mixturo For ~xam~le, phenol can be r~moved by di8t;ll0t;~n until th~ dist;ll~ ;~n rosiduo c~nt-;n~d 50 ~ , by w i~ht o~ phRnol and 50 ~e1~o~t by w i~ht o~ BHPF Methyl-ne chloride, trii~ ~y~ - or tolu-ne can b- -ddod to tho ro3idue and the r-~ulting ~o~ut~~n can be cool~d to bring about cry8lA~ -t;~n of highly purifiod B8PF
Another v ~-~ e for ;~ol-~; n~ ~uro B~PF ~olid from the roaction compris-~ romovinu the - ~a~tosulfonic acid cataly~t, dist;ll;~ phenol from the rosultin~ mixture, to produco a ~till r-5iduo, to which addition of a solvent ;n~--~o~ cryst~ ti~n of BHPF For ~xample, A still re~idue C~nt~; n; n~ 80 ~ L by wei~ht o_ ph-nol and 20 ~01_-~t by weight of BHPF ean b~ diluted with a solvent, for ~ _ 1Q ~; chl oromethano or to'ln9n9, to indue~ ery~tAl1;7~tion of B}IPF.
In adaition, B~PF ean be i~olated rrom a reAetion mixture, by r ~oving tho - ~tosulfonie aeid eataly8t, addin~ to the r~sulting r-aetion mixturo a ~olv nt, whieh fo J an azeotrope with phenol and in whieh B~IPF waa solubl-- in the ~ n~o of }7henol, and removin~ phonol from tho mixturo by azootropic dist;ll~Ation Cy~1~h~"An,~l w_8 . _ 1A y of a ~301v-nt, whieh will form an azeotLv~c with ~henol ana from whieh B~PF will proeipitate upon eool;~g the still resiaue from tho A~o_~ ~ic 10 di~tillation.
~ A ly, ~henol can bo vea $rom the reaetion mixtur-8 by addition o~ a solvent, whieh forms an azeotrope with ~honol Aft-r removing ph-nol by A -~Llo~ie di~t ;llAI ;A~ tho still rosidue was coolod ana B~IPF cryst~ es out from th~ coolod mixture In any of tho purif;e-t;on ~ ~ce~ses whieh r-gult in a cry#tAll;nq produet, th~ eataly~t was opt-;onAlly not 1~ v_d bnfore cryst-ll;~-ti~~ of product but rathcr oithor tolorated in the ~ od~cL or ~ ~d from the cry~tal~, for instanco by w-~h;n~ or othor moans w~thin the skill o~ the art, aft-r ery~tAll;~rtion In ~ome ea~es, tho e A~ t;~~ of phonol with ~-t~--7 or aldo~d~s ean b- run in a xolvont, for _le, methylono ehloride, from whieh th~
produet will prseipitate auring the eourso of tho reaetion, as was do~erib-d in moro d-tail for tho ~ ~ ~tion of b;~h-no3 A
A ,~ at;ve ~olvant u~--d for ery~tA~ t-;on of BIIPF, methylen~
chloriau, can bH ~ d from tho mother liquors by bateh di~t;llAt-~n and reeyeled baek to the ~ ; The 8till bott ~8 c~nt~;n B~IPF and methyl--no ehloriae and ean be eooled to roeovRr additional B~IPF. B~PF
ery~tals thu~ formed were eonv~n;~nt-ly L ~_ v~ usin~ a ba~ket eentrifugo or pres~uro filt-r and ean be roeyeled baek to a main ery~tAll;~~ Crude mothor liquor ean al~o be reeyclod baek to the phenol ~v~l~o~nt~ s-ction When methyleno ~hl~riA~ was used as ~olvont for crystAl~ sJ B~PF, a common vent heaaor for coll-_Lin~ all vent8 from ~torage tanks and ~afety r-lief ffystems was ~c ~-~ Tho vont headnr systom advAnt-~ ~ly ;n~l~A-- a flow mea~ davice in th- inlet to a carbon aa~orption unit and a VOC analyz-r for the ~xit ~a~ The ~xit ~ ~hould C~t-~;~ le~8 than 100 ppm of mothyleno chloride A com~lote effluont troating ~y3tem will advantageously in~ A~ mean8 for removing or~anics from procoss wAters _nd me~n~ for r mov_l of ~_rtic~lAte~ from vent ~_8, ~or ~xAmpl~ a wAter venL~.- flow m t-r to scrub p~rticulAt-~ frcm the vent he_dcr A further advanta~o o~ the cataly8ts u8ed in the practice o~ thi~
invcntion W_8 th~t th~ catalysts c_n be used to i - 70 th~ cru proauct mixturo, which typically c~1-;n~~7 (4-Ly~-v~y~h-nyl)(2-hy~hv~y~honyl) ~ , tho major bi8-(4-hy~lv~y~h_~yl) = __ a~ and c~n~on~-t-~, to p v~ce mor- of the bis-(4-Ly~ v~y~henyl) } __ '~
T - - 7'ti~n o~ A ~_ nAl ~;~h~n~l u8in~ the cat~lysta of tho 1~ invontion wa3 usoful wh~n pr_ctic-d with tho ~ r~ of th- invention or ~epar_t-ly, for example, aftor product formation usin~ catalysts within tho skill of the _rt For in~tance, a mixture o~ p,p-bi~(Ly~ v~y~ yl)fl~oreno ~na o,p-bis(Ly~Lv~y~h_~yl)fluorene w~
contactod with a ~ ~tos~l f~n; C acid c_taly8t, preforably of the Çormula (HS)A-~-(8O3H)b or of formula (a) (HS),-~ -(SOIH)b Fr 1A (A) L

in which ~ wa~ an _lkyleno, cycloAl;phAtic, aryl-ne, alkyl-nearylen-, alkylonecy~loA7;rhAt;c, _lkylencaryl, het-rocyclic or alkyleneheterocyclic r-siduo; a ana b wore ;n~ __ '-~tly ~ lect-d ~rom ;n~ from 1 to 20S L
W_8 an optional 1;~; ng ~roup and - w_s a bond, which c_talytically-active ~pe~ia~ was attached by tho bond - to _n ;n~cl~le or~anic or inor~_nic ~vl~; ana h-atod ~fficion~ly to rosult in ~r t;~ of the p,p (bis (4-l-y~-v~y~h_~yl) prOauct from at l-_st a portion o~ th- o,p (2-L~l.v~y ~ yl, 4-Ly~v~y~he yl proauct Th- catalyst was a ~
(~n~ ;~y polym r) of the ~~ 1A (HS)a-~-(SO3H)b or of formula (A), proforably tho~o pr-forroa for the roaction of an alaohyae or kotone with a phonol a8 a-~criooa horoin, with 3 ~ ~apLv~ _- -L~lfonic _cid most preferroa It was notod that ~uch catalyst~ r-sult in conv~~;en~ly fast _ , 7~; ~n and less f~ ti~n o~ additional Ly-~rv~cts than do acias ~uch a5 meth_ne ~ulf~n;c acia ~ t~ e8, which will vary with the ~ boin~ ;~ ed, were suitably any t- __ ~turo at which ;~- - i7-t;~n takes place, and wer- convon;~n1ly at loast room t~ ~ture (30~C), pre~-rably at lea~t 40~C~ ~ re pre~orably at loast 50~C The t- ~ture was pre~-rably lower th_n that t _-~tur- at which an .

i--ablo amount of additional by-~roduct or polym~r would form, conv~ ntly 1O88 than 100~C, more pr~ferably leRs than 85~C, most pr--f~r bly 1Q83 than 75~C Sovonty e'~_ _85 C~r~tisTraae was a conveni ~nt and ~r--f--rr~d t~ _ -- tur~ It was Eound that incr~asinsr tho t~ _ ~ ~turo within the rang~ speeds isomerization I ik~wi~e, in~ thQ
C~ ' ation of cat~lyst in~ R i r -I 7atir~ Catalyst was pr~ orably ~, o~ ~L in any amount surficient to result in ir - 7~
I--~; waEI no~d~d at highor t~ ratures to obtain a ~ lo rat~ of ~ ~1. 7~ TI, Conv~ tly~ tho catalyst was l?-Q~ in tho same ~ R
ana prof~rr~a rnng~s as for proparation of a bisphenol by the ~ r~g aisclosQa herein The ~r--ssure was not critical, but was al~o conveniently within the ~reforrQa rang-s for the ~roc~ss of }~roparing b:8F~ -18 by th~ p ~c~r~ hor~in ~I!imo for the ;R a -t;r- was proforably that in which, undQr the conditions, rQsultg in ;r :7-1 ;~n 15 of at l-ast a ~ortion, ~re prof~rably a pr--dat~ or aosir d fraction of th-- o,p by-product b--inçr i~omorizQd to the dQsircd ~,~ yroduct ~ore pr-forably th~ ratio of o,~ to l?~P product was le88 than 0 12, ~st pr-fQrably 1-88 than O 1, ~ven morn prof-rably 1O88 than 0 075 Th- time to achi--ve this rosult varios with ;r~ --.7~t;~ conaitions but was 20 conv~ y 1--U8 th~n a day, mor~ ~rof-rably 1~88 than 12 hours, most ~r~f--rably 1--~8 than 8 hours, for cvl~v~Ldion of half of the o,p ploa~;L to l?~F product, Th~ -~ ~Lo~ulfonic acid cataly~st ~ of this invontion woro c~ ably 10~5 corrosiv~ to 81 irl 88 st--Ql than th~ mixed catalysts 25 u~d proviou~ly Corrosion rat-s for st-;r~ s sto~l, below 0 00254 cm/yoar, havo be~n measur--d Th~ reaction mixturos wor~ boli~vod to b sub~ ;Ally frOQ of halido ions, whor--in "subs1-r~ti-lly fr~o" moans 1~88 than 5000 ypm of chloride ions ThQ ~ -8 of this inv~ntion wa~ advAn~ ly carri-d out undor 30 conditions ~uch that tho c r~ of chloride was below 5000 p~m, pr--l~--rably b-low lO00 p~m, ~fft ~r-f~rably b~low lOO ppm It wns b ~ vQd that th~ low corrosion rate was r~lated to tho --9 of minoral acids, such as L~ochloric acid or sulfuric acid, ~rom th~ r--action mixtur--s The oc~ o of corrosion in roActions u~zing 35 minoral acias has b~on notod by Kn--b--l et al , '594 and Fal~r '995, supra The insoluble catalysts of this invention can b-- filt--roa from tho roaction mixtur--s, washea with a mixturs of k~ton~/aldehydo ana ph~nol, --'12-and recyclod to ~u~ run~ ~lt~r~t;voly, the insoluble c_talysts wRro usea in fixod beds ~nd tho c~ ti~ of ~J Q with ~ldohyde/kotone w_s done in C~t~ uQ up_low, cross~low or ~
f~Qh; ~n, When fixod-bea catalytic rQnctor~ woro u~od, th- catAlytically-~ctivo r-~ins ro~ain in tho rosin beds and need not be 1 -v_d _ Furthor _ o~ of thi_ invention will be det~- ~~d by tho r~_ct~nts u~ed, the catalyst sQl-ctea, tho ailuont, if Any, ~na the roactor ~m~loy d For _lo, when usin~ _ solublo c_talyst for the co~ tio~ of phonol with 9-fluo Onv~e, without a ~;lu~t, other than xcoss ph-nol or in the ~r-sence of ~ diluent which does not cauno prOcipitation 0~
vd~L, it will ~on-rAlly b- proforr~d to uso A hi~h r_tio of ~henol to ~luo ~nvne to ~o selectivity to the desired ~;~ph~l product A p_rti~ulA ly preferred proc-ss was on~ wher~in tho ~ lar rAtio o~
15 phenol fluo ~ o e wa5 from 4 1 to 25 1; tho r~action t~ _- ~tur- was from 25~C to 50~c; tho catalyst w~s ~t~ ~ fonic _cid or -~pLoku~ _lf~;c _cid, u~od in an _mount from 5 to 10 molar ~ cc L
with e~e L to fluGLO~on~; the ~ .-PFS was carriea out undor ~ ' ~t pressur- or undor vacuum to r~move wator of roAction _nd incrOasO th~
reaction rato; no cosolvont was usea; the catalyst was 1~ v_d from the product by ~xtrAction with w_ter using a w_sh colu~n or by b_tch extrAction; the wat~r ~xtr_cts thus obtA;~d w rO c -- t.~ted ana r-cycled to th- procoss; the proauct was ;~o~At~d by removing excess ~honol to a woi~ht ratio from 1 5 1 to 0 5 1 of ~henol BEPF _nd the product was procipit_ted with ~ ~hl oromethano When an ~ol~le catalyst was u~ed, a part;c~ ly ~reforred y ,-~8 was ono whor-in thc molar rntio of phenol fl~G, ~ was from 4 1 to 25 1; tho c~--ti~ w_s carri-d out at a t- _ ~ture from 40~C to 60~
C; no cosol~ent was u~ed; the catalyst was PNBSA; the c ~ ;~ was carriea out in a c~ plu~ flow roactor; the roaction was carried out at ~ pr-ssure or und-r ~o -~ s~u~o to r move water of r-action and in~ the reaction rate; the product was ;~ol~tod by rOmovin~ excess phenol to a woight rntio from 1 5 1 to 0 5 1 of phenol B~PF nnd the product was ~ __ pitatea with ~;~hloromethane The ~ .-SE8 for making B~PF can also be carried out at molar ratios of ph-nol flu~ _ one from 7 1 to 5 1 in the ~e=- -~ of 0 05 to 0 15 ~quivalont of ~PSA or ~BSA por molo of fluorOnon~, whor-in methyl-no chloriao was added to tho roaction mixture a~ter CO-lv_~ion of at loa~t 20 p~ ~L Or flu~uv o has OC~ul .od; ~t;~ tho resulting mixturo under ~~ ~ea prossurQ to r ~ ove an azootropo of mothyl~ne chlorido and wator;
and cool;~g the mixtur- At tho ena of the c~~Ao~-ti~~ reaction to caus-5 precipitation of BHPF
Th- c~ ti~~ of phunol with fluol ~ can further be carried out u~inD a f-oa c~~t~i~;~ from 5 1 to 3 1 molar ratio of ph-nol rluo O - - and from 0 05 to 0 15 equival-nt of MPSA or MBSA per molO of flu~ _ ~c, ~;l~ d with from 10 porcent by woi~ht to 30 pe~L
by woight of mothylone chlorido Cryst~lli~ BHPF can bo collected from tho coolod r-action mixture In addition, BHPF can be preparOd from a reaction mixturo, c~t~;~;n~ from 18 1 to 12 1 molar ratios of phenol fluor.luono and 0 025 to 0 075 ~quivalont of MPSA or MBSA por molo of fluo Ono~O at a t~ ~turo from 50~C to 80~C, whoroin tha mixture at tho ~nd of thn roaction was ~;luto~ with 10 to ao volumes of wat-r to ~xtract ~ ~Losulfonic acid catalyst, tho thus-washod mixturo was distillod to a phonol BHPF woight ratio from 1 5 1 to 1 1 And cool-d to bring cryst~ t;~n of BHPF Tho cryst~ll;~A BHPF was ~ 20 ~ v~ by ~ilt-~t;o~ and washed with mothylon- chlorido and thon with wat-r A proc-ss in which th- product was procipitatHd in th- roaction mixturo was pro~Orr-d _or the ~reparation of k;~ 1 A, morO
par~ ly a ~ c-e~s whcrein th- ph-nol ncotono f-od c~~;~ea from 6 1 to 15 1 molar ratio~ of phonol ~eto~; th- ~ ~ ti~~ was carriod out at a t~ _ ~t~ e From 25~C to 35~C~ tho roaction mixture c~~~ up to 5 c_~L by woi~ht of water to low r tho LL~ ~oint of phonol; the cataly~t wa8 3 ~L~ ~ lfonic or 4 ~0Abnt~ ulfonic acid in an amount from 0 05 to 0 50 equival-nt per molo of acotone in th-~-~t~~- ~-- -1 fo-d; tho r-action was carried out undor ~ ~t prossuro;
ana th- cry~t~ll;~e bisph~ol A proauc-d by the ~ =~rs was lO v~d by filtration or contrifu~t;~
Furth-r proces~in~ can include , ~h;~ tho bi~FhA~~l A with water to partially r movo solublO catalyst, nnd romovin~ additional solublo cataly~t by tlO~ ~ with an anion o '~ r-sin It was beliovod that a proforr-d r-actor configuration for thi~ procoss was a ~erios of =_ _ __ _ c~~t;nus~ stirrod tnnk roActors, 80 as to ~1~ mate plug flow reaction conditions Other process vari~t;o~ l A~, but wcro not limitod to (a) ~ro~_ratiou of bis~henol A in n-at Dhenol~ using ~ solu le cat~ly~t, with ~r-cipitation of bi~h~~ol A in the r-action mixturo ~nd _ (b) preparation of b;~Fh~n~l A in ~henol with a _ _l~Y-formin~
cosolvent and soluble catalyst, with ~rocipitation of b; ~Fh-~ol A in the roaction mixturo ~oro p_rticularly, it was preferred to s~lect a cAt~lyst whoroin at l-~st 99 ~c c~nL o~ the bis~hon~l A thAt cryst~ es durin~ the r~action was 4,4~ ~h~~l A 8uch c~talysts ;~lu~ sol~hle o~Lo8ulfonic acidY in which A and b were ench ;~A7~l~A~ 1y ~nt~_~L4 from 1 to 4 Pr-ferr-d conditions include reaction t- _c ~turos from 0~C to 50~C, moro pr-f-rably from 20~C to 40~C
R-pr~ ;ve _ _~Y-formin~ solvents for bi~h~ol A ;n~ll~s di-thyl et~or, ncetone, ot_anol, p ~ol, ~;~Y~n~ acetic ncid, ~ ~n;trile, methylene chloride or c_rbon to~ hloride The _ 1-Y-f~~ '~ solvont~ - _1~Y ~rofor~l;Ally with tho 4,4-A;ph~n~l;c isomer 8e that tho ro~ultin~ compl-x ~as solubility ~~ Lies, di_ferin~ from that of tho ~ _ _1~YAd 2,4-~;~h~~~l;c _ _- ' ana can bo roadily ~opAratod therofrom Thoso ~roc~~e~ can be run undor varyin~ ~rossuro and t~ _- ~ture cona~tions, n~ woll n~ roactant, co~olvent and catAlyst c~ ation~, as can bo ~t~ ~d by routino ~xper; at;~
In ono ~-ct, a ~ st preferrea ~ ~-~~ of this invention was that - _'~ tho kotone was 9-fl 'OL. -, tha ~henol was unsubstitutQd and the ~L wA8 9,9-bi~-(4-LyalvAy~h_~yl)fluorone; the molar ratio of ph0nol to fluv_~v o was from 8 1 to 25 1; the roaction mixture c~~t~ from 0 05 to 0 20 equival-nt of ~ osulfonic acid ~or ~ le o~ fluoreno; the - _~to~ f~~;c acid _ __ ' was 3 J ~t-o~ v~l~~~_lf~;c acid or 4--~Lo~lt -_ 1f ~; C acid nnd the ~rocess was carried out at a tem-from 45~C to 60~C
An equally ~referr-d ~Lcc~rs was that wherein the ketone was ac~tOno, tho ~henol was unsubstituted and the ~roduct was 2,2-bis-(4-35 L~d~VAY~ - ~ yl)~vp~n; the molar ratio of phonol to acetone was from 6 1 to 15 1; th~ r-action mixture ro~t~ from 0 10 to 0 50 equivalont of _ ~-q~LO~ fQ~; C acid ~or molo of acotone; the - ca~tos~l fQ~; C acid __ ~ was 3- --~pL~ ~osulfonic acid or 4 ca~tohut~ fonic acid and tho procnss was carri-d out at a t~ ~ture from 15~C to 60~C
Without ~urther ol~boration, it wa8 believea that one skilloa in the art can, u~in~ th~ ';~ descri~tion, ~t;l;~e the pres-nt invention to the fullest extent The following preferred spocific _a; ~~ ' p wero, therofore, to be construod as merely illu8trative and not limitative of tho ~ r of the ~;~~1O8~ ~ in any way what~oevor In the followin~ ~ _lo~, the t~ _ ~turos were set forth .co~ L~d in ~ Cel~iu~ Unless otherwise indicatod, all parts and 0 ~GlC ~l r~eP wore by weight Roactor Desi~n 1 A 500-mL roactor ~repared from PFA Teflon~
(matorial from DuPont) was fitted with a ~ _~le port, water c~e~oer topped with nitro~en inlet, --~;cAl stirrQr, drain ~ort, and u _~;~ port ~--t;~ was provided with an infrared hoat lnmp and tho t- _ ~ture was controlled with an ~1~_L o~ic t~-- ter/t- _--~L~
controll-r Reactor Design 2 A cap~ea 4-dram ~lass vial with a ma~netic ~tirrer Hoating was rogulat-a by P1A~; ~ tho vial in a t- _- ~L~
controlloa Al ~ block h-ator Reactor Design 3 A 100-m~ jacketea glass reactor wa8 fitted with a 1 h- -tor port, ma~notic stirror, nitro~en inlet, ana ~ _1;~ port ~q was provia-d nnd the t _-l~turo was controlloa by circ~ ;~g glycol sol~lti~ o~ the a~ iate t- _~ ~turo throu~h the j~kete~ fla~k u8ing a Ne~lAb ~odel RTE-220 circ~l~t;~g bath P---ct~-- De~ign 4 A 1 5 L, 2 L, or 3 L jacketoa srlass roactor fitt~a with n ~ - ~r/n~ 5J ~ort, nitroSr,n inlet, and ~ ~~; r-~tirrer Ps~t;rg was ~rovidod and th ~ tA _ - ~ture was controlled by circ~ t;r~g SJlycol loluti~ of tho A~ iate t~ _- aturo, through tho jackotea flask u3inq I No~lab Modol RTl!-220 circulating bath Analytical M-thoa 1 A Vari ~n HPLC Syst m (Modol 9O10 ~olvent deliv--ry ~y8t-m, Model 9095 ~t~- _ l~r, ~odel 9065 Polychrom dioaQ array dotector) intorf Iced with A Varian 8tar workstation wa3 u~sod for ~naly~i Aroa ~ - naly~i~ was re~ortad at 282 nm raL c~, v~ ,ion was ~et -~ by an ~t e~l standard method usinSr calibrated c~ _ ~tion 35 curv-~ for each major -_ _ Analytical HP~C _ ler were yre~arQd by caro~ul quantitativo dilution of roaction ~amplo~ (rang 400-500 times ul;" ) Column Wat--rs Nova-Pak C-18 (60 An~strom, 4 micron, 3 9 X

WO 97J08l22 PCT~US96/13683 150 mm) CL~ to~ _~Ly conditions ~low rat~ 1 0 mL/min, ~olv~nt ~radiont (solvont A = w~t~r, ~olv-nt B ~ acotonitril~) 0 n~t~R 65 ~_ ~nL A/35 ~c ~e t B~ 9 ~-t9~: 60 ~ c_~L A/40 ~Ql.- B, 18 nllt '8:
55 ~Q ~c~L A/45 Q8lc~L B, 24 n~l1~ 45 ~ c~t A/ 55 ~nL B, 48 nl~tQ- 5 ~ClC ~ A/ 95 ~e ~l~t B, 52 n--l o~: method Dnd (10 ~t~
equilibration b~for~ ~nd n-fter run~) Analytical ~thod 2 A Hcwlett-Packard HPBC system (Moa~l lO 84B
~olv-nt d~livory sy_t m, Mod~l 79850B ~C t~~ ) was usod ror analysis Ar~a ~q ~nt analy~i~ was r-port-d at 254 Dm~ r~ ~nt c~v~L~ion wa~
dot ~n~ by ~n _~t~ l standard m thod usin~ calibrated co~nl-ation curvos for oach major _ - ~ Analytical HPLC 8 ~ w re ~roparDd by caroful quantitativ~ dilution of r-action n~mples (r~ng- 400-500 times dilution) Column Wators Nov~-P~k C-18 (60 An~strom, 4 micron, 3 9 X
150 m~) Chromato~raphy conditions ~low rat~ 1 0 mL/min, solv nt ~radient (~olvênt A 8 water, 801vent B ~ ac-tonitril~) 0 n-~ : 65 L A/35 ~ ~L B, 9 n~t~ 60 ~CI ~t A/40 ~~ L B~ 18 ~n--t~P:
55 pOrc-nt, A/45 F- - B, 24 n~t~~ 45 ~_l~nt A/ 55 ~ t B, 36 ~"tqE: 25 L ~ ' A/ 75 ~-~CQ~t B, 38 n~-~e~: 65 ~Q'- , A/35 ~LC
B, 38 nnte~ method ond NOTE This m~thod ~ive~ a - llor ~
(~ Jy on~-half tho area) ~or th- 2,4-B~PF and th- two thr-o adauct B~PF po~ks r~l~tiv- to th- 4,4- B~PF peak than oither th~a 1 or 3 usin~ th- diodo array detector Analytical N-thod 3 A Varian HPBC ~ystem (Modol 9010 Eolvent delivery ~yst m, Nodel 9095 ~"t-_ _ lor, Mod~l 9065 Polychrom diodo array dotoctor) ; n~~ C~C - d with a Varian 8tar workstation was u8-d for analysi8 Ar-a A ~_~L analysis was r~ortod at 282 rm re~L cv~v~l~ion was dot- ~~ by an ini ~ - n~l standard method u~in~ a 801~t;~n of 0 0508 w i~ht ~--c_~t acet~L~ 9 in 60/40 (w~i~ht/wei~ht ~_,~ ) h-nol/wator for ~ro~arin~ the r _lcr Analytical ~PLC ~amples w r-~reparod by careful quantitativn ~;luti~n of reaction _~ Column Wat-rs Nova-Pak C-18 (60 A~L, , 4 micron, 3 9 X 150 mm) CL -to~ ~Ly conditions flow rat- 1 0 mr/min, ~olv nt ~radi~nt (solvent A 5 wat-r, solvent B ~ methanol) 0 n--~ 55 ~Cl ~-t A/45 ~c~ B, 20 ~n~lt~8 15 ~ L A/85 ~c, B, 25 ~n~t~L: 10 ~c,~- t A/90 ~ B, 30 n--t~: 55 ~ercont A/ 45 ~ ~ B, 35 n~t-r mothod ona (10 n~t-n ~quilibration befor- and after runE) -Analytical mothod 4 Tho ~xp-r; t-l sotup of Mothod 1 was u~ed Th~ cL_~ to~ ~Ly conditions w~rH flow rato 1 mL/min, solvent gradiont (solv nt A - wat-r, solvent B = mothanol) 0 ~ t~ 55 ~crc~nL A/45 pcl_cnt B, 20 minutos 15 percont A/85 pe - B, 25 ~teB 10 ~
A/90 ~CL~ - B Analyni~ - T~ l ~tandard method using 0 0508 pGLC
acet~r ~ in 60 percent mothanol/wat-r Av-ra~e r-lative standard d~v~ations ran~cs from 1 to 2 ~c , ~o~ u~on p-Ak analyzed Analytical Method 5 The r~action mixturo was ~ 7t~ with ac-tonitrilo to a c~ ration of 0 01-0 1 ~c - by w ight of - _ r and tho dilutod sample was analyz~d by HPBC on a Wat-rs NovaPak C18 column (10 16 cm x 0 635 cm inner ~;~ -tor~ connect-d to a Varian~
9100 7JV det-ctor, s~t at 280 nm The column t~ _- ~L~ o was 30~C, tho prcssur- wac 140 (14,000 kPa) at 0 ~t~, tho absor~tion full scale for tho d-t-ctor wa~ 2 0, th- i~_ ~tor att~tj~ wa~ 3 and tho chart spood 15 WaB 0 5 cm/ ~ to~ ~he auto sampler inj-cts ao microlitors of sampl~
onto tho column ~v~ry 36 ~to~ Reservoir A c~~t~ o wat-r and ~ v~ir B ~P~C ~rado ac-tonitrilo Th- followin~ protocol was usod Time Flow RatQ %B
(min) (mL/min) T~o poa~ ar-a ~on-rat-a by ~ach _ _ in th~ ~amplo was u~d with its known ~ iactor, and th- dilution ratio, to c-lc~lat- tho c~ ~ations of ~ach _ _ ~ in thc ~amplo ~o~uli~
F1UG ~ - (A1driCh 98 perc-nt), about 0 5 ~ - fluorono and mothyl-fluor-nos Acotone (Bakor lh~~~t, driod ovor ~ uiov-~) D~p~ ylmcthano (Penta T~t_r~ , 99+ porcont distilloa grado) Phenol (Dow ~' 'C~l 99t ~_ .onL), about 100 ppm ~2~ ~ 10O ppm impuriti-s 8oaium 3 7_~Lop o~ fonato ~ource A 90 ~_ ~L purity (Aldrich) ~ourc-- B 90 ~._ ~urity (Raschig Corp ) 3 ~_~;"~Lopropr~ fonic acid (MPSA):

