CA1069236A - Flame retardant, non-dripping compositions of polyphenylene ether and acrylonitrile-butadiene-styrene - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention provides novel flame retardant, non-dripping thermoplastic molding compositions of polyphenylene ether resins or acrylonitrile-butadiene-styrene copolymers which include a flame retardant agent, and polytetrafluoroethylene.

Description

. 8CH-1535 ~6923,6 ' This invention relates to flame retardant, non- ~
dripping thermoplastic molding composi-tions of a poly- . :
: phenylene ether resin or an acrylonitrile-butadiene-styrene , or alpha-methyl styrene copolymer which include a ~lame retardant agent and polytetrafluoroethylene.
The polyphenylene ether resins and acrylonitrile-butadiene-styrene or alpha-methyl styrene (ABS) resins :
are well known thermoplastic materials that are commer- ~
cially available. Bcth of these materials a~e ~ ~ ;

......

.', . . .
'; ~ ~ ,.

, : :

. ~ "~ ,.

., .~ .
~ "

. , .. ~.- .. . .. . . .. . . , :., :- ,, .. :. . ~

0~ ~ ~ 3 6 1 flammable and require the use Df additivesto achieve a

2 commercially acceptable degree of flame retardancy.

4 If a thermoplastic test bar burns vigorQusly enough for a I sufficient ti~e, the bar will gradually soften (absent an un-6 , expected crosslinking reaction) and will begin to exhibit sagging. As the bar becomes softer and less viscous, ~ point 8 will be reached a~ which the bottom pDrtiDn of the bar will 9 separate physically from the remainder of the bar retained in ~he test standO This phenomenon is known as "dripping"0 ~ --Il ` - .
12 In the prior art there have been problems in prepar~ng 13 flame retardant compositions of these materials which did no~

14 ~ form flaming droplets when they are ignited with a direct flame~ ~

16 U. S. 3,671,487 discloses a non-dripping linear polyester 7 molding composition that employs a~glass reinforcemen~, a flame ii retardant additive and a polytetrafluoroethylene resin. This l9 reference empl~yed about 005 toi 2.5 parts by weight per hundred parts of composi~ion of polytetrafluoroethylene.

Applicants have found that it is possible to schieve a ! flame retardant, non-dripping polyphenylene ether mDlding composition by the addition of a flame retardant compound and 25 , ` from 0.1 to 0.~5 parts by weight per hundred parts of composition of polytetra~luoroethy~Iene. In the case of ABS, a flame retardant compound and from 0.5 to 3 parts by weight per hundred ~ : :- :~... ' .
: . : '''"
( 2 ) ; ~

106'J;~
8C~-1535 1 parts of composition will be sufficient to produce a flame 2 retardant non-dripping comp~sition without a glass reinforce-

3 I ment, Accordingly, it is a primary object of the present t

4 invention to prepare flame retardant, non-dripping molding I compositions of polyphenylene ether resins and ABS resins.
S I .
- It is alsD an object of thle present invention to provide .
8 flame retardant non-dr~pping molding compositions of poly- ;
9 . phenylene ether resins and ABS resins that have physical .
10 properties which -are nDt appreciably affected by the presence .
; II ! of the flame retardant-drip preventing system. ~ :

