CA1112393A - Ketone and sulfone polymers - Google Patents

Abstract

ABSTRACT

A polymer of the general formula:
R'-M=Ar-B-Ar' ? MArBAr'?k-2 M-Ar-B-Ar'-R wherein M and B, which can be the same or different, are independently or -SO2-, wherein each Ar is independently or wherein L is , -SO2-, phenyleneoxy, a covalent bond or T, wherein T is as defined below and each Ar' is independently: wherein T is O, S, phenyleneoxy, or -CR2- wherein R is as defined below, or -O-Ar-O- wherein Ar can have any of the values set forth above and wherein R' and R" are independently wherein X is a covalent bond, -O-, -S-, or -CR2- wherein each R is independentlyhydrogen, an alkyl or fluoroalkyl group, preferably of 1 to 10 carbons, phenyl or an electron withdrawing group substituted phenyl, Y is CN, NO2, or or if X is a covalent bond, Y can be hydrogen as well as any of the foregoing;
or Ar"CO- or Ar"SO2-wherein Ar" connotes phenyl, phenoxyphenyl, naphthyl, biphenyl or terphenyl either unsubstituted or substituted with one or more electron withdrawing sub-stituents such as halogen, nitro, or cyano, provided that when Ar" is phenoxy-phenyl there shall be at least one electron withdrawing substituent on the phenoxy moiety and process for the preparation thereof.

Description

23~3 - -This invention relates to polymers, especially polyketones al~d polysulfones, and a process for their manu:EactureO
In the search for organic polymers suitable for use at elevated temperatures, many repeating units involving diverse ccnnecting linkages between aromatic moieties have been suggested, e,g. aromatic structures connected by such linkages as imldes, ethers, sulfones and ketones. Unfortunately, as potential perfoYmance at elevated temperature has ~een enhanced, the amenability of the polymer candidates to classical techniques of melt fabrication for polymers has decline~ or disappeared. More often than not, the same decline in melt processability accompanies attempts to produce high temperature stable polymers having an .
elongation of at least about 50%, a necessary property for many polymer applications, e.g~, if a polymer-; ~ insulated wire is to be capa~le of being twisted about itself without cracking of the,insulation.
Aromatic polyketones are known to enjoy relatively good resistance to thermal degradation. Bonner, in U,SO Patent No. 3,065,205, proposes the Friedel-Crafts -ca-talyzed pol~merization of certain reactants to yield polyarylketones, and lists as typical Friedel-Crafts ., catalysts ferric chloride and boron trifluoride~ The two basic reaction~ tauyht by this patent can be summarized as follows-.

~ 2 -.

'' ~.

1) n(HR-O-RH) -~ n(Cl-A-Cl) ~nHCl + H(R-O-R-A)n ~1 .
and

2) n(HBH) ~ n(Cl-A~Cl)--~ nHCl -~ Cl(A-B)nH
where HBH is a polynuclear aromatic hydrocarbon, e.g., naphthalene, ~-O-RH is a diaromatic ether, e.gO, dlphenyl ether, and Cl-A-Cl is a diacyl chloride, e.g., terephthaloyl chloride or - 2a -

3~3, : `

pho~geneO When phosgene and diphenyl ether are reacted9 the re~ulting poly~er will compri~e repeating unit~ of the structure:

~30~C - ' ' ~, ~ha ~ame repeating u~it i~ ~tated in ~ritish Patent ~o ~, 971, 227 to arise from the sel*-c:onden~ation o~ diphenyl ether-4-carbonyl chloride~ and ~rom the reaction of diphenyl ether with diphenyl ether 4~4l-dicarbonyl chloride.
A dif:~erent approach 1~ taken by ~arnh~m and Johnso~
in ~riti~h Patent No. 1,078,234. ~er~9 polyarylethers ~re produced by reaction o~ a dialkali metal salt o~ a dihydrlc phenol with a dihalo benzenoid compound. The dihydric phenol may contain a ~eto group - thu~ 494'~dihydro~y benzophenone i~ ~tated to yield a polyarylether polyarylketone (~ee~ for - e~ple s ola~ 1 5 ) .
S~ther improved method~ for making polyaryll~etoxle~
h~ve been proposedO For example, ln ~.,S. Pa~ent~ ~o~.
3~441,538 and 3,4429857 there i~ su~geæted the u~e OI ~droge~
fluoride/boro~ tri~luoride catalysis, a cataly~t æy~tem taugh~
in =~
~opchiev et al, Pergamon Pre~ (1959~, pO 122, ~_~
2401 (1961); and I & :6 ChemO 4~, 746 (1951~. ~ further :~ ~uggesbion ~or a~ improved proces~ ~or ~ynthe~ising polyaryl-: ~ ~ ketone~ iæ di~cloæed in ~3ritish Pate~t No., 1 ,08~,û210 .
: . Bri~ish Paterlb ~o~ 1,,086,0 1 di~clo~e~ the ~iedel-;: 25 ~ Cra~t3 co~de~atlon polymerization o~ diacid h~lide~ with a . . . . . .
, second compound contai~ing a1; lea~t two displaceable aromatic ~lly bound hydrogen atoms~ pre~erab]y -the diacid hallde ~nd the ~econd compound being present in substantially equimolar amo~nts; or of a single compound cc)ntaining both an acid halide group and at least one displaceable aromatically bound hydro~en atom~ It l~ ~urther disclosed that molecular weight may be controlled by u~i~g no~-~toichiometric amounts o~ the two compou~ds or by adding a third component which i~ mono~unctional under the conditions o~ the reaction~
Monoacid hal~des are me~tioned a~ examples o~ suitable mono~unctional molecular weight control agent~
Br~tish Speci~ication No. 17109,842 discloses the polymerization reaction o~ aryl disul~onyl ha:Lide~ with CO
pound~ contai~ing at least two di~placeable aromatically bound hydrogens. I~ all the examples o~ this patent 9 a~
i~ those o~ 1,086,021, the proposal is either o~ e~uimolar amoUntB 0~ electrophile and nucleophile or o~ an excess o~
~ the electrophile (i.e~ ~iacid halide). ~hi~ patent ~urther propo~ the quenching o~ residual sulfonyl chloride ~roup~
by po~t polymerization addition o~ ba~e~ ~uch as aniline, 80dium ~arbonate or diphenylether ~ince re~idual sul~onyl chloride groups on the pol~mer chains are stated to cause the product~ to ~uffer from rl~ing vi~cosity when moltenO
I~ U~. PateD~ No~ ~593~400 there is proposed the preparation ~ polyarylketone3 of mean inherent vi~co~ity (Oot % W/Y in ~ul~uric acid~ 0~8 to about 12650 ~he inhere~t v~8co~it~ and molecular weight are controlled by the u~e in ~ppropriate quantitie3 and reaction condition~ o~ selected ~ucleophilic age~t~ who~e reacti~ity to acetylation ~rela-tive , - . .

to a benzene reactivity of 1) is greater than about 150~
The use of nucleophile~ a~ molecular weight control age~t~ in pol~merizations o~ thi,s type ig advantageous ~ince it has been ~ound that othel~ise, in aclditio~ to the problem oP melt in~tability (re~ulting ~rom the presence o~ e~ces~
~lectrophile ~hich in turn results in re~idual acid halide polymer chain end group~) the presence o~ a~ e~cess o~ acid halide groups ~i.e~ 9 electrophile~3 during polymeriza~ion leada to the formatio~ o~ branched chain pGlymers resulting ~rom ortho~acylation of nucleophilic interior segments (~uch . as diphenyl ether moietie3) in a polymer chai~ by the te~minal ac~d halide group~ o~ neighbori~g cha~ns. It i~
believed to be the case that ~rhîle numerou~ sites on the nucleophile are still available linear ohain building ~ill occur but once ~uch sites become low in concentration the ordinarily much ~lower acylation reaction at the ortho position becomes significant. This problem has been discussed ~ ~ngeloS et a (~OS~ Pa~ent No. 3,767,620) whlch describes the formation o~ 9-phenylenexanth-hydrol re~idues ` ~ ~
.. ~0~

.
t~rough ortho acylation durlng the preparation o~ a polymer ha~ing the repeatin~ structural ~orm~la~

~ 5 -.

3'~3 ~3~C13 o ~ .

