CA1051138A - Flame retardant polycarbonate composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

An improved flame retardant polycarbonate composition of an aromatic carbonate polymer in admixture with an organic alkali metal salt or an organic alkaline earth metal salt or mixtures thereof, which composition has in admixture therewith a fluorinatedpolyolefin..

Description

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This invention i8 directe~l to an imprsved ~lame r~tardant polycarhon~ ompo~itioxl of an aromatic c~rbonat~
~ lymer in admixture with an organic alkali m~tal salt or ar~
organic alkalin~ ear~h ~tal ~alt or ~ixtur~s th~r~o~, th~
i~provem0nt whi~h comprise~ havir~q in admixture with th~ poly-c~rbona~e a ~luorina~ed polyolefin in Bll~f~iÇient ~Iuantity to r~ndar the polycarb0~ate aompo~itiorl noa~-dripping..
In the art~ th~re ar~ many ~lame retardan~ additiva~
which ~re employed by mixil~g with polycarbo~a~e to re~der ~uch 10 mat~rials ~el~-~x~iaguishing or flame retardant. Suah flam~
r~tardant additiv~s a~e employ0d irl varying an~:>un~ in order to ~ ~ :
b5 e~e~iva in ~x~ingui~hing burni~g o~ tho~0 produc~ which ~ra co~ustiblo.
E~owever, ~ven if th~3 polycarbonate doe~ not burn, in flamo, it may drip hot particl~ which can iynite material below it.
It ha~ been ~urpri~ingly discovered tha~ an aromatic poly~:~rbon~t~ mat~e flame retard~nt by incorporating with ttle aro~atic polycarbon~ organic ~lkali me~al ~alt~ or organic~

. . .
20 alka in~ e~rth m~tal salt~ or mi~ctvlres ~hsr~oP ca~ ~o rendler~d non-dripping by ~dmixing the ~lam3 r~t~rdant polycarbonat~
with ~ fluorinat~d polyole~in.
The fluorinat~d polyolo~ins used in this inv~ntion a~ ~Irip retardia~g ~g9nt8 are ¢ommerc:ially availabl0 or c:an b~
pr~pared by lc~ proco~ , Th~y ar~s whi~o olid~ obt~ine~l by pDlymeriz2tion of tetrafluoroethyl~neO for exampl~3, ixl aqu~ou~
m~dia with fre~ radical i::atZaly8t;91, 0.g., sodium, potaseium o~
am~llium p~roxydis~alf~a~ at 100 to 1, 000 p~i ~t 0-200~C an~
pref~rably at 20-100 C. See Brubak~r, ~. S . pate~t 2, 393, 967 i~ ued 3uly 23, 1968. Whil~ n~t e~s~tial, i~ i8 pref0;rxed ~o u~e tho re8i~18 in th~ form o~ relatively larg~ parti~les, e.g~, of av~rag~ size û~3 to ~ s~ly 0.5 n~,. The~3 axe ~, ,'.

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~ 8CH-1915 ~05~L33~ :
better than the usual polytetrafluoroethylene powders which have pa~ticles o~ from 0.05 to 0.5 millimicrons in diameter.
It is especially preferred to use the relatively large particle size material because it tends to disperse readily in polymers and bond them together into fibrous materials. Such preferred polytetrafluoroethylenes are designated by ~STM as Type 3, and are available commercially from the E.I. DuPont de Nemour and Company (TFFLO ~ Type 6).
The amount of the fluorinated polyolefin to be used can vary widely but usually will be from about 0.01 to about