13 .j - Description of the-Invention - According to the present in-14 '¦ vention there are provided flame retardant, non-dripping thermo-plastic molding compositions which comprise:
; 16 ' ~a) a normally flammable polyphenylene ether resin or ABS;.
17 (b) a flame retardant additive in a minor proportion lB j~ based on said thèrmoplastic molding composition but in an amount 19 sufficient to render said thermDplastic compos.ition non-burning ~
20 I or self-ext~nguishing; . -II - (c) a polytetrafluoroethylene resin in a minor proportion E
22 ,¦ based on said thermoplastic molding composition i.n an amoun~
;~ at least sùfficient to render said thermoplastic molding com- ~
. ~ po~ition non-dripping. ~ :
25 i . .
26 ~ :
The term "polyphenylene ether resin" includes a family of :
polymers well known to those skilled in the art, and they are .-.
':~",'" ' ' ( 3 ) ~ ,, ,,, . 1-1 06g 2 3 6 8CH-1535 1 made by a variety of catalytic and non-catalytic processes from 2 the corresponding phenols or reactive derivatives thereof.
3 By way of illustration, certain of the polyphenylene ethers 4 . are disclosed in Hay, U. S. 3,306,874 and 3,306,875~ and in I Stamatoff, U. S. 3,257,357 and 3,257,358. In the Hay paten~s, S . the polyphenylene ethers are prepared by an oxidative coupling 7 ` reaction comprising passing an oxygen-con~aining gas through 8 a reaction solution of a phenol and a metal-amine complex g catalys.t. Other disclosures relating to pr.r~cesses or preparing 10 -- polyphenylene ether resins, including graft copolymers of pol~-1I phenylene ethers with styrene type compounds, are found in 12 Fox, U. S. 3,356,761; Sumitomo, U. K. 1,291,609; Bussink et al, 13 . U. S. 3,337,499; Blanchard et al, U. S. 3,219,626; Laakso et aL, 14 U. S. 3,342,892; Borman, U. S. 3,344,166~ Hori et al~ U. S. ~ .
3,384,619; Faurote et al, U. S. 3,440,217; and disclosures ;
16 relating to metal based catalysts which do not include amines, .
17 are known from patents such as Wieden et al, UO S. 3,442,885 18 j (copper-amidines); Nakashio et al, U. S. 3~573,257 (Metal-19 alcoholate or -phenolate); Kobayash;let al, U. S. 3,455,880`
20 I (cobalt chelates); and the like. In the Stamatoff patents,~ . ~1 ..
21 j the polyphenylene ethers are produced by reacting the corres- .
t2 ' ponding phenolate ion with an initiator, such as peroxy acid ~3 jl salt, an acid peroxide, a hypohalite, and the like, in the .. : .`.
24 . presence of a complexing agentO Disclosures relating to non-25 ~ catalytic proc:esses, such as oxidation wi~h lead dioxide, silver 26 oxide, etc., are described~in Price et al, U0 S. 3,382,212. ;
i7 Cizek, U. S. 3~ 383,435 discloses polyphenylene e~her-styrene ,' ' ~ '. ' ' .
- ( 4 ) `~
~ . ' .

1069Z3~ 8CH-1535 I resin compositions.

3 `
- I . .......
4 , The polyphenylene ether resins are preferably of the , type having the repea~ing s.trucltural formula.:
S ~ . . .

ll .. Q

. .
` 13- .. wherein the-oxygen ether atom of one unit is connected ~o the .~
'l . . . . ..
14 benzene nucleus of the next adjoining unit, n is a positive .
. 15 integer and is at least 50a and each Q is a monovalent substi- . -.. 16 ' tuent selected f~om the group consisting o~ hydrogen, halogen, . 17 hydrocarbon radicals free of a tertiary alpha carbon atom, : l8 ,j halohydrocarbon radicals having at least two carbon atoms 1 : . :.
19 between the halogen atom:and the phenyI nucleus, hydrocarbonoxy ;~ 20 ~i radicals and halohydrocarbonoxy radicals having at least two :
l 21 ! carbon atoms.
"~ 22 , . .~ .; ., .
~ 23 ~1 The preferred p~lyphenylene ether resin is poly(2,6-dimethyl~ . -:l 24 l 1,4-phenylene) ether resin~
25 1. ~ .`:
~6 The composition8 which include a polyphenylene ether resin - ~
. ~:., 4~ may als~ include a vinyl aromatic resin. The vinyl aromatic : .

,: ~ ( 5 ) .
~ ~ ' 10692~36 8CH-1535 1 resins are homopolymers or copolymers having at least 25% of 2 their units derived from a monomer having the formula:

4 , 5 ~Rl ~ CHR2 7 ~6 ~ ~ = R4 : B
: 9.
.~ where.in R and R2 are selected from the group consisting of 10 '; ' '- ':
lower alkyl or alkenyl groups of from 1 to 6 carbon a~oms and hydrogen; R and R are selected from the group consisting o~ ..
~ .12 .- . -.
-~ ' chloro, br~mo, hydrogen and lower alkyl of from 1 to 6 carbon ~ .
-; .13 ~, 6 . atoms; R5 and R are selected-rom the group consisting of . :.

hydroge~ and lower alkyl and alkenyl groups of from 1 to 6 .15 -- - 6 carbons or R5.and R may be concatenated together with hydrD-: 16 -.
r carbyl groups to form a naphthyl group. -Materials that may-be copolymeriæed with the units of the ..
19 ' ~ ~
:~ i vinyl aromatic monomer include tho9e having the general formula:

-~ 21 il 22 ,! -. R7 - CH~G - (CH2)n ~ Rg .'~ ' i l ,:.
~; 23 i ¦ R8 24 l ~ -I ' -~ ~ , ,' - 25 wherein R8 and R7 represent a substituen~ se~ected from the 26 group consisl:ing of hydrogen, halogen, an alkyl group of ~-4 ~.
-. 27 carbon atoms" carboalkoxy or R7 and R8 taken together represent ~-~
- ~ - ' .
. ~ ( 6 ) 06~'~ 3 ~

; an anhydride linkage ( - COOOC o ) and Rg is hydrogen, vinyl, 2 an alkyl or alkenyl group having 1 to 12 carbon atoms, cyclo-3 i alkyl, carboalkoxy, alkoxy-alkylJ alkyl carboxy, ketoxy, halogen, 4 .' carboxy, cyano or pyridyl and n i.s a whole number bet~een 0- -:

5 ! and 9.
'' S .1 . , - ,.' 7 - The general formula set forth includes by way of example, . .