Such a residue i~ ~ormed by the reactio~ o~ a diacyl hallde wl~h diphenyl ether such that at least some o~ the diacyl halide acylate~ diphenyl e-ther residues in each ring ortho to the o~ygen atom ~because, vlrtua:Lly all the l~ara pos~tions are already blvcked by prior acylatio~). Such ~ortho acylated moietles are indiçated as ~eading to thermal in3tability~ specificallyD impaired melt processability~
Such deg~adation oan be reduced by h~droge~ation ~reduction3o~ the polymer, ~or example, ~lith ethanol and hydrochloric acid, formic acid or pre~erably triethyl sila~e in homogeneous acid media~ to give the much more stable 9-phenylene~lthene . reeidueO ~hi~ reduction i~ said to lead to products of lighter color and much improved melt stability due to the re~oYal o~ the hydro~yl group and its replacement b~ a - h~drogen atom~
Treatment o~ the abo~e branched polymer~ dlssolved 1~1 aic~Loroacetic acid~ with,trl~thyl silane is also recommended b~ Agolino i~ U.S~ Patent ~o~ 3~668~057 a~ a mean~ o~
~tabil~æi~g branched chairl residue~0 ' 0~ course9 if as proposed in ~.S. Patent ~oO
3~59~ 9 400 the polymerization i~ carried out with the ~ucleophilic agent in exce~g a~d~or molecular ~eight control ~ fected wi~h a nucleophilic compQund, then there i~
~n e~cess o~ ite~ and the above-mentiQ~ed branching ~o reaction will not occur/the ~ame deleteriou~ extent.
' flowever, it has now ~een disco~ered that when -the term-inal yroup on either or both ends of each polymer chain is a phenoxy (or other nucleophilic) moiety having a para position available fQr reaction then, in highly acid media such as the preferred hydroyen fluoride~boron fluoride mixtures, a, hereto-fore unknown, branchIng reaction occurs. It is believed that such branchin~ results from the reaction of the phenoxy (or other nueleophilic) groups (presumably activatedr i.e.~ proton-ated by the acid medium~ with carbonyl groups in the polymer itself leading, it is believed/ to the formation of trisaryl carbonium salts. Irl addition to the deleterious effect of branching per _ on processabilityr such salts are thermally very unstable and lead to degradation and discoloration in the polymer when molten.
As disclosed in copendiny Canadian Application No.
258,689, filed August 9/ 1976, treatment of the polymerized reaction media with certain bases before isolation of solid polymer substantially improves the thermal stability of polymers prepared by Friedel-Crafts condensat;~on polymerization through a controlled decomposition of ketonic and other complexes formed with the catalyst. However, this post-polymerization treatment does nut stop the formation of branehed polymer chains by or-tho acylation. Moreover 7 this treatment does not prevent the herein-above mentioned protonated phenoxy group branching reaction catalyzed by strong acid which takes place concurrently with the polymerization reaetion itsel:E and can continue as long as the polymer is in a strongly acid medium.

3 j`

~hu~ the need ~till exist~ ~or a method of preparing polyarylketones and polyaryl ~ul~ones by a Friedel-Cra~t~
condensation ~olymerization reacti.on that yield3 linear~
~nbranched products o~ reproducibl.e molecular wei~ht, stable and pr~dictable melt vi9eosity 7 and enhanced stability in highly acid solutions~ ~he term "acylation" as used in the in~tant applica-tion connotes the reaction in acidic media o~ the moiety ArCO~ or ArS02 with an aromatic nucleo-phile, Ar representing the residue o~ a protonated monomer or a ~blymer chain which is con-tinuing to undergo polymeriza-tion (chain growth) by means o~ the acylation reaction.
The term acid halide there~ore connotes any reactive species formin~ the moièty ArCO~ or ArS02 under ~riedel-Cra-ft~
reaction conditions. Common example~ include Ar~COCl, Ar-COOH
~nd .Ar-COOR and the sul~onyl analo~ues ~hereof.
The pre~ent invention provides a polymer~ ~hich compri~es repeating units of -the formula ~ M - Ar ~ B - Ar' ~
in which - M and - ~ - which may be the æame or di~erent each represents - CO ~ or $0~ -, Ar repre~en-ts or ~ ~ ~

in ~rhich ~ ~ repre~ents CO -, S02 ~ nHCO -, a covalent bond or - ~ , wherein ~ ~ - represent~ - O -~
S ~ phen~leneo~y~ - O - Ar ~ O -~ or CR2) wherein each R9 which may be the ~ame or different, represent~ hydro~eng an alkyl or ~luoroalkyl group, preferably con-taining from 1 to 10 carbon atom~ 9 an un~ub~tituted phenyl group or a phenyl .
~ 8 ~

group ~ubstituted by an elec-tron withdrawing group 9 and Ar' represents ~ T ~ , the end groups o~ the polymer being ~ormed from a nucleo~hilic or elec-trophilic capping agent~
Preferably, the alkyl or fluoralkyl groups that may constitute R contain from 1 to 10 carbon atoms~
~he repeating ~lits in a given polymer advantageously c~nsist essentially of repeating unit~ of the formula ~ M - Ar - 3 - Ar' ~
a~d the po~ymer i,s advantageously substantially linear and advantageously is a homopolymer. The polymer may, however, contain al~o units that are not a.s specified~ sv.ch a(lditional or units being either of unrelated structure/o~ structure deri~ed from a unit -~ M Ar ~ ~ ~ Ar~ -~ but being -trivalent or o~ other higher ~alency. The polymer may also contain units of two or more identities represented by the general for~ula ~ Ar - 3 - Ar' -~ in combination with other unrelated repeating units. Pre~erably, when Ar~ is ~ T ~
and - T - represent~ 0 - Ar - 0 ~, the Ar ~egment o~ the T moiety is dif-ferent from that of Ar in the M ~ Ar - ~ - Arl ~ unit.
The nucleophilic capping agent is of the general foxmula ~Ys .

., .

_ g _.
, :

w~lerein - X ~ repre~ents a covalent bond~ - O ~ ~ S -, or ~ CR2 - t wherein each R, which may be the same or di~eren-t~
has the meanin~ ~pecified above (prefera~ly - X - repre~ents a covalen-t bond or - O -) and ~herein Y represents - CN, - NO2, - CO ~ ~ S2 ~ ~ or, provided X i~ a covalent bond, hydrogen~
The electro~hilic capping agent i5 of the general ~ormula Ar"COZ or Ar"SO~Zs wherein Z represent~ OH, halogen ~pre~erably chlorine or fluorine) or OAlk, wherein Alk represent~ an alkyl group 9 preferably an alkyl group with up to 10 carbon atom~ 9 and wherein Ar" repre~ents phenyl, nAphthyl, biphenyl 7 ter~henyl, or phenoxyphen~
with at le~t ore electron withdrawing grbup on the phenoxy moiety, preferably with ~uch a group at the ~ara po~itionO
The Ar" radical may otherwise be unsubst}.tuted but i~ pre~era'ol.y ~ubst~tuted by at least one electron withdrawing group~
A~ ~lectron withdrawing group~ halogeno, nitro and cyano are pre~erred.
. Mi~tures o~ two or more nucleophilic or electro-philic capping agents may be employed.
~he polymer may have all its end groups ~ormed ~rom electrophilic capping agent or all from nucleophilic capping agent, or ~o~e from electrophilic and ~ome from mlcleophilic capping agent. In ths preferred ca~e, ~here the polymer i~ linear 9 each chain may have both end group~
~ormed ~rom the electro~hilic~ or nucleophilic 9 or may have one end group ~ormed fro.~ electrophilic and the other from nucleophilic, capping agent, according to the polymerization reaction em~loyedO

_ 10 --~3 I-t will be realized by those skilled in the art that, although in most instances polymer chains have two ends (i.e., are linear), in some circumstances, as for example, ~o produce melt processable polymers with high melt strength, it may be pre:Eerable to provide polymers having chains with three or more ends, i.e., with long chain branches and that, in such circumstances the present invention contemplates capping a]l t.he ends of such molecules even though the term "double" or "doubly" capped is used. ' The present invention also provides a process for the manufacture of a polymer, by Friedel Crafts condensation polymerization of ~ither '(I) at least one first monomer containing diacid halide groups and at least one second monomer containing at least two displaceable aromatically bound hydrogen atoms in the presence of from about 0.002 -- molè to abou~ 0.10 mole of nucleophilic capping agent per mole of said first monomer if said first monomer i5 in excess, ~rom about 0.002 mole to about 0.10 mole of'electrophilic capping ayent per mole of said second monomer if said second monomer is in excess, or from about 0.001 to about 0O05 mole per mole of said first monomer of each of electrophilic and nucleoph.ilic ~5 capping agent i'f said first and second monomers are present in substantially equimolar quantities, or (II) at least one'monomer having at leas-t one acid halide group and at least one displaceable aromatically bound hydrogen atoms, in the presence of ~rom about vg~;;~ , .