2.0 weight percent based on total weight of the resin.
The composition of the instant invention may also include fibrous glass as described in Canadian application of Charles A. Bialous, John B. Luce and Victor Mark, Serial No.
231,463 filed July 14, 1975 and assigned to the same assignee as the present invention. Also, the composition of the instant invention may include the siloxanes described in U.S. Patent No. 3,971,75~ of Charles A. Bialous, John B. Luce and Victor Mark, issued July 26, 1976, and assigned to the same assignee as the present invention. Further, the instant composition can include both fibrous glass and siloxanes.
The organic alkali metal and alkaline earth metal salts employed in the compositions disclosed herein are more fully described and claimed in the following Canadian Patent applications filed in the name of Victor Mark and titled "A
Flame Retardant Polycarbonate Composition" and each of which is commonly assigned herewith:
Serial No. 211,443 filed October 15, 1974 ~erial No. 211,444 filed October 15, 1974 Serial No. 211,459 filed October 15, 1974 Serial No. 212,991 filed November 5, 1974 Serial ~lo., ~12t~92 fil~d N~mber 5, 1974 Seri~l ~lo. 212,993 filed ~ov~ r 5, 1974 Sorial ~o. 212,994 file~l ~o~re~er 5, 1974 ;
S~rial lao. 212,995 fil~d ~ovember 50 1974 Serial l~o. 213,014~ ilE3d llov~ r 5, 1974 . -S~cial ~o. 213,û17 i~ d ~ov~ r 5, 1974 :
Serial ~o. 213,018 ~ 3d l~ov~r~b2r 5, 1974 S~rial ~30. al3, 019 ~ile~ ~7o J~ber 5, 1~74 Sexial ~o. 213,020 ~ d ~aovar~b~r 5, 1974 Serial NoO 216, a83 ~ 3d l~ en~r 16, 1974 Th~ tal ~alt~ of any of ~h~3se applicaltions a~ w011 a~ ~ixtur~ of a~y of the ~n~tal s~lts ~:sf ar~y of th~ appli~:aticsn~
m~y b~ UQ~o Pr~ferr~d Y~1~8 in~lude sodium 2,~ trichloro-benzenoa~lfo~t~; ~odi~ b~zenesulfQ~at~ odium .
n~phthalen~-2,6-disulfonatet ~Oaiu~ p-io~ob~zene~ul~onate;
~odium 4,4'-dibromobiph~nyl-3-~lfonats; sodium 2,3,4,5,6-p0~ta~hloro-bet~t~e~e~ulfo~ate; sodi~m 4,4'-diahlorodiph~yl-~ulfide-3-~ul~on~t~ odium tot~chloro~he~yl~h~r~i~ul- ~ .
onat~5 di~odi~ 494'-dichlor~on~oph2~0~ 3~3'~di~ulfo~ate; ~-~
~o~ium 2,5-diehlorothiophen~-3-sulfonat~s ~dium ~alt of dipA~nylsul~on~-3-~ulf~nic a~i~; sodiu~ dim~thyl 2,4,6-trichloro 5-sul~isophth~ J pota~iu~ ~alt of the sulfonic acid o~
~ichlorophenyl 2,4,5-trl~hlorob~ ne sulfonate; calcium 8alt of 2,4,5-tri~hlorobenz~2~ul~ona~ilido-4'-~ulfona~; sodium ~' ~1,4,5,6,7,7 h~xa~hlo~obicyclo~ [2.2.1~ -h~pt-5-~n-s~do-2~ b~nzeno~ul~onate; di~o~ium h~xa~lu~roglutara~: di~odi~m . .
~hlor~ilates a~d mixtu~es. Th~e s~lt~ ar0 u~ed 1~ amou~ of -;
fr~ doOl to ab~ut 10 weight p~r~nt b~ed on ths w~ight o~
the aro~atic car~nate ~lym~r ~omp~sition.
Th~ ~ro~ati~ carbona~ polymex~ e~ploy~d i~ th~
practi~ sf thi~ ti~n ~rl3 hoMc~poly~srs ~d COpOlylll~r8 th;~
~re pr~par~d by r~a~ting a dihy~ri~ phenol wi~h a carbo~a~e