~ homopolymers such as polystyrene and polymonochlorostyrene, : 9 the modified polystyrenes, such as rubber-modified, high-impact ~:

~ 10 I pDlystyrene and the styrene containing copolymers, such as the ; il ~ styrene acrylonitrile copolymers, styrene butadiene copolymers, I

: 12 ~ styrene-acrylonitrile-~ -alkyl styrene copolymers, styrene- .~

. I3- ~ acrylonitrile-butadiene.copolymers, poly- ~- methylstyrene, co-: :

I polymers of ethylvinyl benzene, and divinylbenzene styrene- ¦

-! maleic anhydride copolymers -and styrene-b~tadiene block copolymers.
16 ; ~ .
- . .
17 The rubber modified high impact polystyrenes may be made with diene rubbers.such as butadiene rubber, styrene-butadiene rubber, acrylonitrile rubber or ethylene-propylene copolymers or EPDM.rubber, -21!1 ` , : `
22 ii . .
~ . The ABS copolymers are well known and many suitable types ~ 23 i are commercially available. Either sn acrylonitrile-butadiene-. styrene or an acrylDnitrile-butadiene -alpha-methyl styrene -~
;i may be used as the ABS component. A useful method for preparing ;
these copolymers comprises grafting 73 parts styrene and 42 parts acrylonitrile onto polybutadiene latex containing 58 part:s~
- ' ,'. ' ( 7 ) ~' . - . . .. . .
- . . . . . . -.. , - : .
. ~ . . , , ~ ~ . . . -~ 069 Z 3 ~ 8C~-1535 1 polybutadiene in the presence of 3 parts soap, 107 parts mer-t captan and 004 parts potassium peroxydisulfa~e at 50C~ The 3 latex is coagulated and the product is then milled ~or 10 4 minutes at 320F. Other useful methods for preparing ~hese copolymers may be found in y. S. 2,505,349; U. S. 2,550,139, S U. S. 2,698,313; U. K. 698,385; U. S.2,713,566; U. S. 2,820,773;
7 and U. S. 2,908,661.

9 . .:
The compositions of the invention may comprise from 10-95 11 parts by weight-of the polyphenylene ether resin or the ABS
- 1~ resin. If a vinyl aromatic resin is combined with the poly-13 phenylene ether resin it may comprise f~om 5 to 90 parts by 14 weight. The flame retardant component may comprise from 2.0 to 25 parts by weight per hundred-parts by weight of the composi-; tion and polytetrafluoroethylene may comprise from 0.1 to 3 ;
parts by weight per hundred parts by weight of compositinnO

:
1~ The nature of the fla~e retardant component is not critical ! and single compound may be used. Optionally, it may be found ! desirable to use as the flame retardant component, a mixture of two or more inldividual flame retardant compounds.
23 , 2~
Among the useful 1ame retardant compounds are those o ~ -the formula:

.... .

~, :
- ~ .

. . ~,.; .. :.~: .
( 8 ) . ~ ,' . , .