0.001 mole to about 0.05 mole per mole of monomer of each of nucleophilic and electroph:ilic capping agent, wherein the nucleophilic capping agent is of the formula ~ X ~ ~
and the electrophilic capping agent is of the general formula Ari'COZ or Ar"S02Z, wherein Ar", X,Y and Z
have the meanings specified above.
The novel double capping process of the present invention provides double capped polymers which have excellent high temperature stability properties and which are melt processable especially extrusible product suitable for uses such as wire and cable insulation. Advantageously, the polymer chain length is within the range of from about 5 to about 500, preferahly about 20 to about 300. Additionally, the polymers of the present invention are fabricable by conventional in~ection moulding techni~ues. Addition- I -ally, these polymers are substantially free from I
uncontrolled chain branchin~, controlled chain branching may be achieved as described below.
The polymers produced by the process of this invention are characterized by light color and excellent thermal stability. In addition, they form stable solutions even in highly acid media such as hydrogen fluoride/boron trifluoride mixtures. Furthermore, the solutions of the polymers according to the invention in sulfuric acid are light in color, the solutions of correspondin~ poly~ers prepared otherwise tllan by the '.

invention being highly colored. Moreover, as these polymers are essentially inert to further reaction with either electrophilic or nucleophilic reagents any residual polymer left in solution in a reactor (for example on the walls of the reactor~ after 12a -3 j ~ompletlon of one polymerization does n.o-t ha~e to be washed out before commancement of another polymerizatlon. In prior a~t processes residual polymer must be completely removed ~rom the reaction apparatus before fur-ther polymeri~ation is carried ou-t, since its presence results in the production of ve~ high molecular weight portions in the product of such ~urther polymeriæation. ~urthermore 3 as pre~iously no-ted, polymer solutions produced by prior art processes have an undesirable tendency to increase in molecular we-'Lgh-t o~ storage.
It is appropriate in order to ~acilîtate a *uller understanding o~ the present invention to distinguish between terms which are ~requently and generally erroneou~ly used interchangeably in the prior art pertaining to ~riedel-Crafts ca~alyzed polymeri~ationsO The term "quenching agent"
denotes a compound, usually a ~ewis ba~e (nucleophile), ~hich is added, almost in~ariably in very substantial exce~s, to a po~ymerization reaction mixture after completion o~ the polymerlzation reaction to react with the polymer end group~
~ -- catalyst comple~ so tha~ -the polymer molecule i5 substantially less likely to undergo f~ther undesirable reactio~ Such roaction is caused b~ reac-ti~e polymer end groups chemically attacking on neighboring molecules with which the polymer mol~cule comes in contact during subsequent proces~ing or u~e9 Molecular weight control~ in contradistinction~ is : 25 ge~erally e~ected by having, during~ and pre~erably ~rom : the ~tart of 9 polymerization~ a molar exce~ o~ either the ~ucleophilic or the electrophilic difunctio~al reactant or by adding, at any time before polymerizatio~ i~ complete, a ~ucleophllic or electrophilic reagent which i~ mono~unctio~al under th~ polymeri~ation reaction co~ditlons and which thereby serYes a~ a chain terminator. ~uch monofunctio~al ~ 13 ~

~23~3 chain termination agent~q are, o~ course, ~lso use~ul when e~fecting polymeri~ation usin~ a monorner h~ing both elec-tro-philic and nucleophi:!ic moieties on the same molecule~ It is, o* course, apparent that a quenching agent can sui-tably S be used in conjunction with a mo]ecular weigh-t control agent.
A cappin~ agent 9 which can b~ either electrophilic or nucleophilic 9 serves a di~ferent ~unction from either a ~uenching or molecular weight control agent. It~ purpose is to form the groups at all (or both in the ca~e o~ a linear molecule) ends of the polymer molecul~ and thereby cause the end groups of the polymer molecule to be at least a~
resistant to chemical attack as the remainder of the molecule.
Its primary function is not to stop the polymerization and in fact, unlike a quenching agent, it may be present in the polymerization mixture throughout the polymerization reaction.
It should be noted that compounds which function as cappin~
agents, as above defined~ can under some circumstances serve the ~unction of molecular weight control or, if adde~ in - ~ large excess~ contrary to the teaching o~ the present lnvention~
can in some in~tances quench the reactionO However, the pr~or art has in~ariably u~ecl either an electrophilic or nucleo-philic molecular weight con-trol agent 1mder conditions which result~ in the polymer ~olecule being reactive io~o7 uncapped a~ herein de~ined, at at lea~t one end. ~o~ e~ampleg British Patent NoO 1,387,303 contains a discu~sion o~ -the use of so-alled capping agents in connection with polymerization reactions analogous to those described herein. However~
it ~hould be noted that 9 in the conte~t o~ that patent~ the ~o~call~d capping agent~ were ln ~ct molecular weight control agent~ ~unc-tioning exclu~ively a~ 3uch and not a~ true cappi.ng agents as de~cribed in the instant speci:~ication. In f2ct, such ~rior art a~ents could not in ~act achieve -t.he objec-tive~
of the pre~ent inventiorl when used as described in said U.~.
pate~t~ Indeed~ the nature and significance o~ double capping as disclo~ed and claimed herein was not appreciated at -the time of said UoK~ patent~
The present invention contemplates the use of a capping a~ent to provide a polymer molecule which i~ unreac-tive and resi~tant to chemical attack at both ends o~ the molecule.
Use of a quenching and/or rnolecular wei~ht con-trol ~gent as hereinabove defined in conjunction with a capping agent provides no useful e~ect and c~n in ~orne circumstances be deleterious. The distinction between quenching agent~ and t5 capping ~gents may be clarified by considering the -former as reducing the tendency of the polymer to attack other molecule~ including nonomer or oligomer (which are less ~ reactive than the polymer), while the latter increases the polymer'~ resistance to attack by species more reactive than the polymerJ Since a quenching agent may only be added after the enti.re polymeriza-tion is complete, the use o~ a molecular weight control agen-t without a capping agent means tha-t in any polymerization reaction mixture there will be present before quenching substantial numbers o~ "completed"
- 25 molecules whose ~row-th has been stopped by the molecular weight control agent but which are nonetheless ~u~ficiently u~stable that they are under.going degradation~ Since other molecule~ arel o~ cour~e7 ~till undergoing ~olymerization, it i~ impractical to deactivate these completed molecule~
.

.

by adding a ~uenclling agent~ Thus/ when the polymeriæa-tlon reaction is finally quenched~ ît will cont~lin a signi~'icant proportion of molecules whose chain growth was com~leted early on and which thereafter degr,aded. 'rhis problem is particularly acute when highly reactive catalysts such as HF-~F3 ~re utilized. This is one of the problems unex~ectedly ~olved by the present invention~
With this background 9 the use o~ the pre~ent - invention to provide controlled branching may be more readily understood. I~ ,the polymerization uses monomer ha~ing a diacid halide and a displaceable hydrogen9 i~e.~ a type II
polyrnerization, a molecular ~eigh-t control agent having more than t~lo chain initiation sites is employed 3 branching will occur, and the nature ~nd molar percen-ta~e of capping " agent will be in~luenced by the number of initiation sites~
~or example, i~ the molecular weight control agent is ~ nucleophile, the end capping agent should be an electro-phile, and be present in a pe.rcentage rnolar ratio equal to the number o~ initiation sites~
Branching ma~r also occur i~ an electrophilic capping agent having multiple ~unctionali-ty is used~ since thi~ may cap several growing chai.ns; if there is u~ed a molecular w~ight control agent in combination~ then if the molecular weight control agent initiates on one side onl~y~
and is otherwise unreacti~e a single branching site results i~ each molecu].e~ which is pre~erred~ Alternati~ely, whiGh is not preferred~ the molecular ~eight con-trol agent i~ polyfunctional~ and can initiate on one side but is still reactive on the other9 and much branching wi.ll OCCUr9 ...

possibly leading to unde~sired ~e7ation7 i.-~ a poly~unction.al.
capping agen-t is used~ In this case, it is a-lvantageou~ to use both a mono~unctional cap~ing agent and a polyf~mctional cappihg a~ent~ wi-th the ratio o-~ t;he concentration of the mono~unc-tlonal cap ing a~ent to that o~ the pol~T~unctional capping agent being equal to the f`unctionali-ty of the latter.
If the molecular ~eight control agent is electrophilic, the capping a~ent ~hould be nucleophilicO
I~ the polymerization is a q'ype I pol.y~erization~
similar considerations apply, except tha-t both the capping agent and the molecular wei~ht control agen-t will be nucleophilic if the electrophile monomer is in excess; and vice versa.
It will be appreciated, howe~er, that although the ln~ention may be employed to provide polymer~ having controlled branching, the pre~erred products of the in~entio~ are ~ssentially linear polymers; the advantages o~ the process of the in~ention including the reproducibili-ty o~ the resulting polymer, and the ability to produce a polymer o~ desired chain length and hence inherent ~iscosityc ~ ~'1 `-The polymers with which the present invention is particularly concerned include polyaryl ketones comprising repeating units of the structure: ¦
O , C~ ......
i.e., poly(benzophenone ether). As especially preferred, there may be mentioned homopolymers and copolymers having such repeating units and having a mean inherent viscosity within the range from about 0.8 ~o about lo 65. Such polymers and the preparati.on thereof are disclosed in British Patent No. 1,387,303.
Secondly, there may be mentioned aromatic ketone I ;
polymers having the repeating unit: I

~ '' '' ' ' O=C~ ~
~ ~ ~ C- and ~ ~
=f ~ O ~
_ r and especially homopolymers o ~-biphenylyloxybenzoyl monomers and also copol~mers thereof incorporating : minor proportions of corresponding o-comonomers, polymers having a mean inherent viscosity between about O.5 and about 107 being particularly preferred.
Analogous polymers and the manner of thelr preparation are described in UOS. Patent No. 3,593,400.
The preaent invention also advantageously provide,s the sulfony~ analogues of the a~ove-indicated polyaryl ketones aDi~ the other polymers described in U.S. Patents l-. ~

, .
.. .. .

