CA1101579A - Flame-retardant flexibilized polyphenylene ether compositions - Google Patents
Flame-retardant flexibilized polyphenylene ether compositionsInfo
- Publication number
- CA1101579A CA1101579A CA292,795A CA292795A CA1101579A CA 1101579 A CA1101579 A CA 1101579A CA 292795 A CA292795 A CA 292795A CA 1101579 A CA1101579 A CA 1101579A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- flame retardant
- parts
- aromatic phosphate
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
There are provided flame retardant, flexibilized thermoplastic compositions which comprise, in admixture, a normally flammable polyphenylene ether resin, an aromatic phosphate plasticizer in an amount at least sufficient to provide a flame retardant, flexibilized composition after molding, and a thermoplastic elastomer comprising a block copolymer of a vinyl aromatic compound and a diene monomer. Preferred features comprise such com-positions which also include a halogenated hydrocarbon alumina trihydrate and/or elemental red phosphorus.
There are provided flame retardant, flexibilized thermoplastic compositions which comprise, in admixture, a normally flammable polyphenylene ether resin, an aromatic phosphate plasticizer in an amount at least sufficient to provide a flame retardant, flexibilized composition after molding, and a thermoplastic elastomer comprising a block copolymer of a vinyl aromatic compound and a diene monomer. Preferred features comprise such com-positions which also include a halogenated hydrocarbon alumina trihydrate and/or elemental red phosphorus.
Description
8C~-2422 i7~ -The present invention relates to flame retardant, flexibili~ed thermoplastic polyphenylene ether composition.
The compositions of this invention comprise the poly-phenylene ether, an aromatic phosphate and a thermoplastic elastomer such as A-s-A block copolymer, e.g., poly-styrene-polybutadiene-polystyrene, and optionally, a halogenated hydrocarbon resin, alumina trihydrate and/or ;~
elemental red phosphorus.
The polyphenylene ether resins are well known in the art as a class of thermoplastics which possess a number of outstanding physical properties. They can be prepared, in general, by oxidative and non-oxidative -~ ;
methods, such as are disclosed, for example, in Hay, U.S. patent No. 3,306,874 dated February 28, 1967 and U.S.
3,306,875 dated February 28, 1967 and Stamatoff, U.S.
Patent No. 3,257,357 and 3,257,358 both dated June 21, 1966.
It is known that the polyphenylene ether resins alone are somewhat difficult to fabricate because of their high ,.~
~3L~15r4~9 temperature thermoplastic moldiny characteristics and this has limited their use in applications where flexibility, such as the need to calendar into relatively thin sheets, wlthout cracking or crazing, is desirable.
In recent years, there has also been increasing concern about the performance and safety of thermoplastic materials, including the afore~mentioned polyphenylene ether com-positions during real-life fire situation.
Of particular interest would be a polyphenylene ether 10 composition which is both flexibilized and flame retardant ;~ -without loss of desirable properties.
It is known that flexible polyphenylene ether blends have ~-been made with fairly high loadings of plasticizers. It has now been found that the capabilities and alternatives in making such blends can be greatly expanded by incorporating rubber in the form of a block copolymer into such blends, and further that if the flexlbilizer is predominately an aromatic ~ 2 ~
!¦ 8CH-2422 ~ 5 7 ~
l phosphate, good self-extinguishing properties are obtained.
3 ~ased on the foregoing discovery, it has also 4 been found possible to further modifiy the blends to make them somewhat less cos~ly, without loss of other beneficial proper-6 tiPs, by replacing some of the aromatic phosphate with a 7 halogenated hydrocarbon resin, e.g., chlorinated paraffin.
8 Complete replacement of the aromatic phosphate is not possible, 9 however, without loss of flame resistance.
ll Furthermore, based on the foregoing discovery, 12 it has also been found possible to decrease the cost of the 13 formulation, without introducing a halogen source, and at the 14 same time, improve the self-extinguishing properties. This lS discovery comprises including alurnina trihydrate in the composi-16 tion.
17 . .
18 Finally, based on the foregoing discovery, it has 19 also been found possible to use higher levels of thermoplas~ic elastomer without disruptin~ flame retardant properties and still 21 keeping a halogen-free system by the addition to the composition 22 of elemental red phosphorus~
24 In addition to being useful by themselves, the new compositions are useful in blends with other resins and elasto-26 mers to improve 1ame retardancy. Of course, conventional 27 additives such as pi~nents, fillers, stabilizers, and the like, 29 can be used with the new compositions of this invention.