CA 02230272 l998-02-24 WO 97/08122 PCT/US96~13683 8Ource A: Prepared from 90 porcent Aldrich sodium 3 - ~ptoprop_nosulfonata ~y roaction with H~l or L ~-~ in ion _~ column urce B: Preparod from 90 percent R~schi~ Corp. sodium 3-~ oprop~nesulfonato _ 8Odium 2-mercaptoelh~ lfonate: 98 ~ ~L ~Aldrich) 4 ~~- ~t~b~t~ fonic ncid (MBSA): prepared from 1,4-~utAn~ultone (Aldrich) by r-action with NaSH, Ba(SH)2 or an alkali metal ~h;oAcotate in _ccord_nce with R. Fi-cher, su~ra, A. Mu~tafa, supra, or Chom. Abs., 90:86742m (1979).
2-Benzyl-4 - ~ hutA~sulfonic acid: prepared from 1,4-~utAn~-ultone (Aldrich) _nd benzyl bL~ A9 in accordanco with M. s.
Smith et al., "Lithium ~1 Hy~rido_~l- ~ydrido Roduction o~
8ultono~ J. Org. Ch~m., Voluma 46 (1981), Pa~e3 101-106 or T. Dur~t et al., "M~t~llA1ion of 5- ~nd 6~ ring 8ultone8,~ C_n. J. Chem., Volumo 47 (1969), Pa~08 1230-1233.
2,3-D~ ~ C~PLV~L~L -aulfonic acid: ~ro~ared from ~odium 2,3-A; - ~ L ~ lf~-te (Aldrich, 95 percent) by noutrAli-~ti~~
with HCl or ~ ~- with an acid io~ hAnye re8in, for ~~ _le, DOWEX~
MSC-1, from The Dow ~- '~-1 C _ _~.
a, 2-Bi~( ~tom~thyl)-1,3-~L~~~A;~--lfonic acid: proparod from 2,2-bi~(b ~ thyl)-1,3-p ~ ;ol (Aldrich, 98 ~rc ) as follows:
A mixtur- of 2,2-bi8-(b ~ -thyl)-1,3-prop-n~A;aulfonic acid (200.0 g, 0.764 mol, 1.00 ~quivalent) and ~odium sulfito (211.7 g, 1.68 mol, 2.20 oquivalHnts) in 500 mL of ~ wat-r wa~ All_ ~ to react undor reflux (108~C) for 28 hours. At this time, additional 80dium sulfito (105.9 g, 0.840 mol, 1.10 oquivalont) was addod and the mixture was ~1 1, ..e~ to roact for 3 adaitional days under roflux. At this point, the mixture consi~ts of a clear solut;~n and a c~naiAerA~lo amount of solids.
Tho mixture was coolea to room tA _~-t~-. and ~aturatoa with g~ 3~ dh~n chloride. An ~xoth-rm to 43~C wa8 ~b-~ v_~. The mixturc and yollow in color during t~o oarly sta~ 8 of ~Cl adaition. A3 the mixturo ~ aturatod with HCl, a vol ~n~u~ whit~
precipitate was formed. The ~olu~;~n was cooled to room t _~-~t~.a and filt-rea to r move ~olid Yalts, which woro ~rimar~ly 30dium chloride and ~odium L '~. Water wa~ ~ v~d from tho filtrato to provide 2,2-bis-(Lyd_v~y thyl)-1,3-QLv~A~A~;~ulfonic acia (190.7 g) as a hi~hly viscous amber oil (~lass) AlternAtiv~ly, the rc_ction mixture can be work_d up by dilution w~th 200 m~ of ~thanol or methanol, after which the 801ia was v ~ by filtration 801v_nt was ~ v_a from the filtrate on a rotary ~v-~o~-tor, to ~roduce a white solid CA'~ J' mainly A;-C~; 2,2-bis-(1,,".1 v~y ~ hyl)-1,3_pro,AA~ ; UlfA---te. C~~ ted hydrochloric acid c_n be added to the ~olid product to give the soluble aisulfonic acid, plu~ insoluble sodium chloride and soaium b ~-~-Xyl-no (400 m~) was rddod to the 2,2-bis-(l~a~v~y thyl)-1,3-prop-~ ulfonic acia _nd the resulting two-phase mixture was heatea under rHflux (135~C to 150~C pot t~ _J _ture) to remove wat~r, ~roduced by the d hyd~-tion, in the form of an A-A_L-v~a in a Dean-8tnrk tra~ A ter 8 bours' ~-~t;--g under roflux, thc mixturc wa~ All~ _~ to cool to room t~ _- ~ture and the u~per xylene phase was d~-cA~to~ from the lowcr viscous o_~L pha~e Wat-r (300 mL) was added to the coolod, lower ~ha~e c~ 2,2-bi~-(lydlv~y thyl)-1,3-~ ~ u~fA~;c acid bis-sultone to ~Lvd~_C~ a large ma~s of whit~ solid The wh~te solid (bis--~ultone) wa~
_ ~. J by filt-At;~~, --lurry washed ~ ively with water and with methanol rnd driea in a vacuum oven To a ~c3~ti~~ of ~odium ~;r--~~~-~e (9.6 ~ 114 mmol, 2.6 ~~uival--nt~) in 30 mI of watar was alowly added th; ol~cetic acia (7.5 2"
96 mmol, 2 2 equivalont~) The r-sulting olution of soaium th;ola~tate wr~ added to a nolution of 2,2-bis-(Lyl v~y thyl)-1,3-~ o~ ~~';sulfonic acid biu-~ultone (10 g, 43 8 mmol, 1 00 equival-nt) in 280 g of acetonitril- After all th~ 1 h~ olA~tate was add d, the resulting mixturo wa~ ' to stana ov~r~;g~t at ~ ~t t- _e -ture 801vent was lV _~ r u~in~ a rotnry _v-~vL-tor to ~ivo 19.6 ~ of ring-opened bis-(th;oac~tatc) adduct as r tan, flaky ~olid Th- th;-~A--tato adduct (18 2 ~) was hydrolyz-d by stirring ov~ ht ~t ~-~t t- _ tur~ in a nitrogon-~aturat-d mixture o_ 10 ~c~nt ~od~um l.~d_v~ do (20 g) and 100 g of wat-r The mixture was A~-i~;fiod to 3 w~th 10 parc-nt a~_~ ~ Ly_lvchloric acid sclutiA~ 801v-nt was _~ v-' from the r-sulting mixtur- in a fumc hood, using r rotary ~v~v -tor The r-siduc was di_solved in 50 mL of water and ~aturated with Ly~_ _ chloride ga~- The resulting solid salt was removed by filtration and tha filtrate was c~n-e~rat~' usin~ a rotary ev_~ol-tor to WO 97/08l22 PCTAJS96/13683 g$ve 2,2-bis-(mercaptomethyl)-1,3-p v~ao aisulfonic acid as a viscous dark-colored oil Altnr~A1;vuly, tho ~h;o~c~tato adduct can bo hydrolyzed by stirrin~
with c ~ ~t~d hydrochloric acid, removing the 801id s~lt ~roauct by filtra~ion and rQmOving water from the filtrate u~ing ~A rotary ~v_~G _tor ~1~;V ' ATIONS
Dm = ~~- ~tors uv ~ ultraviolet r~m ~ revolutions per minute mmol ~
HPLC ~ high p~o~u~e liquid chromato~ y BH~P ~ 9~9-bis-(~-~y~ vAy~henyl)~luor~no - 4,4-inom~r ~ BF
MPSA 3 ~ A ~ ~ 1 ~lfonic A cid ~BSA ~ 4 ~A~t~u~ ulroAic acid FN = Fn = 9-~luv ~-~vn2 2,4-isomer ~ 9-(2-hV1~VAYL-- yl)~9~(4~1~yd v~y~honyl)fluo~ono DPM - di~henyl '-h BPA ~ 2~2-bis-(4-Lyd~y~honyl)~v~aae - bisphonol A
n/d 8 not d~t~- ~
~ = about or a~lV~ te ESAMPliE 1 CUN-- ~4A~ION OP 9_FL~ '~ W~TH PHENOL (3-MERCAPTOPROPANES~LFONIC ACID) 9-Fl~v ~ ~e (20 0 ~, 0 111 ~ 1, 1 0 ~quivalont) and ~ lten phenol (156 7 g, 1 66 ~ 1, 15 0 oquival-nts) woro addod to a 500 m~ PFA Toflon~, mat-rial ~rom DuPont, ~-~tor (reactor dosign 1) Tho r-action mixture was hoated to 65~C with stirring at 300 to350 r~m undor a ~ad of nitrogon 3 ~ c-Itv~ _ ~ s~lfo~;c ncid (0 864 g, 5 53 m~ol, 0 0498 ~quivalent~) was added ~lowly over ~ ~ t-~y 1 minut- to tho roaction mixtur- at 65~C ~he mixtur- turns dark yell~ o qg. upon adding the catalyst and ~radually lados to a 1; ~ht~
y llow color a tho r-action progr-~sos A sli~ht oxoth rm to 66~C wa~
obr~ The ~xot_-rm porsists for 10 ~ee~ boforo tho mixturo cool~ to the roaction t- _ ~L~ ~ of 65~C Tho roaction was monitorod th~v~yLv L
tho r-nction yoriod by co~ Ling ~ _ 105 ana an~Alyzing by HP~C
(Analytical method 1) Th- 9-fluoronone was found to be completoly c~~ -~ within 120 with a ~ vd~oL ~ ition, ~rt- ~-~ by quantitativo HPLC, of 98 ~oL~L of 9,9-bis-(4-l.yl.v~y~h_l.yl)-41uorene~ Tho proauct was furthor ~nalyzed by a ~ tion of HP_C and W (282 nm) and CA~I A;~d % by aroa ~roduct 96 9 9~9-bi~-(4-Lyd v~y~honyl)fluorone (BHPF) 2 4 9-(2-~y~Lv~y~henyl)-9-(4-l~y~lv~y~h-~yl) fluorene (2,4-isomer) 0 7 adduct cA~t~i~;~ two fluoron~ unit~ and t_r~o rh~Alic units (two thr-o adduet) 3XAMP_E 2 C~~~ION OF 3 ~ ~PT~ss~N~sJLFONIC ACIDS FROM T~EIR SODIUM SA_TS IN
THE REACTION MIXTURE
A The ~vcel~ o o-f _lo 1 was r-~o~te~ nxee~t t_at t_o eataly~t wau ~repared in ,BitU 4rAm 90 ~Gl.- ~ sodium 3 --_~tv~ v~-~-s lfonate (0 854 ~s, 4 79 mmol, 0 0431 equivnlsnts) and 95 to 98 ~ ulfuric acid (0 48 ~, 4 9 mmol, 0 044 equival-nts) and tho r-action was eonduetod at 85~C
T_o 9-fluo - wa~ eomplotely eA~- -- b ~ _ 60 and 120 ~t~r, ~iv~n~ n final i~omor di~tr;hut;~, dot1 ~d as in _le 1, ofi % by aroa ~roduet 95 3 4,4-isomer (BRPF) 3 6 2,4-i~omor 1 1 two-thr-e adduet B T_e ~locod~. of Exam~l- 2A was _-~te~ exe-~t that 98 ~ ~t sodium 2 - ~to~h~ l4Onato (0 779 ~s, 4 75 mmol, 0 0427 ~quivalont~) and 95 to 98 ~-- sulfuric aeid (0 48 ~, 4 9 mmol, 0 044 ~~uival-nt~) w re u~-d ns cataly~t~ Tho roaction was cv~l~L-d at 85~C
The 9-fl~vl~ - wa~ eAmpl-tely CA~ -' within 60 '~t-r, ~iving a ~roduet $~omor di~tr;~ltiA~, as doseribod in _lo 2A, of % by nroa ~ vl~cL
91 7 4,4-isomer 6 6 2,4-isAm~r 1 7 two t_r~- aaduct Th-~e ~x~oriment~ domonstrnto that 2 ~ca~Loothan--~ulfA~c acid, ~-norat-d in tho r-aetion mixture, was an ~ffeetive CA~ i~ a~-nt for tho ~ vc-~
-WO 97~08t22 PCTAUS96/13683 CC~ - - A~ION usINa sULFURIc ACID AND 3-MERcA~ OP~OPIv lC ACID (COMPARATIVE
EXAMP~E) 9-Fluorenone (20 0 g, 0 111 mol, 1 0 ~quival-nt) and molt~n ph~nol (156 7 g, 1 66 mol, 15 0 equivalent) w ro ~ad-a to tho r-actor (r~actor - a-si~n 1) Th~ roaction mixture was hented to 65~C with stirring a ~ad of nitrogen 3 ~ topro~ionic acid (0 588 ~, 5 54 mmol, 0 0499 ~~uivalont) was adaea to the re~ction mixturo at 65~C, foll_ ~ by tho slow addition (over 1 minut~) of c ~ ~tod (95-98 ~ ~) sulfuric acid (0 551 0, 5 62 mmol, 0 0506 equi~alent) to the reaction mixture at 65~C
Tho mixtur turn~ ~urpli~h Ol~h9~ upon addin~ the sul~uric acid ana ~raaually faa-s to a y6~ O~ O color within 5 to 10 ~ A slight ~xoth-rm to 66 to 67~c, w~v obs-rvoa The ~xotherm ~orsists ror 15 n~ts~ before the reaction mixture cool~ to tho re~cti on tomporature of 65~C The reaction was monitorOa throu~h~t th~ r-action ~rioa by collocting _ 1~8 and analyzing by ~PLC Tho 9-~luo _~v~o was ~ound to be complet-ly ~o s~ ~ b-L~_- 240 ana 420 ~ut-~ ~P~C analysis (analytical method 3) ~ives product di8tr;~ution:
a 0% by aroA proauct 93 0 9,9-bis-(4-1.~ ~y~h_~yl)fluorene 5 5 2,4-isomer 1 5 two thr-~ ~aauct Thi~ ~xampl- shows that tho ~rior art proc-ss wa8 ~lower than the ~ ~ve~8 of _ 1'~ 1 or 2 and that the r-sultin~ ~ o~L c~t~in~ le of th- 4,4-isomer, th~n producod by tho ~roce~s o~ r _~-~ 1 or 2 EXA~PLF 4 ~FFECT OF ADDED WATER IN F~ P ~IONS USING MPSA (P~ENOL AS
SO~VENT) A 9-Fluv ~ o~n (138 1 ~, 0 770 mol, 1 00 ~quival-nt) ana molt-n ~henol (1500 ~, 15 9 mol, 20 8 ~quivalent) was adaod to tho roactor (rcactor de d ~n 4, a E) . Tho roaction mixturo was heated to 45~C with ~tirrin~ under a pad of nitro~en 3 r~to~ vL~ ~~ul~onic acid (8 28 g, 53 0 mmol, 0 0692 oquivalent) was addod slowly over ~lv~imately 1 minuto to th- roaction mixtur- at 45~C The roaction was monitorea tl ~v~l ~u~ the r-action ~eriod by collectin~ _ _l Q n ana analyzin~ by ~PLC Tho 9-fluo ~ ~ was found to be 22 ~ t c~~~ ~ within 9 ~l es, 52 p-~cOnt conrum~d within 30 minutes, 76 ~LC - nt con~umod within 1 hour, 92 p~ ~L con~um~d within 1 75 hours, and 100 ~Lc~nL conuumod within 3 5 hourA ~PLC analy_is (analytical m thod 3) ~ivo~ the followin~ relativ~
ar-a ~~ ~ent analysis for tho reaction ~ vvu~Ls at 100 ~el -conversion % by arQA Froduct 96 9 9,9-bis(4-Lyv ~y~he~yl) fluorenO
2 4 2,4-isomor 0 6 two thro~ adduct B 9-Fluo e..... v o (6 44 ~, 0 0358 mol, 1 00 oquivalont), molton ph-nol (70 0 ~, 0 744 mol, 20 8 _quival-nt), and ~AiA~;~-d watOr (1 93 ~, 0 107 mol, 3 00 oquivalQnt) wa~ addod to tho rOactor (ro~ctor aosi~n 3) Th- rOaction mixturQ was hOatod to 45~C with ~tirrin~ und~r a pad of n~troAvon 3 ~- ~tv~ vv~sulfonic acid (0 385 ~, a 47 m~ol, 0 0690 ~quival-nt) was advdOd Alowly ov-r ~ - t~ly 1 minut~ to tho r~action mixtur- at 45~C Tho rQaction was monitor-vd tl v~ t tho reaction pcriod by coll-_Lin~ Aam~ and analyzin~ by ~PLC Tho 9-fl~oLe~v~ was found to bo 4 ~91~ L c~n -' w~thin 9 ~t-~, 13 ~rcc~t ~r~ ~ within 1 hour, 29 ~el - cOA -~ within 3 5 hours, and 94 ~e c_nL c~ -d within 20 5 hours RPLC analysi~ (analytical mothod 3) Ayiv~s the followin~
rolativQ aroa ~ ~_~t analysi~ for th- reaction ~roaucts (fl~oL~ . arOa not ;n~ a) at 94 porc-nt cv~OL~ion % by aroa product 96 5 B~PF (4,4-i~omor) 2 9 2,4-isomor 0 6 two thr-o adduct Tho~ ~xp~rimont~ ~how that hi~h-r roaction ratos and lowor ~ -~of ~ L,-~lvd~ct~ wer- obtain d, in thD A~-- - -~ of additional wat-r CONDENSATION OF FLUORENONE WIT~ P~ENOL VSING OT~ER ~_ ~r-~ AGENTS
A 4-NERCA~~ ~-C~T~ONIC ACID
9-Fl~v . ~ (82 9 ~, 0 460 mol, 1 00 Oquivalont) and molten ~honol (900 ~, 9 56 mol, 20 8 oquivalent) was add~d to th~ r-actor (_~ctor d~ n 4, 2 L) Th~ roaction mixtur- was heatOd to 45~C with ~tirrin~
undDr a ~ad of nitro~-n 4-~--c~Lo~ltr~-F~lfonic acid (5 41 ~, 31 8 mmol, 0 0692 equivalent) wa~ added ~lowly over ~ t-ly 1 minut~ to -5~-CA 02230272 l998-02-24 W O g7~8~22 PCT~US96/13683 the r-action mixturo at 45~C. Tho roaction was monitorod th.~ tho roaction ~Oriod by colloctin~ sam~l~s and analyzing by HPLC. The 9-flu~ ~l-e was found to be 17 ~8 ~lL c~- -1 within 5.5 ~t~, 58 ~e c~..L consumed within 30 n~lt~, 83 ~elc~ L C~n -d within 1 hour, 95 5 ~e~ t e~n -~ within 1.75 hour~, and 100 ~ nt consumod within 3.5 ~ hour~. ~PLC nnalysi~ (~nalytical mothod 3) givo~ the following relativo ar~a ~o ._ t analysis for the reaction produets at 100 ~ercenL
eo~v.l~ion:
% by ~roa product 10 97.0 B~PF
2.5 2,4-isomer 0.5 two:thr~o ~dduct B.2,2-BIS-(NERCA~, )-1,3-PROPA~I~-u~FONIC ACID
To A 4-dram vial (r~aetor design 2) was ~dded ~ mixture of 15 fluG ~ .. ...Q (0.40 g, 2.22 ~ l, 1.00 equivalent) and phenol (2.10 g, 22.3 mmol, 10.0 ~quival~nt). Tho ca~-d vial wa~ ~lacod into tho ~~~t;~
control block re~ulatod at 63~C and ~tirring bogan.
2,2-8i8(~ ~Lomethyl)-1,3-~ a;~ c aeid (0.029 g, 0.098 mmol, 0.044 equivalent) was add-d in one ~ortion to tho vial which was thon tightly cappoa. Tho r~t;~ was monitorod th.~Vl ~ the roaction poriod by colloct$ng ~ and analyzing by ~PLC. The 9-fluo~ - wa8 found to be 25 ~ ~L e~ ~' in 1.5 hour~. ~P1C analysis (analytical method 2) giv-s the foll~ ~g relativO arOa ~ 9'. ce~t analysis for tho roaction ~roducts (fluo enGne aroa not included) at 25 ~l. c~vO-dion:
% by area product 95.7 B~PF
3.4 2,4-i~omer 0.9 two:thr-e adduct C. 2,3-DIMERCA~OPROrANES~LFONIC ACID
To a 4-dr~m vial (reactor do~ign 2) was added a mixtura of fl~v ~ - (0.40 g, 2.22 mmol, 1.00 ~quivalent) and ~henol (2.10 g, 22.3 mmol, 10.0 oquivalent) The ca~od vial was placed into tho ~-~t;ng control block rogulated at 63~C and ~tirring was begun.
2,3-n; ~ o~,~ fonic acid (0.021 ~, 0.011 mmol, 0.050 oquivalent) w~ ~ddod in one ~ortion to tho vial which was then tightly cay~od. Tho r-action was monitorod throu~hout the reaction ~eriod by collecting -~am~les and analyzing by HPLC (analytieal method 2) Tho 9-~1uv.a~v o was found to be 5 ~Ple~L e~- -' in 1 5 hours D 3-~ERCAPTOPROPIONIC ACID AND MF~ CVLFONIC ACID
(CONPARATIVE EXANPLE) To a 4-dram vial (reaetor ausi~n 2) was adaea a mixture o~
~1~v~Onvno (0 460 g, 2 55 ol, 1 00 cquiv~lont) and phOenol (5 00 5, 53 1 mmol, 20 8 equivalent) The eapped vial was plaeed into the hsAt;~g eontrol bloek regulatod at 55~C and stirring was begun 3 ~~-~a~topro~;A~;c aeid (0 0217 9, 0 204 mmol, 0 080 e~uivalont) and me~h-~-r~l~onic ncid (0 0197 g, 0 205 mmol, 0 080 ~quivalent) were added in ono portion to the vial whieh was then tightly ea~oa The reaetion was monitored throu~hout the reaetion perioa by eollecting sam~les ana analyzin~ by HPLC The 9-~1~o ~nvn~ wa~ ~ound to be 32 ~CL_a~L e~ -~
within 30 ~t ~, 51 p~L_e..t C~ - ' within 1 hour, and 71 ~
e~ -' w~thin 2 hours HPLC analynis (analytieal method 3) gives the ~ollowing r-lative aroa ~el_Qnt analysis ~or the reaetion produet~
(fluv ~ ~A aroa not ;~ ) at 71 ~ l cv v~ ~ion % by ar-a ~ vd~

5 5 2,4-isomer 0 8 two threo adduet E 3-MERCAE O~ROrIONIC ACID AND ~T~Y~-CVtFANIC ACID (CONPARATIVE
EXANPLE) To a 4-dram vial (r-aetor d-sign 2) wa~ added a mixture o~
~luv.~v..c (0 460 g, 2 55 mmol, 1 00 e~uivalent) and ph-nol (5 00 ~, 53 1 mmol, 20 8 ~quival--nt) T_Q eapl?ed vial was ~laced into th~ heatin~

eontrol block ~ ated at 55~C ~nd stirring was ~egun 3-Nereaptopropionie aeia (0 0217 ~, 0 204 mmol, 0 080 equivAl-nt) and methyl~ fl e aeid (Aldr$eh 98 ~c~co~t) ~0 0227 g, 0 204 mmol, 0 080 ~quival-nt) wero adaod in on~ portion to the vial whieh wa~ thon ti~htly eappod Tho r-action was monitored tL_v ~~ thc reaetion poriod by eolloetin~ ~ an~ analyzin~ by HPLC The 9-~l~ol~v~c wa~ ~ound to b- 13 ~elCent Cv~_~ - ' within 1 hour, and 21 pereont co~ ' within 2 hour~ HPLC analy~is (analytieal method 3) giv-s the ~ollowing rolative arca p_.ccn~ analysis for the reaetion ~roduet~ (fl~o-_ ~ aroa not e~) at 21 ~ ~cnt eonversion CA 02230272 l998-02-24 W O 97/08122 PCT~US96/l3683 % by ar~a product 95.4 BHPF
4.6 2,4-isomor n/d two:three adduct F. SUB~ ON OF r~usr~uNlc ACIDS POR M~CT~T~ONIC ACID
(COMPARAT~VE EXAMP~ES) The r-~ction conaitions doscriboa in r _lo 5D wero repr~t~
~ubstituting oach o~ the ~ollowin~ acids (each at 8 ~ 1 ~_-~ ) for - h~ -l~onic acid in the reaction: sulfamic acid ~Aldrich 98 ~c_co L), methylph~rh~;c acid (Aldrich 98 ~e ~nL), and phonylFh~rhA~;c acid (Aldrich 98 yO~ ). In oach ca~H, v-ry little cvrv~L~ion o~ the fluo.~one was ob8erved in compari8cn with the use of me~h-~~~lfonic acid.
The~o . _l~n ~- -Lrato th~t mixturos o~ a - ~yLO _ __ ' and an acid woro infcrior to 3 ~~ c~ytOy~vya~e sul~fonic or 4--c~pt~but-n~ulfonic acid for catalyzinc the c~ ti~ o~ phenol with ~1uorenon-.

~FF~CT OF WATER ~ ~ATION IN FT~)u~ ~IONS USING MPSA WITH
ao ~Ir~NY ~ T~ AS A CO-SOLVENT
A. 9-Fluv.onv~e (3.65 ~, 0.0200 mol, 1.00 oqu~valent), ~ lton phonol (39.6 ~, 0.420 mol, 20.8 equival-nt), d~io~;~-' wntor (0.055 g, 3.06 mmol, 0.151 oquivalent) and diphenylmethane ~32.83 g) was added to the r-actor ( -~tor desi~n 2). The reaction mixture was heated to 53~C
with stirrin~ undor a pad of nitro~en. 3 r!-~_aytv~ vL -3Ul fonic acid (0.170 g, 1.10 mmol, 0.0537 ~quivalont) was addod ~lowly over a~. -: tely 1 minuto to th- reaction mixture at 53~C. The roaction was monitor-d th~v~yh~ the roaction period by collocting ~ and analyzin~ by HPLC. The 9-fluv-e v o was found to be 49 ~_~ent r~ -~
30 within 2 hours and 77 ~ ~t c~ b~ ~ within 4.5 hours. HP~C analysis (analytical method 3) gives the foll~_~ ~g r-lative area ye~c_~L analy~is for the reaction products (fluG ~ - - area not ;~l~rd) at 77 ~v,.v~.sion:
~ by area product 3596.1 BHPF
3.4 2,4-i~omor 0.5 two:throe aaauct WO 97/08122 PCTnJS96/13683 B. 9-Fl~v~Onv~e (3 65 g, 0 020 mol, 1 0 equivalent), molten ~henol (39 6 ~, 0 420 mol, 20 8 equival-nt), ~ei~;7s~ watHr (0 362 g, 20 1 mmol, 0 994 oquivalont) and diphenylmothano (32 83 ~) was addod to tho roactor (roactor dQsign 2) Th~ r-action mixturo was hOat~d to 53~C
with ~tirrin~ undor a ~ad of nitrog~Yn 3-Mercaptv~L~a~Y~lfonic acid (0 158 g, 1 00 mmol, 0 0500 ~quivalQnt) was added ~Ylowly over ~ Y; oly 1 minuto to the , -~1;~ mixtur- at 53~C The rOaction was monitorOd th.v ~l~t thc rOaction ~-riod by collectin~ ~ _le8 and analyzing by HP~C. The 9-fluo.Ononn was found to be 25 ~Yl_ont cv~ -' 10 within 2 hours, 45 ~ c~ ' within 4 5 hours, and 57 ~YL
c~~ -' with$n 6 hours HPLC analy~is (analytical method 3) ~iVQB thoY
foll~_ in~ r-lativo ar~a ~L_ent analysis for the re~ction products (fl~o .~v~e area not ;~lur~d) at 57 ~L- ~ C~vo YYion:
% by aroa product 3 7 2,4-isomer n/d two thro- adduct C 9-Fl~o. - ~ (3 65 ~, 0 0200 mol, 1 00 equivalent), molton ph-nol (39 6 g, 0 420 mol, 20 8 equivalent), ~ ' water (1 09 g, 60 7 20 mmol, 3 00 equival-nt) and diphenylmethan- (32 83 ~) wa~ add-d to the r-actor (roactor design 2) Th- reaction mixtur- was hoatod to 53~C with ~tirring undOr a ~ad o~ nitro~en 3 ~tv~. _ -~ulfonic acid (0 158 g, 1 00 mmol, 0 0500 equival-nt) was addod ~lowly over ~-v- tely 1 minuto to tho r-action mixtur- at 53~C Th- r-~c~;o~ was ~onitor~d tL~v~lo~t the roacti ~ period by collecting samples and nnalyzing by HPLC. Th- 9-fluo.Onv~o was found to bo 11 ~L-- ~ C~~ - ' within 2 hours, 20 _~c consumed within 4 5 hours, and 23 ~eL. ' C~
within 6 hour~ HP~C analy~is (analytical m thod 3) ~iv 8 th following rolativo ar~a ~- analy~i~ for tho r-action ~vd~Ls (~1~G~ V O ar-a not i~l7~-') at 23 ~- ~ Cv~vOL~ion % by area ~roduct 4 1 2,4-isom r n/d two throo adduct 35 Th-so ~ show that addition of lar~e ~ 8 of wat-r to the roaction mixturos retards the co~ i~ r-action UEMOVAD OF WATER 'JNDER VACUUN WITH AND ~1.~. DIP~wrl~M~ o~ A8 A
CO-SO_VE.~T
A. 9-FluoL~one (127.7 g, 0.709 mol, 1.00 equivalont) and ~ lt-n ~honol (996.1 ~, 10.58 ~ 1, 14.9 equivalont) was ~dded to the roactor (r-actor aesi9n 4, 3 L). The reaction mixture wa8 heated to 45~C with 8tirring unaer a pad of nitrogen. 3 -_~topro~r~ lfonic acid (5.53 ~, 35.4 mmol, 0.0500 oquivalont) wa8 addod slowly ov~r ~ -: t-ly 1 minute to tho r~.action mixtur~ at 45 ~C. Tho roaction wa~ monitor-d tL~u~louL
the reaction yeriod by collectin~ ~ _la~ and analyzin~ by HPLC. Th~7 9- luor-none wAs found to bo 60 ~a c~nL consum d within 1 hour, 88 ~_ ~o~L
c~7~ _a within 2 hours, Ana 95 pc _~t r~n- ' within 2.5 hours. HPLC
~n~ly~is (analytic~1 mothod 2) ~ivos the fo~ relative area ~8YC_.~t analysis for the reaction products at 100 ~e7c~L c~v~ ~ion:
% by ar-a ~roduct 98.0 BHPF
1.4 2,4-i~omer 0.7 two:three adauct B. 9-FluG _~G~C (127.7 ~, 0.709 ~ 1, 1.00 ~quiv~lent) and molton ~h-nol (996.4 ~, 10.59 ~ 1, 14.9 ~quiv~l-nt) was add~d to tho r-actor (using r~actor d-sign four (4), throo (3) L roactor with a Doan-Stark water Je~--At;~7~ trap a d vacuum inl~7t attach-d in lie-l of tho nitro~-n inlet). The re_ction mixtur~ was h~at~d to 45~C with ~tirring.
3 ~ ~Lo7~roF~ fonic acid (5.53 ~, 35.4 mmol, 0.0500 ~quival-nt) was ada-d 810wly ovRr ~ ~ ely 1 minute to the reaction mixtur- at 45~C.
Tho L~-~7'i~7~ mixturo was ~11. .._~ to stir for 15 ~es at ~ --ic ~8~ - e, then vacuum wa~ ap~lied to th- re.nctor. From this point on, the roaction wa~ conduct-d undor 1.- ce~'~ ~ro8sure conditions (<5 mn Hg) with water/~honol di8t; 11 A~ coll- Led in the Dean-Stark tra~. Th~ roaction was monitor-d th~u~ tho roaction ~oriod ~y roll~_Ling ~ _les and anAlyZin~ Jy HPLC. Th- 9-~1~.~ - was found to ~o 68 ~e~e~t C~77 ~7 within 1 hour, 98 ~e~. - c~- -' within 2 hour~, and 100 _~rc c~ ' within 2.5 hours. HPLC analysis (analytical methoa 2) ~iV08 th-ollowing r-lativ~7 ar-a pCl__~t analy~is for the roaction product~ at 100 ~9 c L convors~on:

CA 02230272 l998-02-24 W O 97/08122 PCTnJS96/l3683 % by area proauct 98 1 8~PF
1 3 2,4-isomer 0 6 two thr~ adduct C 9-Fl~.~ ~e (191 5 ~, 1 063 mol, 1 00 oquivalont), molten phenol (1500 g, 15 9 mol, 15 0 equivalent) and diphenylmothano (156 7 g) w ro added to th~ r-actor (r-actor do~i~n 4, 3 L with a Doan-8tark wator n-paration tra~ and vacuum inlot attachoa in liou of the n~tro~en inlot) Tho r-action mixtur- was hoated to 45~C with stirring 3 ~ ~Lv~ v~-~r-~ lfonic acid (8 27 ~, 53 0 mmol, 0 0499 oquivalent) wa~
ad~oa ~lowly ovor ~ to~y 1 minut- to tho reaction mixturo at 45~C
The roaction mixture was All~ ..Oa to stir for 15 ~t~- at - ~3p'~~ - C
pr-~ure, then vacuum was ~Fl;o~ to the roactor From thi~ point on, tho r-action was conauctod undor roduced ~r~s3uro conditions (<5 mm ~) with wator/phonol dist~ t~ coll-_L-d in tho D-an-8tark trnp The reaction wa-- monitorQd th ~l~L the r~action porioa by collocting ~m~les ana an~ly~ing by ~PLC The 9-fluol~ono was founa to bo 20 po__enL c~ -~
within 15 ~t~, 80 _- ce~L c~~ i within 2 hours, 98 ~_~_~L c~~ d within 3 5 hours, and 100 ~ _e L ____L ' within 6 hours ~P~C analy~is (analytical method 2) givos the foll~ r~lativo area ~ nL ~naly8is for the reaction products at 100 ~_~L c~ v.L~ion % by ar~a product 98 3 8~PF
1 2 2,4-isomor 0 5 two throe adduct Tho~- r-Mult~ ~how that r movnl of wat-r from th~ roaction mixturQs, c~1~;~;~g ai~honylmQthano solvQnt, was ~----~9ce~ y. Th-so r-sults show that remo~ing watar ~rom th- r~action mixtures accel-ratod th- rat- of the L ~1-~;~~ reaction, but was not -c ~c-~y for ~ood roaction ratos and c~v~ ~ions ~XAMP~E 8 REACTION OF PE~NO~ WIT~ AC~TONE TO rnvuuv~ BI8P~ENOB A USING MP8A CATALY8T
A To a 4-dram vial (roactor design 2) was rdded a mixture of acetone (0 11 g, 1 8 mmol, 1 0 equivalont) and phenol (2 40 ~, 25 5 mmol, 14 0 ~quivalent) The cappod vial was ~lacod into the ~~~~ control block r~gulated at 62~C and stirring was bogun 3 ~ ~tv~l~ eL~lfonic acid (0 021 g, 0 13 mmol, 0 070 oquivalent) was added in one ~ortion to tho v$al which wa~ th~n tightly cap~od The r-action was monitorod throu~hout th- roaction ~eriod by colloctin~ ~mplos ~nd ~nalyz$ng by ~PLC Tho ~cotono wa8 round to bo ~ ~ly 70 ~ ~t co~
within 2 hours ~PLC analysis (analytical mothod 2) giv~s a rolativo ~roa ~r ~61-~ ratio of 97 0 3 0 for the do~irod r-action ~roduct 2,2-bi~-(4-l~dA~y~h-nyl)~_ ~ - (4,4-b$~ ol A) r~l~tivo to tho i- -ric im~urity 2-(2-lyd o~he~yl)-2-(4-L~ll~y~h-~yl)-~ v~c (2,4-bis~henol A) at 70 p~ t conv~sion~
B To a 4-dram vial (r0actor dosi~n 2) w~s addod A mixturo o~
acoton- (O 11 ~, 1 8 mmol, l O ~~uiv~lont) and ~henol (2 40 ~, 25 5 ~ol, 14 0 oquiv~lont) The capped vial was pl~cod into the ~~~t;n~ control block regulated at 25~C and stirrin~ was be~un 3 -- ~t~ ~A~ f~;c acid (0 074 ~, 0 47 mmol, 0 25 oyuivrAl-nt) was addod in onu ~ortion to th-vi~l wh$ch w~s th n ti~htly c~od Tho r~action was monitored tL~v~l ut tho roaction p-riod by collectin~ P and ~nalyzin~ by ~PLC Tho ~cotono was found to be ~y~. - t~ly 70 ~c. _~L c__~ within 2 hours Durin~ tho latQr st~s of re~ction, th~ ro~ction product bo~ins to crystAAl1;~o ~rom th~ ro~ction mixture ~PLC an~lysis (analytical methoa 2) giv-s a r-lative aroa ~c ~t ratio of 98 9 1 1 for tho d-sir-d r~action ~roduct 2,2-bi~-(4-hy~L~y-~h_~yl)~ ~ne (4,4-b;~F- -1 A) relrAtiv to tho i~om~ric impurity 2-(2-hyd~v~y~honyl)-2-(4-h~a~v~y~h-nyl)propan- (2,4-b;q~l A) for the bulk rcaction ~o~ut;~
8eparat$on of tho cry~ ~.~d~ ~ from tho roaction mixturo fol1 _~ by rinsin~ of the crystrAl3 with wat-r to removo ~urfaco impuritie~ providon 4,4-b$sp~ -1 A ~roduct c~A;~;n~ 1 - ~8 than 500 parts per ll;~ of tho 2,4-b; ~h~~~l A impurity C (Com~ar_tiv _le) To a 4-drnm vi_l (ro_ctor dosign 2) wa3 addod a mixture of acetone (0 11 ~, 1 8 mmol, 1 0 equival~nt) and phHnol (2 40 g, 2 5 5 mmol, 14 0 ~quivalent) The ca~p-d vial wa3 ~lac-d into th- h--t;ng control block regulatod _t 62~C and stirring wa~ ~egun 3 - ~a~topropionic acid (0 014 g, 0 13 ~ l, 0 070 equiv_lont) and me~h-~ lfonic acid (0 013 g, 0 13 mmol, 0 070 oquivalont) w ro added in one portion to the vial which was then tightly ca~-d The r-~ction wns monitorod thro~gh~t tho roaction p~riod by colloctin~ sam~l~s ~nd an~lyzing by ~PLC Th~ _cotono was found to ~o ~. - -7y 70 ~orcent consumea within 2 hours HPIC analy~is (analytical method 2) gives a r--lative aroa ~-- c~, L ratio of 96 2 3 8 for t_e desirod reaction product 2~2-bi3-~4-LYv-~ yL yl)~ v~o (4,4-bisphenol A) rolativo to th ~- c im~?urity 2-(2-lyl v,,y~"henyl)-2-(4-lyl,v y-phenyl)~;lv~o 5 (2,4-~ rh~ A) at 70 ~ o. ~lt cv v L~iOn Thosn nxpnriments show that MPSA s~ive8 a ~roduct, with a hi~h r 4,4-i~omor ratio than ~rior art cataly~ts EX~MPL~! 9 PREPARATION OF THE POIYMER- su~rOR.~LI MERCAPTOS~lLFONIC ACID CATAI,YST
10 (PMB8A) A PREPARATION OF 8~LTONE ~
1,4-Rut--~e~~lton (3 00 S~, 22 0 mmol, 1 00 oquivalent) was ndded to dry THF (150 ml,) under a nitrogen r~ ~~ '~. The E~olution was cooloa to -78~C us$ng a dry ico/acotono bath n-Butyllithium (1 6 molar in h~ ~ E, 13 8 mI, 1 00 oquival--nt) was added slowly dropwiso to tho -78~C ~J~lut;~
via An ada$tion funnel over c ~ ~ t~ly 40 r~t~~ with vi~orous ~tirring Th h- _ - ~ r~ action mixturo wa~ Al1_ _d to stir ~or an add$tional 10 to 15 r~t-r at -78~C Poly(vinylbonzylchloride) (3 3 çr, ~ t-ly 1 0 equivalont of chloromothyl groups, 60/40 mixture of 3-20 and 4-;- ~, Alar$ch ~ cAl Co ) in dry THF (10 ml) was _daea over ~ -~ t--ly 2 ~rn~tep to the r--action mixturo at -78~C Tho roaction mixtur-- was All~ _~ to slowly w_rm to room t-- _= ~ture in th~ cool;~J bath ov-r ~ ly 3 hours A whit ~ preci3;~itato forms in the roaction mixtur-- auring tho r--action ~?--rioa ana ~ as a ~olid as the mixture --rh_~ room t~ _- ~turo Wator (100 mL) was aadod to tho roaction mixturo and the white (;~ol~ l~) solid was ,~d by filtration under vacuum The solid w_~ 81~ y-W "h'~d w$th water, thon w$th ~mall volum 8 of methanol and mothyl-ne chloria-- and driod in a vacuum ov--n, providing 4 77 S~ of a whit ~ 801ia 8ultono-~unctional polymor B CONVERSION OF THE SlJITONE-FVNt; _ '~ POLYMER TO POIYMER-~u~~O~.cl MERCAPTOS~FONIC ACID (PMBSA) The sultono-functional ~olymor from above (4 00 ~, ~ tely 15 9 mmol ~ulton--) was added to THF (125 mL) Pot-~; th; o-cotato (2 20 g, 19 0 mmol, 1 20 ~quivalont) was add d as a solid to th- slurry of the 3;~olysultone in THF On-- arop of 50 ~c~ nt tetrabutyl~ ; chloriae was~ aad--d to the rnpidly stirroa slurry Th-- t~ _ ~turo rose to 26~C over ~--v ral r 1--r~th--n slowly l v~ed to 20~C Two additional dro~s of 50 W O 97/08122 PCT~US96/l3683 v- _~nL t~trabutyl~ i chlorid- were added and tha 801ution wa~ warmea to 40~C for 15 nl~tsA Water (100 mL) was slowly adaed over 1 hour to tho r-action mixturo at 40~C Sub~t~Ati-7 uolid ;A~ in tho mixturo at all st~gos o~ the r-action Tho wat-r~T~F r-action mixture was allowed to r-act 15 hour8 at 40~C The solvent was L. ._d by rotary A~V~o ation ~na the reDultant oOlid was ~round to a fino ~owdOr T~F (125 mA) wa~ again addoa to tho Aolid, forming ~ ~lurry AdaitionrAl vot. ~ i thi o~Cetate (a 20 ~, 19 0 mmol, 1 20 ~quivalent) was added, r-sultin~ in an ~xoth-rm to 26~C Sev ral dropt7 of 50 porcent tQtrabutyl~ ; chlorid~ w ro added and the r-action mixtur- was h-at-d to 40~C for 15 hour~ The ~olv nt w~s _~ v~ by rotary ~vO~oLa~ion Th- tan ~701ia was slurriea in a 2 1 (by volume) m xture of tolue~e/eth~T~Al C~ ted ky~vcLloric ~cid (50 mL) was added and the mixture wa3 ~tirr~d at room t- _el~turO
overnight Most of tho ~Cl wrAA~ ~ v~d by ~7~ar~in~ th- mixture with nitro~-n, th-n tho ~olventA~ w r- ~ a by rotn V~AVV ~tion The li~ht tan ~olid waO 8 lurry ~ d ~ t iv~ly with 10 ~L ~t hydrochloric acid and with wat-r Dryin~ ov~ ht in a vacuum oven (60~C/full vacuum) yrovid-~ 4 18 g of tho ~olymor-~o Lod - ~Lonulfonic acid ~8 a lig~t tan ~olid C PREPARATION OF A GEL PMB8A r~TYST (PMBSA-M~R) A catalyst was pre~ar~d rAs abov , startin~ with ~-rr;f;Al'~ r-Oin (200 to 400, 2 ~LOo ~ cro8~Al;A-l d, ~ol), trOatOd with hut~A~rultone The ~L ~d~_ L W~A8 jd~At~f;~a ~_ PMDSA-M~R
D PREPARATION OF CATALYST FROM BROMOM~nT~n MACROE~R-uB-' POLYSTYRA~NE (PMBSA-XEBR) A catrAlyst wrAs ~rO~roa A8 ~bovo, ~tArtin~ with bA~ Lhylatod AA~berlit ~ XE-305 ma~lvvv v~8 resin (4 ~_ ~ L cro~;Al d, 20 to 50 me8h, 3 7 meq Br/g) E PREPARATION OF CATAhYST FROM C~TO~- ~ ~Y ~ MACR-urvROu~
PO~ ~ ~ (PMDSA--XA~CAL) A cataly8t was ~rw~ared as above, 8tarting with chlG~ ~hylatea A~bwrlit- macAoVG~vAs r~sin (4 ~rc croP~ d, 20 to 50 mosh, 4 3 ~ lw ~ C l / g ) F PREPAR~TION OF CATALYST FROM h~nnI~A~D~ RESlN AND 1,3-PROP~C~TTONA- (PMPSA-MER) Catalyst was ~re~arQd abovo, by troatin~ Mwrr;f;~ reOin (2 ~rc~nt cro8s ~ 200 to 400 mwsh, 4 3 m~q C1~Y) with li ~t~ 1,3 ~~~r~ltono, which can be preparod in acco~d~ce with T Durst et al , "A n-w route to 5- and 6- ~- ~d ring sulton-s", Can J Chem , Volume 48 (1970), Pagos 845-851 EXA~P~E 10 EVA~UATION OF A MERCAPTOSUBFONIC ACID PO~Y~ER (PMBSA) IN THE REACTION OF
PHENOL WITH F~UORENONE
A To a 4-dr~m vial ~~uip~od with a ~t;-ri~ bar (roactor dQsign 2) wns aadod 4 33 ~ of a 20 8 1 molo ratio mixturo o phonol to fl~vl.~v~o and 0 26 g [(6 pe~ L by weight of the roactant soluti~n)] of the ~Losulfonic acid polymer (PMBSA) preparod as in _le 9B Tho r~action mixtur~ consistod of a ~ _ - ~ liquid ph~so plu~ n 3-p-rato hetolv~ polymer catalyst phase Tho mixtur~ was hoat-d to 36~C for 3 hours To in. -~c the rate of rnaction, tho t _-~ture was increased to 50~C for 18 hours Monitoring of the r-action by HPLC show~ svmo rcaction 15 at 36~C and 100 ~Cl~ ' Cv v~-~ion aftQr 18 hours at 50~C HPLC analysis (analytical method 2) ~ives tho foll_ ng relntive area ~_-c~nL analysis for the products aft~r 18 hours of r-action (100 ~ ._~L cv v~ldion) by aroa vroauct 0 98 2,4-isvmer 0 16 two throo adduct B(Comparative _l~) DOWEX 50WX4 (a cro~ d ~ulfonatod poly,Ly ~ne r-nin, from The Dow ~ c-l C _ y) promoted with 2,2-a$methyl~h~7oli~in~ (25 ~ ~L of the r~sin 8~lf~n;c acid cquival-nt~) was wa~hed on a ~lass _iltcr frit with phenol at 55~C to remove wnt-r The resin wns th-n wa~hod with a mixturo consistin~ of a 20 8 1 molo ratio mixture of phenol to fl~v-bnv~ at 55~C to ~;opl~- the original phenol wa~h To a 4-dram vial equippod with a stirring bar (r-actor d~sign 2) wa3 addod 2 13 ~ of a 20 8 1 ~ lo ratio mixturo of 30 phenol to fl~v - ~nd 0 74 ~ (35 ~OL.~L by w-ight of the roactant ~ol~ ~n) of th- promot-d DOWEX 50WX4, from The Dow r c-l C _ y~
catalyst activat-d a~ dQscrib-d above The wuight of catalyst us-d was d~t~ aft~r the reaction by _ v~ly of tho r-sin from th~ reaction mixture by filtration, w-nh;~g th~ r-sin with tol-- ~ and h~xane, nnd drying to a constant weight in a vacuum oven at 50~C for 6 hour~
Tho r-action mixtur- consi~tod of a h- ~ ~_ o liquid phas~ plus a ~-p- ~t~ hot~~ _ o polymor catalyst pha~e Tho mixture was h at~d to CA 02230272 l998-02-24 W O 97~08122 PCT~US96/13683 50~C for 18 hour~ Monitorin~ of th- r-Action by HPLC showoa ~ - tely 17 ~-rcont cv~v~ -ion aft~r 4 hours and 73 ~elcenL ~v~ve~ion after 18 hour~ at 50~C HPLC analysis (analytical method 2) and g~ve the foll~w ~g relati~ ar~a ~e.c~nt analysis ~or the ~roductn aftor 18 hours of roAction 5 (73 ~vr A~t c~v_-Oion) % by ~r~ ~v~L

6 78 2,4-isom r 1 90 two throo ndauct 10 C (Comparntive r _lo) To a 4-dr~m ~ial ~quipped with a Otirrin~ bar (reactor design 2) was added 2 16 ~rams of a 20 8 1 molo ratio mixture of ~henol to fl~ - and 0 34 ~ (16 ~_~_L ~Y w~ight of the r-actant 80l~7~) o~ dry Amb~rlyOt 15 (a cro~7sl;~l~ ~ r7ulfonat-d ~O1YDLY~- - reDin fr ~ Ro~7m and Haas C _ _~) Thc r-action mixture consiHtod of a ~ o~g liquid phaDe ~1UD ~ s-~arato h-t~
~olymer cataly~t ~h~o The mixtur- W~8 ho~t-a to 50~C for 18 hours Monitoring o~ the r-action by HPLC oh0w d ~-~ tely 24 percent ~v~v.~ion aÇt-r 4 hours and 64 ~e~- ' co~v~ion after 18 hours at 50~C
HP~C analy8is (analytical m thod 2)and ~ave tha fo~ g relativo ~roA
20 ~2- ~ an~lysis for the ~roaucts ~ftor 18 hours of roaction (64 ~-rcent c~.,v~ Oion) % by ar-a ~.vd~cL

3 93 2,4-isomer 250 25 two thr-e adduct The~o _ ' 'q showea that u8e of the catalysts ~i~c~~' h-roin gavo higher c~ v_.~ions of fl~oL~ - nna highor 4,4~2,4-i~om r ratios than tho prior art catalystO

EXAMPr~E 11 ~c~v~Y AND RECYC~ING OF S08ID ~TY-CT (PM8SA) A ~Tyc~ ~C~v~
The . ~t;o~ mixturo from Example 10A wa~7 cooled to 40~C and the mixtur-wa~ centrifu~-d The u~-r liquid layer was ~ Y - o~ and Additional warm (40 to 45~C) 20 8 1 ~ lo ratio ph nol/fl~vl~o~ ol-~tiA~ (~ f ~ly 3 to 4 tim 8 tho catalyst volume) was ndd~d ThD mixtur- was stirred, c-ntrifu~ed, and the warm d liquid layer was ~ This wash ~-vcel~ . was ~ t~d for a total of thr-e wa~hes, thon the required , CA 02230272 l998-02-24 W O 97/08122 PCT~US96/13683 amount of phenol/fluor~none roactant mixture was added and tho r-action b-gan B FIRST RECYCrE
To tho 4-dram vial c~t~ ~ the ~ _~Losulfonic acid polymnr ~: .G~Od (a~ d-scribQd above) from Exam~le llA was add-d 4 33 grams of a 20 8 1 molo ratio mixture of phsnol to fl~ol~n~l.e Tho mixturo was heatod to 50~C for 4 hours ~onitorin~ of the roaction by HPLC showed _~ ~xlmatoly 90 ~o ~..L cv~V~ldion aftQr 4 hours at 50~C HPLC analysis (analytical mothod 2) and gav- the followin~ r-lative area ~-~
analysi~ for the products aft~r 4 hours of rQaction (90 ~ ~tconv-rsion) % by area product 1 09 2,4-is ~er 0 14 two thrQo adduct To th- 4-dram vial c~;~i~ thQ ~tosulfonic acid ~olymor _avv~ (a8 d-scriboa above) from tho fir~t r~cycl- was added 4 00 grams of a 20 8 1 molo ratio mixture of ph-nol to fluol~nG~o ThQ mixtur~ was hoated to 50~C for 18 hours ~onitorin~ of tho roaction by HPLC shows ~ RJy 83 p_ _~nL c~v~L~ion aftor 4 hours and 100 ~c c~v.r~ion aftor 18 hour~ at 50~C HPLC analysis (analytical mothod 2) giv-s the fol 1 ~..in~ relativQ ar~a ~ l_~L analysis for th- products aftQr 18 hour of r-action (100 ~cLa~L co~v_~dion) % by ar-a product 1 10 2,4-isomQr 0 11 two throQ adduct D THI D RECYCLE
To the 4-dram vial c~t~ th~ ~ _~to~ul f~; C acid ~olymor _~C~v~l_~ (as ~--~r;~o~ abovQ) from tho socond rQcyclQ addod 2 00 ~ram~ of a 20 8 1 mol~ rntio miXturQ of phQnol to fluoL~ - Tho mixturo was h-at-d to 40~C for 18 hours ~onitorin~ of thc reaction by HPLC shows 35 a~ ~; t~ly 90 porc~nt c~vO ~ion aft-r 4 5 hours and 100 ~_ ~n~
co v~l~ion after 18 hours at 40~C ~PBC analysis (analytical method 2) SJives the following relativo Aroa percont e~ne~lysis for t_o ~?roductls ~fter 18 hours of roaction (100 ~eLc~ t c~ v~ liion) % o~ area product 0 92 Z,4~ omor - * two throo e~dduct * not detectable ThH8e ~~periments showed that tho ce~talyst con b- rocycled rersAt~ 7ly without loss of e~ctivity ~!XAMPI E 12 COMPOSITE EXP~RTM~AT. 1)~ r A'l'ION OF PIT~ rT!T~e FOR TEIE C'~ A~ION OF
PHENoL WITH FT (3-MPSA, DI~ n~L~Y~ -M~A-T~A~) E~porimonts wer~ run in ~tirrod i801 h- 1 batch r~Actor8 (reaCtor ~o~ignQ 2 or 3) to dot~ 'n9 the effect of t __ ~ture, molar ratios of rH_ctsnts and amount of MPSA on reaction rat 8 and }~roduct distr;hu~ n, Re~ults woro ~_own in Te~bl~ I
GrArh;c-l e~nalysis of the rosult8 in Table I ahows that f, t;-~n of 2,4-B~IPF wa8 relatod to the reaction t _ ~ aturo As th-- t~ _ e turo incroas--d, the 2,4/4,4 rntio in~ In contrAst, t_o ~henol/Fn ~lo ratio _as littlo e~f~ct on t_e 2,4/4,4 re~tio T_~ yi--ld of 2 3 Aaduct incr-~e3 --ko~ly as the ratio of ph~nol/Fn decreases _rom 15 1 to 2 5 1 and the r-action t~ eL-u-~g was i c, - ~' ~rom 25~C to 85~C
GrA~h;cAl ~ne~ly_is o~ r~sults for runD e~t 18 molo rercont ol~ D~PSA~
in torm~ o_ initial roeaction re~tos (B}~PF ~108/L~hr) ~howod a me~rkod rate 25 incr--as~e in goinS~ ~rom 25~C to 85~C
Inc ~-~;nsJ the c ~n~nt~ ation o~ MPSA catalyst also s~ivo8 th~
~~ect--d i~ in the reaction rato Tho phonol ~1 -o~ ~ o ratio al80 al~~ects tho roeaction rat-- It we~s Bolioved that hiSrher ratio# o~ ~henol to ~1~c, - were 7~rsfic;Al for ccn~nQ~t;~na, run in a solvent, such a8 30 ~i r~ , lmnthane .~

TABBE I
P~ENOL + Fn ~ > B~PF
Cataly~t MPSA, 10% Fn in DPM
~ alytical Metho~ 2 - W Dot~ctor Run TQmp.Nol~ Molo% 2,4/4,4 2:3/4,4 Conv. In$t$al # (~C)RatioNPSA Ar-a Aroa (%) Rat-~f 1 558.6212.8 0.0261 0.0198 99 0.16 2 252.467.9 14 0.0002 3 85 2.46 7.9 0.0389 0.114 62 0.047 4 2514.757.9 12 0.028 8514.757.9 0.0299 0.0098 99 0.53 6 252.4617.7 5 0.001 7 852.4617.7 0.0334 0.102 67 0.59 8 2514.75 17.7 0.0202 0.0074 99 0.041 9 851-.7517.7 0.0317 0.0106 99 0.88 258.6212.8 0.0239 0.0179 99 0.0042 11 858.6212.8 0.0354 0.0244 99 0.73 12 552.4612.8 0.0252 0.0673 57 0.035 135514.75 12.8 0.0237 0.0076 99 0.17 14 558.627.9 0.0264 0.0177 99 0.12 558.G217.7 0.0291 0.0248 99 0.42 16 558.6212.8 0.0285 0.0185 99 0.15 17 6314.7512.8 0.026 0.00911 99 186314.75 12.8 0.0259 0.0088 99 19 6314.7512.8 0.026 0.0088 99 6314.7512.8 0.0266 0.0084 99 0.29 21~ 6314.7512.8 0.0272 0.0096 99 22 6314.7512.8 0.0265 0.0098 98 236314.75 12.8 0.0269 0.0092 98 24 5514.7517.7 0.0255 0.0084 98 0.36 S52.4617.7 - - 24 0.14 26 639.9 5 0.0258 0.015 98 0.078 27 a514.7512.8 0.0178 0.0067 98 0.013 Fool~t-- to Tabl- I:
BF ~ BXPF (4,4-$~omor) 2s3 - t~o:thr~o adduct ~BXPF mol-~/L hr.
~ r-cyclo TABLE II
Pu~OL ~ Fn -----> BHPF
Catalyst MPSA, Various % Pn in Solvents Analytical Nethod 2 - UV DetHctor Run ~emp Solvent % Fn* Mol~ MO1Q% 2,4/4,4 2z3/4,4 i~ %
_ Ratio MPSA Ar-a Area hr Conv lA 27 DPM/MC 29 21 4 6 0 010 0 005 19 5 100 2A 35 ~ 55 21 8 0 015 0 004 6 5 86 15 3A 35 ~lr - - 13 21 25 6 0 018 0 005 3 25 99 4A 35 2,4,6T~Ph 14 2114 6 0 014 0 002 3 38 *I~ nolvent DPM ~ d~phenyl t~-~
DPM/MC ~ diphonyl- -~-~o ~ methylene ~h- ~r~
e o ~ methyl l~ ~o r - ~ chlo~

2,4,6T~tPh ~ Z,4,6-~rimothylPhe~l Th- result~ in Table I showed that th~ 2,4/4,4 ratio ~tayg const~nt cv~v~ dion i c ~ the 2 3/4,4 ratio in~

Th~ nmount of MPSA cataly8t w re r~lated to th- ~mount of 2,4-i- ~ iC proauct formed ~i~h 2,4/4,4 ratios at hi~h ~v -~ tl~tions o~
MP8A wer~ prob~bly r-lat~a to a ~hift toward nn acia-catalyzed roaction to ~roauc- relntiv~ly hi~h-r ~ r of 2,4-isomer ~XAMPLE 13 B OF SOLVENTS ON rk-v~u~- DIS.~l~u 1~_ AND CONVERSIONS
Ex~orimentN wer- run in ~tirr_d tank batch r-actors to d-t~ -wheth-r u~e of a ~olvent was aav~ . Results of thosQ experiments w ro shown in Tabl- II The use of a ~olvont do-s not a~p-ar to b~
adv-~1r~ Comparison of a run usin~ 10 ~e ~ent DPM with neat run, at th~ Aam~ ~P8A ~ ation, showed that re-~~ rates wer- hiqh~r for th n-at run, although tho DPM run u~es 2 5 tim-s mor- catalyst/Fn ~i~h-r 2,4/4,4 and 2 3-aaduct ratios for th r~ti~ in DPM wa~
anothor A; ~- ~v~n~e It was th-r-fore preferred to run the CAn~ t j in oxc-ss phonol a8 solvent -WO 97/08122 PCT/US96/l3683 EXaMPI.E 14 ~rrr~C~S OF TEMPERATURE, MPSA CUNCr.~ AATION AND PHENOL/FLu~ RATIOS ON
Pk~J~uuc. DI~.,~I~u.l~w:i (EXCESS P~}ENOL AS SOLV~NT) R--actions wore done in iso1 hr- 1 stirrod tank rQactors as d--scribed 5 above. Results were };~reso~to;l in Table III. Tb~- rosults domonstratQ
that $--~ Q;rl~ the amount o~ catalyst incro~s~d tho 2,4/4,4 isomer ratio.
IncrozL~ing tho r--action ton~oratur-- or decroa~ing tho phenol/Fn mole ratio l-ad~ to hi~hor ~ -~ of 2:3 adduct in tho product mixturo.

10 R~cuv~nY AND RECYCLING OF MPSA FROM THE R3lACTION ~m~S
Runs ol~ lOO mI. to 1.5 L (roactor d--signs 3 and 4) were dono to ~let~ whether MPSA can bo ~xtracted from th- n--at BRPF reaction ~olution with wat~r and rccyclod to 8~ t rum-. Tb-- efi~oct o~
~tirrer rpm on tho timo requirod ~or hroakin5J a rosulting ~ w~re 15 ~l_o investi5rat-~d.
Phenol wa_ wni5Jhed and charSrod into the reaction v ~88el. Fluo ..no..a was .~ ;STb-' and charged to tho roaction v-ssol, followod by a . iS,' -~quantity ol~ MP6A cataly~t.