~06923~ 8CH-l535 ~ (Y)d ~ ~b ~
3 Ar R Ar' ~ ! ~

6 wherein R is an alkylene, alkylidene or cyclo-

7 l aliphatic linkaget e.g., methylene, ethylene, prDpylene, iso-

8 propylene, isopropyiidene, butylene, isobutylene, amylene, g cycloXexylene, cyclopentylidene, and the like; a linkage 0 selected from the group~consisting of ether; carbonyl; a sul- .
, .
11 fur-containing linkage, eOg., sulfide, sulfoxide, sulfone, li carbonate; a phosphorus-~ontaining linkage; and the likeO R
13 can alsD consist of tWD or more alkylene or alkylidene linkages 14 ; connected by such groups as aromatic, ether, ester, carbonyl, sulfide, sulfoxide, sul~one, a phosphorus-containing linkage, 16 snd the llke. R can be a dihydric phenol, e.g., bisphenol-A~
17 carbonate linkageO Other groups which are represen~ed by R w~ll 18 j occ~r to those ~killed in the art.
, . - . :
~ lQ
- 20 j ` Ar and Ar' are mono- or polycarbocyclic aromatic groups~
~ 21 I su~h as phenylene, biphenylene, terphenylene, naphthylene, ~ ~
.. . . 1 :.
j~ 22 and the like. Ar and Ar' may be the same or different.
5.,~ .:
23 i1 ` - -;
~' 24 Y is a sllbstituent selected` from the group consisting of ~ -~
organic, inorganic or orgsnometallic radicals. The substituents 26 represented by Y include (1) halogen, e.g., chlorine, bromine,~ , 2i iodine, or fl!lorine or (2) ether groups of the general formula~, ~ ¦
Z8 OE, wherein E is a monovalent hydrocarbon radical similar to~
~9 ;X or (3) mono~alent hydrocarbon groups of the type represented :, t 9 ) ~0b;~236 l by R or (4) other substituents, e.g., nitro, cyano, etc., 2 said substituents being essentially inert provided there be 3 at least one and preferably two halogen ato~s per aryl, e.g., 4 phenyl nucleus.

.' S j X is a monovalent hydrocarbon group exemplified by the - ' ; following: 'alkyl, such as methyl, ethyl, propyl, isopropyl, O ..... ~ . .
~ -butyl, decyl and the like; aryl groups, such as pheny~, .

9 naphthyl, biphenyl, xylyl, tolyl, and the Like; aralkyl groups, 0 such as benzyl, ethylphenyl, and the like; cycloaliphatic 11 groups, such as cyclopentyl, cyclohexyl, and the like; as well 12 as ~onovalent hydrocarbon groups containing inert substituents 13 therein. It wiil be understDod that where more than one X `

14 is used they may be alike or different.

l .C . . . ...... . . . . . . .
The letter d represents a whole number ranging from l to ~' 17 a maximum equivalent to the number of replaceable hydrogens substituted on ~he aromàtic rings comprising Ar or Arl. The letter'e represents a whole number ranging from O to a maximum '~
controlled by the number of replaceable hydrogens on R. The ! letters a, b, and c represent whol'e numbers including 0. When ~' , ) ;
-; I b is not 0, neither a noric may be 0. Where by is 0, the ' l aromatic grou]ps' are ~o~ned by a direct carbon-to-carbon bond, ; ' ` 24 ' 25 ; The hydroxyl and Y substituents on the aromatic groups, Ar and Ar' can be varied in the ortho, meta or para positions on ; the aromatic rings and the groups can be in any possible~ ' .':. ' ' , ' ( 10 ) ", : ' ~06~236 8CH-15 35 1 geometric relationship with respect to one another.

3 Included within the scope of the above formul~ are 4 i diaromatics of which the following ara representative:

S ' 2,2-bis-(3,5-dichlorophenyl?propane 7 ' . bis(2-chlorophenyl)methane -' bis(Z,6-dibromophenyl~methane ~:
9 l,l-bis-(4-iodophenyl)ethane 1,2-bis(2,6-dichlorophenyl)ethane , 11 . l,l-bis(2-chloro~4-Lodophenyl)ethane' 12 l,l-bis(2-chloro-4-methylphenyl)ethane 13 ., l,l-bis(3,5-dichlorophenyljethane 14 ;i 2,2-bis~3-phenyl-4-bromophenyl)ethane 2,3-bis(4,6-dichloronaphthyl)propane 16 2,2-bis(2,6-dichlorophenyl)pentane 17 2,2-bis(3,5-dichlorophenyl)hexane 18 jj bis(4-chlorophenyl)phenylmethane 19 bis (3,5-dich10rophenyl)cyclohexylmethane i bis (3 . ni~ro-4-brGmophenyl) methane 21 1 - bis(4-hydroxy-2,6-dichloro-3-methoxyphenyl)methane -~
22 1 2,2-bisC3,5-dichloro-4-hydroxyphenyl)propane 2,2-bis(3-broms-4-hydroxyphenyl)propane ::.
,1 i ' ' 25 '' i '! The preparation of these and other applicable biphenyls 26 !
. ~ are known in the art. In place of the divalent aliphatic grsup : in the above-examples may be substituted sulfide, sulfoxy ~ 28 and the like.
. - , - . :

~ .
~ 11 ) , .

lC)69Z3G
I l . 8CH-15 35 1 Included within the above structural ormula are substi-2 tuted benzenes exemplified by tetrabromobenzene, hexachloro-3 ; benzene, hexabromobenzene, and biphenyls such as 2,2'- :
4 ! dichlorobiphenyl, 2,4!dibromobiphenyl, 2,4'-dichlorobiphenyl, hexabromobiphenyl, octabromobiphenyl, decabromobiphenyl and S jl halogenated diphenyl ethers, containing 2 to 10 halogen atoms.
? ~ - :