3~

~os. 3,441,538, 3,442,857, 3,321,449, and Briti~sh Patents 971,227 to Goodman et al and 1,016,245 to Jones, to the disclosures of which the reader is referred to avoid unnecessary enlargement of the present specification, and corresponding processes for their manufacture.
Particularly useful solvents for use in such polymerizations include nitrobenzene, o-dichloro-benzene, sym-tetrachloroethane, methylene chloride, mixtures of any o~ the foregoing, and also anhydrous hydrogen fluoride. The common Friedel-Crafts catalysts can suitably be employed in the polymerization process including, for example, aluminum chloride, aluminum bromide, boron trifluorlde, hydrogen fluoride, ferric chloride, stannic chloride, indium chloride and titanium tetrachloride. Aluminum, indium and ferric chlorides are preferred ca~alysts and mixtures of ,, hydrogen fluoride and boron trifluoride are particularly preferred.
The amount of, for example, the preferred catalysts such as aluminum chloride or boron trifluoride will ordinarily be at least one molar equivalent per carbonyl or sul~onyl group of the monomeric reactants. In the case of ferric or indium chloride less than a molar equivalent i5 ordinarily used.
The polymers with which the present invention is concerned are prepared b~ condensation polymerizationO
The condensation polymerizations used in the instant invention are of two types~ In type I there are two " , .

~ ' 3~3 monomeric starting materials, a first monomeric reactant which is an electrophilic reagent, and is generally a diacid halide, and a second monomeric reactant containiny at least two displaceable aromatically bound hydrogen atoms, a nucleophilic reagent. If [EE7 is the molar concentration of the electrophilic reagent and ~N~i.s the molax concentration of the nucleophilic reagent and EE is in excess, then the molecular weight, MW, of the resulting polymer iR given ~y the formula:

[EE~ ~ [~N~
MW = ~ ~,c w ~E~ [N~ 2 where w is the molecular weight of the repeating unit (i.e~, the EENN residue?-of the polymer.
Thus, use of an excess o~ EE effects molecular weight control. Conversely, if NN iS in excess to r ~ control molecular weight, the molecular weight is equal to:

[~ ~ [EE~
_ _ - x 2 ~NN] -- [EE]

~ If EE is in molar excess then the polymer chàins will 20 tend to have acid halide end groups which,as is well known to those skilled in the art, readily react further leadin~ to branched polymer chains and instability of the polymer w~en molten.

- 20 ~

~1 , It has been unexpectedly discovered that when ~N
is used in excess in an effort to effect molecular weight control and NN contains phenoxy ~roups or groups similar in reactivity to acylation -to a phenoxy group,which groups will be at at least one end of the polymer chain because of the excess of ~, then reaction of these end groups with the ketone catalyst complex during or after polymerization tends to occur , -so as also to cause branching, it is believed, through the formation of trisaryl carbonium ion salts.
Furthermore, it has also been discovered that molecular weight control through the addition of monofunctional molecular weight control compounds to a stoichiometric mixture of the starting materials will not avoid either of the above problems as, ~
depending on whether the monofunctional agent is an~ ~`
electrophile or a nucleophile, each polymer molecule - . will have an electrophilic or a nucleophilic group respectively at the end of the polymer molecule distant from the weight control agent residue which end group can react further an~ cause chain branching.
The molecular weight Q~` the resultant polymer is given by the formula:
Cc~ ~ w , . ' ~ MW = - _ where [C~ = r~N~ = [E~ and ~ ~ ~:

wherein [T~ is the molar concentration of molecular wei~ht control agent used, and w is the molecular weight o~ the repeating unit of the polymer~ It is thus apparent that molecular weight control for the polymer in a type I reaction by use of excess nucleophilic monofunctional molecular weight control compound does not in any way address or solve the problems of polymer stability to which the present invention is directed. I
In the other type of polymerization (type II) only one monomer, having both an acid halide group and at least one aromatically bound displaceable hydrogen is usedO If the molar concentration of th'e monomer is [EN] and a monofunctional molecular weight control agent is use~ -then the molecular weight of the polymer is given byo .

~EN~ x w - M~ = ~ ~ ,` ' [T~

wher~ln in [T] and w are as defined above. Again, use of a monofunctional a~ent for molecular weight control suffers from the disadvantage that at least one end of each polymer molecule is terminated either by a reactive nucleophilic or electrophilic group ~hich can serve as a branch initiatorn Accordîngly, the instant invention provides Friedel Crafts condensation polymers whose molecules are capped at both ends by groups which do not sPrve as ~ranch initiators under polymerization conditions.
For a Type I condensation polymerization either the electrophile or the nucleophile can be present in .~ ' ' .
_ 22 -.

f.~ 3 excess or both can be present in equimolar amounts.
In the first and second cas~s the molecular weight s controlled by the excess r~a~tant, as above indicated. In the first case, a nucleophilic cappiny agen-t will effectively cap both ends o-f the polymer chain. In the second case an electrophilic capping agenk will cap both ends of the polymer molecule. In a Type I polymerization, when equimolar amounts of el~ctrophile and nucleophile are present or in a Type II polymerization both an electrophilic and a nucleophilic capping agent are added and the polymer chain is capped with the nucleophilic cap at one end and the electrophilic cap at the other. A further advantage of the present invention is that under such circum~ ances the capping a~ents will serve the additional function of molecular weight control agent.
The el~ctrophilic polymer end cap for the polymers produced in accordance with the instant invention will have the structure Ar"CO- or AR"$O2-wherein ~R" is as previously defined for the electrophilic capping agentO The nucleophilic polymer end cap will have the structure:
I

I

~o~ 0~ ~50~ 1 wherein Y and X are as previously define~ for the nucleophilic capping agent.
Preferred ratios of ingredients in accordance with the instant invention for type I polymerizations are as follows~

~ ' Case a [EEl ~ ~N~
Molar fraction of difunctional electrophile [EE] : 1 Molar fraction of difunctional nucleophile [~N~ a Molar -fraction of nucleophilic cappirlg agent 2a Case b [MN~ [EE~
Molar fraction of difunctional electrophile [EE~: 1 Molar fraction of difunctional nucleophile [NN~ a Molar fraction of electrophilic capping agent: 2a Case c [NN~ = [EE]
Molar fraction of difunctional reagents (EE ~ NN) Molar fraction of nucleophilic capping agent~ a Molar fraction of electrophilic capping agent: a .
Note that in cases a and b the capping agent may be added at any stage of the polymerization, including after polymerization is complete, and no separate molecular weight control agen~ is necessary. In case c, one of the capping agents functions also as a moleaular weight control agent and therefore is preferably added early in the pol~erization, most preferably at the beginning of the reaction. The other capping agent in contradistinction can be added at any time. It will preferably be electrophilic but can b~
nucleophilicu Preferably, in all three cases, the capping agent~s) are added at the begiIming of or early in the course of the polymerization D
For a condensation polymerization of type II, as in case Ic, the objectives of the inventions are attained by adding about equal molar fractions of both electrophilic and nucleop~ilic capping agents~ Under - ~4 ~lZ3~3 these circumstances, a separate molecular weight control agent is not required. The ratios of ingredients for a type II condensation are:

Molar fraction of Type II monomer 1 Molar fraction of nucleophilic capping agent a Molar fraction of electrophilic capping agent a In practice it is fre~uently difficult to select precisely the same amount of each capping agent, but it is found that extreme precision is not required. It is preferable, where precise equivalence of electrophilic and nucleophilic capping acJents cannot be provided, to use a very slight exce~s of the nucleophilic gent.
For both Type I and ~ype II reactions, ~he lS numerical value of a will preferably vary from akout 0.001 to about 0.05, preferably 0.002 to 0,01 based on a value of 1 for the monomer, as above indicated.
As hereinbefore indicated, thè capping agents utiliæed in the practice of the present invention can 20 be either nucleophilic or electrophilic. ;~
Preferred nucleophilic capping agents include biphenyl, 4-phenoxy benzophenone, or an equimolax ;
mi~ture of diphenyl ether and b2nzoic acid or a derivative -thereof which ~orms 4-phenoxy benzophenone in situ ~ ..
Preferred nucleophilic capping agents include benzoic acid, benzene 9~foni~ acid or the corresponding acid halides.
The polymers of the present invention preferably .