TAB~E lII _ PH ENOL f Fn - - - - - > B~PF
Cat~ly~t NPSA, Neat Reaction~ - no ~olvent ~ Analytioal Nethod 2 - UV Dotector 5 Run TOEmp Nole Mole % Time 2,4/4,4 2 3/4,4% % MPSA
~ (~C) Ratio MPSA ~hr. ) Aro~ Al~ Co~. ~
1 65 10 5 2 2 0 017 o oll 99 0,0470 3 s5 21 8 1 5 0 016 0 004 100 0 0382 4 63 lo 2 7 5 0 014 0 008 97 0 0187 6 28 lo s 20 o 011 O OOB 92 o 0470 7 45 lo 5 5 0 012 0 007 91 0 0470 9 36 213 9 7 25 O OlZ 0 005 95 o ols lo2 3621 4 6 5 0 012 0 007 96 0 0202 11 35 21159 1 83 0 028 0 011 loo 0 6932 12~ 4515 5 2.5 0.013 0.006 99 0 0330 13 45 15 5 3.5 0.014 0.007 100 0. 0330 20 14~ 5521 3 2 0.0~4 0.006 99 0.0146 153 35 21 18 mpa 20 0 034 0.011 100 0.0580 5.2 msa ~acuum used to romove water aurin~ reaction ~ ~ les~L

~ c.. l ~ 8i - ve~ u~ed to remove wat-r whilo roaction wa~ taking placo mor- catalynt was added 2 Fn ~ddod c~ ~u~ly over 43 min 3 ~SA (mot~ - 14onic acid) ana NPA (I- ~Lopropionic ~cid) u~ea in~t-ad o4 NPSA

~r WO 97/08122 PCT~US96/13683 Tho c -- t~tions of matorial~ in tho r-sulting mixturos were followea by HPLC (Analytical Mothod 4) The following mixtures wor- u~od Neat Runs DPM Runs Chom wt% th-ory Chcm wt% th-ory Phonol 82 35 Phonol 47 Fn0 00 Fn 0 00 NP8A0 50 MP8A 0 2l H2O 0 84 H~O 0 48 lO BHPF16 31 BHPF 9 3 To tho roactor Wa8 ada-d 200 mL of the mixture _nd 200 mL of watcr The ro3ulting mixturo was stirrod for lO ~n~te~ Th~ ~ha~08 woro A
to n-parato and tho ~oparation time not-d A ~amplo (lO mL) of the or~anic pha~o wa~ ~ vod for analysi3 by HPLC nnd I C (ion _L~ to~ ~hy) Tho a~uoous phaso W~8 rot~inod ~or analysis Tho oxtraction of tho _ ;n;ng or~anic layor wa8 re~-t~, usin~ an ~qual volumo of wat-r (l90 m~) At tho ~na of the oxtraction and ~o~aration, lO mL of tho oryanic layor was ret-;ns~
Tho ~ ;~; ng 180 mL of or~anic layer wa3 oxtract-d with 180 mL of wat-r A lO-mL ~amplo of tho or~anic layor was rotain~d, as beforu The aquoous oxtract was distilloa und-r vacuum to ~ivo a g~lu~; ~n Of yhonol, MPSA ana ~mall ~ r of BHPF Acid titration nna I C analysis ~n~;c-t~ that ~ll of tho NPSA was ~_v_ ~ from tho mixtures Rosults of ~_~ ~~ -t;ve oxtractions wero ~iv n in Table IV

W O 97~08t22 PCr~US96/l3683 T~1Q IV
~xtraction Data for Neat 21 1 (Ph~nol/Fn) Run (500 rpm Stirrin~ Rate) - ~xtraction 1 2 3 5 Pha~e Or~ Aq Or~ Aq Org Aq g u~nd 217 200 251 4 190 216 2 180 end 262 2 154 9 226 9 214 5 196 4 199 8 % C _ in Phase Phonol 62 8 6 71 57 6 6 63 59 2 6 39 10 Fn ~ ~~ 0 ~ 0 ~ ~~ ~ ~ ~ ~~

~2~ 23 7 92 7 28 0 93 3 25 1 93 6 ~PF 13 4 0 0098 14 4 15 8 0 0073 (150 rpm Stirrin~ R~tu) ~xtr~ction 1 2 3 Ph~o Or~. Ag. Or~ A~. Org Aq g us~a 217 200 258 190 226 4 180 g on~ 268 6 148 4 237 Z 200 5 195 36 200 6 % C _ - in Phase phenol 60 1 6 37 61 6 7 17 61 1 6 82 ~n o 00 0 0 0 00 0 0 o 00 P-l H2O 27 1 93 1 24 2 92 7 23 5 93 2 25 P-2 B~PF 12 7 0 0088 14 3 - 15 4 ~ 4th and 5th extraction~ oqu~l volumos of organic and water lay-rs MPSA in orgnnic 0 0030 (4th), 0 0005 (5th), in wat~r 0 0143 (4th), 0 0025 (5th) ~XAMPLE 16 ~ ~IOW 8TUDY IN T~E r~ OF MPSA
Aeaction~ wero done in stirr-d batch isot - l reactor~ (r-actor a~ n 2) To the .-~t~ was char~od a mixtur- of 83 2 ~- c-nt by woi~ht of ph-nol, 0 09 ~ c by wei~ht of fl~o~ ~, 13 2 ~e.cant by wei~ht o~
B~PF, c~-;~i~g 0 92 ~_.co t by wei~ht of 2,4-isomer and 0 68 ~alcenL by ~ei~ht Or 2 3 adduct Various ~ ~ of MPSA wore ch~r~oa to the r~nctor Tho resulting mixturos were ~tirred and heatoa Th-~ tions in the reactor at various times w~re det~ -~ by analytical methoa 4 ~ itions of other reaction mixturos were given in Table V
R~ults woro giv~n in Table VI

CA 02230272 l998-02-24 Thea~ r-sult~ ~howod th~t ~-!~;~ mixturos, in thQ pr~nc~ of MPSA, brin~s about ~ - ;7~iA~ Or th~ r-action mixtur~s toward high~r c~ r~ -ations of 9,9-bis-(4-hyd~o~y~he~yl)-fluor~nQ. Tho c~ ation o~ hi~h~r adaucts also i~ 8 a8 a r~ult o~ prol~ng~
TABLE V
COMPOSITIONS FOR ISOMERIZATION ST~DY
T-mp mole/~ mol~L g Rx g _un ~C MPSA Ph~nol Mix PSA
10 1 70 0.642 9.250 5.42 0.5710 2 55 0.340 9.705 5.42 0.2878 4 55 0.920 8.835 5.42 0.8540 6 55 0.642 9.250 5.42 0.5710 8 70 0.340 9.705 5.42 0.2878 15 9 70 0.920 8.835 5.42 0.8540 lS 55 0.180 9.940 5.42 0.1520 W O 97~08l22 PCTnUS96/l3683 TABLE VI
ISOMERIZATION ~uvI~S
% in R~action ~ixtur- % Total+ Tot~l*
Time Ph~nol Fn BHPF 2:4 A 2:3* 2nd add.*

Run 1 0 75.27 0.08 11.94 1.74 0.62 0.00 89.6 99.2 8#1 4 76.86 0.00 13.09 1.61 0.26 0.018 91.8 101.4 S#2 22.5 74.64 0.00 14.05 1.01 0.17 0.15 90.0 99.5 - 8#3 52 76.18 0.00 14.30 0.88 0.14 0.23 91.71 01.3 Run 2 0 79.00 0.09 12.66 1.84 0.65 0.00 94.2 99.3 8#1 4 81.9 0.0 13.1 1.9 0.5 0.00 97.4 102.5 B#2 21 76.71 0.00 13.21 1.56 0.29 0.0242 91.76 96.8 S#3 29 80.41 0.00 14.07 1.53 0.23 0.0169 96.25 101.3 15 8#4 94 80.96 0.00 14.18 0.89 0.14 0.07 92.17 101.2 8#5 101 77.22 0.00 14.62 0.94 0.21 0.10 92.99 98.0 Run 4 0 71.88 0.08 11.52 1.66 0.59 0.00 85.7 99.3 8#1 2 67.53 0.06 12.25 1.68 0.40 0.00 81.92 95.5 20 8#2 4.5 69.3 0.0 12.2 1.5 0.3 0.013 83.3 96.9 8#3 24.5 74.49 0.07 13.18 0.95 0.15 0.04 88.88 102.5 ~#4 88 67.54 0.00 13.95 0.70 0.11 0.22 82.29 95.9 Run 6 0 76.02 0.08 12.06 1.75 0.62 0.00 90.5 100.1 25 8#1 2 73.72 0.00 13.01 1.83 0.51 0.00 89.0 98.6 8#2 4.5 75.4 0.0 13.2 1.8 0.4 0.0 90.8 100.3 8#3 24.5 78.39 0.00 13.36 1.17 0.18 0.02 93.13 102.7 8#4 88 74.06 0.00 14.99 0.76 0.10 0.12 89.90 99.4 30 Run 8 0 84.03 0.09 13.33 1.94 0.69 0.00 100.1 105.1 8#1 7 78.92 0.00 14.00 1.69 0.29 0.00 94.90 99.0 S#2 23 76.1 0.00 14.6 1.2 0.2 0.1 92.2 97.2 8#3 52 79.09 0.00 14.92 1.02 0.15 0.12 95.30 100.3 35 Run 9 0 72.59 0.08 11.52 1.68 0.59 0.00 86.5 100.1 8#1 3 68.42 0.00 12.90 1.31 0.20 0.03 82.87 96.5 ~#2 7 70.5 0.0 13.2 1.0 0.2 0.1 84.8 98.4 8#3 22.5 70.86 0.00 12.99 0.76 0.16 0.19 84.95 98.6 40 Run 15 0 80.93 0.09 12.97 1.87 0.66 0.00 96.5 99.1 8#1 2 83.36 0.00 13.83 2.01 0.66 0.00 99.8 102.6 * -~t~
~ AI~ c~t~lyst EXaMPL~ 17 ruKI~l~ATION OF 9,9-BIS-(4-HY~v~xY~n~ ~)F~ORENONE
A. PK~ lrl ATION FRO~ M~.~T~T.T~M~ ~T.~RTnT~
A ~ynthotic re~etion mixture (105.5 ~: 63 ~e ~ ' by woi~ht, 66.5 50 of phonol~ 20 Acrc~nt by wQi~ht, 21.1 ~ of 4,4-BRPF ~nd 17 ~ ~L by w i~ht, 18 ~ of water) wa8 ~laeed in a 500-mL round-bottom th~
flask equi~-d w$th a ~--t;~ mantla/Variac, 1'- -tor, ~tirrin~ bar and di~t~ t;A~ arm. A ',~1- o-Wateh" wa~ u~ed to control t~ _~~turQ of the liquid in the ~la~k. A ~o~arate 1 hr t~r wa~ plaead in the d$s~;ll~t;~~ towor to monitor t~ t~a in thc va~or phaca.

CA 02230272 l998-02-24 W 0 97/08122 PCTAJS96/l3683 The mixturo was stirred and heatOd at ~ ' ant prO_8ur- up to a t~ _- atur- of 160~C, during which time dist;ll A~; on of phonol ~nd wat-r occurred Analysis of the rOaction mixture ;nra;~-t-~ the phonol BHPF mass ratio wao 1 1 The rOaction mixturo, whilo still hot, wAs 810wly addod to 176 g of BHPF-saturatOd methylene chlorid- and the resulting mixturo wa~
~lowly swirlod to produco a h~ a #olution, cl0ar and yOllow in color Tho mixtur- wa8 allowOd to cool to room t _- ~tur- which causos cryst-ll; 7~; A~ to occur The rod-lik- crystals ~.~~ - in the ma~ma were analyz~d by microscopo prior to filtr_tion A~L-- t~ly 80 p~ -O L o4 th~ crystals vl-wod wore longer than 100 microns nd havo a diamet-r bcL~-n 20 and 50 micron~
Tho crystal magma was filterOd on A medium porosity gla~s frit, using a vncuum ~ ~ ~d by wat-r jet The ~iltor cako was al;o~l-f t ~hoa 15 with 79 g of BHPP-satur_t-d methylOnO chlorid- and then 72 g o~ hot (90~C) w_ter A~t-r drying _t 65~C in air ov~-n;~h~, 12 9 g of white ~Lvd~vL was ~C_v~L~ a, T~ol~A~tqd yiola wa~ 61 ~- ~ and HPLC purity was 99 8 -~L
B ~lrTr~S WITH S0DI W nIc~ ~ SOL~TION
Synthotic roaction mixturO (105 5 g as in Exam~le 17A) was with 100 mL o~ a 2 ~- .~L by woight a~ ~_ ~ soln~;~~ o~ sodium ~ic--~An-te Tho mixturo was agitated and th-n the or~nnic and aA~uoou~
lay rs w r- A~ to ~-parat- in a separAtory funnel The organic layor wa8 dr_wn o4f This proc-s~ was p-r~ormed a total o4 4 timos Washod 25 r-action mixturo (85 2 g 58 _-~.~t, 58 g of ~h-nol; 17 4 _ ~a~L, 17 g of 4,4-BHPF and 25 pCl _~L, 21 g o4 w~t-r) w_s placod in the ap~aratus, d-~crib-a in ~ _~o 17A
Th- mlxtur~ wan stirr-d and hoat-d at a prossuro of 80 to 100 mm Hg, u~ to a tr _~ ~tur- o4 160~C, duriny which tim~ distillation o~ ~h-nol and wat-r ocv~ ~d BHPF-~aturat-d phenol (100 ~) was then adaOd to tho r-act~on mlxture and th- t~ _ aturO of the mixtur~ was controllod -t 65~C
Cry~tAll;~-t; An b-gan within 1 hour The slurry was ~tirrod o~ rniuht, aft-r wh~ch tho rod-liko crystals ~l_- 1' in tho magma woro nnalysod by miv~ b-fore filtration A~prA~; ~ly 30 p~lc~t of th- crystals 35 ~i-wed ha~e a length grOater than 100 micron8 and a diam~tor b_L ~ 10 nd 30 microns CA 02230272 l998-02-24 W O 97~0g122 PCTAUS96/13683 Th~ crystAl magma was ~iltor-d on ~ m~dium poro~ity ~lass ~rit usi~g vacuum producod by a wat~r jot Tho brown ~ilter cake was ~nhsd with 200 mL of room-t~ _~ aturQ water and th~n stir-wa~hed with tho samQ amount of watQr Tho brown/boiu~ cryst~ls worc th~n wn~hod with sHpF-~turated m~thylon~ chloridQ and th~n with ethylene ~ o id- Aft~r drying at 65~C in air overnight, 7 g of brown ~ vl~L
wero ~a~ The ;~ t~d yield was 47 ~v~a~- and ~P~C ~urity was 99 7 ~- __.L
C DISTILLATION OF PHENOL, CRYS~TTT~ION FROM TOLUENE
10 Synthotic r-action mixture (149 ~ 17 5 _~ c~ by weight, 24 g o~
4,4-BHPF; 95 g of phonol and 30 g of water) w r~ charg d to tbo r~actor, d-scrib~ in ~xampl~ 17A Tho mixturo w~s 3tirr-d and hoated at a ~ro~ur- o~ 80 to 100 mm H~ up to a t~ tur~ o~ 160~C, durin~ which timo dist~ ti~ of phenol and wator oc~ d until the ~henol B~PF m 88 ratio wa~ ~ to L~L - tely 1 1 Th~rQ wa~ no incr-aso in adduct ~.. ~.1 LCLtion~
Tho rosulting mixtur- was added whilo 8till hot, to 121 g of BHPF-~aL~ cted tolu~ - The rosulting ~ solution was ~ a d to cool to room t~ _- ~L~ro, during which cryst~ll;7-ti~ oc_~ ~d Tho r-sulting ao rOa-lik. cry~t~ls p ~ ~ in the magma w re analyz~d by mi~ o~co~u prior to ~iltration A~ - ~ly 20 ~e~~_ L of the cry8tals vi-wed had a length ~ -t~r than 100 microns and a ~;~ er bet ~ 10 and 50 micron~
Th~ cry~tal magma was ~iltorod on a m~dium ~orosity glass rrit uning a vacuum ~ l~-d by a water j-t Tha pink ~iltor cnke was treat-d 25 5; ' 1 ~- ly to other ~ Aft-r drying at 65~C in air ov~-~ig~f, 18~5 of pink product wor- L~_~. ~d J~-~at~d yield was 77 ~ _~t and HPLC
purity wns 98 1 ~_.~nL
D DISTILLATION OF PHENO~; cRysT~TrTy~TIoN FROM ~U~T.~.

~'Ur.~)}2TnTC
30 Ph-nol and fluo.. r - w ro - ' ~' in tho ~-es__~n of 3-~ a~L~,~ 1 f~; c acid (~PSA) to producH a reaction mixture which, aft-r ~i~g to remove th- acid cat_ly8t, co~tA;~d 20 w i~ht ~9 of 4,4-BHPF, 64 wei~ht ~- ce~L of ph-nol and 16 weight ~ ~ t wnter Tho r-action mixtur- Wa8 di~tillod under wat-r jet vacuum (a~ - tsd 80 mm H~) up to a t- _- ature of 160~C to yi-ld a residu-, c~tA;~;~g ~- -l t~ly 50 wei~ht ~ ~. of phenol and 50 weight ~-rcont of 4,4-B~PF, that is, a 1 1 ~h~nol 4,4-B~PF ma~s ratio -n-f W O 97/08122 PCT~US96/13683 The 1 1 mixtur- was cooled to 120~C and thOn pourod into 176 ~ of room t~ _- ,ture mQthyl-nQ chlorid-, that had been proviously saturated with 4,4-B8PF This re8ults in a cl- r ~ ~ solution at re~lux, wh~ch wa~ ~lle~' to cool to room t~ _~ atur~ ThQ cryst~ ed mixture wa3 ~ilt-rOd undor vacuum at room to _-~at~ ~ The filtor cake was ~;~pl~c ~ wa~hQd with 79 g of BHPF-8aturated methyl-ne chloride (no ~t$rring oi tho filter cake durin~ the wa~h) and thQn sti~ d with 72 g of hot water (90~C) ThQ reaultin~ whit- filtor cakO w~s driod in air at 60~C to provide a yi-la of 61 woi~ht ~B' -_~L Or the 4,4-B8PF orig;~lly d-t-ctod in the r-action mixture ~ REMOVA~ OF P8ENO~-WATER AZEOTROPE
A~p v- t~ly 380 g of a r-action mixtur- si~;l~ to thnt Of _le 17D w r ~lowly dripyQa into 4 B of wator at a t~ ature of 84~C at a prQ~ur- of 300 mm Hg This dilution in water wns ~c~ _~~;e~3 by tho r moval or phenol in the form of a wat~r/ph-nol ~-,L ~ ThQ wator-insoluble mat-rial~ th n procipitatQ from the liquid phase as a white powd-r ~p - t~ly 64 ~ of "cruae" BHPF was obtainod in this mannOr The "crud~" BHPF CA~ ~' all th impuritio8 ori~;~71y ro~t-;--' in thQ
r-action mixtur- The ~roduct wa8 filterO-d, washed with bA~ 1 ;n~ wat~r and 20 dri-a in air at 60~C to provide a .ec~ ~y of 96 wQi~ht ~7. ~ of the 4,4-BHPF originnlly aot-ct-d in the reaction mixtur~
F CRYS~TTT7'~ION FROM TT~TT~ROEY~P~r'~-~NE
A reaction mixturo (55 8 ~ 63 1 ~e ~_ t by w~i~ht, 35 g of ~henol;

14 ~_ c_nL by woi~ht of 4,4-B~PF and 23 ~e ~o~t by w i~ht, 12 8 ~ of wat-r) was cLa.~_' to a 250-mL round bott_m flask, otherwi~e fitted out as in _3~ 17A Trii~ (TIPB, 106 6 ~) was add-d to the mixtur- in thQ flask, a~ a renult of which thOe mixture ~e~ ~tOs into two ~h~-~, of which tho yollow reaction mixture was thc lowOr The mixture wa~ ~tirrOd and heated under vacuum, ~ by wator ~et (ca 80 mm) After rOmoval of wat-r at 50 to 88~C, the mixtur- appQar~d ~ ~e - ~ Th mixture was ~tirroa and ~ to cool Solias ap~ear when the t _J~r~L~ e r-ached 70~C Tho m$xture was ~11_ d to cool to roo~ t- _~ ,turQ ana filteroa on a gla~n frit undOr vacuum ThQ white sol$ds on the frit w ro washod with TIPB Th~ f$1t-r cako was left ov~r~;g~t und-r vacuum (water j-t) whilo air was ~ullea throu~h thD filt~r cakO

CA 02230272 l998-02-24 Wo 97/08122 PC~nJS96J13683 Analysis of the r~sultin~ mother liguor showed that littl~ of tho ph-nol in the ~eod was ~. v.~ ~8 ~ ro~ult o~ dis~ ~. The 4ilter c~k~ c~~ 4.2 g of whito, uoarly free-flowin~ product (54 p~ L
~c_v~ry, 98.8 ~ c~t purity by ~PLC).
O. DISTILLA~ION TO REMOVE PHENOL; CRYS~TTT~IoN FROM M~VT.~.
,~ ~UT.I~T~ TnT~
A roaction mixturo (98.8 ~: 61 ~ ~L by wei~ht, 60.3 g of ~hnnol;
19.4 pc by weight, 19.2 g o~
4,4-~PF and 19.6 ~8~C~L by woi~ht, 19-4 g of wator) W~8 char~ed to an ~p~aratus, do3cribQd iA Examplo 17F. A colloction flask was attached to tho di~t~la~j~n arm and a~ e_L~ to a vacuum source (a wator jet). Tho t _~ aturo ~ot point was adjustea to 100~C and ~-t;~ bo~n.

~omp (~C) Observations/Actions 50_55 ho;l;~ g ana aigt;ll A1;~ occur 100 ~light b 1~bl;r5r ~ot point raisoa to 120~C
105 di~t;~l~ti~ restarts 115 ; ~ o; 5~; f irAr~t aist~11Atj~
~et point raisoa to 140~C
120 visJorous bQ;l;~g, l$ttl- ais~; 1 At~
va~or t~oraturo risin~
121 vigorous ho;l;rçr, diE~t;ll A~ starting, vapor t~ _ = ature 115~C
122 vapor t- _- tur-- 118~C
}~re ~k vacuum and romovo sam;plo 34 Si of dist;ll Ate ~ll~cLod, mixturc in pot _as phenol:B~PF ma~s ratio of ca 2 1 r~c~ c L vacuum sourc ~ nd, . -~ h~At;r~5r 124 vapor t~ raturo was 119~C, dist;ll~ti~
~t Irts 125 vapor t~ _ ~turn was 119~C
bre~k vacuum ~na ~le mixturo 13.9 g o~ di8t~llAte coll - cL - d ~--t point 120~C at al ~-~ ic pros~ure c_ - L vacuum and ~ hoating ~honol B~IPF 1 6 1 mass ratio in pot 129 vn~or t~ _- .tur- 121~C
~li8t; 11 A~ starts 131 vapor t~ _- ~ture 123~C
stop ol?oration, r~movo ~am~le 42.4 sr remain in ~ot; mixture in ~ot _a8 ~_enol:B}IPF ratio ca 1.12:1s 6.7 ~ o~ di8~ te Q~l l ~_ ~ea WO 97/08122 PCT~US96~13683 Tha pot r~siauQ at 110~C wAs add-d to 172 g of fro~h d ~l~dc mothylonQ chlorido in ~ bottlo Tho addition was done ~lowly in order to avoid _ c-q~ive flA~hing or bo;l ;n~ of th- methylene c_lorido The r-8ultin~ mixtur- ~ ro or 1O88 separatod into two layQrs, o_ which the upper layer W~8 richer in the ~honol BHPF _ _ The mixturo wa8 - ~wirl-d and b-came h ~ e~8 Th- bottle wAs seal-d and placed in a ~_n of cold wat-r (~ t-ly 10~C) Tim Ob~or~ations/Actions (hr min ) lO0 08 ~ _onc.~s yollow solution 0 18 ~ e~u8 yellow ~olutiAn 0 56 yollow oolu~i~n, ~osP;~ly small crystal~
1 18 samc 2 00 ~ame 152 24 cryst~ll;~A~ti~n ~n~o;n5, quit- ~ fQw crystAl8 17 48 solid yellow cry~t-ll;nA mass breaks u~
~nsily filter und-r vacuum t_rou~h glas~ frit to obtain nl;gh~ly yollow crystals; ___~ ~L
158 8g of yollow mother liquors Tho cryst~ bottl- was rinsod with 29 7 ~ of fre8h methylenQ
chlorido (not all ~olids ais801ve), the rRsulting mixture being us-d to A~O~1A- ' wash the filtor cakG, which ; ~ slightly in color The ~iltor caka was slurry wa~hod with 49 4 g of _rosh methyl-ne chlorid~ nnd the r-~ulting ~lurry wns ~iltorod und-r vAcuum Th- color of tho filter cako was ~n~A~
The ~iltor cak~ w~8 ~i~l A- wa~hod with 33 ~ o_ cold water, without a chango in tho color o_ the cako Tho _iltor cako was slurry-wash~d with 40 g o~ ~oil;ng wator, without a chango in tho color of the cake Th- cako wa8 dr~-d in air undor vacuum _or ~ - tely 2 hours, tran~forrod to a watch glass and driod in an oven ov~T~;ght at 65~C The cako w~8 sl;gh~ly yellow Tho mass b-l An- ~ for the ~ =-~8 was WO 97/08l22 PCTnJS96/l3683 of BHPF
19.2in ~nitial mixtur-8.lin mother liquors at ~nd o~ oporation 9.1;~ t~' ~roauct 1.7in wash 0.3~ co~t~ ~or H. CRYS~TTT7-~IoN FROM Dl~n~Y.M~
1. A mixture of 28 ~ of DPM, 17.5 g of ~h-nol, 5.4 ~ of BHPF
(98:2 4,4- to 2,4- isomers, by HPLC) nna 12 mg of MPSA was washed w~th water. The rosulting layors wer- s-paratod ~nd the wator layor wac . y~d. Phenol was distilled from the or~nic layer to ~ive a mixture e~t-;~;~g 21.8 ~ of DPN, 3.8 ~ of ~henol and 5.4 ~ of BHPF. Tho mixture wa~ to bo cool~d to room t~ _- ~L~ a to ~ive an off-white precipitate~
whieh wax filt-roa and wash-d with DPM. The washed cake was dri~d in an oven at 60~C to giVQ 6.1 ~ of mat-rial, c~i~;~;~ 70 pe _~L by woi~ht of BHPF and 30 ~ . - by w i~ht of phonol. The mixtura wAs strippod at 140~C
under nitro~en at < 80 mm Hg to ~ive 4.2 g of white 301id. The solid, by ~PLC analy~is (analytical method 5), c~~t-; ~~ 99.6 ~ c_nL by ar~a Or the 4,4-i~om r ana 0.04 ~ by area of 2,4-isomor.
2. A r-action mixture from 15:1 phonol:fl~v ~nv~G~ c~t~ ~g 34.5 ~ c~nt by wei~ht of phenol and 10.5 ~9 ~nt by wei~ht of BHPF, wa3 tod with 55 ~2'~ ' by woi~ht of DPM. Phonol (80 ~e~ -- of that $niti~11y ~l~- , t~ ~turo 105~C, 4.5 mm H~) was 1- v~d by di~t~ t;~ to yive, after cryst~ll;=-tio~ from DPM, white BHPF meltin~
at 221 to 222~C. Th- 1~ _v_l~ of BHPF was 78 ~el -~t. Th- material cA~t~ 99.6 ~ . of the 4,4-i~omor by HPLC.
I. CRY8~TTT7~ION FROM NEAT PEENOL
P~onol was distillud from the r-action mixturo8 to ~ v~c~ mixturos, eA~t~;~;ng l-~8 than 50:50 phenol:BHPF by wei~ht. The r-~ultin~ materials can bo wanhoa with mothyleno chloride. Th- products were ;~ist-nt in color and e~t-;~ ~mall cry~tals, usually of the size of 10 to 70 micron~.
J. rn~- ~l-.ATION OF BHPF BY ADDl.lO.. TO WATER
Addition o~ r-action mixturo~ to koili~ wator or stoam z- ~d 30me phonol a8 a ph-nol-wator A-H_LL~o. Tho r-~ulting ~roduct retained most of th~ : - ~ i n ~ ~ and adducts ana co~ ris-d vory ~mall cryst~

wo 97/a8122 PCTAUS96/13683 th~ ~izc of the order of lO to 20 microns. The purity wa~ 97 to 98 ~e ._ Analytical data (HP~C) was given in T ble VII for S _le8, ~ ed ~ in accG d~.co with the practice of thQ invention and for - - cially-av~;l~hl~ material~.
K. REMOVAL AND k~-uv~nr OF PHENoL FROM BHPF REACTION ~n~
Excoss phenol was 1. v~d from a reaction mixture to a l:l ratio of phenol:BHPF usin~ a fA~l;n~ film ~v~y~l~tor. This was ac~ at 120~
C/120 mm H~. At thi3 t~ _ ~tur-, B~PF ~ol~ ty in ~honol w~ 45 ~ ~QnL.
After removin~ phenol, the BHPF-~henol mixture was ke~t at 90~C and stirrQa prior to adaition of methylene chlorido or other cryg~ll; ;ng ~olvent.
B~PF was cryst~ at room t~ ture under a nitrogen -y~d. A
batch cry~t~ w~ cool-d to 5 to 10~C for several hour~ auring which BHPF cryst~ sOlia BHPF was separat~a from the rosultin~ slurry u~ing a batch yr~s~ure filt~r or ba~k~t ~ilter. Opti~-lly~ a pressuro ~iltor can bc uuod. Nethylene chloride or other solvQnt can be recycl-d to the p .~8.
BHPF crystals wer~ dried undor vacuum.
B~PF from 8losg (R; ~gh , ~1~ T_Q xample ~v~lu~t~1 was a ~ry solia, from lot number 9307-03.
BHPF from Isonova (Austria): The sample ev~ tr1 was ~eqi~~t~
"Isonova lO/93".
BHPF from Rut~r~-Nea~e (Stat~ Coll~_-, Pennsylvania): The dry ~olid was from lot numbor 9306099.
BHPF from I~ovolta (~ , Austria): The shmple, u~od a~ standard _or th- comparative ~tudie~, was roc~ived in 1988 ana was ~-sig~-t-~

"Isovolta 1988."
Analy~is of the r-sults in Tablo VII s_ows that 4,4-BHPF, ~urifiod by ai3t;1~tivQ removal of phenol:water azeotrope and ~xtraction with m~t_yl~n~ c_loride, produces high ~urity BHPF.