8 In general~ the pr~ferred phosphate compounds ~re selected g from elemental phosphorus or organic phosphonic acids, phosphonates, phosphinates, phosphonites, phosphinites, phosphine l1 oxides, phosphines, phosphites or phosphates O Illustrative 12 ;i is triphenyl phosphine oxide. These can be used alone or mixed 13; with hexabromobenzene or.-a chlorinated biphenyl and, optionally, 14 sntimony oxide.
15 ; ... - . ~ :

l~ , `Typical of the preferred phosphorus compounds to be `
17 employed in this invention would be those having the general ;
18 jl fOrmula 19 ~ - o ` `

20 ~1 . Q0 Il OQ
: 21 iI - IQ -, 22,l . ~ . . . .
~ ,1 .
~3 ~¦ and nitrogen ~Inalogs thereof where each Q represents the same or different radicals including hydrocarbon radicals such as 25., alkyl, cycloalkyl, aryl, alkyl substituted aryl and aryl ~! substituted alkyl; halogen, hydrogen and combinations thereof 27 provided that at least one of said Q's is aryl. Typical examples . . . .

2 ) ::

~9 2 3 6 1 of suitable phosphates include, phenylbisdodecyl phosphate, 2 phenylbisneopentyl phosphate, phenylethylene hydrvgen phosphate, 3 phenyl-bis-3,5,5'-trimethylhexyl phosphate), ethyldiphenyl !l 4 il phosphate, 2-ethylhexyl di(p-~olyl) phosphate, diphenyl hydrogen ~, phosphatë, bis(2-ethyl-hexyl) p-tolylphosphate, tritolyl S Ij phosphate, bis(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl) 7 ; phosphate, phenylmethyl hydrogen phosphate, di(dodecyl) p-tolyl 8 j phosphate, tricresyl phosphate 9 triphenyl phosphate, halogenated 9. triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyl- -~
diphenyl phsophate, p-tolyL bis(2,5,5'-trimethylhe~yl) phosphate, F
11 2-ethylhexyldiphenyl phospha~e, diphenyl hydrogen phosphate, 12 and the like. The preferred phosphates are those where each 13 ~ Q is-aryl. The most preferred phosphate is triphenyl phosphate.
14 It ~s also preferred to use ~riphenyl phosphate in combination with hèxabromobenzene and, optionally, antimony oxideO

17 Also suitable as flame~retardant additives for this invention ¦ are compounds containing phosphorus-nitrog_n bonds, such as `
9 I phosphDnitrilic chloride, phosphorus ester amides, phosphoric ~1 acid amide~, phosphonic acid amides or phosphinic acid amides.
! These flame-retardant additives are commercially available.
22 `~

t4 `

; The preferr.ed compounds for this invention are aromatic ; ~ halogen compounds such as brominated benzene, chlorinated ~-biphenyl, or a compound comprising two phenyl radicals ~:..':
,,',' ( 13 ) , ; ~

~ 9 2 3 6 i! l 1 j separated by a divalent alkenyl group and having at least two 2 chlorine or bromine atoms per phenyl nucleus, polycarbonates, 3 j chlorine containing aromatic polycarbonates, and mixtures 4 ,l of at least two Df the foregoillg.
.!
6 Especially preferred are h~xabromobenzene and triphenyl 7 ; phosphateD ~
8 , 9 ~ The compositions of the invention may also include rein-forcing fillers, such as aluminum, iron or nickel, and the like 11 ; and non-metals, such as carbon filaments, silicates, such as -lt ¦ acicular calcium silicate, asbestos, titanium dioxide, 13 ' potassium titanate and:titanate whiskers, glass flakes and 14 ~ fibers. It is also to be ~nderstood that, unless the filler ;
adds to the strength and stiffness of the composition, it is 16 ' only a filler and not a reinforcing filler, as contemplated l? herein. In-particular, the reinrorcing fillers increase the 8 il flexural strengthj the flèxural modulus, the tensile strength 19 and the heat distortion temperatureO
~0 11 , , ~
21 ,¦In partic:ular, the preferred reinforcing fillers are of 22 i glass and it iLs preferred to use ~ibrous glass filaments j¦ comprised of llme-aluminum borosilicate-glass that is relatively 24 !~
soda free. This is known as "E" glassO However, other glasses i! are useful~where electrical properties are not so important, 'r eOg,, the low soda glass known as "C" glass. The filaments are made by st:andard processes, e~g., by steam or air blowing, : ' ~ ( 14 ) - `

.