.
3_ ~ ~ , ~
. , .~s ~ ?, ; . - ~ ~
GE-45( 3L~lO~LS~3i ~CH-2422 1 Description of the Invention.- Accordingly, ~he
The compositions of this invention comprise the poly-phenylene ether, an aromatic phosphate and a thermoplastic elastomer such as A-s-A block copolymer, e.g., poly-styrene-polybutadiene-polystyrene, and optionally, a halogenated hydrocarbon resin, alumina trihydrate and/or ;~
elemental red phosphorus.
The polyphenylene ether resins are well known in the art as a class of thermoplastics which possess a number of outstanding physical properties. They can be prepared, in general, by oxidative and non-oxidative -~ ;
methods, such as are disclosed, for example, in Hay, U.S. patent No. 3,306,874 dated February 28, 1967 and U.S.
3,306,875 dated February 28, 1967 and Stamatoff, U.S.
Patent No. 3,257,357 and 3,257,358 both dated June 21, 1966.
It is known that the polyphenylene ether resins alone are somewhat difficult to fabricate because of their high ,.~
~3L~15r4~9 temperature thermoplastic moldiny characteristics and this has limited their use in applications where flexibility, such as the need to calendar into relatively thin sheets, wlthout cracking or crazing, is desirable.
In recent years, there has also been increasing concern about the performance and safety of thermoplastic materials, including the afore~mentioned polyphenylene ether com-positions during real-life fire situation.
Of particular interest would be a polyphenylene ether 10 composition which is both flexibilized and flame retardant ;~ -without loss of desirable properties.
It is known that flexible polyphenylene ether blends have ~-been made with fairly high loadings of plasticizers. It has now been found that the capabilities and alternatives in making such blends can be greatly expanded by incorporating rubber in the form of a block copolymer into such blends, and further that if the flexlbilizer is predominately an aromatic ~ 2 ~
!¦ 8CH-2422 ~ 5 7 ~
l phosphate, good self-extinguishing properties are obtained.
3 ~ased on the foregoing discovery, it has also 4 been found possible to further modifiy the blends to make them somewhat less cos~ly, without loss of other beneficial proper-6 tiPs, by replacing some of the aromatic phosphate with a 7 halogenated hydrocarbon resin, e.g., chlorinated paraffin.
8 Complete replacement of the aromatic phosphate is not possible, 9 however, without loss of flame resistance.
ll Furthermore, based on the foregoing discovery, 12 it has also been found possible to decrease the cost of the 13 formulation, without introducing a halogen source, and at the 14 same time, improve the self-extinguishing properties. This lS discovery comprises including alurnina trihydrate in the composi-16 tion.
17 . .
18 Finally, based on the foregoing discovery, it has 19 also been found possible to use higher levels of thermoplas~ic elastomer without disruptin~ flame retardant properties and still 21 keeping a halogen-free system by the addition to the composition 22 of elemental red phosphorus~
24 In addition to being useful by themselves, the new compositions are useful in blends with other resins and elasto-26 mers to improve 1ame retardancy. Of course, conventional 27 additives such as pi~nents, fillers, stabilizers, and the like, 29 can be used with the new compositions of this invention.
.
3_ ~ ~ , ~
. , .~s ~ ?, ; . - ~ ~
GE-45( 3L~lO~LS~3i ~CH-2422 1 Description of the Invention.- Accordingly, ~he
2 pre~ent ~n~en~ r~1 des Ln ~ts ~ro~de~ a~pe~t~, a flame
3 retardant flexibilized thermoplastic composition which comprises,
4 in admixture:
(a) a normally flammable polyphenylene ether 6 resin;
7 (b) a flame retardant aromatic phosphate plasticizer 8 in an amount at least sufficient to provide a flexibilized composition after molding; and (c) a thermoplastic elastomer comprising an A-B-A ;
11 block copolymer wherein terminal blocks A and Al are polymeric 12 units of a vinyl aromatic compound and center block B is a 13 polymer of a conjugated diene.
As employed herein, the term "flexibilized" is ~ 16 used in its art-recognized sense to clefine compositions which ; 17 are calenderable into relatively thin sheets, e.g., 1/4 inch ;~
18 or less in thickness, which can be bent without causing cracking 19 or crazing. Such thermoplastic compositions are suitable, 2p in appropriately thin forms, for products such as shower curtains 21 wall coverlngs, automotive upholstery, and the like.