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.. . . ... . ~. ,: , , : ., ~OS~38 precu~or" Th~ dihy~xis~ phenol~ that caA b~3 employ~ are bi3phanol~ such as bi~(4-hydrc~xyph~nyl) m~thane, 2,2-bi~(4-hydr~xyph~nyl) propane (hereinaf~sr r~erred to a~ bispher~ol-A~, 2, 2-bis ~4-hydroxy-3-m~thylph~slyl) p~opane, 4, 4 bi~ ~4-hydr~Dxy-pSenyl) h~pta~0, 2-2-bis(4 hy~rcxy-3,5~dic~hloropherlyl) propan~, ;
~, 2-}3is ~4-hydroxy-3, 5-dib~omo~hsr.yl) propan~, ~atc!o ~ dihydri~
phelaol ~ther~ such as bis~4 hyd~oxyph~ylj oth~3r, bis(3,5-di~ sro-4-hyar6~xyp~enyl) ~ ther, et~.: dihydrc~xydiph~nyl~ ~uch ~ p, p ' -dihy~roxyt~ip!h~nyl" 3, 3 ' -diahloro-4~ 4 ' -dihydroxydiphenyl, ~tc.; dihydroxy~ryl su~ono~ 8us~ EI bi~ ~4~hy~roxyp~enyl~
suli~ono, bi~(3,5-dinaethyl-4-hy~rt~xy~h~nyl) sulfone, ~tc~
dih~roxy ~nzenes, resor~inol, hydroguinon~, balo~ and alkyl~
~ub~titut~d dihydroxy be~zen~s such a~ 1,4-dihydxoxy-2,5-dichloro~enzene, 1~4-dihydroxy-3~m~thylbenæena, ot~ nd dihyaxoxy dipheny~ sulfoxid~. ~u~ a~ bis(4-hydroxyphe~yl) sulfoxiae, bis~3,5-dibromo-4-hydr~xyphenyl) ~lfoxide, et~.
A variety of additio~l dihydric ph~nols aro al~o av~ilable to pxo~ida carbonate polym~r3 a~d ~r~ disclo$ea in U.S. pa~t~
2,999,835 i~u~d S~pt~ber 12, l9S1~ 3,028,365 issu~d April 3, 1962 ~d 3,1S3,008 is~u~d O¢teb~r 13d ~d64~ Also suitabl3 ~or p~eparing ~he aromatic ~a~bonat~ polym~rs ax~ cop~ly~er~
pr~par~d fro~ any of the above copolym~riæ~d with h~log~n-~ontainin~ dihydric phenols ~uch as 2,2-bi~(3,5 dichloro-4~
hydroxyph~yl) prop~na, 2,2-bis(3,5-dibxomo-4-hydr~xyph~nyl) propan~9 ~c. It is o~ ~o~rs~ pPsaibl~ ~o ~mploy two or ~ore dif~rent ~ihydric phenols or ~ cop~lym~r ~ a dihydric p~enol with a glycol or ~ith hydroxy or aaid termi~at0d polyeBter~ or wi~h a dibasic a~id in th~ eve~ a c~rbonate copolym~r or interpolymer r~ther th~n a homop~lymer i~ desir~ fo~ use in th~ preparatiQn of the aromatic carbo~te polymar~ of ~his i~s~tion. Also employ~d in th~ practice of this in~entio~ ~ay b~ blends of any of the above ~a~ri~l~ to provide ~he ~roma~ic

- 4 -. ' ~3C~f-1915 ~S~138 carbona~ polym~r~, ~he ca~bonat0 precu~or Alay be ei~hor a carbo~l h~lide, a carbona~e e~ter or a haloformate. The carbor~yl ~:
h~liaes which can J~e ~mployed h~3r~in are~ carbollyl bxo~i~
carbonyl chloride and mixtur~s ~h~re~ Typic~l o~ tha ~:
aa~bonate~ er3 whi~h ~ay be ~3mploy~d h~rein are diphen~l ~rbonat-3, di- ~haloph~nyl ~ carbGn~tes such a~ di-chloropheny 1 ) :~
carbonats, di- (bromophel~yl) carbon~eO di- (trichlvroph~nyl) carbon~t~, di~ ribromophe~nyl) carhon~t~, etc., di~ lXylph3~yl) ~:arb~te suc~h as di- (tolyl) car~o~ t~, e~c:., di- (naphthyl) c~r}:onate, di- (chloron~phthyl) c~rbonate, ph~nyl tolyl carbonate, chlorophenyl ahloronaph~hyl earb~ s, ~tc., or IRaxture~ . :
theraof~ Th~ haloformal~o~ suitabla ~or u~ herein incluae bis-halo~or~ dihydric phan~ bi~chloroform~as of eths~lene glycol, n~opentyl gly~ol, ~lya~hyl~ne glycol, eta.) `~
Whils other c~rbo~ate pr~cur~s3r~ will o~cur ~o thos~D skill~d in rt, ~:~rboE~yl chloride al~o kllo~n as ph~g~n~ i3 pr~rr~d.
~ inclua~d are th~ ~ly~3rlc IQat;e~ial3 o~ a dihy~ric phenol, ~ ~licarbo~ic a~ d carboni~: aei~. Th~se ar~ di~cl~3s0d ~n U.S, patent 3,169,121 i3su~d ~ebr~alry 9, 1965.
The aroma~i~ carbonat~ rs of this irlvent~ on ar-3 -pr~p~r~d by e~ploying ~ ~ol~cular waight r~gula~o~, an acid acc~ptor and a cataly~tO The ~le~ular ~eig~t regulats~ which ~y b~ employe~ in ~arrying out th~ prsce~s of thi8 inv~ti~n i~clud~ ph~ol, cycloh~xa~ol, m~hanol, p~ra-~rtiarybutyl-phenol, parabromoph~nol, ~tc. Prefe~ably ph~slol :i~ employ4d a~ 3cular ~0ight regul~tor.
A a3ui~cabl~ aci~ alc¢~ptor may be ei~hsr ~n orga~i~ or inorgania ~ a~:coptoE. A ~itabl~ oxgallic a<:id a~:ci3p~0r ~ a ~ertiary ami~e and inclu~o~ ~ur:h mat~3ri~l1s a~ pyxidina, ~. .
tri~thylami~a, dimethylanili~a, tributylamine, etc~ 9rh0 :~
inorganic ;acid acceptor ~ay b0 on~ which ~an bo ei~aer a _ 5_ ;