~0~9236 1 flame bl~wing and mechanical pulling. The preferred filaments 2 for plastics reinforcement are made by mechanical pulling. The 3 filament diameters range from about 0.000112 to 0.00075 inch, . . .
4 'i but this is not critical to the present invention.
S
j In general, best properties will be obtained if the sized 7 filamentous glass reinforcement comprises from about 1 to about 8 80% by weight based on the combined weight of glass and polymers 9 and preferably from about 10 to about 50% by weight. Especially preferably the glass will comprise from about 10 to about 40%
ll by weight based on the combined weight of glass and resin.
12 , Generally, for direct molding use, up to abou~ 6070 of glass 13 can be present without causing flow problemsO However, it is 14 ; useful also to prepare th~e compositions containing substan-tially greater quantities, e.g., up to 70-80% by weight of 16 glass. These concentrates can then be custom blended wit~
17 blends of resins tha~ are not glass rein~orced to provide any 18 j! desired gl8SS content of 8 l-ower V81Ue~
19 .' . , .

20 ! The length of glass filaments and whether or not-they are bundled into fibers and the fibers bundled in turn to yarns~ ;
ropes or rovi~gs, or woven into mats, and the like, are also not critical to the invention. However, in preparing the present ; compositions i.t is convenient to use the filamentous glass , in the form oi chopped strands of from about 1/8" to about 1"
long, preferably less than 1i4" long. In articles molded 27 from the compositions, onthe other hand, even shorter lengths `: :
,`' ` . ( :~. "

,j ~L06~Z3~ 8CH-1535 I will be encountered because, during compounding, considerable fragmentation will occur. This is desirable, however, because 3 il the best properties are exhibitled by thermoplastic injection ~ 4 ll molded articles in which the filament lengths lie between about - 5 ¦¦ O.OOOOOS" and 0.125 (1/8't)o S 11 , . .
; 7 ~! - The composition of the invention may be prepared by 8 il ~umbling the componen~s, extruding the mixture ~hus obtained.

9 , into a continuous strand, chopping the strand into pellets and . thereafter molding the pellets into the desired shape. These 11 " techniques are well known to those skilled in this art and ii , .
12 ii are not a critical feature of the inven~ion. ~
' 13~! .
. . .. ..
~: 14 l Description of the Preferred Embodiments ~ The present 15, invention is further illustrated in the following examples 16 I which are set forth as a further description of the invention.
17 i ~`` 19'il , , , ~

¦~ Blends were prepared and test samples were made as ¦ described in Table }. All of the numbers refer to parts by ` 23 `''. 24l1 25 ~
26, ~ 27 ~', . " ' '',:
6~
-: .:
.:
~ : ~ :~:,''-.... . .. - . .. , ~- , . . ... .. . ~

106~2~6 - 8CH-1535 U~ Lr) ` O U~ O. 0 ' '~
C~l ~ .-I .-1 U~ :
P~ l O O O O O
S rl ~ , cr7 ~ ~ .~

E-l I . ,_i -I -I -I ' I . ' . .
~ , . ~ o oo . . , . -.; ~. ~ . .:
.' ~ . , . ....... . ., .:
U~ ~ ' U~ U~ U~ U~ ~ ' ~Q~ ~i ~_i ~o ~1 ~ o, ' , ~:
~ :~ : .
~ ~''-'''"'.' e . . . .
.
..
O O - O O . o O tl. ' .
oo 0 . a:~ oo 0 u~. . ~ , .

'~1 ~a~ ~o o O O ~0 O ,,~
. .. ~
. . . .,:
a~ .
C6L ~c c~l ~ ~ ~ ~
X ''`: '', ', .
' :':
( 17 ) ~:
~\ ' ~' :':, -,. . :

~69;~36 .~ .
. .

E ~ ~ ô _I :
.~ _1~ ~. ~ C~ oo ~, ~ "
C c~J ~, ~ ~. ~D ~ . ~ ~ , ' :":
~C ~ I~ ~ ~ _ C~ ~
~n -~ ~ ~ OD O~ C~ ~ ' U~ ~ ,. .
._1 ~ a~ c~ ^. ' c~l ~J - . :.
::1 ~, ~ , ~ . _1 O^ S~ QJ ..
C ,~ r~ ~ .~ ~ E
3^ o~ o c~c~l c~l a~ ~ o X~ ~ ,~ ~ ~ ~ ~ ~
1~~ S~ ~ o~ ~ O ~ , ~1~ _I N C~l tr) _ , ~ _ - _I C
_1_I ~ _ ~ ~1 ~ O~ ~ C9 ~1 ' U~~ ~ ~ _l .~ ~ ~ ' '"' ' ~1 ' ~ _ , ~ ~ . ~ ~1 ~ . ~ .
O~ e~ _ ~ ~O -I ~o~ _l O a~ 1 ~ ,1 ~ ~ ~ . o~
~ u~~ ~ ~ _ ~ . .
:~--~ _I ~1 0 ~ ) _~ ~1 _~ ~ ~1 ~D ~