23 The term "normally flammable" as used herein, des-24 cribes compositions which do not meet the V-O and V-l require-ments of the Underwriters' Laboratories Bulletin No. 94 tes~.
27 In a preferred feature, the new compositions will 2~ also include: ~ -29 (d) a minor propOrtiOn of flame retardant halogenated plasticizer based on the amount of aromatic phosphate V~ ' ''''~
!¦ 8CH-2422 j~-45~
~ p~ne~t (b). Especially preferred halogenated hydroc~rb~ns 2 are chlorinated paraffins. The amount can vary, but up to 3 equal parts by weight, 50: 50, based on the aromatic phosphate 4 are preferred, and 50:50 is most economical. A useul chlori-nated parafin is available from ICI A~erica, Inc., under the 6 designation Creclor S-45.
8 Another preferred feature is the new composition 9 which also includes:
(ej a minor proportion of alumina trihydrate, 11 sufficient to enhance the flame re~ardant capability of 12 aromatic phospha~e component (b). The amount can vary widely 13 within these limits but preferably, the amount of alumina tri-14 hydrate (which is a standard item of commerce), comprises from about 5 to about 40 parts by weight per 100 parts by weight ; 16 of components (a) and (b) combined.
18 Still another preferred feature is the new composi-l9 tion which also includes:
(f) a minor proportion of elemental red phosphorus, 21 sufficient to enhance the f'ame retardant capability of aromatic 22 phosphate component (b). Elemental red phosphorus can be used 23 in fairly broad ranges in amount but preferably, it will com-24 prise from about 1 to abou~ 10 parts by weight per 100 parts by weight of components (a), (b) and (c) combined.
27 The normally flammable polyphenylene ether resin (a) 28 is preferably of the type having the structural formula:
~ .. _ ._ __ .. _.__ _._.. ,.. ,. .. ~. _ . .. . ___~_ !, . , ~
~,E-45 ~ liO15798CH-:Z422 ~ - r n 6 . Q
' 8 . ~ ~:
9 , :-, wherein the oxygen ether atom of one unit is connected to the 11 benzene nucleus of the next adjoining unit, n is a positive 12 integer and is at least 50, and each ~ is a monovalent sub- ~ :~
13 stituent selected from the group consisting of hydrogen, halogen, : 14 hydrocarbon radicals free of a tertiary alpha-carbon atom, lS halohydrocarbon radicals having at least two carbon atoms be~ween 16 the halogen atom and the phenyl nueleus, hydrocarbonoxy radicals 17 and halohydrocarbonoxy radicals having at least two carbon atoms i8 between the halogen atom and the phenyl nucleus.
19 . ',' A more preferred class of polyphenyLene ether resins : ;
21 for the compositions of this invention includes those o~ the 2~ above formula wherein each Q is alkyl, most preferablyj having 23 irom l to 4 carbon atoms. Illustrati~ely, members of this 24 class include poly(2,6-dimethyl-1,4-phenylene~ether; poly-(2,6-diethyl-1,4-phenylene)ether; poly(2-methyl-6-ethyl-1,4-26 phenylene)ether; poly(2-methyl-6-propyl-1,4-phenylene)ether; . .
27 poly(2,6-dipropyl-1,4-phenylene)ether; poly(2-ethyl-6-propyl-1,4- ~ :
28 phenyLene)ether; and the like.
29 .
.
. . .
GE-459 ~ 8CH-2422 l Especially preferred is poly(2,6-dimethyl-1,4-2 phenylene~ether, preferably, having an intrinsic viscosity 3 o about 0.45 deciliters per gr~m (dl./g.) as measured in 4 chloroform at 30C.
6 The choice of an aromatic phosphate plasticizer can vary broadly.
The phosphate plasticizer is preferably a compound o the formula:
~ 11 .
16 oR2 17 . -wherein Rl, R2 and R3 are the same or different and are aryl, 19 alkyl substituted aryl, or hydroxyalkyl. To keep the amount of halogen low, it is preferred that no halogen be present 21 in component (b).
2~
23 Examples include cresyl diphenyl phosphate, tri-24 cresyl phosphate, triiosopropylphenyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, or mixtures thereof.
26 Especially preferred is triphenyl phosphate.
28 Commercially available aromatic phosphates which 29 have been found to be particularly useful are FMC Corporations's Kronitex 50 and ~ronitex 300, which are isopropylated triphenyl 31 phosphate compounds.