TABLE VII
SamplQLot No 4,4-BHPF 2,4-BHPF 2 3 Other Total Sourc- BHPF Impur Aaa.
810x~9307-03 100 -0 0 0 0 I~onov_ 10/93100 0 0 0 00 ~Cl~Ex 17D 99 94 0 06 0 06 WaterEx 17E97 591 87 0 40 0 14 2 41 ppt'd I~ovolta 1988 100 0 0 0 Rutg-r~ 9306009999 28 0 58 0 14 0 72 Noa~-DPNEx 17H 99 6 EXANP~E 18 ~RR~SI~M ~ ~l~
A REACTION MIXTURES FOR BHPF PROCESS
Corrosion t-~ts werQ ~erformed using A LC~ ~-- ' atiVe r-action mlxturo for tho c~~~tion of ph-nol with ~l OL~e usin~ various cataly~t~ The t-st~ were done usin~ motal ~ 3 81 cm in len~th, 10 1 59 cm in w$dt_, 0 32 cm thick, and havin~ a 0 64 cm hol- cont~rod in ono ~nd Tho _~ wHre ~ol~At~-~ from ~ach other and the ';~ rack u d n~ polytQI A~ ~ro~thylene ~h~Ul~r ~ Tho ~ wer~
~ d to both the liquid and vapor pha~e~ of ~ach t-st c-ll The contA~t~ o~ tho c~118 w-ro ~tirred c~ o~ly and wer- ~A;~ at the nel-ct~a t~ _- ~tur~ u~ing YSI tffmy-rature controll-rs and C'' ~OT.~
~-a~;n~ -lor Th~ t-st~ w-re run under a nitro~en ~ad T_e chloride co71 ~t- o_ the t-st mixtur-~ was ~500 ~pm Th~ tost~ woro run at 65~C _or 13 day~ (312 hour~) C _-~itions te~ted and rosults are ~ in Tabl~ VIII
Rosults in Tabl- VIII d~mon~tratQ t_at tho r-action mixtur~s usea w re c~;do ~bly l-ns corrosive than co v~~ Ally u~o~ roaction m$xtur-~

CA 02230272 l998-02-24 W 0 97/08122 PCTAUS96n3683 TAB~E VIII
Cn~OSIn~ i~ ~lN~ FOR BHPF REACTION ~l~ ~K~S
A R~actor Mixture 90 2 ~orcent of Phenol, 8 3 ~orc~nt of Flu~ ~ ~o, 1 5 ~L~ - nL of MPSA (by woight) Corrosion Rate (mpy)*
M-tal~iquid Vapor R~
316L ~8** nil*** < 0 1 uniform corrosion 904L ~8nil 0 1 ~;f~~ eorrosion 2205 8Bnil < 0 1 unifonm corro~ion 10 254 8M0 8~ nil nil ,,~;c corro~ion B Water Fxtraction Mixturo 8 0 ~lccnL of Phenol, 91 ~eY~ L of Water ana 1 0 porc~nt o~ MPSA (by weight) Corro8ion Rate (mpy) M-talLi~uid Vapor R _k~

15 316L ~80 1 0 1 ~;f~ corrosion 904L ~8< O 1 < O 1 uniform corrosion 2205 ~< O 1 ~ O 1 uniform corro~ion 254 SMO ~ < 0 1 < 0 1 uniform corrosion C Rocyclo C~-~trat~ 29 87 ~c~ of Ph-nol, 69 23 ~cL~nL of Water 20 ana 0 9 ~ c~nL of ~PSA (by wei~ht) Corrosion Rato (mpy) MotalLiquia Vayor R~ _k~
316L ~8 0.1 0.1 uniform corro~ion 904L ~8< 0 1 < 0 1 ~;' corrosion 25 T~ol 625< 0 1 < 0 1 ~;f~ corrosion ~a~telloy C-27 0 1 < 0 1 uniform corro8ion HastQlloy G-30 < 0 1 < 0 1 ~;f:_ corro~ion * mpy 3 mils per year; 1 mpy = O 00254 cm/yr ** 5~ = stainlo~s st-el *** nil ~ < O 01 mpy B REACTION rll~ UK~S FOR BI~r~NuL A PROCESS
A mixtur~ c~nt~in;ng 94 35 porcont by woight of phenol, 4 15 ~eL~llt by woi~ht of acetone and 1 50 perc-nt of MPSA was ~valuatod as in Exam~l~

Th- fo~low ng r-sults WorQ ~t-in~d Corrosion Rato ~etal Li~uid Vapor 304L ~ ~a~s ~ass pasg =
316L ~ p~8~ pa~s< 0 00254 cm/y ar 904L 88 pasD paDs a205 ns pa~s pas~
825 N-i p~88 pas8 Tho corrosion rat~s in both the liquid and vapor pha~es was < 0 00254 cm/y-ar Tho corro~ion was uniform Tho rat- of corro~ion was bolow that for cv~v~8i~n-l reaction mixturos for making b;~rh~n~l A

A PR~PA~ION OF BI~r '~ A ~SING PMBSA
Ri ~ A was proparod from 14 1 ~henol acoton~ (molo ratio) at 50~
C, cQ~t~in;~ th~ i~;iic~t~ ~ r of nolid cataly~t Th proauct distrih~ti~ was dct-- ~n~ by analytical mothod 2 The PMB8A cataly8t of Examplo 9B, at a l~vol of 6 ~e~c~L by weight, givos 75 L ~ ' Cv~v~ iOn aftor 5 hours Tho ~roduct c~"~t~ 99 0 1 0 of 4,4 2,4~ (ar-a ~- c ~) Tho PMBSA wa~ ~_vv~lJ~ and rousea in a ~ocond cyclo The c~lv~LDion after 4 hourD was 60 ~ c_~L Tho proauct c~nt-;n-~ 99 1 0 9 of 4,4 2,4-; n ~ (~r~
DOWEX~ 50WX4, from Tho Dow C' c~l C _ y, (35 ,~ c by woight a~ dry ma~), promot-d with 25 ~ by woight of 2,2-dim~thylth;~-o~ , was u~-d in a ~ oxp-rim nt The c~v_~dion aft-r 4 hour~ was 43 ~_~c and tho yroauct c~nt~in-~ 98 0 2 0 (ar ar-a ) of 4,4 2 4-ir ~ D .
Th-so oxp-rim nt~ showod that a polymer-~ ~o Led catalyst of this inv~ntion gavo high-r c~v~L~ions and ~ higher yi-ld of 4,4-isomer than a ~L~ r- -~ivo prior art catalyst B REACTION ~SING P~BSA IN A DOWNF~OW CN LNUUUS REACTOR
Tho r-actor co~ri~oa a vertical tubo~ The bottom ~art of tho tub~
wa~ filloa with glass b~ad~, on top of which was ~rovid-~ ~ bod Or PMBSA

.

CA 02230272 l998-02-24 Wo 97~08122 PCT~U596/13683 catAlyst ro~in Tho L~ ~ of the tube was fillod with ~lass b-ads The tub~ wa~ fitted with ~ prQ~surs ~au~e, a pr-~sure ro~ulator, h--t;~
mean8 ~Yt~ to the catalyst bod and iood moan~ at th~ bottom of tho - t~ 7~ roactor for intro~u~;~ tho ph~nol and flUV ~~v~.O reaetants The ~Ooa was pr-pared in a e~~ , provided wlth a nitro~en stream and _ hoated - e_n~lly by a fluid A valve was ;nt~ -~;ate th~ food pr-~aration e~~~ r and a ~ump for introduc;~ the f~od into tho bottom of tho r~actor A roliof ~alvo wa~ ~lacea ~L~ the ~ump and the roactor Tho f-ed wa8 i~L~od~ced into the r-actor at a ~ _~-t~ r~to and pa8~8 u~waraly t_rou~h tho lower bod of ~lan8 boads, w~ich functioned as a pro-hoator, throu~h tho catalyst bod and the upper bed of ~la88 beads, wher-u~on the product wa8 . vel from the to~ part of the roactor for analysis or further ~roce~sin~
~vp~-; ~ usin~ 21 1 ~h-nol fluo _~v~e and P~BSA catalyst gave tho following ro~ults a~ a function of flow rate and reaetion t~ t~ e 49 C 69~C
Conv r~ion (%) 80 lOO
BHPF in ~honol (%) 14 16 20 Productiv~ity (~ B~PF/g eat/h) 0 57 0 44 Seleetivity (% 4,4-BHPF) 98 97 Flow rate (~ foed/g eat_) 4 39 2 71 Tho~o ox~orimont~ ~howed that lower roaetion t~ ~ture~ favored proaucti~ity and selectivity toward 4,4-BHPF, ~- _ ;od by aecreased cv~v~,~io~
C CONVERSION OF ACETONE AS A FUNCTION OF REACTION TE~PERAT~R~
Phonol-aeetono mixture~ (6 ~el~nL by weight acetone) were c~ v~,Led to b;~ 1 A, using MPSA a8 catalyst in batch reactors The following rosult~ w~r- obtain-d (T blo IX) TAs LE IX
Acetone Convornion 25~C~ 35~C~ 55~C~ 65~C 75~C
Time (min) 0 0 0.10 0.22 0.25 0.26 0.40 0.48 0.49 0.04 0.42 0.59 0.62 0.67 48 0.65 0.69 0.77 0.06 0.56 0.69 0.75 72 0.82 go 0,09 0.79 0.85 0.89 120 0.13 0.72 0.83 0.89 0.94 180 0.20 0.80 0.95 0.96 240 0.26 0.97 300 0.98 360 0.32 0.99 * mixture c~ d 2 2% by woi~ht of MPSA and 2-3% by woight of wat--r mixturo cA~t~ 1 3% by weight Or MPSA and no added wat--r D REMOVAL OF MP8A CATAI YST USING ION-s!Y~ RESIN;
PURIFICATION OF CRYS~Ts T~ BIS~ ~ A
C~ A~r~--t;on of phonol with ac ton (4 ~-~c_~L hy wei5~ht), cA~ g 2 by w--ight of wator, usinsJ 2 5 ~ "t by weight of MPSA, wa~
don-- at 35~C in plu~ ~low moaQ, with a 3-hour r~ui~ timo Cry~t~ t;r- of l; ~ph~ A oc~ _d in the roactor The crystal~3 w ro ~-ol~t~d ~y filtration and ro~iA~ ~c tone in the moth--r liquor~ wnE~
r-cycl-d to the ~ vv at 50~C TEIE ~thor liquors wore dried at 50~C (20 mm ~Ig? and the cyclo was ~ etv~~t~ after addition o~ m~ko-up f--od A~out 90 1, c of tho ~Icotone was cv~ v, I ed to ~;F~F~ -1 A por pa-- ~
Catalyst wa~ v~d ~rom tho product by first moltin5r the crystals nd ~ ~7';"sr tho r-~ulting oil with water, and thon ~xtracting the or~anic layor with wat--r, which ~ r tho acid c~ ation below lOO ppm ft~r thro oquili~rium ~tagos The ~ ~ cataly~t was ~ v_~ usinlJ Ln ~nion ~ a~ ed (<50 p~nn, the limit of dotection) W O 97JO8'122 PCT/US96~136~3 Bi8~henol A, i~ool~t~ by a sin~lo crystA~ tion st~p, w~8 of higher purity th~n ~roduct~, ~n~rally ~~tA;n~d u~ing two crystAll;~tions. R; o~h~l A ;~l~ted. by a sin~le cry#tAl1;7AI;~, ~ c~~t-;~d a ' of 1200 p~m of 2,4-bisrh~~~l. The proc~ss of this invention thorefore ~ ;f;~n thQ ~o~ti~~ of high purity of ~;~F~: -1 _ A, ~l~~~t~ ~At~ by oily hi~her ~ te~.
EXA~PLE 20 SOT-ID CATALYST PREPARED FROM POLY~Yn~ BY ~T~-yR~mIoN WITH A~YL RT~MTn~
SULFONATION AND T~T~-~IOU
~. Poly~L~,_ ~ (Amborlite~ XE 305) wa~ alkylated with allyl b ~ Ag in the ~l~P~ ~e of trifluo ~ ~~;c acid in 1,2-aichlol~ ~ano at 50~C, gQner~lly in aCcv~a~c~ w~th Tomoi et al., "A
Novel One-~ot Sy~h~ of 8~cQr- modifi~d Polymer Su~ort~ and Phase-tr~nsfer C~talytic Activity of ph~.h....; Salts Bouna to the PolymQr 15 8~ Lsn, RQactive Polymer~, Volume 3 (1985), ~a~Q8 341-349, to produce a matcrial having 2-bromo-1-methylethyl chains. This material was sul~AT-~, ~e~-rA~ly ~t th~ ortho-~osition with .~e_L to the 8ide chain, by t~_~ with chloro8~lfo~;c acid. The r~8ultin~ ~ulfonyl chloride wa8 ~o~v.~Led to a sodium ~alt by reaction w~th sodium ao hiCA~ho~At~. The material wa~ v~rLod to a c~--9~ -A;~ thiol by r-action with ~odium ~h;o~ei~te nnd c~v~L-d to a co ~ A;~ acid by acidic hydrolysis. ~at-ri~ls Vl~a ~ co. e~d to 28 and 48 ~ nL of ~lkyl _~Lan functi~l;ty (XEMSA).
B. Tho thus-pr-paroa ~olymer~ (XEMSA) w~re u~d nt a l-vel of 6 ~l-.~L by waight ~or roaction ~_~.._ phonol and fl~v~e~one (20.8:1 mole ratio) at 50~C. Product ~ _-8ition wa8 detr- ~d by nnalytical methoa 3.
Tho polymer co~;~;~ 28 ~e~c~L o~ alkyl ~ ~vt~n funct;o~l;ty givos 75 v~ L c~v_~ion nft-r 5 hours. Th- product aistrihnti~ was 96.8:3.2 of 4,4:2,4-; - ~ (nr-a v~
The v~od~cL c~~ 48 ~-~c ~t o~ alkyl --~Lan runct;~Al;ty givos 15 ~ ~v_ ~ion ~rt~r 2 hours. The product aistr;huti~ wa~
96.8:3.2 of 4,4:2,4-;~ (ar-a ~_l~nL).

CA 02230272 l998-02-24 I~ SITU MET~OD FOR PREPARING THE POLYMER-xu~PO~ MERCAPTOSULFONIC ACID
CATALYST (PMBSA CLASS) A SULTONE ~T.~VT.~ ~ION
S To a mixtur- of 1,4-b~ ultono (30 0 ~, 220 0 mmol, 1 00 ~quival-nt) ana ~oly(vinylbon~ylchlorido) (PVBC, 33 6 g, ~ - t-ly 220 mmol, 1 00 oquival-nt) of chlG-~ hyl group8) was addod via a ~ 1 A dry t-traLy~ ~f~L~ (600 mL) una~r a nitrogen a~ a Tho mixture w~s ~tirred at room t~ _ ~ture until a h ~ n 801ution was obtainod Tho ~oluti ~n was thon coolod to -78~C u~in~ a dry ic-/nc~tonQ bath n-Butyllithium (2 5 molar in h -~, 88 1 mL, 1 00 equivalont) was aaa-d nlowly dro-ywin- to tho -78~C ~olut7~ of 1,4-but -nultono and ~oly(vinylb-nzylchloridc) via an addition funnel ov-r ~yy~-;~ trly 2 5 hour3 with vigorous stirrin~ A whito 801ia bo~ins to procipitato from tho roaction miXturQ as the n-butyllithium addition was bogun, w;th procl~itation c~t;~;~g throu~hout th- n-butyll~th~um add~tion y~riod By the ond o~ tho ada~tion, a largo amount of whito solia has formod within the r-action ~';
Th~ r~action mixturo (~lurry) was A ll ~' to 810wly warm to room t~ _- ~turo in tho cool;ng bath (ovor ~yy - to~y 3 to 4 hours) ana was ~ to stir at room t~ ~turo overnight The white ~-~ ~7itatQ
which has form d in the roaction mixtur- auring th- n-butyllithium ~ddltion yoriod ~ ol~hle a~ th- mixturo ~c~-- room t~ _- ~turo Th- whito (;~-ollhl~) 801id was ~Oa by vacuum filtration The yolymor can b- washQd with wat-r or wator can be aadoa to thQ THF/polymer slurry yrior to ~iltration Ada~tion of wat-r somotim 8 r-~ults in in~.~a~;~g tho tim r-quirod for filtration Tho 801ia was 81~.-y-~ ~h~d with THF, then with mothanol and ~inally with methylon~ chloriao (c-~ni~g uomo _ 11;~g) The solia wan dri~d ov~rn;~ht in a vacuum ovon to ~rovide 53 4 g of a whit- solia sultono-runctional yolymor B T~T~T ~ION
To th~ ~ulton~-_unctional polymer from abovo (110 0 ~ from two h~t~-~-, ~y~. - --ly 0 440 mol of sulton-) was addQd nitrogon-~aturntod THF (500 mL) In a ~e~- ~t- r-actor, a 801~1;~ of lithium 1h;~-~atat- wa~ -yr-yar-a by the dro~7wi~0 aaaition of th;ol~tic acid (49 8 g, 0 650 mol) to a slurry of lithium c~-ho~e (24 2 g, 0 330 mol) ~n water (100 mL, nitro~on saturatoa) The lithium th;oAc-tat~ solution W O 97/08122 PCT~US96/13683 wa~ added 810wly via ~nn~ to th~ polymer/THF slurry at such ~ r~to th~t th~ t~ _- Aturo docE not risc abov~ 35~C. Th~ yolym~r ~wells substAnf;~lly durirA~ tho lithium ~h;o~etate adaition. After the lithium th;o~etate ition wa8 complete, an additional 350 mIJ of water (nitro~on saturatoa) was addod. The polymor sw~ to a volum~ of ~ t~ly 1 L. The mixturo wa~ ho~toa to 50~c, nnd was a~low_~ to roact ove ni~ht~ The ~el-liko ~olymer wa~ thon filtorea usin~ a coar~e ~lass-fritted funnel. The polymer w~s washed with wat-r, thon with moth~nol, th~n with mothylono chloride, and ~inally with ~dditional wator. The polymer slurry ~ometimes filtor~ vory slowly durin~ thQ ~iltration process. In this case, the W - ~h~ st~ps ro~uired ~ OA: t~ly two days.
A~tcr th~ ~-A~h;nA~ step~, cA~A~n1~atQd hydrochloric acid (300 mL, ~ -t t-~y 37 ~c _~t by woi~ht in wat-r) was addod to the yolymer.
Tho A~olym~r ~hrinks in volume ana tho HAC1 ~olution was easily - .ed by _iltration. More cc~n~ ~t~' HC1 (300 mL) was addod to th~ filttr~d ~olid, and the mixturc wa8 ~11 _ .. d to st~nd ~t room t~ _ ~ture over 2 d~y~. Tho ~olym~r w~s th~n washod -~I-n~ively with dilut~ HCl solution, foll ~-' by A~ -n~ivo water washos. The polymor was thon washod with mQthanol ~na ~inally with ~ ~rom~thane. Dryin~ ov--~;g~t in a vacuum oven (60~C/full vacuum) provided thc polym~r-~A~ALod - c~pLosul~onic acid. The product was iA - ~t; fi ~' a8 PMBSA-SU.
C. CONVERSION OF ~P~SST- RED PO~Y~.~ ~ RAT~SIN A~O
MERCAPTOSULFONIC ACID POLYNER
A c -l~ially-availablo (Fluka ~h~ ) Cro~ n~A
25 chloromethylat-d Merri~ield~ ro~in (2 p c~lAL divinyl~ , 200 to 400 me~h, ~~ y 4.3 mmol Cl/~ , 51.2 ~, 1.0 equivalent) was react-d with 1,4-h~ ltone (1.05 ~quivalonts) and n-butyllithium (1.0 oquiva-lont) according to the ~ e d-scrib-d above to ~rovido a sulton--~unctional ~olymer (70.0 g). S~ e_~-nt thiolA~;~n of the sultone ~olymor in a m~nner gi '1-- to that describod above ~rovided the c~ ~ i ng ~t~_ lfon~c acid ~olymer (79.0 g dry mAss). Thi~ matQri_l wa~
~ i f; ~ ~ a~ PMBSA-N~R.
In this reaction ~-quonce, the lithium I h; ~A~etate reaaent was formod in s~tu by slowly addin~ solid lithium c--h~n-t~ to a mixture of the ~ultone ~olymer and ~h;olAcetic acid in a 3:2 volume ratio of nitro~on-~aturated T~F/water.

PREPARATION OF POLYMER-~u~v_~ ~ MERCAPTOSULFONIC ACID CATAY~yST (X~SA
C~SS ) A ~TY~YT~ION OF POL~-Y~l~ ~
To Amberlite~ XE-305 (75 0 ~, ~- -; t-ly 0 720 mol of ~Ly ~ -r-p-at units, 1 00 oquivalont) was aaaea 600 mL of 1,2-dichlG~
(PDC) The polymer was A~ a to swell in the Lolvent overni~ht 5-Bromo-1-F - ~ (75 3 g, 0 702 oquivalont) and PDC (125 mL) were nda-a to n aadition 4unnel The reactor c~~ (polymer slurry and 5-bromo-1-~e~1~ - solution) wor~ ~vacuatoa ana back-4illed with nitrogon sRvoral timos Trifluoromet~-n~rulfonic acid (20 0 ~, 0 133 mol, 0 19 equivalent) wa~ aaaed to tho polymer/PDC slurry The ~lurry solution turnea a dark ~mber color The ~olymer slurry wa~ hoatod to 45 to 50~C, and ~low, d ~ ~ addition of th~ 5-bromo-1-~e~1-n~ sslut;~n was begun The 5-bromo-l-~ ~ ~ solution w_s addoa slowly over ~1 - tely 3 aays to tho ~tirred ~olymer slurry at 50~C A~t-r tho 5-bromo-1-~ -- addition was com~l~to, the roaction was All~ !e~ to ~tir an aaditional 1 aay at 50~C
The polymor slurry was vory dark-colorea throughsut the addition ~oriod Tho polymor slurry (very dark rea-brown) was cooloa to room t~ _- ~ture and filt-rea The boads worQ wa~hed ~Yt-~Qiv-ly with ~hl~romothnn- (~till aark color-d b-ads) and th-n w~r~ washed ~Y~-n~ively with wator to remove most of the color The bead8 were then wa~hea w$th the fsll- ng ~Hri-s of ~olvents methanol, acotone, ~ichl~ , -tl -, ac-tone, and, _inally, mothnnol After drying in a vacuum oven at 60~C ovo-~;ghl, 96 46 g of noarly white Ll. - lkylatod ~olymer bead~ w r- obtain-d The mas~ u~tako cor~ -' to a d gre- o4 funct;~nAl;~-t~n (DF) of ~ - ~Iy 0 20 B 8a~FONATION
To tho driod b ~ -l~yl_ted ~olymcr beads ~reyar-d abovo (a~ ~ ly 0 720 ~ 1 of ~Ly ~ ~ ro~oat unit~) was add-d 650 m~ of ~;~hlo ~ -h~n_ una~r a nitro~-n A F_ ~ ~r~ . Th~ ~olymer nlurry was cool~d to 0~C using an ico wat-r bath Chloro~ulfonic acia (258 2 g, a 22 mol, 3 08 oquivalonts) wan aaded slowly dro~wi~e to the ~olymer slurry at 0~C ov-r 2 hour~ 40 n ~P The ~olym r beaas turn c___~ -colorod during th- chlo ~ fonic acid addition A~tor th~ adaition was com~leto, the roaction mixturo wa~ Al 1 _ ..ud to ~lowly warm to room t~ _- ~tur~ within th~
wat-r bath Tho volume of the swollen ~olymer was a~L~ - tely 500 to 600 mL within the roactor Aftor w- ~g to room tompQr~tur~, thQ polymor ~lurry wa~ ~llowod to st~nd ov~r~ht without stirring Th- liquia layer was th-n ~d from tho ~olymer u8in~ a _mall-boro ran~ The b-ads w r~ th~n wa8hed sevQral times with dichloromethane (Tho liquid layor and ~;~hloromothano w~shos w r~ ~lowly ~nd c~rQfully q~l~h~d in a ~parat~ ves~Ql using ico ) The polymer bQads worQ then carofully tran3forred to a fritted-gla88 funnol, and the polymer beads were qu~
by 810w, carorul addition or ic- wat-r Artor w-~h;~ tho boad~ ~Yt- ~ively with w~ter, oXC-s~ solia sodium bic- h~-t- wa_ ~lowly nddod to a s~a~e~ai~~ of tho polymer bead8 in w_tor ThQ mixture wa8 Alle,, d to 8t_nd oV~rn;ght at room t~ _ ~turo Tho ~olymer/soaium bi~- ~-to miYturo Wa3 thon h~atod to 50~C for 2 hour~
Tho polymQr ~1 rry was all_r_d to stand at roam t- _~ ~ture for 6 days Tho ~olymor was light-colored and ~ re hi~hly ~_llo~ at this point Th-15 81urry wa8 heat-d to 50~C and All_ ~~~ to react ovDrnight, givin~ a pH 4 _oluti~ of ov~n mor~ ~wollon polymor (~r~mat-ly 600 to 700 mL
volumo) Addition of a small amount of sodium bica~hA~-te ~ive8 a ~X 7 ~olution C THIO~ATION
To th~ aqu-ous ~olymor boad ~lurry from above was added sodium bic--h~-t- (60 5 g, 0 720 mol) The mixturo was e~Ac~ats~ and back-f~ d with nitrogen three times Th;ola~etic acid (41 1 ~, 0 540 mol) wa8 addQa slowly dropwiso over 1 hours 10 ~t9P to the ~olymor ~lurry at room t- _ ~turo Tho mixture wa8 810wly warmed to 80~C over s-veral hours 25 and all~ ' to react at 80~C for 3 aays After rooli~g to 40~C, the _ _ -~t ~olution was , _d u8ing a ~mall-bore c-~ The ~olymor was wa~hed ~-veral timos with wator, givin~ ~l;gh~y off-whito color-d ~olymor b-ads C ~~~ ~ted Lyd ~hloric acid (250 mL) was addod to the ~olymcr and tho slurry was heated to 50~C for 3 hours Aftor r~ol;~g to roam t- _ ~ture, the hyd,o.Lloric acid ~olution was ~ v ' u~ing A
~mall-boro ~a~ . Tho polymor bQnds wore th-n washQd sev-ral timos with Lyd ~-Lloric acid and the beads were transforr-d to a fritt-d-glan~ runnel The boads were again washod ~ t~'ly w~th ~;lute~
Lyd~ll~ic acia followed by ~Yt-~;vo w-~h~ngR with water, giving 35 ~ligh1 ly off-white wat-r-swollcn boaa~ (Th- wat-r-~ 1l~ volume of the polymor beads was ,~l - t~ly 900 m~ ) The beads were wa8hed with methanol (mot_anol-s7_11 ~n volume a~r ~ ~ly 600 mL) and finally with methane After dryin~ in a vacuum oven at 60~C ov~ night, the dark-color~d b-ads 'ad a dry volume of ~y~ ~ ~tsly 200 mL Thi8 ~roduct va~ r7.~n7~; fi-d ag Xl~qSA-5C
D PREPA'~ATION OF CATALYST FROM POLY~ YKILN~ AND 11-BROMO-1-UN~ (X3MSA-llC) Catalyst was ~re~arQd as abovo, starting with ma~ ~OLO~8 poly~Ly ~ (An~berliterM XE-305) ald 11-bromo-1-~n~ec EVALUATION OF POTVM~T'TC lqERCAPTOS'J~FONIC ACID ~'~TYSTS
A 3VAL'JATION OF THE MERCAPTOSULFONIC ACID POLYMER ~X3MSA-SC) IN
THE REACTION OF PHENOL WITH FL'JOR'-~NONE
To a 4-dram vial ~qui~ed with a ~tirrin~ bar wa~ add-d 4 32 g o~ a 20 8 1 ~ lar ratio mixturo of ~henol to fluo ~ - and 0 26 g (6 ~c.~t by wei~ht of tho r-actant solution) o~ the merca~tosulfonic acid ~olymer (XEMSA-5C) pr-par-d as describod in _le 22A-C Tho r-action mixtur~
consi~t~ of ~ ~ ~_~co~s liquid ~_axs ~lus a se~rnte hste .~ n ~oly~nor cataly~t p_ase Th~ mixture wa8 heated to 50~C for 5 hours Tho r-action was monitored th ~ the reaction ~-riod by colloctin~
~ample~ and analyzin~ by HPLC Thc 9-fluo _n~ was found to be 36 ~ - c_~L c~ -' wit'-~in 2 hours and 76 ~- c ~v = -' within 5 hours HPLC analysis (analytical m~thod 3) gives the following relative ar-a p~ . analy~is for the products after 5 hours of r-action (76 ~?~
c~v.l-ion) 9~9-bi~-(4-Lyd ~Ay~7- yl)fluorcno (97 45 ar-a ~c~e~L) 9-(2-Lyl ~Ay~7-_~yl)-9-(4-Lydh~Ay~'--~yl)fluor-ne (2 17 area ~~-~enL) adduct c~nt-~n;ng two fluor-ne unit~ and three ~',- -l;c un~ts (0 39 ar-a p~L) B 3VAL'JATION OF THF M3RCAPTOS'JLFONIC ACID POBYMER (XEMSA) IN THE
REACTION OF PH3NOL WITH FLul ~
To a 4-dram vial ~quipped w$th a stirring bar was add d 4 32 g of a 30 20 8 1 molar ratio mixture of phenol to fluo ~ ~ and 0 26 g (6 ~a~ce~L