I I I I I I ~ ~
. .
, . ; ~. , . ' ' . .
i . . " ' ' ' ~ . . .
~,, ' t~ ~ .~
E3 : c~ . ~ ~ .
, ' . ~ , . ' . , ~ ~'~.. ''''' ' ' : ' ' ~ : ;'' .

.

( 17a ) ~ :
, : :

,: . :

3~( t69236 8CH-1535 J-O .Q
4~ 6 s~ ~

~, . .

V :, :~ C ' ' . ' ~ ~ .
~U C~.O .
1~ ~1 . ..
W
a.

~ O
W _I . ...
ll.
.5 ~q , C) ~ .
W ,t - . .:
~I Q~ . .
oS
o ~:
_~ .,,, . ~- :

~ ~ ~' a~ .E - : ~ -~ " 8 a~ o ....

x ~ u c w ~ -: x x J~
~C O c~ o . . .
~ o) ~ o 0 ~ o ~
.ç x ~ ~ x -l ~ 0 ~ o ~:
~D O ~ S

~ c o ~ ~ ~

( 18)--:: . -~)692;~6 1Table I shows that tetrabromobisphenol-A, by itself, 2does n~t prevent dripping but that ~he addition of polytetra- ..
3fluor~ethylene to these composi.tions results in a non-dripping 4 compositiDn even at O.l parts ~y wei~ht. The composition of control Example 6 shows .that by itself, the polytetra-S fluoroethylene does not exert any appreciable flame retardant 7 effectO When dripping is prevented, t~e total burning time B may be_increased because the "drip" has a cooling effect on a burning polymer. By delaying dripping, therefore, heat is retained in the sample and greater flame propagation may 11 result. Also, whPn dripping is delayed, sagging of the sample 12 -may induce cracks in the surface of the charred sample which 13 furnish fresh fuel supplies for the propagating flame.
' 17 These examples show the effect of polytetrafluoroethylene with a phosphorus flame retardan~O
19 '~
! :: ~

21 , `: :

:'~

: -t7 . :, ~':

( 19 ) ' ,~
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Claims (31)

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

1. A flame retardant, non-dripping thermoplastic molding composition which comprises:
(a) a normally flammable resin selected from:
(i) a resin blend comprising from 10-95 parts by weight of a normally flammable poly(phenylene ether) resin and from 90-5 parts by weight of a vinyl aromatic resin, and (ii) an acrylonitrile-butadiene-styrene copolymer, (b) a flame retardant additive in a minor proportion based on said thermoplastic molding composition but in an amount sufficient to render said thermoplastic composition non-burning or self-extinguishing; and (c) a polytetrafluoroethylene resin in a minor proportion based on said thermoplastic molding composition in an amount at least sufficient to render said thermoplastic molding composition non-dripping.

2. A flame retardant composition as defined in claim 1 wherein the normally flammable material is a polyphenylene ether resin vinyl aromatic resin blend as defined therein.

3. A flame retardant composition as defined in claim 1 wherein the normally flammable material is an acryloni-trile-butadiene-styrene copolymer.

4. A flame retardant composition as defined in claim 2 wherein said vinyl aromatic resin is selected from polystyrene and rubber modified polystyrene.

5. A flame retardant composition as defined in claim 2 or 4 wherein the polyphenylene ether resin has units of the formula:

wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining units, n is a positive integer and is at least 50, and each Q is a monovalent substi-tuent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.

6. A flame retardant composition as defined in claim 1 wherein component (b) is a halogen-containing compound, a halogen-containing compound in admixture with antimony oxide; elemental phosphorus or a phosphorus compound; a halogen-containing com-pound in admixture with a phosphorus compound; a compound containing phosphorus-nitrogen bonds; or a mixture of the foregoing, and said compound is present in an amount of from 0.1 to 50 parts by weight per hundred parts of said resin.

7. A flame retardant composition as defined in claim 6 wherein said halogen containing compound is an aromatic halogen con-taining compound selected from the group consisting of chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl, brominated terphenyl, a compound comprising two phenyl radicals separated by a divalent alkylene or oxygen group and having at least two substituents selected from the group consisting of chlorine and bromine per phenyl radical; and a mixture thereof.