3~ 1 have viscosities ranging Erom about 0.5 to 200 and containing from about 5 to about 300 repeating unitsO
As is apparent, ~oth horno and copolymers can be prepared in accordance with the teaching of the instant invention by using a l~xture of electrophilic and/or nucleophilic bifunctional monomers and/or a mixture of monomers of the EN type.
The following examples, in which "Te~lon" and "Waring" are trade marks, illustrate the invention.
All parts are by weight and temperatures are in C
unless otherwlse noted. Throughout, mean inherent viscosity is determined according to the method of Sorenson et a , Preparative Methods of Pol~mer Chemistry Interscience (1968), p~44 [0.1 g pol~mer in 100 ml. soln. of conc. H2SO~ at 25 C~. Electronic spectra of polymer solu-tions were determined with a Perkin-Elmer 450 spectrophotometer using silica cells having a 1 cm path length. A polymer sample of 0.02 -to 0.05 g was dissolved in 5~00 ml of dichloroacetic acid at 150 -160 ~y agitating the sample for 15 to 20 min. The solution was recorded against a dichloroacetic acid blank. The absorbance reading obtained at 495 nm was divided by the s~lution concentration in grams per milliliter to give an absorbancy index value (As) which is a measure of branched sites in the polymer.

BRANCHING DUE TO PHENOXY END GROUPS INTERACTING WITH
CARBONYL LINKAGES IN T~ POLYMER. MODEL COMPOUND
STUDY.

_ 26 -.

A sample of 2.36 g ~10 mmoles) of p-phenoxy-benzoyl chloride containing 00573 mole % of biphenyl and 0.573 mole % benzoic acid was polymerized in the standard manner. One half of the reaction solution was worked up by precipitation to give a polymer of inherent viscosity 1.33 and an As value of 10 at 495 nm. This product was compression molded at 400 for 5 min. to give a colorless slab of the same inherent viscosity 1.33. To the other half of the polymer ~olution was added 205 g (ca 10-~noles) of

4~bromodiphenyl ether acting as a ~Imodel~ ~or reactive end gr~ups formed by prior art polymerizations. This mixture was stirred for 16 hr at room temperature and then recovered by precipitation into water. The polymer precipitate was washed with acetone to remove any excess 4-bromodiphenyl ether followed ~y drying to give a colorless product of inherent visco~ity 1~33 and an As-value of 540 at 495 nm indicating a considerable amount of tris-aryl carbonyl structures forrned. ~his product was compression molded at 400 for 5 min to give a slab of decreased inherent viscosity ( l-o 2~ 3 ~XAMP~ 2 SUPP~ESSIO~ OF GEL FORMATIO~ DURING POLY~ RIZATIO~

A sample of 37~9 parts of p-phenoxybenzoyl chloride containing 0.134 parts (0.50 mole %) of biphenyl was placed in a cold ~ca 0) pressure reactor lined with FEP polymer and PqUipped with an %~3 agitator, heating and cooling coils, a number of nozzles, pressure and temperature regulating and controlling devices. ~Ihydrous hydrogen fluoride was cooIed to -20 in a separate vessel and about 105 parts were slowly added to the monomer with stirring.
The reaction temperature was slowly raised to 20 while maintaining a slow nitrogen purge. Hydrogen chloride which evolved during this process was allowed to escape through a condenser (held at -10~
and absorbed in a scrubber. The monomer solution was then cooled to 0 and boron trifluoride gas was -a~mitted to give a system pressure of 2.45 kg/cm2 and a reaction temperature of 14 . These pressure/
temperature conditions were maintained for 4.5 hr.
Then the boron trifluoride supply was discontinued, and khe reactor and contents were cooled to ~7, followed by venting of boron trifluoride to the scrubber until ambient pressure was establîshed. The resulting polymer solution was transferred to a larger vessel and diluted with hydrogen fluoride and 13.6 parts of water to give a solids content of 4.5~.
This solution was pressure fed via a polypropylene cartridge filter (lO~) to a two~fluid spray nozzle for recovery of solid polymer by spray drying as described in U~SO patent 3,751,398. During this process, -the filter cartridge bec~me obstructed by gelatinous polymer material and had to be replaced four times - before completing the run. The polymer recovered by -spray drying was colorless ~nd had an inherent ~ 28 -~.

3~

viscosity of 1.38. The gelatinous material removed from the cartridge filter was found to be insoluble , in hydrogen fluoride, hydrogen fluoride/boron trifluoride mixture, or concentrat~d sulEuric acid.
This insoluble material was suspended in hydrogen fluoride and agitated overnight, followed by filtration. The filter residue was washed with water and then dried at 110 /20 mm Hg/16 hr to give a slightly pink polymer coagulate. Compression molding at 400 for 5 min gave an incompletely fused, dark brown slab. The-fused material was not soluble in concentrated sulfuric acid. Differential scanning calorimetry indicated a melting point at 365, a glass transition temperature of 165 and a recrystallization temperature of 263j the corr~sponding numbers for the hydrogen fluoride soluble spray dried polymer are 365, 165 and 210 , respectively~ , A sample of 0.0174 g of coagulate from . the insoluble residue was dissolved in 5 ml of , dichloroacetic acid at 160 to give a deep red solution, which'was diluted 1:20 with dichloroacetic acid and anaIyzed 'by electronic absorption spectroscopy.
A strong band was observed at 495 mm showing an ;
ab~orbance of 0.8. ~Trisphenoxyphenylcarbinol exhibits ~ strong absorption in dichloroacetic acid at 495 ~m with an extinction coefficient,of 1.1 X 10 . Assuming that the s~me type of structure Pxists in the polymer coagulate, c~ulation would,suggest ca 2 mole % of ;
brancheæ/crosslinks.
The above polymer preparation which l~ an example of the best available prior art technique w~ repeated )3 a number of times leadlng invariably to filtex obstruction of differing severity. When the polymer preparation was repeated in the presence of 0.50 mole % of biphenyl and 0.475 mole % of benzoic acid in accordance with the teachings of the instan~ invention a polyrner of inherent viscosity 1.35 was obtained and the batch could be flltered and spray dried without interruption, in ~act a number of batches could be filtered through the same cartridge b~fore change became necessary due to ~ccumulation of foreign, nonpolymeric material.

EXAMP:I:E 3 BRANCHING DURI~G POL~ER PR:EPARATIO~
Batches of polymer using 37.9 parts of p-phenoxy-benzoyl chloride were prepared in an FEP lined pressure - reactor as described in Example 2, i.e., not in r accordance with the instant invention. In two sets of experiments no effort was~~nade to remove residual pol~mer left in the reactor from previous runs (A~
A-2). Then two experiments were run where the reactor was t~oroughly-cleaned of old polymer be~ore charging new monomer and anhydrous hydrogen 1uoride (B~1, B-2)o The polymers were recovered by spray drying and the I
inherent viscosity of powders and compression molded slabs determined. Slab color (rating: 1 - colorless, I
10 = dark brown~, A5 of the po~der, and extrusibility of the powder in a % inch Brabender extruder were evalua~edO The résults obtained are shown belowv , , .
~ 30 .`~i ~ .

Batch A (495nm) Inheren-t Color E~trud-s ~iscosity ~o. ~ility powder. sla~

A 1 250 1.35 1.21 8 No A-2 314 1.45 1.35 8 No B-1 14 1.31 1~35 2 Yes B-2 70 1.40 lo 39 5 Yes In spi~e of careful removal of old polymer from the reactor before charging new monomer during a sequence of ten experiments AS values between 10 and ca 70 analogous to B-1 and B-2 were observed. This did not have a severe adverse effect on extrusibility but undesirable color variations in the extrudate were 'notèd. When polymerizations were controlled by t 15 dicapping with'biphe~yl and benzoic acid in accordance with the teachings of the 'instant invention instead :~
; of single capping with biphenyl only a~ taught by the prior a_t Ag values equal to or less than 25 were .
consistently ob~erved.
.