~C~-lgl5 ~S~131~ ~
hydr~xide, a c:arbo~ate, a bicarlDo~ata, or a pho~phat~ or an ~lkali or allcali ~arth matal, Obvioll~ly oth~r ~ateri~l~ c~ al~o b~ ~mpls~y~3d with th~s aromatic c~rbo~te polyme~r o~ thi~ invellt ~n and inclu~
~u~ ~at~rial~ a~ a~nti-statia ageIlt~,, pigm6~nts, m~ld relea~e ~g~t~, t~9rmal sg~bilizar~, ultraviolet llght ~talbili~r~, reinforcing ill~r~ and the lik~., The compo~iti~n o~ ventisn i8 pr~par~d by admixing the arom~ arbonats poly~ex with ~he g~rg~nic alkali 10 ~etal or alkaline ~arth ~at21 salt~ a th~3 fluorinated p~lyol~fin.
Th~ follcwing ~32arnpl~s are se~ ~orth to illustrat~
more clearly ~h~ principle ana~ prac~ice of thi3 inv~ntion to th~ killod in ~hs art. U~le~3 ot:herwi~ ci ~ied, whera par~s or porc~er~t~ ax~ tion~, they a~ part~ o~ per~ent~
by weight.
A pol~¢arbs~nat~ com~ition i8 pr~ rod by esstru~ing ~ homopc lymar o~ 2~ 2~ (4-hy~lroxyph~yl) pr~pane (h~raillaft~s r~r~d t~ as bi~phe~ol-A) prop~-r~ by roa~ctilsg 0~e~atially 20 oquilGolar a~aoun~ of bi~ nol-~ and phQ~gan~ in ~n organic medium with triethylami~, sodi~m hydroxide, aAd phe~s~l, ul~der ~ta~lard cc)~di~ion~. Thel xesultislg p~lymer ~ n ~d to an ~:
~xtruder, which ~xtrud~r i~ operat~ld at about 265&, ~lld ~h~
ex~rudat~ i8 co~ut~d into pell2t~
Th~ pell~t~ are th~ll injec~i~sn ~ld~a~l a~ ab~ut 315 C
il~tO ~est bars of about 5 in. by 1/2 in. by about 1/16-1/8 in.
thick. ~rhe t2~t barg (5 for ~e~c:ll a~ditiv~ te~l in th~
Table~) ar~ ~ubj0~:t~d ts~ t6~t proeedure ~3t forth in Underwrit6~rs ' L~borato~i~3, In~:O Bull~lstar~ 94, su:rni~ag T9~ iEor 39 Cla~iying Materials (h~rei~a~r re~erred to ~ 94~o In accordanc:e with thi9 t~8~ pro~e~v.reg mat~3rial~ ~ inv~tigated `':