8. A flame retardant composition as defined in claim 7 wherein said organic halogen compound is tetrabromobisphenol-A.

:

9. A flame retardant composition as defined in claim 7 wherein said organic halogen compound is hexabromobenzene.

10. A flame retardant composition as defined in claim 7 wherein said organic halogen compound is a chlorinated biphenyl.

11. A flame retardant composition as defined in claim 6 wherein said flame retardant additive is hexabromobenzene in admixture with antimony oxide.

12. A flame retardant composition as defined in claim 6 wherein said flame retardant additive is selected from the group consisting of elemental phosphorus, organic phosphonic acid, phosphonates, phosphinates, phosphonites, phosphinites, phosphine oxides, phosphines, phosphites, phosphates and mixtures thereof.

13. A flame retardant composition as defined in claim 12 wherein said flame retardant additive is triphenyl phosphate.

14. A flame retardant composition as defined in claim 6 wherein said flame retardant additive is a mixture of tetrabromobisphenol-A, and triphenyl phosphate.

15. A flame retardant, non-dripping thermoplastic molding composition which comprises:
a) a normally flammable copolymer of acrylonitrile-butadiene-styrene;
b) a halogenated flame retardant additive in a minor proportion based on said thermoplastic molding composition but in an amount sufficient to render said thermoplastic com-position non-burning or self-extinguishing; and c) a polytetrafluoroethylene resin in a minor proportion based on said thermoplastic molding composition in an amount at least sufficient to render said thermoplastic molding composition non-dripping.

16. A flame retardant composition as defined in claim 1 wherein the flame retardant component comprises from 2.0 to 25 parts by weight per hundred parts by weight of the composition.

17. A flame retardant composition as defined in claim 16 wherein the polytetrafluoroethylene comprises from 0.1 to 3 parts by weight per hundred parts by weight of composition.

18. A flame retardant composition as defined in claim 3 wherein the halogenated flame retardant is a chlorine containing compounds.

19. A flame retardant, non-dripping thermoplastic molding composition which comprises:
a) from 10-95 parts by weight of a normally flammable polyphenylene ether resin;
b) from 5-90 parts by weight of a vinyl aromatic resin;
c) from 2 to 25 parts by weight per hundred parts by weight of the composition of a flame retardant additive; and d) from 0.1 to 0.25 parts by weight per hundred parts by weight of the composition of polytetrafluoroethylene.

20. A composition as defined in claim 19 wherein the vinyl aromatic resin is rubber-modified, high-impact polystyrene.

21. A flame retardant composition as defined in claim 19 or 20 wherein the polyphenylene ether resin has units of the formula:

wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent substituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.

22. A flame retardant composition as defined in claim 19 or 20 wherein component (c) is a halogen-containing compound, a halogen-containing compound in admixture with antimony oxide;
elemental phosphorus or a phosphorus compound; a halogen-containing compound in admixture with a phosphorus compound; a compound containing phosphorus-nitrogen bonds; or a mixture of the foregoing, and said compound is present in an amount of from 0.1 to 50 parts by weight per hundred parts of said resin.

23. A flame retardant composition as defined in claiml9 or 20 wherein component (c) is an aromatic halogen containing compound selected from the group consisting of chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl, brominated terphenyl, a compound comprising two phenyl radicals separated by a divalent alkylene or oxygen group and having at least two substituents selected from the group consisting of chlorine and bromine per phenyl radical; and a mixture thereof.

24. A flame retardant composition as defined in claiml9 or 20 wherein component (c) is tetrabromobisphenol-A.

25. A flame retardant composition as defined in claim 19 or 20 wherein component (c) is hexabromobenzene.

26. A flame retardant composition as defined in claim 19 or 20 wherein component (c) is a chlorinated biphenyl.

27. A flame retardant composition as defined in claim 19 or 20 wherein component (c) is hexabromobenzene in admixture with antimony oxide.

28. A flame retardant composition as defined in claim 19 or 20 wherein component (c) is selected from the group consisting of elemental phosphorus, organic phosphonic acids, phosphonates, phosphinates, phosphonites, phosphinites, phosphine oxides, phosphines, phosphites, phosphates and mixtures thereof.

29. A flame retardant composition as defined in claim 19 or 20 wherein component (c) is triphenyl phosphate.

30. A flame retardant composition as defined in claim 19 or 20 wherein component (c) is a mixture of tetra-bromobisphenol-A, and triphenyl phosphate.

31. A flame retardant composition as defined in claim 19 or 20 wherein component (a) is poly(2,6-dimethyl-1,4-phenylene) ether.