SHELF LIFE EV~LUTION OF MONO VERSUS DICAPPED poLy~æR
SOLUTIO~S .
- ~ .
Samples o'f -~.32 parts o-f p-phenoxybenzoyl chloride , containing 0.50 moIe % of the respective capping agents lis-ted in the table below were polymerized at room temperature in 8,parts of anhydrous hydrogen :Eluoride under a boron trifluoride pressure of 2.1 kg/cm -for :~
4 to 90 hr. The resulting polymer solution~ were worked.-~ y..-,precipitation into water. Evaluation for 31 - .

. : .

inherent viscosity was conducted in the usual manner and the results are shown below~

1~IMæ I~HæRENT VISCOSITY

hr Reagënt DiPhenyl- 1,4 diphen Biphenyl/
ether benzophenone Benzoic ~cid ~0.5 mole %
--- -- of each) 41.2* 1.2* 1.5~
9~1.8* 2.3* 1.5+

* These experiments were not in accordance with the instant invention. I
t These experiments were in accordance with the instant invention.

This example indicates that double capping in accordance with the teaching of ~he present invention provides a consistent vi~c05ity product unaffected by wide variations in reaction time.

,. . ~ . I

POLYMERIZATION IN HYDROGEl~ FLUORIDE CONTAINING SULFUR
DIOXIDlE. MONOCAYPING VERSUS DICAPPING

Samples oE p-phenoxybenzoyl chloride containing 0060 mole % of blp~enyl or a mixture of 0.60 mole %
of biphenyl and 0.60 mole % benzoyl chloride were polymerized at a monomer concentration of 20% in ~
of variable ~ulfur dioxide content for 4 hr at room temperature and 2ul kg/cm boron trifluoride pressure.
The resulting polymers were recovered in the standard manner and evaluated for inherent viscosity, the results are shown below.

.~ .

, SULFUR DIOXIDE: INHERENI' VI ',COSITY
CONC.
% Monocapped* Dicappedt ~ 1.3 1.3 1.8 1u4 crosslinked 1.4 Aliquots of the abo~e polymer solutions containing hydrogen fluo~id~ only as solvent were diluted after polymerization with sulfur dioxide to give a solids content of 5%O These solutions were then held for 24 hr under a pressure of 2.1 kgjcm2 boron trifluoride pressure. Inherent viscosity measurements showed a substantial increase.for the monocapped polymer while the dicapped polymer-showed no change.
, . .

SULFUR DI~XIDE . I~IERE~ VISCOSIIY
CONC .
, . % ~ Monocapped~ Dicapped .~ ~ .

O 1.3 1.3 2.3 l.3 ., .
* ~ot in accordance with the instant invention t In accordance with the instant invention .' ' ' ' POSTPOLYMERIZATIO~ OF DICAPPED VERSUS MONOCAPPED
POLYMER - -~_ ~
A. A 150 ml:polychlorotrifluoroethylene tube was . ~ charged with 2.3265 g (10.00 mmoles) of p-phenoxybenzoyl chloride 0.0077 g ~0.()5 mmoles) :' . ' .

3~3 1, of biphenyl, O.057 g (O005 mmoles) o~ benzoic acid, and a stir bar. To this mixture was slowly added 10 ml of anhydrous hydrogen fluoride. The tube was then connected to a polychlorotri-fluorethylene vacuum lin~ (Toho Kasei CoO Ltd~, Osaka, Japan) which had been purged with nitrogen.
Boron trifluoride gas was admitted and the reaction mixtur~ was held at 2.9 kg/cm~ pre~sure for 4 hr to give a vi~cous orange solution. Exces~ ¦
boron trifluoride wa~ purged from the reaction 1, system after being cooled to -78C. The polymer solution was diluted with aqueous hydro~en fluoride and then poured into rapidly stirred water. The re~ultant polymar precipitate was iltered and washed with water, followed by drying at 120/20 mm - Hg to yield colorles~ fluffy material of inherent viscosity 1.360 r ~ B. The same proc~duxe was used as in Section A. How-ever the polymerization time was increa~ed to 8 ~r and the inherent viscoRity of the product was 1039.
C~ This polymer was prepared following the procedure of Section A. After 4 hr of polyrnerization, excess boron trifluoride wa3 purged from the reaction sy~tem and 0.0146 g (O.04 mmoles~ of 4,4' diphenyl ether diacid chloride was added to the solution.
Polymerization wa continued for 4 hr~ The in-hexent vi~co~ity of the product was 1~340 A, ~ C
are in accordance with the in3tant invention.
D. A 1$0 ~l polychlorotrifluoroethylene tube was _ 34 -' charged with 2.3265 g (10.00 mmoles~ of p-phenoxy-benzoyl chloride, 0oO185 g (O.05 mmoles) of 4,4l_ diphenoxyben~ophenone, ancl a ,stir bar. To this mixture wa~ slowly added 10 ml of hydrogen fluoride.
The tube was connected to a polychlorotrifluor-ethylene vacuum line ~hich had been purged with nitrogen. Boron trifluoride gas was admitted and the reaction mixture was held at 2.1 kg/cm pressure for 4 hr to give a vi~cous orange solution. Excess boron trifluoride was purged from the reaction system aftar being cooled to -78C. The polymer solution was diluted with aqueous hydrogen fluoride ¦
and then poured into rapidly stirred water. The resultant polymer precipitate was f.ilt~red and wa~hed with water, followecl by drying at 125/20 mm H~ to yield colorles~ fluffy ma~erial. The in~
herent viscosity of the product w~s 1.30. ~.
E. The same procedure wa~ used as in Section D, h~w~
ever the polymeriæation time wa~ increased to 8 hrO
The inherent vi~cosity ~f the product wa~ 1.31 n F. Thi~ polymer wa~ prepared following the procedure3 o~ Section D. Af`ter 4 hr of polymerization, excess boron trifluorid~ was purged from the reaction ~ystem and 0.014~ g (0.04 mmoles) of 4,4'-diphenyl .
ether diacid chloride was added to the ~olution.
~hen polymerization was continued for 4 hr. The inherent viscosity of ~h~ re~ulting polymer was 4~20. mis ~xperiment wa~ repeated to give a polymer of inherent visco~ity 4.26. D, E & F
are not in accordance with the instank :invention ~1 . ' .

and indicate the sensitivity of the prior art product~ to continued polymerization leading to excessively high molecular w~3ight when contacted with additional monomer.
EXAMPLE 7 .
MOLECUI~R WE:IGHT CO~TROl: BY DICAPPIl~G WIm BIPHE~E A~D j BENZOIC ACID ~
A series of polymerization experiments was run with 10 mmoles of p-phenoxybenzoyl chloride in hydrogen fluoride (25% solids concentration~ at room temperature for 4 hr and 2.1 kg/cm of boron trifluoride pre3sure.
Molecular weight was controlled by the addition of bi I -phenyl and benzoic acid in accordance with the instant invention over an inherent viscosity range of 1.0 to 1.6~ The results are shown below.
~ ~ .
DICAPPI~G MOLE % INHERENT VISCOSITY

0~00 0~380 1 o58 - 400 o 380 1 ~ 6 2 0~ 600 Oo 570 1 J 23 .
0~ 600 0 ~ 570 1 ~ 27 0~ 700 0 ~ 665 1 ~15 0~700 0~665 1~15 0~800 0~764 1~03 0~800 0~764 1~04 0~900 0~355 0~95 O~ ~00 0 ~ 855 0 ~ g6 EXA~IPLE 8 Using the apparatus and procedures of Example 6, .
a mixture of p-phenoxybenzoyl chloride, p-phenoxybenzo-phenone (0.5 mol %) and benzoic acid (0.5 mol ~O) were .
- 3~ - -~ , polymerized to yield a product having e~sentially the same propertie~ and viscosity as materi.al A, B ~. C of example 6 when polymerized for like periods of time and .
under similar conditions~

Using the apparatu~ and procedure~ of example 6 .
a mixture of 4, 4'-diphenoxybenzoph~none (4.95 mmoles~, terephthaloyl chloride (5.00 mmole~)and p-phenoxybenæo-phenone (0.1 mmoles) was polymerized to yield a light .
colored fluffy polymer substantially identical.to that ~:
of Example 6A and which ormed a stable ~olution in hydrogen -fluoride.
EXAMPLE 10 .
Using the apparatu3 and procedures of Example 6 a mixture of ~,4'-diphenoxybenzophenone (5.0 rnmoles) ter- .
ephthaloyl chloride (4.95 mmoles) and benzoic acid (0.1 1 mmole~) was polymerized to yield a material ~ub~tantially ...
identical to that of the last example. :
EX~MPLE 11 Using the apparatus an~ procedureq of Example 6 a mixture of ~-phenoxybenzoyl chlorid~, ~enzoic acid ~0.5 mole %~ and, in three experimentQ, 0.5 mole % of -p-cyanodip~enylether, p-nitrodiphenylether, and p-phenoxy 1~
diphenyl ~ulfone re~pectively to yield polymeric products 1-of significant stability in ~ydrogen fluoride solution. .~.