GE-459 ¦¦
~ :, 1 The plasticizer (b) is added in amounts which will 2 be sufficient to provide a flexibilized composition within the ,i 3 meaning of the term described above. In general, the plasticizer 4 i9 present in amounts ran~ing from at least about 10 to 100, pre-S ~erably from about 15 to about 65 parts by weight of plasticizer, 6 per 100 parts of resin component (a).
7 The present compositions also include thermoplastic :~
8 elastomers ~c), which are A-B-Al block copolymers. In general, these resins comprise a polymerized center block B which is derived from a conjugaced diene, e.g., butadiene, isoprene, 11 1,3-pentadiene, and the like, and polymerized terminal blocks 12 A and Al which are derived from vinyl aromatic, e.g., styrene ;
13 compounds, such as styrene, e~~methyl styrene, vinyl toluene, 14 vinyl xylene, vinyl naphthalene, and the like. Preferably, the A-B-Al block copolymer will have terminal blocks A and Al 16 comprised of polystyrene and a center block comprised of poly-17 butadiene.
19 The linear A-B-Al block copolymers are made by an -~
organometallic initiated polymerization process using, for ;~ 21 example, sodium or lithium metal or an organic derivative 22 thereof. The diene menomers can be polymerized with a mono-23 functional or difunctional initiator, as is described in 24 Kennedy et al, Interscience Publishers, Vol. 23, Part II (1969), - .!5~-.~9 .
'~ pages ~ Other methods of preparing these block copolymers 26 are described in Zelinski, U.S. 3,251,905 dated May 17,1966 27 and Holden et al, U.S. patent No. 3,231,635 dated 28 January 25, 1966. ~
~ 2g .
;
,, .. , . ,, ., "~, ", . ....... . .. . .
L57~ :
~E-459 1 1 Commercially available A-B-A block copolymers include 2 Kraton~ 411g, poly(styrene-butadiene-styrene) with 20% mineral oil 3 and the Kratons designated as K-1101 (polystyrene-polybutadiene-1 4 polystyrene), K-1102 (polystyrene-polybutadiene-polystyrene), and K-1107 (polystyrene-polyiso~rene-polystyrene), all from Shell 6 Chemical Company, Polymers Division. .
; 8 Hydrogenated A~B-A block copolymers can also be used as thermoplastic elastomers in the present compositions. These are prepared by techniques which are well known in the art. Seet ;;
11 for instance, the disclosure in Jones, U.S. 3,431,323, dated 12 March 4, 1969. A preferred commercially available copolymer 13 of this type is Shell Chemical's KG-6521 resin.
14 :-I The thermo~lastic elastomer (c) ean vary broadly in 16 amount, but generally is present in amounts from about 10 to about 17 10~, more preferably from about 15 to about 65 parts by weight of 18 thermoplastic elastomer per 100 parts of polyphenylene ether (a).
19 :
Other ingredients, such as fillers, reinforcements, 21 pigments, stabili.zers, lubricants, and the like, m~y be added 22 for their conventional purposes.
24 The manner in which the present compositions are prepared is not critical and conventional methods can be employed.
26 ¦ Preferably, however, each of the ingredients is added as part of 27 ¦ blend premix, and the latter is passed through an extruder, e.g , :
28 a 28 mm WP twin screw extruder, at a~ extrusion temperature of 29 from about 350 to about 550F., dependent on the needs of the particular composition The strands emerging from the extruder . ., ~ ,_ J-459 l 1 ~ may be cooled, chopped into Pellets, and molded or calendered to 2 any deslred shape.
4 Description of the Preferred Embodiments - The _ .
following examples are illustrative of the compositions of this invention. They are not intended to limit the invention in any 8 manner. -9 EXAMPLES 1-10 . : -1~ . ,, ~
11 The ollowing blends were prepared in a 28 mm Werner 12 Pfleiderer twin screw extruder and tested for physical properties 13 and flame retardancy by the Underwriters' Laboratory U.L. 94 test 14 and the GE Oxygen Index Test, with results set forth in Table 1:
7 ~ - ;-~
,~ 19 I . '. ~ :, 20 ~ :~
22 1 ~`~
2g ~ , ' .' '. ''' '_ -10- ::
.,, .~
. _ . - ~
E-459 S 75~ :, . , .~
O u~ 0 r~
~ ~ ~ `I o 1~ ~
~o " ~ , .
J rl u~ O r~
u~ cr I lt- ~J I I I C'`l l O l ~ ~ "l 4 h ~ ~--1 ..
. ~
o u~ o r~ ~ ,~
.,J C~ 00 1 u~ ~ I I ~ I I O u~ ~.