~-1915 ,~' ~ S~ILgL3 a~ r~ted ~i~her UI.~94 V~0" U~ 94 V I, tJT~-g~ V~ a~ed on ~e re~ults ~3~ 5 ~psci~0n3. The ~rit3ria ~3r ~ach V ratin~ per -UL-94 i~ bri~ly ~!18 ~oll Gw8 . .
"~-94 V-ON: -Aver3gs 1ar~ing ~nd/or glowi~g a~ter ; ~ :
ro~o~al o~ th~ ig~ ing ~la~ ~ball ~ot ~xceed 5 ~conds, and n~la o~ tn~
ep0cime~ hall dlrip particle~ whic:h ignite ~b~orbent cotton.
W~3L-94 V~ P,v~ra~ flamillg ~nd/ox ~l~wing af~r r~val of the ignitirlg ~l~FAe ahall nc~
exc~0d 25 ~e~o~sS~ a~d one of th~
specimesn~ shall drip partial~3 which ig~ite absorbe~t ~ to~.
94 V II": Ave~r~ge fla~slg and/or flowil~g a~t~r r~oval o~ tha ignitia~ fla~o shall not exceed 25 s~ond~ ;~nd the sp~3dm~n~ drip .
fl~ing pzlrticl~ which ig~it~ ~Ibsorbent . ~
cotton. ; ~ ~.
In ~dditi~n, a t~st bar whic~h l::on~$nua~ ~3 burn for m~re than 25 .
20 ~ ond~ ~te:r remo~l Qf lthe ig~iting ~lamel i~ cla~sifi0d, not by UL-94, but b~ ~he starld~ds of th~ t inv~ntion, ~ ~ :
3~3 U~ur~ing." Furth~r, UI.-94 r~s~uir~ that all te~t b~r~ .`
r~u~t neod the ~ typ~ rating to achiovs the partacular rating. Otherwis~ 5 b~r~ rec~iv~ the r~ting o~ th0 ~or~t ~i~gl~ kar. For ~x~pl~, if OAe ~bar i~ clas~i~iod :~ .
94 V-i~I an~ esther four (~ r~ cl~3i~ied as Ul-94 V-9, thell the rating ~Dr ;~11 5 b~ Ul-94 V~
~he r~ult~ ~re 8~ tho !I!abl~3,.

8~ 5 ~ ~ ;

~SE

To ~ polyc:arbo~a~e of E:s~mplo I i~ ad~od 0.,5 p~rt~ of ~ 2,~,s-~riahlorcs~ 0~s~ul~Q~at~o l~he ~ix~ur~ i~ ex~ lbd" ~oldod, a~d ~e~t~l in r as ~ ri~ x~pl~ I .

~ ', :

To th~ polycar~onatQ o~ Exa~pl~ I i~ ~ddod 0.5 p~rts of so~liu~ 2,4JS-trichlorol~n~e~sul~ollat~ ~d 0.05 poly~ tra~ o~hyl3n~a), (~old by ~ t ~o~emo~ d Company Zl8 TEFLO~-6) . 'rh~ ~ix~ure i~ :;
axtrudodl, mold~ a~l tost~d in ~he s;~ae m~anner as d~cri~d i31 ~x~npl~ ~.

The re~ai~ing COM~ Bre prop~rod by the ~ethod~ o~ Exa~ple~ I to III.

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As can b~ ~een ~rom the ~la~a in ~he Tabl~, wh~n ~he polycar~onate compo~itions contair~ fluori~ated polyolefin :;~
in addition to the flame retardant additiv~,, the poly-c:arbs~l-at6~ doe~ not drip an~ r;E~tea ~ither UL-94 V-O, or Ul.-94 V~
Other flame r~tardan~ addi~iv~ and ~luorir~t0d pt~lyole~ins c3n be ~Ab~tituted for those o~ ~he T~bla with 3.r r~3~ults.
~t ~ill ~hu~ bo s~30n tha~ the3 objsct~ forth 10 ~bov~ a~ng th08~ ~nade appar~nt ~o~ the p~eoHding descrîption ar~ ~ficien11 y att3ined and sirlCe~ C0rt in ahang~s may be Enade in carrying DUt ~he above pro~ and in ~ha co~position 8et forth withou~ depart~ng ~rom the ~ope3 o~
thi8 inve~tion, it i8 int~nd~d ~at all ma~tax~ co~tained in :`~
the abov~ de~Griptiols ~hall be interpr~ted as illu~rativ~
and not irl a limiting ~ens~.
.

; 11 - '

Claims (5)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. An improved flame retardant polycarbonate composition of an aromatic carbonate polymer in admixture with an organic alkali metal salt or an organic alkaline earth metal salt or mixtures thereof, the improvement which comprises having in admixture with the flame retardant polycarbonate polytetrafluoroethylene in sufficient quantity to render the polycarbonate composition non-dripping.

2. The composition of claim 1 wherein the polytetrafluoroethylene is present in an amount of from 0.01 to about 2.0 weight percent based on the total weight of the polycarbonate.

3. The composition of claim 1 wherein the organic alkali metal salt is sodium 2,4,5-trichlorobenzenesulfonate.

4. The composition of claim 1 wherein the organic alkali metal salt is sodium benzene sulfonate.

5. The composition of claim 1, 2 or 3 wherein said polytetrafluoroethylene is admixed in the form of particles having a size generally in the range 0.3 to 0.7 mm.