EX~MPLE 12 In a ~imilar manner to that of Example 11 pol~meric ¦:
makerials were prepared from p-phenoxybenzoyl chloride, biphenyl ~005 mole %) and, in threa experiment~, 0.5 .

~ 37 - .
' I

~- ~

mole % of p-anisic acid, p-phenyl benzoic acicl, and p-(4-chlorophenoxy) benzoic acid, saicl materials having stable viscosities in hydrogen fluoride~

In a cooled 150 ml Teflon (polytetrafluoroethylene) flask equipped with a ptfe coated st:irrer was placed para-phenoxy benzoyl chloride (23.25 parts), biphenyl (0.077 parts, 0.50 mol % nucleophilic capping agent~, benzoic acid (0.057 parts, 0~50 mol % electrophilic capping agent) and a~hydrous hydrogen fluoride (100 parts).
The mixture was stirred at 0C and 2.1 kg/cm2 boron fluoride presqure applied~ The mi~ture was allowed to warm to room temperature and stirring continued for 100 hour~. The polymer solution thereby obtained wa~ diluted to about 5% solids content with hydrogen fluoride contain-ing 5% w/v water and poured intQ water in a Waring Blendor. The granular ,product wa washed copiously with I' water and dried in vacuwm (15 mm Hg3 at 150C for four hours. m e polymer, obtained in quantitative yiald, had an inherent viscosity of 1.4 and an As-value of 10 at 495 nm. Thi~ polymer wa~ melt stable and could be readily , ' extruded.

This is an example using the teaching of the prior art. The procedure of example ~3 wa~ repeated except that the benzoic acid electrophilic capping agent was omitted~ The recovered polymer had an inherent viæcosity of 1~5 and an A~~value of 400 at 495 mm~ This material ' i 3t3~

w~s essentially inextrusible due to excessive decom-posi~ion when extrusion was attempted.

The procedure of example 13 was followed except that after 4 hours at room temperature the boron fluroide was ven~ed and the polymer solution ~tirred for another 96 hours. ~he re~ultant polymer had the same good physical 1, properties including extrusibility and appearanc~ as that o Example 13.

This i~ an examplecarried out in accordance with prior art teachings. The procedure of example 15 wa~
followed except that ~he benzoic acid was omitted. ~he recovered polymer had an inherent viscosity of 1.45 and an As-value of 350. Polymer prepared in this way was found to be inextrusible without extensive deco~positionO
If the polymer is recovered immediately after venting the boron fluoride (i.e., after 4 ho,urs) a product with an inherent vi~co~ity of 1.4 and an A~ value of 35 i~
obtained. Polymer recovered rapidly in this way has satisfactoxy extru~ion performance but this example shows that the reaction mixtur~ obtaîned by the prior art proce~es cannot be ~tored for any appreciable length of time without impairment of the pol~mer processability.
Thi~ ~ensitivity makes the commercial production of such prior art polymers ver~ difficult to contxol~ In con-tradistinction, example 15 shows the novel pol~mer~ of ;~ the in~tant invention pos~e~s great ~tability in solution in acidic media rendering them of great commerciial uti~it~. I

~ 39 l~e procedure of example 13 was followed except that after adding the boron trifluoride the reaction mixture was stirred at 50C for four hours and then worked up as in example 13. Polymer produced in this manner ha~ an inherent viscosity of 'I.40 and an As value of 20 and can be extruded sa~isfactoxily.

This is an example carried out in accordance with prior art teachings~ The procedure of example 16 was ~ollowed except for the omission of benzoic acid. Polymer produced in this manner has an inherent visco~ity of 1.5 and an A8-value of 415. Thi~ material suffers extensive cros3linking and discoloration during extrusion. Examples 16 and ~7 show that pol~merizations carried out in accordance with the instant invention are very little affected by the temperature of polymerization whereas polymerizations by prior art processes are extremely sensitive to reaction temperature. Polymer ~f examples 13-17 comprises recurring units of the structure.

_ _ ~ o~ ' _ i ~~_o~ ~
: _ _ ' POLYMæRIZATION OF p PHENOXYBENZENESULFONYL CHLORIDE.
MONOCAPPING VS. DICAPPING

Sodium p-phenoxybenzene sulfonate .
To a dry 3-neck 5-liter flask, equipped with a mechanical stirrer and a dropping flmnel, was charged .
400 g (2.35 mole~) o freshly distilled dip~l~nyl ether~
While stirring, 1200 ml of dry dist. methylene chloride was added slowly. A continuous stream of dry N2 was passed through the reaction assembly and the flac;k was 1-cooled to -23 with a dry ice/carbon tetrachloride slush bath.
From the dropping funnel was added 910wly (ca~ 1 .
hr) with stirring 152 ml ~273 g, 2.35 moles) of dist.
chloro~ulfonic cacid. The reaction mixture was stirred for 12 hr at -23 and then fox 12 hr at room temperature.
Then 3 liters of ice cold water was slowly added and the resulting mixture was transferred to a separatory funnel with the aid of 3 liters of water. The organic phas~
was separated and the aqueou3 phase wa3 extracted with ether (3 x 80~ ml). The combined organic pha3es were extracted with water (2 x 1000 ml) then dri~d (.MgSO~) and freed of solvent (40-50/20 mm) to yiPld 61037 g (0.36 moles) of diphenyl ather. ~he combined a~ueous extracts w~re briefly heatad to expel organic solv~nts and then 1500 g of solid sodium chloride was added slow:Ly with .
sti.rring~ After cooling to room temperature, the crystalline precipitate was allowod to stand overnight. .
It was filtexed by centriEugation and washed w.ith 1~/o ~ ' .

3 .

sodium chloride solution. The slightly wet ~ilter cake was once more recrystallized from water. Work-up of the mother liquor gave a second crop. ~he filter cakes were freed of water by centrifuging at ~500 rpm for 1/2 hr, followed by drying at 110Jo.5 mm overnight to aEford 543.4 g (2.0 moles, approximately 10~%, containing ~ome sodium chloride) of colorless crystal~ine material.

p-Phenoxybenzene sulonyl chloride A dry 3-neck, 5-liter flask equipped with a mechanical stirxer, a dropping -funnel, and a nitrogen sparge was charged with 610 g (2.42 moles) of finely ground sodium p-phenoxybenzene sulfonate suspended in 1650 ml of dry dimethyl formamude. The reaction flask was submerged in an ice bath and 195 ml (319 g, 2.68 moles) of distilled thionyl chloride was slowly added with stirring within one hr~ The ~uspension was stirred at ro~m temperature for 4 hr and then poured into a cold 0) mixture of ether (1.5 l) and water (l.5 l~ with viyorous stirring. ~he aquaous p~ase was separated and extracted with 300 ml of ether. ~he combined organic extracts were washed with cold watex (300 ml), 10% ~aOH
~olution (2 x 300 ml) and water (2 x 150 ml). The final wa~h water had a pH o~ 6.5 to 7. The ether solution was dried (MgS04) and freed of solvent [40-50 (bath)/20 mm~
to give a light yellow oil. A sample o 5 g o finely ground dry sodium chloride was added and the resulting suspen~ion was subjected to a short path distillation at 150~160 (bath~j3 x 10 5 mm Hg using a 15 cm Vigraauz colu~n. The column was jacketed with a haating tapa kept at approximately 160~ A banana shap~d receiver - ~2 -' 3:~

cooled by running water was usedO A colorless distillate of 534.9 g ~1.99 moles, 82%) was obtalned~ The dis-tillate crystallized on standing, mp 41 43. Two recrystallizations from ether/pentane under rigorously anhydrous conditions gave 480 g (1.78 moles, 74%) of colorle33 crystals~ mp 43.0-43.5 Zone refining and/or vacuum sublimation did not raise the mp.