6 u~to ,~ ,1 ~: h .
o a~ ., u~ O u~ ~ ., 7 ~ ~ t~ o~o ~
,~ o ,~
U~ o C~l 8 ~ 0 O O o o ll~ .14 .
-. 9 o ~ ~t I o I ~ o ~) h I "
t~ ,~
~0 , ~ ~ ~q O O O O O~ p~
h ~r)l ~ I ~ O ~ I I O u) rl I
11 J_l ¢~ ,-1 ~ ~ : .
12 a~ u~
., a~ I o o o o ,~ ~1 :
~¢ ~1 ~ o~ u~ I
14 o ~ o o o ~ c~l .c ~ ~: .
,~ ta :
o~ o P~ ~ o o o o r~ r~ ~.
1~ ~a o ~1 ~o I ~ ~ I II ol~ I ' -'~ ' a~ ~ c~ , :
17 N 1:4 .
r~ ~ O O O O O ~
18 ,n ~ ,~ o~o I -rl r~ I~ ,~
X ~ ~ ., 19 ~ o .,1 o o o~ sl :.
¢ ¢ ~ I ~ I I I I O ~D ~ I . .
~ ,~
. Q) I b~
21 ,~ o ~
,~ ~ (U ~ ~ I a) ~1 ~ i ,. . .
22 ~ ,~, ~ 0 ~ ~ ,~ o ~ . ~
~ ~ ~ ~ o ~ ~ U~ ~ :: , .E-1 ~J h-rl ~ u~ O u rl rl 23 ,~:
bC ~ q 0 1 1 O ~
~1 G ~ OC) a) 1: ~. .
~ ~ r' '1 ~
24 3~ 1 a) o u~ D o a~~ ~J u ~ 0 .:
X O ~ :
~ ~ h 0 0 1--I aJ ~ ~ O ~ ]J ~O ~C r .~ ,s:: a) ~ ~ 0 1~ JJJ-) ~1 ~ ,CL, I u~ ,c:~ O O ~I
~ Q p ~ a~ tn O O 1~
0 ~ ~ e~ elJ 51 ~ ~ ~ E~ - r-l r-l ~D
~: u ~ o o ~ a~ u~r~ X X r-l r l r~ C~
v S-I rl ~ ~ U U~:) r-lal~1 al I r~ O X S~ a, al ea e~ ~ aJ ~ U~ ~ 0 .~~. 0 _ U C) U ^ U~ ~ ~ U U U C 1 ~
P I 1 0 ~-- (U Q~ U C)~ 0 0 ~ rl a ~ ~ ~-,1 rl r~ 0 ~ 7 ~_~ ~ o u r~ O 1 0 ~ ~ a) ~ O E3 ^ ~; X ~ C E¦ U U U
t:~r-l rl rl C~l aJ tJ ~ J 0 0 h ~ ~rl e~ tq rl ~1 0 0 aJ e~ e~
OC~J ~,U J~ O O S~ ~ S~ O U ,1, a S~ S~ ,~ S~ SJ
2 8 rl ~ ~ td e~ O U ~ ~ e~ ~
u P 0 Z El s-l 0 U u U u u S-l u~ rl rl W rl ~1 O
aJ rl r~l (~ 0 0 0 U U) 0 la 0 U~ ~ ~ U u~ a u ~1 s~ u, u~ r-l r-l r-l r~
29 ~ cq o c s~ s~ ~ ~ h ~ O ~1 ~ U - - ~ r l r-l r-l P~ O P~ d U D ~ .~: aJ a~ r-l X ~ ) C) al C~ C~
~ ~ ~ E~ O o~::X~
~ O ~ ~ ~ O ~) h 1~
~ r~ ~ 0 D U ~ a~ e~ b4 ~ ' .
.
, ~ v' _ .. ... . , .... ... _ _, _ . . _, . . _ , _ _ _ . ., . , . _ . _ _ . . . . _ ~E-459 li 1 It is o~ particular interest to note that in the 2 above flexible blends which contain an aromatic phosphate as the 3 plas~icizer, good self-extinguishing properties are obtained.
4 Thus, the present compositions, particularly those containing between 20 and 80 parts by weight of A-B-Al block copolymer 6 per 100 parts by weight of polyphenylene ether and aromatic 7 phosphate, are flame retardant without the chance to produce l~
8 toxic and corrosive halogen-derived products on incineration.
EXAMPLES 11 and 12 . ~ .