by w-ight o~ the roactant #olut$on) of the mercapto~ulfonic acid polymer (X~MSA, daçlr--e of functiA"~ at;,r "J,~- ~ t--ly 0 28 from L.~ rylation E~t~p) prepar~d as d-scribod in Examplo 20 The r~ action mixture consi~ted o~' a ~ liquid pha3- pIu8 a soparate 35 hote ~ polymer catalyst l?ha~-- Th-- mixture was h--at--d to 50~C l~or 5 hour~ Tll- r--action was ~nitored throu~hout tho r--action p--riod by c~~l-cL$n~ and analyzinçr by HPLC The 9-fl~o., v o w~s ~ound to CA 02230272 l998-02-24 WO 97/08122 PCT,'US96~13683 bo 44 p_ .-~' c~ -' within 2 hours ana 75 ~ ~ 0 consum d within 5 hours HPLC an~lysis (an~lytical mcthod 3) ~ives tho following relative area ~e.c~t analysi8 for the ~roduct8 after 5 hours of reaction (75 ~ c_ L cv.v~.sion) 9,9-bis-(4-l.y~ v~y~hc yl)fluorene (96 10 ar-a ~_l. ) 9-(2-Lyd v~y~h-nyl)-9-(4-Lyd v~y~honyl)fluor-ne (3 52 nrea ~- _Gn~): adauct C~tA;~i~ two fluorene unit8 and throe r~ -l;c units (0 38 area ~e.~ ) C EVALUATION OF MERCAPTOS~BFONIC ACID POEY~ER (PMBSA-MER) IN THE
REACTION OF PHENOL W~TH FLUI
To a 4-dram vial e~uippea with a ntirring bar wa8 added 4 32 ~ of a 20 8 1 molar ratio of ~henol fluoL~o~ and 0 26 g (6 ~Ll_~nL by wei~ht of tho roaction nolution) of PMBSA-MER o~ Ex~myle 21C Tho r~nction mixturo consists of a h~ liquid pha8e ~lus a s~pA~ato heto o~ no~
polymeric cataly8t ~hA8e The mixture was heated at 50~C for 2 hour~ The re~ct;o~ was monitor-d by collectin~ _- _l~n, which werQ anAly~-d by HPLC
Tho 9-~luor~none wan 99 5 ~_ _~L ~v = ' within 2 hours The product after 2 hours cA~A;~s~ 96 83 aroa ~L~ ~ of 9,9-bi8-(4-L~11V~YL~- yl)fluorene, 2 44 ar~a ~o __~L of 9-(2-Ly~Lv~y~h-nyl)-9-(4-Ly~v~y~he~yl)-luor-no and 0 72 aroa ~e ~ of An adduct c~ A;~;~g two ~luoreno units and throo ~ ;c units by HPLC (analytical mothod 3) D EV~T~n~I~ OF MERCAPTOSULPONIC ACID POLYMER (PMBSA-SU) FOR T~E
REACTION OF PHENoL WITL F
To a 4-dram vi~l oqui~pod with a ~tirring har was ~dded 4 32 ~ of 20 8 1 ~ lar ratio mixturo o_ yh-nol _l~o envnn ~nd 0 26 ~ (6 ~ by weight of the r-A~t~t sQlutio~) of the polymer o~ Exam~le 21B (PMBSA-SU) The reaction mixture consint-d o_ a ~ ~ liquid ~ha~o ~lus a ~o~ar~t~ h-t~ n ~olymor catalyst ~haso Th~ mixturo was h~at~d to 50~C for 5 hours Tho ~v~ 8 of tho roaction wns fol~ by HPLC At the ~nd of 2 hours, 67 ~--c~nL of the fluG - was ____ d, and 85 ~_~ce~t at the ~nd of 5 hour~ At the ~nd of 5 hours, th~ reaction mixtur- c~t-; -~ 97 09 ar~a ~ _~t of 9~9-bi~-(4-hydlv~y_~ yl)fluor-n~, 2 25 aroa ~ercent of 9-(2-hyd v~y~honyl)-9-(4-Lyd v~y~henyl)fluoren~ and 0 66 area ~_o~t of an adduct c~t~;~;~ two fluorono units nnd throe ~-~o~;c units by HPLC analy~is R-sults for tho evaluation of various ~olymer ~ osulfonic acid~
for ~ ~ -;~g ~h~nol with fluol~on~ were given in Table X
i WO 97/08122 PCT/US96/l3683 TABLE X
CONVERSION OF FLIJ~ - (%) USING 6% BY WEIGRT OF POT~YM~T~C CATALYSTS AT
50~C
Reaction tim~ (h) Rosin 0 2 4 5 7 18 PMBSA-MER ~ 99~5 PNBSA-~;U (PVBC) 0 67 85 P~BSA (PVBC~ 0 66 (AT~ erlyt oTM XE--305) ~CEMSA O 49 75 82 (Ambe~rlyteTM XE-305) DOWEX* 50 (DMT promotod) ~ 17 73 *Tr~ k of The Dow ~ C
5 *AmborlytoTM Tr~ k of Rohm and Haas EVALUATION OF THE MERCAPTOSIJ~FONIC ACID ptlT-YUlP!T~ C IN THE REACTTON OF PHENOCB
WITH ACETONE
To a 4-dram vial equipy--d with a stirrinSr bar was addod 4 33 51 of a 14 1 molar ratio mixturo of phenol to acotono and 0 26 g (6 ~L ~,O'rLI. by woight of the r--actant nolution) o~ the ~", v~,liato ;~os.lfonic acid polymor Tho reaction mixturo typically cons~ista of a ~ ~ liquid pha~- plu~ a ~oparato hQtc vg~ 2 polymor catalyst pha-o The mixtur 15 W~l~ hoat--d and Illow d to roact at 50~C The r-~rt;~ wa~ monitored tl~ t tho reaction poriod by collectinsr _ l~r9 and analyzing by HPLC HPLC anAlysis (analytical mothod 3) ~hows tho followinsJ acetono cG~v_l, ion dat~ (bas~d u~on th~ ~auAntity of 1~;8p~- ~1 A produced) for the difforent cataly~ts aro givon in Tablo XI

CA 02230272 l998-02-24 WO 97/08l22 PCTnUS96/13683 TABLE XI
% ACETONE CONVERSION
(BASED UPON BISPWENOL A pT~nurT~n) Roaction time (h) Resin 0 01 02 252 54 05 0 DOWEX* 50WX4, 25% DMT ~romoted 0 18 44 PMBSA (from uncroY~ PVBC) 0 35 60 75 X~MSA-5C (DF - 0 20) 0 38 82 XEMSA (DF - 0 28) 0 23 32 PNBSA-MER (2% cros~-l;~T ~, 200- 0 66 88 400 mo~h) *Tr~d _ k of The Dow ~- c~l C _ Y
DMT wa~ 2,2-dimothyl~h;~7ol;A;~s A PREPARATION OF B~PF; ~TUVT.~ ~UT.~T~Tn~ AZEOTROPE TO REMOVE
WATER; rn~lrl ATION FROM MFTT~T-~ ~UT.~RTnT~; 5 75 1 MOLAR RATIO OF P~ENOL
TO 9-FL~ORENONE; COEK~clrI~ATION WITH ~T'~T~WT~ ~Y
To a roactor (i~oth~ 1 ~tirrod batch roactor; reactor design 4) wa~
charg-d 75 0 g (0 80 mole) of phonol and 24 98 g (0 1386 mole) of 9-fluo ~none The mixture was hoatQd to 40~C and catalyst (0 973 g, 0 0062 mole, 3 - ~tv~ ~ ~lfonic acid) was char~ed to tho r-actor U-~t;~
was c~t;~-' The cour~e of tho reaction was fo~ d by HPLC
(analytical mothoa 3) At 30 ~ c~ v.~ion, methylene chlorid~ (15 g) was ndded to t_o ,~ ;~ mixtur- so a8 to k-Q~ thQ mixtur- stirrod, nnd to U8 - A wator/mothyleno c_lorido ~-~ t_.~ D ( 180 mm ~g, T 5 37~C) to r mov~ wator of roaction The reaction mixtur- was cool-d at t_e end of th~ reaction (n arly complate fl~o-en~ e ~__s _t~on, >99 ~- _ant of theoratical wat-r) to increasQ th- amount of cryst~ll; - ~ pitate Tho of the run is givon in Tablo XII
Th- r-action m~xture (about 97 ~e c t sQlecti~ity to 4,4-B~PF, little unr-act-d fluo. -) was ~plit into two parts Tho first fraction (53 3 ~) wa~ filt-rad The filter cako wa~ washQd with methylone chlorid~ (49 ~) nnd thon with hot wator (55 g) The ~c_v~ y wa~ 6 4 g (first crop) _ W 097/081Z2 PCT~US96/l3683 ~na 0 6 g (socona crop) of white crystals, Co~l~b~ ~ g to 99 ~olc6~t purity 4,4-BHPF (33 pc ~L ec~v~ y) To tho ~A - of tho mixturo (70 3 g) was addod 61 ~ of t-trachloroothylene Tho cry~tals were ~ v~a by filtration and the filt~r cak~ was wash-a with 50 g o~ tetrachloroethylone ana th-n with 115 of hot water Th- c~eloa product weighod 11 5 g (43 p- , ~c_v_~v, 99 p~-~t a8 4,4-B~PF, white solia) The~e r-sults showea that use of tctr~chloroethylene, in c ';~-~i~
with methylene chlorido, ~ives higher ~ A~ V~ y of 99 ~cnL pure 4,4-10 B~PF) TABBE XI~
T Tomp mm Hg Ob~ervations, Actions h min ~C
OsO 37 760 Add MPSA; turns orango, thon dark green brown 0:20 36 760 Color light L ~ ;nh Os40 36 760 S~mplo taken lsl5 36 760 Seod crystal add-a 2slO 36 760 Sampl- taken 2s28 36 760 Methylone chlorido (15 g) and ~ead cry~tal addod; no cry~t~ i~; temp rai~ea to 45~C
2s30 37 -180 Sample tak-n; seed crystal not di~solving 3 10 45 -180 ~eater ~et at 40~C
3s30 40 -180 80ed cry~tals ada-a 3s50 40 -180 Mixturo hazy 4s30 40 -180 Mixturo hazy 5;10 40 -180 S~mplo tak-n 6s43 40 760 Vncuum turned off, stirr-r #p-ea increasod 9s30 40 760 Sam~lo takon; methylono chlorido (about 20 g) adaea to mixture; stirrer speod inc ~ ; hoater turnod off __ CA 02230272 l998-02-24 WO 97/08122 PCT~US96~23683 B USE OF MFTR~T~ c~T~RTnT AZEOTROPE TO ~rTCTT'T~T' REACTION;
5 75;1 ~OLAR RATIO OF PHENOL TO 9-FLuu~
To a reactor (reactor desiqn 5) was chargod, 75 0 g (0 80 molu) of phenol, 24 98 g (0 1386 mol~) of 9-fl~o ~Jr - and 15 0 g o~ mothylene chloride The mixturo was hoated to 40~C Cataly8t (3-~Lopropan-sulfonic acid, 0 757 ~, 0 0049 mole) was charg-a to the roactor and the mixture was stirr-d The r~action wa~ fo~ a by ~PLC
(an~lytical mothod 3) At the ena of the reaction, methylene chloride wa8 added to ~ nce a mixture of 30 30 about 30 pe ~L by weight of methylen~
chloriae BHPF phonol and the mixtur- was h-atod to dissolve the cryst~ll;~s material Aaditional methylono chloride was added to the ~olution and the 80~uti~ was cooled to ~romote cry8t~ t;~
Tho pro~rosg of the reaction was shown in Tabl~ XIII
At the ena of th- roactio~, half of th- resulting mixturo was filt-rod and the filtar cake wa~ wash-d with 64 ~ of methylene chloride The first crop Or B~PF wei~hs 7 0 ~ (dried ov~-n;~ht at 40~C) and was white with vory littlo pink coloration A ~econd cro~ of crystals w~s collocted nnd wa3hea w~th 28 ~ of methyl-no chlorido Weight, 4 1 g (dried ove-n; gh~
at 40~C, xlightly pink), 99 ~c purity after a further 7, nh;n~ with wat-r Tho ~ ;~A~r of tho reaction mixture was filt~red ~nd tho filter cake wa5 washed with mothylone chlorid- and hot water and dri-d ovor~; ~h1 at 40~
C The ec~ly was 14 ~ (51 ~_L~_~L overall ~.c v~ y)~ 99 ~er~-- L ~urity by ~PLC

_99_ TABL~ XIII
Tim-A-Temp mm ~g Ob#ervations, ~ction~
h min ~C
0 0 45 760 Add MPSA, turn~ dark 0 09 45 760 Add 20 ~ Or methylene chloride;
color wa8 dar~ L ;~h 0 30 45 760 T.; gh1 A brown; roducA pr_ssurQ to ~bout 180 mm 1 00 45 -180 Soed crystal added; no cryst~ll;7-tion obsorved 2 00 45 -180 8-ed crystal adaod; no crys~ tion ob~Lv~d 3 00 45 -180 S~mple t~kon; seed cryst~l ~ddodt cryst~l not di~#ol~ing 3 45 45-~ -180 ~oater sot nt 40~C; crystal#
f L '"I
4 00 40 -180 Mor_ cryst~ls rorming 6 30 40 8~mp1_ t~kon; solid cry#t~
mass; stirrin~ inof~ectivo;
yellowi~h color; ~cuum turn_d o~f 19s0040 760 8~mplo t~kon; ~bout 50 to 70% o~
BE~PF cry8t~ 5 33% by w ig_t of methylene chlorid~ ~dded;
t- _- ~turo increased to 58~C
bout 58 760 _ _- ~t~o lowOred to ~40~C;
20 30 mothylone chloride Added to 80%
mak_ up by w-i~ht o r mixture 24 760 Cooled to room tA _ t CA 02230272 l998-02-24 W ~ 97/~8122 PCTAUS96~l3683 C REACTION VSING Me~YTT~Ne r~T~RTn~ AS SOLV_NT 3 5 1 ~OLAR RATIO
OF PH_NOL TO FLu~ ~
Phonol (30 0 ~, 0 32 molo), 9-fluo ~v~o (16 41 ~, 0 0911 ~ lo) and - 15 0 g of mothylo~- chlorido woro ch~r~od to a rcactor (roactor d~sign 4) The mixtur- was stirred and h-at~d at 40~C and 1 122 g (0 0072 mole) of MPSA was adaea over about 1 minute T~ ;~ was c~ at 41~C ror tho duration of tho roaction Th- fo~ nu ~~~v~tion~ woro mado duriny the run Timo (h) Tomp (~C) Obs~rv~tions, Actions 0 41 ~PSA addod; turns orange to brown to dark brown within 30 ~ec 0 18 41 purplo color 0 5 41 sampl~ takon 1 5 41 sample taken 1 67 41 orang~ mixturo so-dQd with crystal~
3 41 ~rmplo tak-n; honter ofr; left ov~-~;~ht 4 41 hoat~r off 6 room samplQ tak-n; about 80% co~v~ dion; ~ re 2 3 aaauct than 2,4 adduct T_e cryst~l;~ solid was 1~ v~d by filtration and tho filtor cako was washed with mct_ylone chlorid~ A socond crop of crystals was I.- v~l~d from the ~ thor liquors The yield was 0 86 g (first cro~), 8 66 g (second crop), 3 5 g (third crop), ovor~ll 13 g (41 ~P ~ ), >99 p~rcont purity by ~P~C (methoa 3) C P~ENOL FLu~ MOLAR RATIO OF 15 1; MPSA ~TYST; PH_NOL
R~MOVED BY DISTILLATION; cRys~T~T~T7T~n FRO~ Me~UYn~ ~T.OpTne To a mixtur- of phonol and fl~v~ 15 1 molar ratio), hoatod to 65~

C, was adaod 0 0498 ~quivalent o~
3 ~ ~-~tv~..~ fonic acid (with rQspect to fl~v~o) Tho rosultin~ mixturo was heat-d at 65~C for 2 hours, after which the reaction mixtur- was wa~hod with water (14 timos th- volumo of tho mixture) to r movo MPSA The wa~hoa r-action mixtur- was distillod to a ph-nol BHPF
weight ratio of 1 1 and cool-d to brin~ about cryst~ t;~ of BHPF
Cry~t~ll;~ matorial was ~ va~ by filtration, washea with mcthylono chloriae, wa~hea with wato~ and driod to give BHPF (99 8 ~e c~ t by weight of 4,4-isomer) , CA 02230272 l998-02-24 W097/08l22 PCT~US96/l3683 C~ TION OF PHENOL ArYD ACETONE TO PRODVCE 2,2-BIS-(4-TrYn~ Y y ~ ) PROPArYE
A FEED C-A-M~TMTMG 6 ~c _~ ~ BY WEIGHT OF ACETONE, P~VS WATER, sATnRrT~ CATA~YSTS BATCH REACTION
The reaetion was carri~d out in a 2-L jacketed barfl-d resin pot, ~quippod with a eA~ er and nitro~en pur~e IsothA 1 tomp~ratur~
eontrol wa~ providoa by a fluid material, circulat-d throu~h the reactor jack~t Stirrin~ wa~ provided by a T-;gh~;~ Labmastor~ TS2510 stirrer, ~quipped with an A-310 ; ~ r.
To the r-actor was charged 1200 g o~ fecd, cA~t~;~;n~ 90 0 ~orc~nt by weight of ~h-nol, 6 0 Aera~nt by w~ight of acetone, 1 8 ~e~ ~ut by wei~ht of wat~r ana 2 2 ~e e~nL by wei~ht of MPSA The mixturc was hcat~d at 35~
C At the nnd of 2 hours ~--t;~, cryst~ 7~tiA~ occurs in th~ r-action mixtur~ Tho r-Action wa~ cA~t;~ 1 hour mor~, at the ~nd of which 80 pc _~t of tho ~cctonc was reactod (HPLC) The reaction mixtur- was ~ v.~ from the r-actor and rilterod The w~i~ht of ~ vel~a crystals W~8 17 pOlC~t, consisting of a 1 1 adduct of BPA phonol (molar ratio) ; The cry~t-~ Adduct was w~3hcd with phenol Tho washod adduct 20 cont~; -~ 57 7 ~? ~ by wei~ht of 4,4-bispAh-~Al, 160 ppm of 2,4--A;~p~ -1, 200 ppm of tri~- ~1, 2270 p~m of other traee bisL~ -l;c impuriti~s and 1170 ~pm of MPSA, tho ~lA~e b-ing phenol The mother liquor cA~tA;~-~ 8 44 ~ _~L by wei~ht of 4,4-bi~ph-nol, 0 26 percant by ; wcight of 2,4-~;~F~ ~, 0 13 ~--c~,L by wei~ht of tr; n~h~Al 0. 62 ~ _~L
by woight of othor bi~L~ -l;c impuritio~, 0 81 ~e c~nt by wei~ht of nc-tono, 2 95 ~ - by woi~ht of w~tor and 2 78 ~e e~ t by weight o~
MP8A, the 'A~ A~- being phonol B R~ACTION VSING RECYC~ED MOTHER ~IQ~ORS
Th~ ~ thor liquor from (A) wa~ charged to a rotary ev~ol-tor with 30 ~ko-up ph nol (181 g) Th~ ~v~ ~tor was h-at-d at 50~C for 30 ~~"t~P, i ~t th- nd o~ which tho conv~r8ion of aceton~ wa~ 90 ~IC ~ Pro~sure wa~ reduced to 10 mm ~g absolute for 30 ~t~~, at the end o~ which the mixture cA~ -' 1 4 ~_lCw~L by w ight of wat-r Tho ac~ton- c~A~te~t was bolo~ the d-tr L i A~ limit T_o dri-d mother liquor was ~t ~d to tha ~ctor, alon~ with make-up phonol, ac-tone, wat-r and MPSA to give a mixtur- cA~lA;~;ng 92 0 perc~nt by wwight of ph~nol, 4 0 percwnt by wwight of acwtone, 1 8 ~a~ce..L by ;

CA 02230272 l998-02-24 W O 97~08l22 PCTAUS96/13683 weight of water ana 2 2 ~ c by wei~ht of MPSA Tho tot~l mass CvL -,b~ ~-.~n to (A) minus th~ woight of ~ _l~a ~ v~d Tho mixture was ~tirrea ~na heatea at 35~C for 3 houra Cryst-~ i~n of BPA wa8 obser~ed after thc initial 30 n~t~ of hAat;n~ At the end of 3 hours --t;-g, acotone cv v_L~ion was 80 ~e c~ t Tho ra~ction mixtur_ was proc-rsed ~ in (A) Recycling of the mothor liquors was o~Q~ted for 12 cycles Rosults ar_ gi~en in Tabl~8 XIV and XV
Th-sA ~xp~riment8 ~- -L ~tQ that catalyat and unreactea m~t-ri~ls c~n b- _Cvv_LOd ~na r-cycled without --lv_l~ely aff~ctin~ tho proc~ss nna that r-sult~ for suc~siv~ runs w ro ~on~rally consi8tent and ~reaictabl_ C REACTION USING 10 ~c ~_~t BY WEIGHT OF ACETONE IN THE FEED WITH 3 ~a~. BY WEIGHT OF WATER
An experim~nt wa8 don~ ~3 in (A), using 1200 U o-f foea, c~-~ ~ 85 5 ~ by woight of ph-nol, 10 0 ~eL- ' by wei~ht of acetone, 3 0 ~c ~-~L by w igAt of water and 2 2 ~c c~t by weight of MPSA The reaction was dono ~t 25~C Cry~t-ll;~~ BPA wa3 visiblo a_t-r 13 hours at this tA _- ~ture At th ~nd 04 24 hour~, the co v~ ~ion of ac~tone wns 40 ~
Cry~t-ll;ns ~roduct, l~ from the r-action mixture by filtr-tion, conDtitut-s 15 ~ c_~L o~ the mixture Th- crystals, a 1 1 adduct of BPA ~h-nol, wer- w~h-a with phonol Tho wash_a crynt~ls c~-1-;- 51 8 . by we~ght of the 4,4-isomer, 60 ppm of 2,4-inomer, <20 ppm of tri~ -1, 690 ppm of other trace ~;~rh--~ln nnd 840 ~m of MPSA, the ~ sr bein~ ph-nol The moth~r liquors cn-~ 6 73 ~_ ~ent by 25 w_i~ht of 4,4-i~omer, 0 15 ~ ~enL by wei~ht of 2,4-i~omer, 0 08 ~
by w_i~ht of tr;~hAn~l, 0 76 ~e~ nL by wei~ht of othor biDL~--olR, 5 71 ~ ~ L by weight of ~c-tono, 4 97 ~ ~L by wei~ht o_ w~ter nna 2 66 _-- by weight 04 ~PSA, th~ _ ; n~r b-in~ phonol TABLE XIV
1-~ O~L-.LV~ OF WASHED BI~r~1~.J~ A CRYSTALS
CYC1- CrY8t~1 4,4- 2,4- Tri8- OthOr MPSA
NO. % i80mer i80mOr phonol bi~- PPm Wt. % PPm ~Pm phonol PPm 1 17 57.7 160 200 2270 1170 2 22 60.4 420 n/aA 1730 1940 3 17 59.7 460 270 2380 670 4 18 60.7 560 260 2270 1440 26 57.9 870 410 1840 1070 6 18 59.3 790 330 2050 2110 7 18 59.3 790 390 2150 740 8 19 59.6 770 280 2100 750 9 22 59.4 840 390 2000 860 31 62.5 920 380 2210 1060 11 21 64.0 710 350 2020 1410 12 23 63.0 770 280 1900 1500 AVg. 22'5 61+2 800'70 350~50 2100 1100 Cycl~ lOO ~300 * n/a = nOt dOtOCt-a CA 02230272 l998-02-24 WO 97/08122 PCTtUS96tl3683 TABLE XV

MOTXER LIQUOR C~ ~OSl~ lVW~
Cycle 4,4- 2,4- Tris- Other Acetone Water MPSA
No Isom~r Isom~r ~henol bisphen wt % wt % wt X
wt % wt % wt % -olics wt %

9 8 09 0 84 0 36 0 45 0 72 3 0a 2 44 Avg 7,7to,5 0 88 0 41 0 45 0 5~0 2 3 0'0 2 2 8 Cyclos t~0 09 ~0 06 '0 02 l0 2 r le 27 Pr-~aration of a Ro~ Os~Lative [( - ~Loalkyl)(Sulfo)Phenylalkyl]
8ulfonated Poly~Ly ~e Catalyst (Desi~natQd DPMSA-~ER3C) A Alkylation A 15 00 g samplQ o~ 200 to 400 mesh chloromethylatQd poly~LylOne/2 ~ ~e.t aiviny~ copolymor beadQd (~l~- tely 4 3 mmol Cl/g resin, ~l~- te~y 64 5 mmolO Cl) known in the art as a Morrif~
re3in (av~ ~le from Fluka C~emi~ AG) was adaOa to a round bottom glass fla~k (r~actor) unaor a ~ad of plant nitrogan with a soaium l.y~lan -crubber attachea (to ~ra~ evolved BCl) (3-B ~ ~ ~yl)~~~-_ - (102 7 g, 78 4 mL, 8 0 oquival-nts) was adaea to the dry resin beaas Dri-d (over 3 A~L l~ ~ siQv 8) nit ~ e (50 mL) wa8 added, ana the beaas were ~lowly 8tirred at room t~ aturQ to allow for swQlling of tho b-aas The rOactor wa~ cooled to 0~C in an ic~ water ~ath A 20 mL
~am~lQ of 1 0 M ~1 ' chlorid in nit Q~ ~ avail~lo from Aldrich ~ 'c~l Co was 81Owly aaa~a via ~yringQ to the cold ~olymer slurry with ra~ia ~tirring ov~r ~l~- t~y 10 '~l~t~l . Tho miXturQ turns dark rod a~ ~oon ~8 th~ ~l ' chlor~de 801~;~ was adaed ana oxotherms to ~ly 4~C within tho first 15 ~t-~ of r~action with XCl ~ein~

., WO 97/0812Z PCT~US96/13683 ovolvQd ~rom th ~olution Aft-r the addition of the AlCl3/nitroh~7~e ~olution wa~ compl-te, the mixture Wa# slowly stirred at 0~C for 2 to 3 hour~, thon was ~ d to room t _- ~ture and slowly stirrea overnight Th- mixtur- wa~ slowly ~our-d onto ice to qu-nch th- aluminum chlorid-Thon the boad~ were sQparated using a gla~s-rritt-d funnel with vacuum ~iltration The bead~ were s~_lA~ y washod with wator, ac-tone, ~; rh~ ~romethano, methanol, ailute a~u-ous hydrochloric acid, wat-r and mothanol, th-n wQrQ driod ov~r~;~ht in a vacuum oven at 70~C (dry mass 23 52 ~) B ~ulfonation Thn polymor boaa~ from _lo 27A (23 30 g, est; tP~ 161 3 mmole of phonyl ~roups) wore add-d to a ~lass reactor with adaition funnel and NaOH acrubbor attnched Di~hlorom thane (100 mL) was addod to tho ~lask and tho beads w-r- Al 1~ d to ~well (rapid ll;~g wa~ ~h-Y- v~) . Tho ~lurry was cool-d to 0~C in an ic- wat-r bath Chloro~u~ f~; c acid (37 6 ~, 21 4 mL, 320 mmolo, ~r ~ tely 2 0 ~~uivalents per ~quival-nt ~henyl groups) was slowly add-d dropwi~e over ~1 ~ tely 2 hours to the polym r ~lurry at 0~C The mixtur- wa3 allowed to slowly warm to room t _--~turo ove-n~ ght in tho water bath Th- mixture was slowly poured onto ico to quench tho ~xc-~s c_lorosulfonic acid, then the b-ads wor-~-parat-d using a ~lass-fritt-d funnel with vacuum filtration Th- beads wor- thon wa#hod A~ iv-ly with wat-r Wator was add-d to make a lurry, then ~olid sodium bic--h~~~te was slowly aaded in small portions ovor ~1 - e3y 2 hour~ until no more b '~h~ wa~ f'-~ v_d (all active acid 3~t~ noutraliz-d) The mixture was A~l_A ~ to stand 3 d_ys in the aqueou~ ~odium bi~ t- ~olu~ omo -dditional boad _ ~l;~g was ~ v_d ovor thi~ time period) Th- b-ads were wash-d with w~ter and trannf-rrod to a ~la~ reactor with 100 mL of water The bead~ wero thon h-atoa to 70-80~C over 2 hours to en~ure hydrolysis of any re~
~ulronyl chlorido ~roups C. ~h~ol~
Tho aqu-ous polym r ~lurry from _le 27B was cooled to room t- _- ~ture 80dium h,l~ h~-t - was ~lowly added until the 81urry was neutral (no h ~hhl ;n~ ob~orvea) ~ th-n additional sodium bic~ to (27 1 35 y, 323 mmol) was added to the aquoous b-ad slurry ~h;ol~etic acid (24 6 g, 23 1 mL, 323 mmol) was added to an aadition fuDnel Tho reactor was ev~ At-~ and r-filled with nitro~en ~everal tim 8 to ~; ~e th air WO 97/08122 PCT/US96~13683 c~ntnnt The ~h;ol~cetic acid was 81Owly addea over ~ - t~ly 15 to In~ltes to tho a~ueous b~aa slurry with r~id stirrin~ The Addition rat~ wa~ adjustoa to control tho offervcscont ~vol~ti~n of carbon Ai QYi~
which was formod in the noutr~ t;An ~lOC~-8 After the Ih;ol~cetic acid addition was complete, tho mixture was h~ated to 70~C and W~8 ~
to roact overnight with n; 1 stirrin~ Tho mixturo was then coolod to room t- _ ~turo ana tho boads woro collocted by filtration u8ing a frittoa-glA~8 funnel The beads were wa8hed ~Yt~ Q;v ly with wator, then with ~; ~hl ~romethane, and thon w~hed a~ain with wat-r The boads w re transr-rr-d back to tho glass roactor, th-n c~n~ent atQd (12 molarl Iyalochloric acid (100 m~) was add-d Th~ mixture wa8 heat-d with mild stirring to 50~C for 4 to 5 hour8, thon was coolea to room t~ _- tur-D~;~n;~-~ wat-r (100 mB) w~s addoa -nd tho boads woro a~ain collectod by filtration usin~ ~ ~ritted-~lass funnel Tho boads were wa8hod with water, thon were washed ~Y~n~ively (~1 - t~ly 500 mL) with dilutQ
(~L-~- tely 3 molar) a~ueous h~1~.Lloric acid The beads woro thon washed a~ain with A~; ~n;~~ wator and finally were wa3hed with methanol to A; ~~1~ tho watQr ~nd shrink the polymer beads The boads w re dri-d ov~-n;ghl in a vacuum oven at 70 ~C (dry mass 34 17 g) Tho final ~olymQr catalyst was d-signatod as DPMSA-~ER3C
D Pre~aration of Thr-o-Carbon DPMSA Polymor From Morr;f;~
Ro3in B-ads Anothor ~ ~to8ulfonic acid polymor was pro~arod usin~ tho ~ oced~l~ of ~top8 A to C of _le 27, exce~t u d n~ a chloromethylated 25 ~olyDLy ~_o r-sin (2 ~o ~_nL divinylh~n~- -, 200 to 400 mesh, - tvly 4,3 mmol Cl/g r-~in), a M-rrifield~ r-sin c - ~ially AV~ ~ from Fluka Ch~mi- AO as the ~olymoric ~o L and (3-L~ - in tho alkylation Dtop of the roaction The resultin~

~olymer was ; A~~t ~f;oa as DPMSA-MER3C
E Proparation of Threo-Carbon DP~SA Polymer From Chlo ~ -hylatea a~l-R~ in B0aas Anoth-r - ~to~ulf~n;c acid polymor was preparaa usin~ thQ
_o-~ ~ of Dt-p~ A to C of _1Q 27, oxcopt usin~ a chloromethylated 1 5 ~el~ol~L cros81;n~A poly~Ly~no gol-rnsin (-30t70 mesh, a~l~imatoly 4 3 mmol Cl/~ ro~in) a~ tho ~olymoric D~ L ~nd (3-L _ ~yl) ~- - -in tho al~ylation sto~ of tho roaction Thi3 ~olymor wa3 ; ~nt; fied as F Proparation of Two-Carbon DP~SA Polymer From Chlorom thylated Gel-Rosin B-ads Another - ~tosulfonic acid ~olymer was preparOd using the ~ : ~ O of ste~ A to C of Example Z7, excopt usin~ a chloromethylat-a 1 5 ~o1~nL cro~sli~1 ' poly~Ly1enO gel-resin (-30170 mesh, ~ - tsly 4 3 mmol Cl/~ rosin) as the polymoric 8~ L and (2-L ~ _thyl) ~ ~9 ~n the alkylation ~to~ of tho reaction This polym r was id~t;fi~d as DPMSA-l 5X2C
~ PrOparation of thr-e Carbon DPMSA from 6 ~CLr ' Cro~
MaO~ ~L-~8 ROsin Anothor ~tosulfonic acid polymer was uDin~ the ~ oc-~ e of st-p~ A to C of Exam~le 27, except using a chloromothylatod 6 ~ ~
crsrqli~l-~ ma~ O~O~U8 ~O1YDLY e~o resin (~ v~ mately 30 to 70 mOsh, _~ t~y 4 3 mmol Cl/g r-sin) as the polymHric s~1L and (3-L~ ~yl)~7-~~ in tho alkylation ste~ of the r-action This polymer wa~ i~-~t~fied as DP~SA-6/42-3C
H Pre~rntion of three Car~on DPMSA from 6 5 ~oLco~t Cror81; ~k~a Gol Rosin Another ~tor lf~;c acid pol-ymOr was usin~ the ~ --~ O of ao ~t-~s A to C of _lo 27, exc-~t usin~ a chloromethylated 6 5 k~olt cro~sli~l ' uniform particl- size poly~Ly1_~o ~ol-r-sin (380 micron, ~v~ -; t-ly 4 3 mmol Cl/g r-8in) aB the ~olymeric ~o L and ~3-b1~ _ ~yl)~ - - in the alkylation ~top of the roact~on Thi~
~olymor wa~ i~t~fi~a a8 DPMSA-6 5X3C

~VA~UATION OF CATA~YSTS IN CONTINUOUS ~0~
A fix-d bed downflow reactor, ha~in~ a volume of lO-mL, waD co~DL ~Led ~rom a ~ rtical tub-, 4ill-d with cataly~t ~t-r~l to tho catnlyst bed was a pr~t ar--a, packed with çrla~s wool~ A y ~qll;~ ~
i~ a ~ ~ e re5~ulator, r--li~f valve, ~ump and hoater for th f----a The f--ed was heat-a by ~--t;r~ luid, circ~lA~ ~d through th~ feOa pot, ana wa~ k-pt under a nitrogen paa Th-- f--od wa8 ~h-nol (99 9 ~"~ c .t) and fl G ~ .o~e (about 99 ~-r. ~ ) in a 21 1 molar ratio Tho h--t;r~lJ fluid, h~At;rtr ta~e and rOactor were turnoa on The s--l--ctea catalyst was slurriod in ~honol at about 45~C Catalyst-phenol mixturo was pi5~etted into the reactor, at the bottom of which a ~lug of WO 97108122 PCT~US96~13683 ~lass wool/~lass beads was ~laced to ~ .vOnt catalyst from loa~in~ th~
r-actor. The ~honol:flu~L~ ~ wa~ ~daod to th~ r~d ~ot ~t 55~C. Th~
~ro~uro w~ najustoa to ~bout O.34 b~r~.
Phonol: f luoronono ~ood wa~ introduced into the rcactor and th~
c _-Lition of tho ~fflu~nt from the reactor was fsll_ _a by HP1C.