Ir (KBr~ 1181 (s) and 1385 (9) cm 1 (sulfonyl chloride~, 1255 (9) cm 1(ether~, 3080 (w), 1578 (~), 1490 (s) cm 1 (aromatic structure~. Nmr (CDCL3~ ~a 7092 (d, 2H, additional fine splitting, ~b 7~03 (d, 2H, additional fine splitting), Jab, 9.1 Hz, 6.9-7.7 (multiplet, 5H) ppm. Anal. Calcd for C12HgClO3S C, 53.64; H, 3.38, Cl, 13~19, S 11.93. Found:
C, 53.77, 5~.50, 53.59; H, 3.47, 3.40, 3.42, Cl, 13~06, 13.14, 13.26, S, 11.77, 11.86, 11.96. Tlc, A~ter con-version with pip~ridine to give the sulfonamide [SiO2, hexane/ether (1/1) a~ ~olvent~: one spot>
; .
- ~ p-Phenoxybenzenesulfonyl chloride samples of two purity yrade~ were used -for this experiment. One grade melted at 41-43 and the other at 43-43.5. Samples of the rPspective monomers (10 mmole) containing either 0.50 mole % biphenyl (mono capped) or 0.50 mole /0 biphenyl and 0.48 mole /0 benzoic acid (dicapped) were polymeriæed in 10 ml of anhydrous hydrogen fluoride at room temperature .
and a BF3 pre~sure o~ 30 psi for 16 hr. The resultant viscou~ solution~ contained some gelatinous material when the les~ p~re monbmer was u~ed with biphenyl as capping : reagent only. The other solutions were all free of gelO
Standard work~up gave c~lorless polymers which were ~valuated for înherent visco~ity before and after ~ompre~ion molding at 400/5 minO The data obtainPd are shown below. I

MONOCAPPED DICAPPED
Pres~nce Color Presence Color Monomer Purity ~inh of of ~inh of of _ _mp powder slab qels Slab powder slab g~ ___ Slab 41-43 1~05 0.50~ Yes Brown 1~00 1.00 No Color-less 43-43.5 1.00 0~98 No Color- 1.02 1.03 No Color-less less The slab dissolved incompletely in conc. H~S04, the gelatinous material was removed by filtratlon before viscosity determination.

A sample of ~.32 parts of p-phenoxybenzoyl chloride containing 0,5 mole % diphenyl ether and 1.0 mole % ben~oic aci.d in accord-ance with the teachings of the present invention was polymerized in 10 parts of anhydrous hydrogen fluoride for 4 hr at room tem-perature under a boron trifluoride pressure of 30 psi. ~he pol~mer solution was worked up as in example 9 to give a colorless material which had an inherent viscosity of 1.46 and an As-value of 15 This exp0riment was repeated, but the reaction time was extended to 9Q hr. The xesultant polymer had an inherent` viscosity of 1051 and an As-value o~ 25. In another set of experimerlts the above prepaxation of polymer was repeated except that in one experiment only 0.5 mole % of benzoic acid was used and in the other no benzoic aci~ was used. In both experiments after four hrs of reaction the polymer had an inherent viscosity of about 1.45 and a low As but after 90 hrs of reaction the inherent viscosities were much higher, the racovered polymers contained gel particles, were highly colored and had ver~ high As values. These experiments illustrate the distinct function performed by a molecular weight ~ontrol reagent ~diphenyl ether ? and a capping reagent (benzoic acid)~

i~ '

Claims (45)

1. A polymer comprising repeating units of the formula -[- M - Ar - B - Ar1 -]-in which - M - and - B - which may be the same or different each represents- CO - or - SO2 -, Ar represents or in which - L - represents - CO -, - SO2 -, - NHCO -, a covalent bond or - T -, wherein - T - represents - O -, - S -, phenyleneoxy, - O - Ar - O -, or CR2, wherein each R, which may be the same or different, represents hydrogen, an alkyl or fluoroalkyl group, an unsubstituted phenyl group or a phenyl group substituted by an electron withdrawing group, and Ar' represents the polymer having end groups of the formula R' or R", each R' and R" being independently selected from a group of the formula , - CO - Ar" or - SO2-Ar" , wherein - X - represents a covalent bond, - O -, - S -, or CR2 wherein R has the meaning given above, Y represents CN, NO2, or or, provided - X -represents a covalent bond hydrogen, and Ar" represents phenyl, naphthyl, biphenyl, terphenyl or phenoxyphenyl unsubstituted or substituted by at least one electron withdrawing group, when Ar" represents phenoxyphenyl there being at least one electron withdrawing group on the phenoxy moiety.

2. A polymer as claimed in claim 1, in which there is present a group R, and in which the group R contains from 1 to 10 carbon atoms.

3. A polymer as claimed in claim 1, wherein -B- and -M-both represent -CO-.

4. A polymer as claimed in claim 1 or claim 2, wherein -B-and -M- both represent -SO2-.

5. A polymer as claimed in any one of claims 1 to 3, where-in -Ar- represents phenylene.

6. A polymer as claimed in any one of claims 1 to 3, wherein -Ar- represents p-phenylene.

7. A polymer as claimed in any one of claims 1 to 3, wherein -Ar- represents

8. A polymer as claimed in any one of claims 1 to 3, wherein -Ar- represents

9. A polymer as claimed in claim 1, wherein -L- represents -CO-.

10. A polymer as claimed in claim 1, wherein -L- represents -O-.

11. A polymer as claimed in claim 1, wherein the -T- of Ar' is -O- or phenyleneoxy.

12. A polymer as claimed in claim 1, wherein -T- is -O-.

13. A polymer as claimed in any one o-f claims 1 to 3, wherein R' and R", which may be the same or different, represent or

14. A polymer as claimed in any one of claims 1 to 3, wherein both R' and R' represent

15. A polymer as claimed in any one of claims 1 to 3, wherein one of R' and R" represents or and the other

16. A polymer as claimed in any one of claims 1 to 3, in which Ar" represents a phenoxyphenyl group having an electron withdrawing substituent in the para position of the phenoxy moiety.

17. A polymer as claimed in any one of claims 1 to 3, in which there is present an electron withdrawing substituent, and in which the substituent is a halogeno, nitro or cyano group.

18. A polymer as claimed in claim 1, wherein the repeating units consist essentially of repeating units of the formula -[- M - Ar - B - Ar'-]-

19. A polymer as claimed in claim 18, which is a linear polymer.

20. The polymer of claim 1 which is

21. The polymer of claim 1 which is

22. The polymer of claim 1 which is

23. The polymer of claim 1 comprising recurring units of the structure

24. The polymer of claim 1 which is

25. The polymer of claim 1 which is

26. The polymer of claim 1 comprising recurring units of the structure

27. The polymer of claim 1 which is

28. The polymer of claim 1 which is

29. The polymer of claim 1 comprising recurring units of the structure

30. The polymer of claim 1 comprising recurring units of the structure wherein -Q- is -CO- or -SO2-.

31. The polymer of claim 1 which is

32. The polymer of claim 1 comprising recurring units of the structure

33. A polymer as claimed in any one of claims 1 to 3, which has an inherent viscosity within the range of from about 0.5 to about 2.0

34. A shaped structure, comprising a polymer as claimed in claim 1.

35. An electrical component insulated by a material com-prising a polymer as claimed in claim 1.

36. A process for the manufacture of a polymer by Friedel-Crafts condensation polymerization of either (I) at least one first monomer containing diacid halide groups and at least one second monomer containing at least two displaceable aromatically bound hydrogen atoms in the presence of from about 0.002 mole to about 0.10 mole of nucleo-philic capping agent per mole of said first monomer if said first monomer is in excess; from about 0.002 mole to about 0.10 mole of electrophilic capping agent per mole of said second monomer if said second monomer is in excess; or from about 0.001 to about 0.05 mole per mole of said first monomer of each of electrophilic and nucleophilic capping agent if said first and second monomers are present in substantially equimolar quantities, or (II) at least one monomer having at least one acid halide group and at least one displaceable aromatically bound hydrogen atom, in the presence of from about 0.001 mole to about 0.05 mole per mole of monomer of each of nucleophilic and electrophilic capping agent, wherein the nucleophilic capping agent if present is of the formula and the electrophilic capping agent if present is of the general formula Ar"COZ or Ar"SO2Z, wherein Ar", X and Y have the meanings specified in claim 1, and Z represents OH, halogen or OAlk, in which Alk represents an alkyl group.

37. A process as claimed in claim 36, wherein an agent containing a substituent Z is present, and wherein Z represents OAlk, and wherein Alk represents an alkyl group having up to 10 carbon atoms.

38. A process as claimed in claim 36, wherein there is a nucleophilic capping agent present, said agent being biphenyl, p-phenoxybenzophenone or equimolar quantities of diphenyl ether and benzoic acid.

39. A process as claimed in claim 36 or 38, wherein there is an electrophilic capping agent present, and the agent is benzoic acid or benzene sulfonic acid.

40. A process as claimed in claim 36, wherein capping agent is added at the beginning of polymerization.

41. A process as claimed in claim 36, which is carried out in the presence of an HF/BF3 catalyst.

42. A process as claimed in claim 36, wherein both electro-philic and nucleophilic capping agents are present, and they are present in substantially equimolar amounts.

43. A process as claimed in claim 42, wherein both agents are present in an amount of from 0.002 to 0.01 mole per mole of monomer.

44. A process as claimed in claim 36, wherein the resulting polymer is a homopolymer.

45. A process as claimed in claim 36, wherein the resulting polymer is linear.