CA 02230272 l998-02-24 Tho rollowing results wore obtained:
T~ble XVI
PMBSA-~er c~t~ly.t (~x~mple 9C) ~t 50~C:
proauctivity 1.4 g B~PF/~ cat h con~ersion time (h) % fl~vl~no~ cv~v~ ~ion 0.33 99.7 28 lOO.0 53 lO0.0 69 99.7 89 99.9 113 100.0 137 99.8 144 99.6 162 99.6 158-1Octivity 98% 4,4-B~PF
PNBSA-XEBr ( _le 9D) ~t 69~C:
yroductivity 0.6 g B~PF/g cAt h cv v~.~ion time (h) % fl~o~vne cvnv~l~ion 2 99.8 lOO.O
39 lOO.0 63 98.9 79 99.0 103 95.5 127 87.1 164 83.4 8010ctivity 98% 4,4-BhPF

WO 97/08122 PCT~US96/13683 PNBSA-XECl (Ex~mplO 9E) ~ 56~C:
productivity 1.48 ~ BHPF/~ cat h cv v~ ~ion tim~ (h) % ~l~v Onv~n cv,.v~6ion 2 99.2 27 99.1 63 99.3 87 98.7 111 98.9 135 98.6 159 98.3 164 98.0 x-l-ctivity 98~ 4~4-B~PF
XENSA-llC (~xampl~ 22D) at 60~C:
cv.~voL~ion timO (h) % rl~O ~nv~u convorsion 1 99.2 17 94~4 41 92.2 91.0 DP~SA-MER3C (~x~mpl~ 27D) ~t 50~C:
8O1-ctivity 98% p~p-B~PF
~roductivity 4 1~ B~PF/ lb cat~lyst/hour ~ 4 k~/k~/h co..v_L~ion tim~ (h) % fluo~O~v..o cv~VO ~ion 99.9 24 99.9 39 99.9 48 100.0 66.5 100.0 75.5 98.9 99.5 99.1 103 98.6 104 98.7 XEMSA-5C (Exampl~ 22) at 55~C:
~oloctivity 98% ~,p-B~PF
proauctivity 0.43 LB B~PF/LB catalyst/hour =0.43 k~/k~/h c~........................ v~L~ion time (h) ~c ~~--t fl~o~o-~ convor#ion 4 99.7 a2 100.O
46 100.0 100.0 77 99.7 94 99,7 118 99.7 142 99.5 144 99.4 ~68 99.3 192 99.0 216 99.0 240 98.6 264 98.6 DPMSA-XE3C ~Examplo 27A-C) at 56~C:
8010ctivity 98 ~cl~L 4,4-B~PF
c~.. v.. l6ion time (h) % fl~ o no~ c~.. ~ ion 98.0 48 95.1 72 94.7 96 92.3 123 87.3 144 86.1 170 83.8 240 77.1 Th-~o ro~ults ~how that P~BSA, XE~SA, nn~ DP~SA cat~lyst~ of th~
invontion can ~xh~bit ~ta~ility ovor tim~, thus, have very u8-~ul li r--time~ .

~J

WO 97/08122 PCT~US96~l3683 Cv lNUUU~ PROCES~ FOR ~A~ING BHPF VSING NERCAPTOPROP~N~e~q~ONIC ACID
CATALYST
~he r-actor cvn~ri8c~ a three-staged con~;n~u~ reactor (i~oi hr- 1 porr-ctly ~tirred ty~o) Th~ roaction W~8 run at 46~C at ~ 21 1 mol~r ratio o~ phonol fluoronone (98 ~o~c , Aldrich), tho amount of NPSA bein~
0 05 to 0 07 ~quival-nt of MPSA mole of fluo.enone The _ _-sition of tho product~ was fo~ J~ by HPLC
Tho roaction w~s c~ntinu~d for 228 hour8, At tho end of which ~luo ~ ono cv~v. ~ion wa~ 99 95 E ~c~ t (reactor 2) or 99 9 ~ercent (rcactor 1) n~d 8electivity to 4,4-BHPF wa~ 98 32 ~orco L ( _~ct~~ 2) or 95 2 ~ = ~ (reactor 1) ~XA~PLE 30 ~VAhVATION OF CATA YST OF EXAMPBE 22D (XEMSA-5C) IN Cu_ l..JUU~ PROCESS FOR
~AKING BISPHENOL A
~he reactor compriso~ a vortic~l u~low column of 8~;nl-P8 ~toel tubing, ~ack-a with re~in atop A ~croen ana ~la8~ beads The col = was ~oated by a water jacket Thc ~Lv~ FP of the roaction was follc ~ as abov~ by RPLC
Tho followin~ ros~lts wuro o~t~;n~d CA 02230272 l998-02-24 Tabl-- XVII
Te~t 25% ~ ~ -tcd XEMSA-5C
*_~ 50Wx4 Example 22D
Ac$d capacity dry meq/g 4 0 3 5 w t meq/mh 0 84 1 17 Swell t-3t p_enol/w~t-r vol 0 55 0 72 Reaction t~st~
30 min r-s t$me 4% acetono, 65~C
4,4 % by wt 12 7 14 0 c~v~.~ion 0 83 >0 95 ~d~cLivity 8 2 9 0 ~ 0 2 2,4/4,4 0 28 0 024 ~ 0 001 6~ ac-tone, 65~C
4,4 % Dy wt -15 19 1 ~ 0 6 ~o,.v.. ~ion -0 7 0 92 proauctivity -10 12 2 ~ 0 4 2,4/4,4 -0 27 0 025 ~ 0 003 4% ~et~-, 55~C
4,4 10 7 13 0 ~0 1 cv~v_l~ion 0 67 0 92 ~ 0 01 productivity 7 2 8 3 ~ 0 06 2,4/4,4 0 21 0 019 ' 0 001 A.~_ ~ . k of Tho Dow :' c-~ Campnny ~XAMPhE 31 PREPAR~TlON OF BI8P~ENOL F
Phenol nnd f- 1 a.~hyao wor- roacted to p ~ ~c~ '~;~F' -I F S; ~_ r-~ult~ w re obtninod T_e ~c-';ng o ~ can be . ~-tev with ~ ucce~s Dy ~U~D~titUt$n~ t_e generically or ~pocif;c~ 7 1 y aescribed reactants and/or operatin~ cond$tions o~ this invention for t_ose u~ed in the p.~~La;~
=- ~_p, CA 02230272 l998-02-24 W O 97~08122 PCT~US96/13683 From the fo~_ ;n~ aQscri~tion, on~ skill~d in th~ ~rt can e~8ily a~certain tho ~ ch~rA-te~;~tics Or this inv~ntion ~nd without a~Artin~ from th~ ~pirit and scope thereof, can make variou~ changes and ';ficAtions of the invention to ada~t it to various usage~ and conditions EXA~1~ 32 Alt-rn~t~ Pro~aration of a Re2r-s-ntAtive [(L'_~c~Loalkyl)(Sulfo)-Phenylalkyl] Sulfonated Poly~Lylene Catalyst (DQ~isnated DPMSAA-0 25-1 5X2C) A Preparntion of (2-Bromo~thyl)bonzyl Chloride (Al) In an ~Y~e~~ion of the ~ OC6-1u e doscribod by Selva, M; Trotta, F ;
and Tundo, P Sy~h-ri~, 1991, 1003-1004, (2-L ~thyl)benzylchlorid~ wa8 pr~arod by th~ f ollowing ~ ~--~ a C~- -~~tad sulruric acid (132 m~) was slowly added to ice cold 15 ~ n;z~ wat-r (66 m~) in a 1 L tL ~e n~cked glA88 reactor fitt-d with ~
~~hAn;c-l ~tirrer, roflux co~ , and t~ _--~L~ ~rob- Tho r-~ctor c~tnlA;~;n~ tho ~ul~uric acid 80l~ ~ w~s cool~d in an ice bath, then (a-b ~ ~thyl)}-- - (92 5 g, 0 50 mol) was addod foll_l_l by 50 ~
tetr_butyl~ ; chloride in w_tor (10 ~ of nolution), parA8 l~hyde 20 (20 0~, 0 666 mol, 1 33 ~quiv_lents), and finally ~odium chloride (80 0 ~, 1 37 mol, 2 74 aquivalonts) The slurry was stirrea at ~ ~ ~ely 1000 rpm (v ry vigorous) and heated to 80~C for 2 25 hours ThQ reaction was 1-88 than 50 ~el~el~L _ _let~ as dot- -' by gas ~L~ to~-ap_ic analysis Adaitional parAf- l~-~yd- (20 0 ~, 0 666 mol, 1 33 25 oquivalents) was nadoa and tho mixtur- was stirrea (600-700 rpm) an adaitional 3 5 hours at 80~C ThD roaction was ~r ~ l y 50 p~ ~ ~
complQte as aet- ~ ~A by gas ch~ og_a~_ic analysis T_e mixtur- was A11~J~ to cool ana was tran~ferr-d to a s-~aratory funnel Th- organic ph~o was se~arnt~d and sav d for further r~action (A2) Alt--~Atively, (2-B _thyl)h~ - (92 5 ~, 0 50 mol), c -~ l ~tea (12 ~ lar) hydrochloric acia (125 mL, 1 5 molo HCl, 3 oquivale~ts HCl), ana ~ar~f~ lA-hyde (22 5 g, 0 75 mol, 1 5 aquivalents) w r- aaded to a 1 ~ three-neckQd glass reactor fittad with n '- ;c-l ~tirrer, addition funnel, and t~ ~ ~ a ~robo C -- l~t-d ~ulfuric 35 acia (111 m~, ~ ~ tely 205 g, ~ ~ t~ly 4 oquival-nts of sulfuric acia) was ndded to the nddition funnel A nmall ~ortion (~t ~ tely ~ 10-15 mL) of t_e sulfuric acid was adaod to the reaction mixture from tho _ -115-, ad~lition Cunn--l and the slurry WA8 h~atod to 80~C with stirrin~ at a~ ~tely 1000 rpm Aft_r th~ r~action reaches 80~C, the s ;r~;ng c~ ~_rl ratod sulCuric acia wau adaod dro~wis~ ovor 3 hours After an addition 1 hour r action time, the r-action wa3 loss than 50 ~
5 com~l--to as deto ~ by gas cLL~ to~ aphic analysis The mixturo w~s ~llowod to cool ~nd was transferroa to a 8 paratory f-unnol Th-- or~anic phas~ wa~ ~e~r~ltoa and savod Cor furthor roaction Tho - ~;r9~ proaucts from r _ le 32, parts Al and A2 r~~t~ Sr unr-actea (2-bromoethyl)b~~ ~ and c~loromothylatoa (2-b~ ~Lhyl)~
lO product (mixture of i ~ 8 ) wore furth-r chloromethylatoa according to tho p~,c- ' ~ doscribQd in part A1 The reaction was pel r~ -d usinsr ~ufficient time and ~ ~ ~L~ (~ar~C l~z~hyd~, soaium chlorid~, sulfuric acia) charg--s to compl~tely ~ th-- (2-Ll~ _thyl)~ - starting material, ÇrivinÇr a mixtur- of (2-L. ~~thyl)ben~yl chloride;~ b alonçr 15 with highor-ho;l;nçr Ly -~ .~1~ cts Th- mixture of (2-b ~ -=thyl)benzyl chloride ~ wa~ i~o~ Ate' by oil-pum;p vacuum bulb-to-bulb Xu~lrohr di~ t; ~ (up to 140-145~C) Tho ;~ol~t-i ~ro~uct wa~ a wat--r-whit~
oil whJch acl;~f;~ upon st~;"SJ at room t~ _--c.L-~_. Gau cLL~ tog--aphy analysis ~hows that unreacted (2-b~ a hyl)~ - - ana tho 20 hi~her boi~ g Ly-~.v~l.Lcts w~r-- --r~ lly absont ~Crom th~ aistillod (2-L ~ ~I thyl)b-nzyl chlorido; -~ .,d~1 E~ Alkylation gLy ...~/divinyl~ ~ - co-yolymor rosin boads (lO OO sr, -30170 me3h, 1 5 ~ t a~vinyl~ L -; t-ly 96 0 mmolo ~Ly _no r peat units) 25 woro add--d to ~ round bottom 5JlaE~ flask (ronctor) under a pad of nitro~on with a soaium Ly~llv8id ~crubb--r attnched (to trap ovolvod ~ICl) A
~o~ of (2-L~. ~thyl)benzyl cl~1ori~~ (mixturo of a ic rin~
-- ~, ~, .' ' .-t~ly par~) (lO O sr, 0 238 oquival--nts oasoa upon ~ Ly . -_ ~vt~uSr units) in 30 l,2-q;~h1o~ - (25 mL) was added to tho dry ro~in b-aas Tho b-aas w r-- ~11 9d to ~woll for ~ t-ly 5 to lO Tnlt-~, then aaditional l,2~ hlo~ ~Lh-r - (35 ml~) wa~ addod to the ~woll--n beads Anhydrous tin(IV) chlorido (2 5 mI, .~p - -oly 5 57 Çr~ .L - t-ly 21 4 mmol) was Ellowly addod via ~yrin~ to tho polymor ~~lurry at room t~ turo 35 ov--r ~p - t ~ly lO 1 ~ with rapid stirrin~ Tho mixtur-- turnea light yellow whcn tho tin(IV) chlorid-- was add--d Tha mixturo wns slowly w~rmoa (in 5~C inc ~ -~) to 40~C ovor ~ tely 30 r~t~E~ and was W O 97~08122 PCTAUS96/13683 allow a to react at 40~C for 1 hour At thi~ time the light oran~e mixture was slowly warmQd (in 5~C incr_ ~) to 60~C over a~~ t-ly 1 hour 30 ~ t~ ana was Al 1 Oz - a to r~act ov-rni~ht at 60~c with slow xtirrin~ Aftor ovorni~ht r-~ction, th- mixturo w~8 cOOlOa to ro ~
tomp-rature ~nd was qu-~hsd by slowly addin~ moth_nol to the w~ stirred polymer slurry The beads were s-~arat~d from the solution usin~ a glass-4rittQd ~ = el with vacuum filtration Th- b~aa8 woro ~ ly washod (throo portions ~ach) with dichloromethano, wat-r, totraL~a ~L~ ~u, and methanol, then the boads wHro driod oV~rni~ht in _ vacuum ov n at 80~C
(dry mass 13 89 g) hooL tical mass yi~ld ~ 14 49 ~ Alkyl~tion yiold (by ma~s uptA~o) ~ 87 porc-nt A~r~Y; to d-~r-o of ~olymor funct;~Al~r-tion (by mass yiold) - 0 21 C Sulf~ A t; t'~
The ~olymer b~ads from Exam~lo 32B (13 89 ~, Qst; -~1 116 mmolo of ~honyl groups) wor- addoa to a gla~ roactor with addition f = el and NaOH
~crubbor attachod Di~hloromethane (75 mL) was addQd to the flask and the b-ads w r~ All_ _~ to swoll (ra~id swollin~ was obs~ v ') Th slurry was cOOl.a to ~ - t~l y 3 to 5 ~c in an ico wat~r bath Chlorosulfonic acid (11 7 mL, a~ - ~ly 20 5 ~, ~ ~ t~ly 176 mmol, t'~l''-~ 91y 1 5 equival-nts por ~quival~nt o~ ~henyl ~rou~s) was slowly addQd dro~wi~e over ,~ t~y 30 '~tv~ to the cold ~olymer slurry with stirring The mixturo was A71e.., ~ to r-act at a~l-- t~ly 3 to 5~C in an ic- wator bath for 1 hour The mixturo was 1 ~d from th- ic~ bath and All d to wnrm to room t~ ~turQ ovor 2 hours 45 ~t-- At this tim , thQ
~olymor slurry wa~ again coolod to 3-5~C in an ico wat-r bath, and wat~r wa~ slowly addod with ra~id stirrin~ to quench th- ~XCQ88 chlorouulfo~;c ncid Tho beads w rQ ~ ~r~Ated using a glass-~rittod f = ~1 with vacuum filtration Th- b-ads w ro th n wash-d ~Y~ iVQly with wator Watar wa~
ada~d to mako a slurry, thon solid sodium bicA-~Ate was slowly nddod in ~mall portion~ with stirring until no ~ r~ ~1;~ was -b~ v~d (all activ acid sitos w~re n-utraliz~d) Tho b-ads WQr~ wash-d with wator nd transf-rrOd back to the ~la~s reactor with 100 mL of water Tho boAd~
wore thon hontod to 60 to 70~C ov r 2 hours to onsur- hydrolysis of any l_ri~u-l ~ulfonyl chlorid- groups D qh~lAti~n Tho nquoous ~olymer 31urry from Exam~l- 32C (est; t-' ~ - t ly 20 mmol- Br) was coolod to room t~ ~ ~ 0 Sodium bicA h~nAt- was W O 97/08122 PCT~US96/13683 ~lowly Add~d until tho ~lurry was neutral (no ~Uhhl in~ observed), then additional sodium bi~A b~nAte (5 30 g, 63 0 mmol, a~rv~imatoly 3 ~quivalQnts relative to est; te~ b~ c~nt~t in boads) was added to th- aquoou~ b-Ad ~lurry Th;olA~otic acia (4 5 mL, ~ ~_ ~ly 4 8 g, ~ ~ ~ t~ly 63 mmol, ~ m_tely 3 equivalents relative to Qst~- t~
L ~ c~nte~t in be_ds) wAs added to an addition ~unnel The r actor wa~ evA~uAt~ and r~f;71r~ with nitro~en soveral times to ~; '-e the air c~nt~nt . Th- th;olA~tic acid was slowly added over ~ - t~ly 10-15 ~ to~ to the aqueous bead slurry at room t~ _- ~turo with ra~id ~tirrin~ Tha th;olAcetic acid addition rate was adjusted to control the ~f4- v_~c- evolution o4 carbon ~;o~i~e which wAs 40rmed in tho n~v~ Al;~At;o~ ~ _~8 A4ter tho th;ol~A~etic Acia ~ddition was complete, tho mixtur- was heat-d to 70~C and was allowed to react ov~- n~ ght with ~ tirrin~ The mixturo was thon cooled to room t' _~ ~ ~ and the b-ad~ woro colloctod by filtration u~in~ a frittea-~la~s funnel Tho b-aa~ w re washed o~ ;v-ly with water, then with dichloromoth~ne ; (o~tional), and th-n wa~hod again with water The beaas wore transf-rrod back to the gla~ reactor, then c~~ ~ated (12 molar) L~ o~Lloric acid (100 m~) wa~ addcd Th~ mixture was hoated with mild stirring to 50~C ror 20 2-3 hours, thon wa cooled to room t~ _ tU e De; ~n; ~ water (100 mL) wa~ add-d and the beads were a~ain collocted by filtration u~ing n 4ritt-d-~la~s funnel The beads wore wa~hnd with water, thon w re wash-d -~t-~ivoly (a~ ~; t~ly 500 mL) with dilute (~ - t~ly 3 mol_r) aqu-ou~ Lya ocLloric ncid Tho beads wero then washed again with ~-i on; ~ed water and wer- tran~f-rred to a ~tora~e bottlo without any add$tional drying The final ~olymer catalyst has a titrated w-t- ~_t (water ~wollen) acid ca~acity o4 0 ôO ll;r_~ival-nt/mL cataly~t The ~inal ~olymer cataly~t wa~ i~n-t-' as DPNSAA-0 25-1 5X2C
E Pr-paration o~ DPMSAA Ro~in with 0 71 Equival~nts Alkylation Anothor c~to~ ~n;c acid yolymer was ~reparea from 1 5 ~ t cro~l;nl ~ ~Ly ~ -/divinyl~ -~~~o co-polymer beadc (-30~70 mesh) using tho ~ ~-~ ~ doscrib-d in ~teps B-D of Ex g le 32, oxc-pt using 0 71 equivalontY of (2-L ~ -~thyl)b~nzyl chlorid- in the ~lkylation r6~c~i~n Chloro~ulronic ~cid ~2 0 ~quivalont- r-lntive to th- c-lc~lAte~ total ~quival-nts of ~honyl ~roups in the polymer) was used in tho 8Ulfon~tion r-action ~h;ol~c tic acid and sodium hic~ te (3 0 oquival-nt~ of ~~ch r-aWont rolative to the C'1C~ ~tF~ ~mount o~ LL~ ~9 in the polymor) =

W O 97~8~22 PCTAUS96/13683 worc usod in tho 1 h; ol~ti~n ro~ction Tho ~ass yiold oAf polyA~or oA~tainod from the alkylation r-action co 1~ to a 83 ~e1C~AA~ yield in the alkylation reaction and a degroe of functi~nAl;ty of 0 59 The final polymor cataly~t Ahas a titr~toa water-wot (water _,_ll~n) acid cn~acity of 5' 0 94 ll;~A~uival-nt/A~ catalyst TA~AO final polymer catalyst was ~A~i~n~ted a8 DPNSAA-0 75-1 5X2C
F Preparation of DPMSAA Resin with O 43 Equivalonts Alkylation AnotAhor --~to~lf~n;c acia polyAmor was ~repared from 1 5 A~
cro~sl;n~ ' ~Lyl~no/divinyl~en~en~ co-polymer bead8 (-30170 mo8h) usin~
10 the ~locFAd~e de8cribed in 8teps B-D of _le 32, except usin~ 0 43 oquival-nts of (2-bl ~~thyl)~onzyl chlorido in tho ~lkylation roaction Ghloro~ulA'onic acia (2 0 equivnlonts rolativo to tho calcul~te~ total equivalent8 of phenyl ~roup8 in the ~olymer) wa8 in the ~nlf~n~ti~n r-action ~hiol~cetic acid ana 80dium h;C~ _h~n~te (3 0 ~quivalont~ or o~ch ~ nt rolativo to tho ~1C ~t~~ ~mount OAC AD ~ n_ in the polymor) wero usoa in tho th;ola~;~n roaction The mas~ yield of Apolymer obtained from tho alkylation reaction C0~ -d to a 81 ~Ol ' yield in the alkylation r-action ana a aegroo of f~n~t;~l;ty o~ 0 35 Tho fin~l polymor catalyst h~s a titr~tod w~tor-wot (w~tor swollon) acia C~pACity OA' 20 0 . 85 11 i r _~ivalont/mL cataly~t Tho final polymer catalyst was ~~iq"~teA a3 DPMSAA-0 45-1 5X2C
C Preparation of DPMSA~ with 0 095 Equivalent~ Alkylation Another - ~ o~ulf~n;c ~cid ~olymer was pre~aroa A'rom 1 5 A~o~AAL
croAA~l~n~,~ ~y,~ /divinyl~ co polyA~or b~ad8 ( 30~70 m~shA) u8in~
25 the ~ occ~ o d-seribed in steps B-D o_ _lo 32, exeept usin~ 0 095 ~quivalents of ( 2 -AJ~ thyl)honzyl chloride in tho alkylation roaction Chloro~ f~n;c ac$d (1 5 oquiv~lonts r-lativo to the ~lc~ t~ total ~quival-nts of phenyl groups in tho polymer) was u~ed in the sulf~n~t;~n r-action Th;o~aartic acid and ~odium hie-~h~n-te (3 0 equival-nts of ~aeh relntivo to tho ~lc~ t~~ ~mount of L~ - in tho polymQr) w ro u~od in the thiolation reaction Tho mass yield of ~olymor oht-;n~~
from the alkylation reaction corrospondn to a 99 ~elc~nt yield in tho alkylation r-action and a d-gr~o of func~ion~l;ty o~ 0 094 The _inal polymer cataly~t has a titratod wator-wot (wator ~ ~n) acid ca~acity of ~5 0 80 'll;~_~ivalont/mD catalyst The final polymor catalyst was te' ns DPMSAA-0 10-1 5X2C

H Preparation of DPMSAA with 0 42 Equival-nts of (2-B ~ -ethyl)b-nzylchlorido Alkylation and 0 30 Equivaltants of Bonzyl Chlorid- Alkylation Another ~ ~aptoGulfonic acid ~olymer was prepared from 1 5 pez cro~ tyrene/divinyl~~~~ - co-~olym~r beads (-30170 mosh) usin~
the p .-- doscribed in ste~s B-D of Example 32, ~xcept using 0 42 ~quival-nt~ of (2-L ~ hyl)benzyl chloride and 0 30 ~aquivalents of b-nzyl chloride in the alkylation -ctio~ Chlorosulfonic acid (2 0 ~quivalont~ r-lative to tho c_lculAted total equivalonts of phenyl grou~s in th~ polymer) was used in the sulf~~Ati~ reaction ~h; ~A~t; C acid and soaium b~cA h~-te (3 0 eguival-nts of ~ach r-a~ent relativ~ to the calc~lat~d amount of L ~9 in the ~olymer) wore used in tho t h;olA,~ j~
re_ction Tho final polymor catalyst has a titratod wator-wet (water ~woll-n) acid ca~acity of 0 94 milliequival-nt/mL catalyst Tho fin_l 15 polymer catalyst was A~~;g~-t6d as DPMSAA-0 45/0 30-1 5X2C
I Preparation o~ DP~SAA Rcsin having 0 423 Equival-nts Alkylation Anothor - ~ptosulfonic acid polymer was preparod from 1 5 peice~L
cro~rl;~l- d ~Ly~ /diviny~ co-polymor bonds (-30l70 mesh) usin~
20 th~ p ~_~ ~ of st-ps B-D of _le 32, ~axcept usin~ 0 423 ~quival~nt8 of (2-Ll -_thyl)benzyl chloridt3 in tho alkylation e~ti~ and air-ctly carrying tho polymer slurry ~ht-;~A from the alkylation r-action dirtctly on to tho ~ul~Ati~ reaction without any qu~h;~ olA~ti~, or w-~hi~ st-ps aft-r tho nlkylntion reaction Chlorosulfonic acid (1 25 ~quival-nts r-lative to tho total equival-ntD of ph-nyl oroups p oso~L in all r-actants) was addea directly to the polymer ~lurry aft-r the alkyl_tion reaction waQ _ _l to Worku~ and ~ ~ent jPolAti~ of tho product afttar ~Ulf~Ati~ w_s as in Example 32, except that more ~ ive ~ ~h~ wa~ r-quir~a to remova soluble roaction L~-~ ~cts from the polym r ~lurry ~h;olA-etic acid and ~odium hic--h~-to (3 0 ~quival~nts of each rJ - r-lat$ve to the ~sti ~-d amount of L,~ --~ in the polymor) w rQ u~ed in the thiolation r-action The ~inal polymor cataly8t ha~ a titrated w-t- -w~t (water ~ ) acid cnp~city of 0 78 'l~ valent/mL cataly~t The ~inal polymer catalyst was 35 ~~~i5F~Atr l as DJ?~SAA--0.45NW--1.5X2C.

W O g7108122 PCT~US96/13683 J Preparation of DP~SAA Rosin with 0 238 Equivalonts Alkylation Anoth~r -~o~Lo~ul~onic ~cid polym r was ~r-~arod from 1 5 ~arcolt cro~sl;~-~ ~Ly__nD/diviny~ co-~olymer boads (-30+70 me8h) using a variation of tho ~oc~du~O do~cribed in Exam~l- 32 The alkylation and ~ul~Ation r-actions were ~orForm d in onQ ste~ ~t;li~;~ chlorosulfonic acid a3 th~ alkylation c~t~lyst and ~ulfonation 8~y..~e/divinyl~7~~~ co-polymer rosin b-ads (10 00 g, -30+70 mosh, 1 5 ~ercont divinyl~ tely 96 0 m~ol ~Ly ~n~ re~at units) woro add-d to a round bottom glass flask (ro~ctor) undor a pad of ~lant nitro~An with ~ ~odium L~a~ido scrubber attached (to trap evolved HCl) ~ olution of (2-~ ~ -~thyl)benzyl chloride (mixtur~ o~ a~ tic ring ir_ ~ 8, ~L~ a~ tely ~ar~) (5 32 g, 0 238 ~quivalonts banod u~on styreno ro~-at unit~) in 1, 2-a; chl oroothano (25 m~) wa~ added to tho dry re~in bead8 The b_ads woro All~ el to swell for ~L~ ely 5 to 10 ~OA-, th~n adaitional 1, 2~ hl oroeeh~s (35 mL) was adaod to tho ~ _11~ boads Tho slurry wa~
cool-d 2 to 3~C in an ico bath, thon chloronulf~;c acid (la 0 mL, ~ ely 21 0 g, 1 5 _quivalent8 ba8ed u~on total equival-nt~ of phonyl group8 in the mixtur_) was ada-d slowly aro~wiso ov~r ~1 - t-ly 20 1 hour 45 '~'lteP. Tho mixturO was All~ to ~tir an additional 1 hour at 3 to 4~C, th~n was ~ v_d to room t- _a ~turo and Al 1 ~ d to react an additional 1 5 hours The mixture w~8 then cooloa in an ice wator bath and wat-r wa~ ~lowly adaea to quench tho _xcAss chlorosulfonic acid Thereart-r tho bAaas worO iPol~At-~ according to th- ~ O d~3cribod in 25 ~art C 04 _ le 32 T-; k-W; -Q~ tho th;o~Ati~~ r-action was a8 in ~art D
of _lo 32 u8ing th;o~Af~ic acid and aodium h;c~_~At - (3.0 ~quivalonts O r each rea~-nt rAlative to tho o~l; -t~A~ amount of Ll ' - in tho ~olymer) The final ~olym~Ar catalyst has a titrat-d wator-wet (wat-r - ~) acid ca~acity of 0 94 ~ ~ivalont/m~ catalyst 30 The ~inal polymor catalyst was ~--i~At-d as DPMSAA-2S-0 25-1 5X2C
X Pro~aration of DP~SAA Resin Havin~ 6 5 ~o~ce~L Cro~sl;~king Anothor -7~Losulfonic acid ~olymor was ~re~ar~d from 6 5 cro~ -ed ~Ly,~ -/divinylh-n~- ~ co-~olymer b~aas (380 micron ~;f-particle si~ 8~ ) using the ~roD~ ~ d-scribed in sto~s B to D of 35 Example 32, oxco~t using 0 427 Oquivalents of (2-b~ ~thyl)benzyl chloride in tho alkylation roaction -W O 97/08122 PCT~US96/l3683 Chlorosulfonic acid (1 5 oquivalont~ relativo to tho calc~late~
total oguival-nts of ph-nyl groups in tho polymor) wa~ usea in the ~ulfonation roaction ~h;o7~etic acid nnd ~odium bir--h~--te (3 0 oquivalonts of oach r~agent rnlative to tho c~lc~lAted amount of b ~e in tho polymor) W~rQ used in the ~h;ol~t;on roaction Tho m 88 yield of polymor obtainea from tho alkylation r-action oo~ ' to a 57 porcont v yi-ld in tho alkylation roaction and a de~roo of func~ ty of 0 24 Tho final polymor catalyst han a titratod wator-wet (water _r 11~) acid c~pacity of 1 75 milli-quiv~lont/mL catalyst Tho 4inal polymor catalyst 10 was ~-r;~-te~ as DP~8AA-0 45-6 5X2C
L Pr~paration of DPMSAA Rosin with 0 25 Equival~nts Alkylation and Havin~ 1 8 ~e _~L Croggl;~k;~g Another ~ _~Losulfonic acia polymor wa~ pr-par-d from 1 8 p~ c_~L
cro~Pl ;~k~a ~Ly _ne/divinyll- - ~ copolymor boaas (-25~40 mosh) using tho 15 ~loc~a~ ~ d-~cribod in ~top~ B through D of r _le 32, oxcopt usin~ 0 25 equival-nt~ o~ (2-L~ - 'hyl)b-nzyl chloride in tho alkylation reaction Chlorosulfon$c ~cid (1 5 oquivalont8 relativo to the calc~late~
total ~quiv~l-nts of phenyl ~roup3 in tho polymer) was usod in the nulfA~t;~n r-action ~h;olA~etic acid and ~odium hic~ ho~t~ (3 0 ~quivalont~ of ~ach ~ relativ- to tho c~lc~ t-1 amount of L '~o in tho polymor) were usod in tho th;Alatio~ r-action The ma~s yiola of yolymor ~t~ from the alkylation reaction co~ to an 86 pOI~t y~-la in tho alkylation r-action and a dogroo of func~ ;ty of 0 22 The final polymor cataly~t had a titratoa water-wet (wator swollen) acid capacity of 0 85 ~ ~i~alont/m~ cataly~t The final polymor cataly~t wa~ d n~g~-t-~ a~ DP~8AA-0 25-1 8X2C
M Prer~a~t~ of DPMSAA Rosin with 0 10 Equivalonts Alkylation and ~avin~ 1 8 ~VI_ ~ CrOrr~i~k;~
~tl- - _~tosulfonic acia polymer wa8 proparod from 1 8 po,.- -30 ~ rl~ sLy,. -/diviny1ho~- ~ co-polymer b-ad~ (-25~40 me~h) usin~
tho ~loce~ doacrib-d in st-ps B to D of _~e 32, ~xcopt using 0 10 oquival-nt~ of (2-L, -~thyl)bonzyl ehlorid- in tho alkylation r-action Chloros~lfo~;c acid (1 5 oquivalonts relative to tho r-lc~1at~d total ~quival-nts of phonyl groups in the polymor) wa~ u~od in the sulf~-ti~~
r-action ~h;ol~otic acid and nodium bic- h~-t6 (3 0 equival-nt~ of ~nch r-a~ont rolative to th- c-1c~lated amount of b, ~~ in thH polymer) w re un-d in tho 1 h;o~t;o~ r~aetion The final ~olymer catalyst ha~ a CA 02230272 l998-02-24 W ~ 97~08122 PCT~US96~13683 titrated water-wet (water 8wollen) acid capacity of 0 81 millioquivalent/m~ catalyst The fin~l polymor catalyst was dAoi7~tPd a~

N Proparation o~ 1 5 ~ ~L Cro8nl;~e~ DP~SAA Resin with 0 10 Equivalent8 Alkylation and U8ing Sodium ~yd~ u~ in the ~,hiol~
Roaction Anothor -~to~ulronic acid ~olymor was pr~parcd from 1 5 ~L~_-L
cro~ Ly .~o/diviny7~-~-~ ~ co-polymer boads (-30~70 mesh) usin~ a variation o~ the ~LOCedu~ ~ described in 8to~s B to D of Exa~ple 32, ~xce~t using 0 10 Qquivalonts of (2-L ~ ~thyl)b~nzyl chlorid~ in th~ alkylation roaction and ~odium Lyd G~ulfido in th~ th; ol at;~ r-action Chloron~f~;c acid (1 5 e~uivalent~ relative to the c-lc~ tefl total e~uivalent8 of phenyl grou~8 in the ~olymor) wa~ u~od in tho uulf~~tio~
ruaction 80dium Lyd ~ulfi~s (6 4 ~quival~nt~ rolativo to th~ c~lc~lat~
amount of L ~ ~9 in the ~olymor) wa~ usod in th- 1h~ol~ti~n reaction The ma8s yield of polymer obtain-d from the alkylation rcaction COrrQ~F~Q to a dogr~e of func~ ;ty of 0 10 Tho final polym~r catalyst ha~ ~ titrat~d w~tor-wot (wator ~, ll~) acid capacity oÇ 0 82 millioquival-nt/m~ catalyst The final ~olymer catalyst was deni9n~te~ as 0 Preyaration of DP~SAA Rosin with 0 25 Equivalunts Alkylation and Having 4 ~ ' Cro~ol;~;~g Anothor --c~p~osul_onic acid polymer wa8 propar-d from 4 pL~ ~
cros~ 8tyrone/divinylh-~~ ~ co-~olymer b-ads (360 micron uniform ~art$clo si2e ~hc ~) u~ing tho ~ _~~ e describ~d in ~te~ B-D of _~e 32, ~xcopt using 0 25 oquivalonts of (2-L ~ ~~thyl)ben2yl ~h~ori~e in the alkylation reaction ChlorosulfoniC acid (1 5 ~quivalents r-lative to the ~lc~ ted total ~quivalent~ of phonyl grou~s in the ~olymer) was u~od in tho ~ul~n~ reaction ~h;o~a atic acid ana ~oaium bic-~h~n~te (3 0 ~quivalonts of oach rea~ent relativo to tho r~l c~ t~ amount o~ bL. ~ n~ in th- ~olym r) w ro u~ea in th ~h; ol~t; ~n roaction Tho mass yiOla of polymnr oht~ rom the alkylation roaction o~- _ _ '~ to a 73 ~CL~_ ~ yiela in tho alkylation r-~ction and a d-groo of ~uncti~n~l;ty o~ 0 18 Thc final ~olymor catalyst wa~ dQsignated as 35 DP~SAA-0 25-4X2C
P Pro~aration o~ DP~SAA Rosin with 0 10 Equival-nts Alkylation and Having 4 ~ - Cro~l;~;~

CA 02230272 l998-02-24 W O 97/08122 PCT~US96/13683 Anothor -~Lo~ l fA~; C acid ~olymor was prc~arcd from 4 ~n c~nL
crsr~li~k~d -Ly, --/divinyl~ --ns co-polymer beads (360 micron uniform particl- 8ize sphoro~) usin~ th~ ~C~d~Lo doscribod in ste~s B-D of Exampl~ 3Z, oxcOpt usin~ 0 10 oqui~alents of (2-Ll ~~thyl)benzyl chloridQ
in the alkylation r~action C_lorosulfonic acid (1 5 equival-nts rolativQ
to the calculatod total Qquivalents of phenyl groups in t_o polymer) was u~d in the ~ulfo~-t; A~ rOaction. ~h;ol~etic acid and sodium hic-~hA~Ate (3 0 ~quival-nts Of ~ach L~-_ t rolativo to tho calculAttd amount of b~ in the polymer) worO u~od in the fh;ol~;~ roaction The ma~s yiold of polymQr oht~ from the alkylation r-actio~ GG~ ~ P_ '~ to an 74 ~_ cel~L yiold in tho alkylation roaction and a do~re~ of funct~ A~l i ty Of O 074 The final polymQr catalyst was d~riD~ted as DP~SAA-0 10-4X2C
_~ 33 Evaluation of Catalysts in a CA~t;~l~~u~ Proces~
A t_ro--stagQ up-flow r-actor wa~ constructed from t_roQ vertical ~t-~ s st-ol tubos with ~-m~l;~g ports bLt~_- oach soction Each rOactor ~ta~- was wator jacketod for t- _--~tura control wit_ all co~ocLing lines heat-tracod to ~ OvonL reactor lino ~lu~ing Lik-wi~e tb~ 2L roactor f - od tank was jack-ted 80 that ~ e control Of the r-actor ~-oa can be obtained From the f-ed tank, foQd flows t_rou~h an n70_L lcally hoat-tracod ~oction of tubin~ for control of feed input t-mp-ratur-Each ctor s-ction was yacked wit_ 10-20 mL of wat-r-wet catalyst Tho reactor foOd consi~ts of a solution of 4 weight ~ ~ L acetonO
in ph-nol Thu ac-tono ~_Onol mixturO was ~ ~ -ly mot-red into t_~
t- _~ ~ture controll-d r0actor system at a ~~fi--d c '-~Atio~ of flow rat- (1 0 mL/min to 2 0 mL/min) ana roactor t~ _ ~turo (55~C to 65~C) U~on ~tart-up of ~ach new lo~;n~ of cataly~t, the foOd ~assos t_rou~h tho catalyst for at loast 12 hours boforo moa~ Y were ~ ' to r~movo water from th~ catalynt Product __~ition of the roactor effluont from ~ach of tho thr-e stages was analyzod by ~PLC while gns ~L~ tG~ ~Ly was u~-d to analyze for acotono and wator The r-sults A~t~;--' from tost~ of th- catalyKts at various timos of ..~cti~ (r-actor ~ ~e tim 8) w~ro ~rovia-d in Tablo XIX Productivity was ~xpr-ssod in terms of ~ounds of ~i,r_~ -1 A ~l~ ~er hour ~or cubic foot of water-~wollon catalyst charged into th~ r-actor (NOTE Unl-ss ot~ -w 80 not-d, all of the catalyst r-~ults w~re obt~inod at 55DC ) Table XIX

Claims (68)

WHAT IS CLAIMED IS:

1. A process for the condensation of an aldehyde or ketone starting material with a phenol, unsubstituted in at least one position, wherein the aldehyde or ketone starting material is reacted with the phenol in a reaction mixture in the presence of a soluble or insoluble mercaptosulfonic acid compound under conditions sufficient to bring about formation of a geminal bisphenolic moiety at each aldehyde or ketone moiety in the starting material;
provided that the soluble mercaptosulfonic acid compound was characterized by the formula (HS)a-.theta.-(SO3H)b wherein .theta. was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocylic residue and a and b were independently selected from integers from 1 to 20, and the insoluble mercaptosulfonic acid comprises a catalytically-active species represented by the formula (IMG) in which .theta.' was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecyloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20; L
was an optional linking group and - was a bond, which catalytically-active species was attached by the bond - to an insoluble organic or inorganic support;
or a catalytically-active species represented by the unit formula (IMG) wherein .theta." was an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocycle or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20;
L' was an optional linking group and - was a bond, wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

2. The process of Claim 1, wherein the mercaptosulfonic acid compound was soluble in the reaction mixture and was characterized by the formula (HS)a-~-(SO3H)b wherein ~ was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue and a and b were independently selected from integers from 1 to 10, wherein the mercaptosulfonic acid catalyzes insomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

3. The process of Claim 1, wherein the ketone was fluorenono, the phenol was unsubstituted and the product was 9,9-bis-(4-hydroxyphenyl) fluorene, wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

4. The process of Claim 2, comprising a process for making a bisphenol by the step of contacting an adehyde or a ketone with excess phenolic compound in the presence of a catalytic amount of mercaptosulfonic acid catalyst, which was soluble in the reaction mixture, at a temperature selected such that a bisphenol was formed and crystalizes in the reaction mixture, wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bis -(4-hydroxyphenyl) compound than would be produced without isomerization.

5. The process of Claim 4, wherein the ketone was acetone, the phenolic compound was phenol, and the bisphenol was bisphenol A,wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

6. The process of Claim 1, wherein the catalyst was represented by the formula (HS)~-~-(SO3~H)b wherein ~ was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylene-cycloaliphatic, alkylone-aryl, hetorocyclic, or alkylene-heterocyclic moiety, and a and b wero each independently integers averaging from 1 to 4, wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

7. The process of Claim 6, wherein the catalyst was represented by the formula (HS)-~-(SO3H) wherein ~ was an alkylene, cycloalkylene or arylene moiety having from 2 to 10 carbon atoms, wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

8. The process of Claim 1, wherein the mercaptosulfonic acid was an insoluble material comprising a catalytically-active species represented by the formula in which ~' was an alkylene cycloaliphatic, arylene, alkylenearylene, alkylenocycloaliphatic, alkylenearyl, hetorocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20; L
was an optional linking group and - was a bond, which catalytically-active species was attached by the bond - to an insoluble organic or inorganic support;
or a catalytically-active species represented by the unit formula wherein ~" wan an alkylene, arylene, cyrloalphatic, alkylonoarylene, alkylenecycloaliphatic, alkylenearyle hetrocyclic or alkyleneheterocyclic residue; a and b independently selected from integers from 1 to 5; L' was an optional linking group ana -was a bond, wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce moro bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

9. The process of Claim 8, wherein the catalytically-active species was attached to the backbone of a polymer from at least one ethylenic monomer, wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would bo produce without isomerization.

10. The process of Claim 8, wherein the catalytically-active species was incorporated in a polystyrene resin, wherein the mercaptosulfonic acid catalyzos isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

11. The process of Claim 10, wherein the polystrene resin includes unit structurce represented by the formula wherein B was a bridging group, R ana R2 were independently selected H, alkyl and aryl, -CnH2n- was straight or branched chain alkylene and n was an integer from 0 to 20, wherein the mercaptosulfonic acid catalyzes isomerization of crude producet mixture to produce more bis-(4-hydroxphenyl)compound than would be produced without isomerization,

12. The process of Claim 10, wherein the polystrene resin was made by the steps of (a) treating polystyrene an alkenyl halide of the formula RC(R1)=C(R2)CmH2mCH(R3)X, wherein R, R1, R2 and R3 were independently selected from H, alkyl or aryl X was selected from F, C1, Br or I and m was 0 to 10; to produce a haloalkylpolystyrene;
(b) sulfonating the resulting haloalkylpolystyrene to produce a sulfo (haloalkyl) polystyrene, (c) optionally the converting the sulfo function to an alkali metal or alkaline earth metal salt, (d) reacting the halo function with a reactive thiolate to produce a corresponding mercaptan function and (e) optionally acidifying to produce a corresponding sulfonic acid function, (f) isomerizating crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization in the presence of the mercaptosulfonic acid.

13. The procoss of Claim 12, wherein the alkenyl halide was an allyl halide of the formula RC(R1)-C(R2)CH(R3)X, wherein each of R, R1, R2 and R3 was H independently H or alkyl of 1-5 carbon atoms.

14. The process of Claim 10, wherein the polystyrene includes unit structures represented by the formula wherein the mercaptosulfonic acid catalzes isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

15. The process of Claim 10, wherein the polystyrene resin was made by the steps of:
(a) alkylating a haloalkylated polystyrene with a haloalkylarylene compound to produce an intermediate having [(haloalkyl)phenylalkyl] styrene units;
(b) sulfonating the tus-produced intermediate to produce an intermediate containing [(haloalkyl)(sulfo)phenylalkyl] sulfostyrene units;

(c) optionally converting the sulfo functions to corresponding alkali metal salts;
(d) thiolating the thus-produce intermediate which contained sulfostyrene units;
(e) and hydrolyzing the thus-thiolated intermediate with an acid to produce a polymer containing [(mercaptoalkyl)(sulfo)-phenylalkyl) sulfopolystyrene units.

16. The process of Claim 10, wherein the polystyrene resin was made by the steps of (a) reacting a haloalkystyrene polymer with a lithiated sultone, (b) treating a resulting sultone-functionalized polymer with a reactive thiolate and (c) acidfying the resulting intermediate to produce a polymer containing (mercaptosufoalkyl)styrene units.

17. A process to make a bisphenol, wherein an aldehyde or a kotone is contacted with excess phenolic compound in the presence of a catalytic amount of a mercaptosulfonic acid catalyst, which was soluble in the reaction mixture, at a temperature selected such that a bisphenol was formed and crystallized in the roaction mixture and wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bio-(4-hydroxyphenyl) compound than would be produced without isomerization.

18 The process of Claim 15, wherein the catalyst was represented by the formula:
(HS),-~'-(SO3H)b wherein ~ was an alkylene, cycloaliphatic, arylene, alkylene-arylene, alkylene-cycloaliphatic, alkylene-aryl, hetorocyclic, or alkylene-heterocyclic moiety, and a and b were each independently integers averaging from 1 to 4.

19. The process of Claim 15, wherein the mercaptosulfonic acid catalyzes isomerization of crude product mixture to produce more bis-(4-hydroxyphenyl) compound than would be produced without isomerization.

20. A process of isomerizing an o,p-bisphenol to form a corresponding p,p-bisphenol wherein the o,p-bisphenol is contacted with a mercaptosulfonic acid at a temperature sufficient to result in isomerization of the o,p-bisphenol to form a p,p-bisphonol.
(HS),-~-(SO3H)b wherein .theta. was an alkylene, cycloaliphatic arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, hetorocyclic or alkyleneheterocyclic residue and a and b were independently selected from integers from 1 to 20; and the insolube mercaptosulfonic acid comprises a catalytically-active species represented by the formula in which .theta.' was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20; L
was an optional linking group and - was a bond, which catalytically-active species was attached by tho bond - to an insoluble organic or inorganic support;
or a catalytically-active species represented by the unit formula wherein .theta." was an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20;
L' was an optional linking group and - was a bond.

21. The process of Claim 20, wherein the mercaptosulfonic acid compound was soluble in the reaction mixture and was charactorized by the formula (HS)a-.theta.-(SO3H)b wherein .theta. was an alkylene, cycloaliphatic,arylene, alkylenearylene, alkylenecycloaliphatic alkylenearyl, heterocyclic or alkyleneheterocyclic residue and a and b were independently selected from integers from 1 to 10.

22. The process of Claim 20,wherein each of a and b were independently selected from 1 to 4

23. The process of Claim 20, wherein each a and b were each 1

24. The process of Claim 20, wherein the mercaptosulfonic acid compound was generated in the reaction mixture by reaction between an alkali metal salt of a mercaptosulfonic acid and a mineral acid.

25. The process of Claim 24,wherein the alkali metal salt of the mercaptosulfonic acid compound was generated in the reaction mixture by reaction between a mercaptosulfonate ester and an alkali metal hydroxide.

26. The process of Claim 22, wherein the mercaptosulfonic acid compound was generated in the reaction mixture by reaction between a mercaptosulfonyl halide and a mineral acid.

27. The process of Claim 21, wherein the mercaptosulfonic acid compound was a mercaptoalkanesulfonic acid of up to 20 atoms between the mercapto and sulfonic acid groups.

28. The process of Claim 21,wherein the mercaptosulfonic acid compound was 3-mercaptopropanesulfonic acid.

29. The process of Claim 21, wherein the mercaptosulfonic acid compound was 4-mercaptobutanesulfonic acid.

30. The process of Claim 21, wherein the mercaptosulfonic acid compound was 2-mercaptonethanesulfonic acid.

31. The process of Claim 21, wherein the mercaptosulfonic acid was free of or substantially free of chloride ions.

32. The process of Claim 20, carried out at a temperature from 15°C
to 60°C.

33. The process of Claim 20, wherein the reaction mixture contained from 0.01 to 2.0 equivalent of mercaptosulfonic acid per mole of aldahyde or ketone.

34. The process of Claim 20, carried out with removal of water from the reaction mixture.

35. The process of Claim 20, wherein the reaction mixture contained from 0.02 to 1.0 equivalent of mercaptosulfonic acid per mole of aldehyde or ketone.

36. The process of Claim 20, wherein the ketone was fluorenone, the phenol was unsubstituted and the product was 9,9 -bis-(4-hydroxyphenyl)fluorene.

37. The process of Claim 20, wherein the ketone was acetone, the phenol was unsubstituted and the product was 2, 2-bis-(4-hydroxyphenyl)propane.

38. The process of Claim 20,wherein the ketone was 4-hydroxyacetophenone, the phenol was unsubstituted and the product was 1,1,1-tris-(4-hydroxyphenyl) ethane.

39. The process of claim 20, wherein crude product,resulting from the condensation, was extracted with water to remove (HS)a-.theta.-(SO3H)b from the product.

40. The process of Claim 20, wherein crude product, resulting from the condensation, was extracted with an aqueous solution of an alkali metal hydroxide, carbonate or bicarbonate to remove (HS)a-.theta.-(SO3H)b from the product.

41. The process of Claim 20, wherein crude product, resulting from the condensation, was treated with an anion-exchange resin to remove (HS)a-.theta.-(SO3H)b from the product.

42. The process of Claim 39, wherein the resulting aqueous extract is further concentrated and the thus-concentrated solution of extracted (HS)a-.theta.-(SO3H)b is recycled to the process.

43. The process of Claim 20, wherein the mercaptosulfonic acid was an insoluble material comprising a catalytically-active species represented by the formula in which .theta.' was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkylenehetorocyclic residue; a and b were independently selected from integers from 1 to 20; L
was an optional linking group and -was a bond, which catalytically-active species was attached by the bond - to an insoluble organic or inorganic support;
or a catalytically-active species represented by the unit formula wherein .theta." was an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 5; L' was an optional linking group and -was a bond.

44. The process of Claim 43, wherein the catalytically-active species was attached to the backbone of a polymer from at least one ethylenic monomer.

45. The process of Claim 43, wherein the catalytically-active species was incorporated in a polystyrene resin.

46. The process of Claim 45, wherein the polystyrene resin includes unit structures represented by the formula wherein B was a bridging group, R and R1 were independently selected from H, alkyl and aryl, -CnH2n- was straight or branched chain alkylene and n was an integer from 0 to 20

47. The process of Claim 46, wherein B was CH2 and -CnH2n- was -CH2CH2- or -CH2-.

48. The process of Claim 45,wherein the polystyrene resin was made by the steps of (a) treating polystyrene with an alkenyl halide of the formula RC(R1)=C(R2)CmH2mCH(R3)X, wherein R, R1, R2 and R3 were independently selected from H, alkyl or aryl; X was selected from F, Cl, Br or I and m was 0 to 10; to produce a haloalkylpolystyrene;
(b) sulfonating the resulting haloalkylpolystyrene to produce a sulfo(haloalkyl) polystyrene, (c) optionally converting the sulfo function to an alkali metal or alkaline earth metal salt, (d) reacting the halo function with a reactive thiolate to produce corresponding mercaptan function and (e) optionally acidifying to produce a corresponding sulfonic acid function.

49. The process of Claim 48, wherein the alkenyl halide was an allyl halide of the formula RC(R1)=C(R2)CH(R3)X, wherein each of R, R1, R2 and R3 was H independently H or alkyl of 1 to 5 carbon atoms.

50. The process of Claim 49, wherein each of R, R1 and R2 was H.

51. The process of Claim 48, wherein the alkenyl halide was 5-bromo-pentene or 11-bromo-1-undecene.

52. The process of Claim 49, wherein the polystyrene resin includes unit structures represented by the formula

53. The process of Claim 49, wherein the ketone was fluorenone, the phenol was unsubstituted and the product was 9,9-bis -(4-hydroxyphenyl)fluorene.

54. A catalytically-active material characterized in that there is an insoluble organic or inorganic support in which incorporated a mercaptosulfonic acid residue represented by the formula in which ~ was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20; L was an optional linking group and - was a bond, which catalytically-active species was attached by the bond - to the insoluble organic or inorganic support.

55. The process of Claim 20, carried out in a stainless steel reactor, wherein the corrosion rate of the stainless steel reactor was less than 0.00254 cm/year.

56. The process of Claim 31, carried out in a stainless steel reactor, wherein the corrosion rate of the stainless steel reactor was less than 0.00254 cm/year.

57. The process of Claim 20, carried out in the absence of a diluent, other than excess phenol.

58. The process of Claim 20, carried out in the presence of diphenylmethane an a diluent.

59. The process of Claim 43, including the further steps of separating the catalytically-active material from the mixture; washing the catalytically-active material with a mixture to phenol and -aldehyde or ketone and recycling the thus-washed material to the process.

60. The process of Claim 20, carried out in a batch reactor

61. The process of Claim 20, carried out in a continuous reactor.

62. The process of Claim 37, carried out in the presence of a diluent which forms an adduct with 2,2-bis-(4-hydroxy-phenyl)propane under conditions such that 2,2-bis-(4-hydroxy-phenyl)propane crystallizes in the reaction mixture.

63. The process of Claim 45, wherein the polystyrene resin was made by the steps of:
(a) alkylating a haloalkylated polystyrene resin with a haloalkylarylene compound to produce an intermediate having [(haloalkl)phenylalkyl] styrene units;
(b) sulfonating the thus-produced intermediate to produce an intermediate containing [(haloalkyl)(sulfo)phenylalkyl]sulfostyrene units;
(c) optionally converting the sulfo-functions to corresponding alkali metal salts;
(d) thiolating the thus-produced intermediate which contained sulfostyrene units;
(e) and hydrolyzing the thus-thiolated intermediate with an acid to produce a polymer containing [(mercaptoalkyl)(sulfo)-phenylalkyl) sulfopolystyrene units.

64. The process of Claim 63, wherein the haloalkylarylene compound was selected from chlorobenzene, chloromethylbenzene, chloroethylbenzene, chloropropylbenzene, chlorobutybenzene or corresponding fluoro,bromo or iodo analogues.

65. The process of Claim 64, wherein the haloalkylarylene compound was selected from bromobenzene, bromomethylbenzene, bromethylbenzene, bromopropylbenzene or bromobutylbenzene.

66. The process of Claim 45, wherein the polystyrene resin was made by the steps of (a) reacting a haloalkystyrene polymer with a lithiated sultone, (b) treating a resulting sultone-functionalized polymer with a reactive thiolate and (c) acidifying the resulting intermediate to produce a polymer containing (mercaptosulfoalkyl)styrene units.

67. The process of Claim 66,wherein the lithiated sultone was a lithiated 1,3-propanesultone.

68. The process of Claim 66, wherein the lithiated sultone was a lithiated 1,4-butanesultone.