:
11 Following the procedure of Examples 1-10, the 12 listed compositions are prepared, having the properties set '6 forth i able 2: ;
221 . ' .
22 . . :' .
24 .
~8 ~
29 .
. ~ ' ~ , __. __ ~ _ ..
q~
J~-459 1~
2 ~ c 4 ~ ~ . ~ ~
~ .~ ., 6 c~ ~ ~ ~
8 ~0 ~ `
¢ ~a h O ~ : -~ u a) o~') o oo ~ ~ .1 p, , n u~ Op::l ~ I ~ ~ O ~ ~1 h ,1 .:
7 ~ ~1 0 .~
rC ~ C~ ~ , 11 C) aJ u7 C ~ ,~ h ,. .~ ~ ~
L .~: ~ ~ ~ O .: :
~ b~C`J 00~') O O ~ C~
a~ o ~ ~ I O U~ O
13 ~ ~ c~ ~ co ~ ~ o ~
P~ ~d ~ ~
?~:~ , ~ C
14 'o' ~ ~
~:4 C ~ ~d o C S~ ~ ~
1 6 tn E~ ~d I ~ ~ td : ~ h ,~~1 0 o ~ o o ~ t~ .,~
~'17 ~ ~1 ~ ~ or~ ~t~
O O ,~ 1 td ,~
1~3 ~ ~) ~ o ~,1 .
~n .~: ~d u~ ~
19 ~o o ~ X ~ .
V :q ~
2 0 tn,l , ~n~;
O ¢ ~ a)o ~ ~
21 ~ ,~ t~ ~ tn~ O
O I ~ ~ 1 0 ~ ¢ ~1 ~ n .
q ~ ~ I a) ~ ~1 ~ ~
., . ~ ~ ~ td ~ :~ d O aJ
. ~ O v ~ ~ ~ a) ,s~ v " t~ a) ,~ td J~ ~ V p~ td .) ~ I a) tn ~ 4J'~ td ~n ,~1 O ~ d I 4~~) ~ ,s; o ~4 tn J
~-1 ~ ~ q) td ,~ tU ~ X ~ C ~
24 D r~ S ~: S tD P h tn tD tD tD tn ~ tn tU
cd V U p. t~ cd ~, I tn ~ O - O ~
E~ tn (D tU tn o h C~ 4~ ~~ ~ S~ tU ,~ p ~rl ~ ~ O r~ ~ ^ ~ ~ r~ trJ ~ r~.~
~ ~r~ tU S~ U UL~ ~ ~ ~ tU t~ ~ tD V C) (D
I td ~ C P. tn tn ~ tu ,_1 cn tU X ~ o cd rl ~d P-26 ¦ * ~ o " ,~ td ~ p (U ~ ~ V o tD~ W
I P ~ p~ ti ~ ~ O E3 ^ 'P cd 1~ S~ h O ~ p V o o ,~ tn ,~ 0 tn ~1 ~ ta ~ tU ,~
2 7 ,~ --~ tu td El ~L ~ h tU (D ~ H tU O O E3 O
~ ~,s:: Ei h o IJ o rl ~1 td '~ ~E3 P ~ h tn ,~ ¢ rl ~U ,1 ~J ~ tU ~ tn ._ ~ ." ~ ~rl tu J- td Q ,~tn O ~ S S ~ tn ~, ~ J bO ~ t~ cU H 5 C!~ O ~1, td ~ ~J tU C O ,~ ~ O ~ .C C 7 0 . ~ ~ Q ~ tU ,~ , t~ ~ t~ H ~
'ir~A tdE~ , ~ O E~ ~Ll ~ O
X O td ,L~ o ~ S I
W C) ~ td ,Q t~ ~ tD
.
~ .. .,---- . . ., ... , -- . .---- ~-- .
,E-459 ~ 5~ ~
l I~ is noteworthy that in these compositions, comple~e~
2 replacement of the aromatic phosphate by chlorinated paraffin 3 is catastrophic to the flame resistance, whereas up to 50% ,' replacement is only slightly detrimental.
7 Follo~ing the procedure of Examples 1-10, the ,, listed compositions are prepared, having the properties set . ,' forth in Table 3: ,~
2 , , .''. '~
' 17 . . ' ~' ' .
1~ . ' ~'':' ' . . :'' ' ~24 . ~ :
"
26 ~ :
29 .
~ ~ :
l :
3 .
4 tJ ~, N
S ~ n I o c~ ~7 o o ~ ,,5 ' E~ ~ OLn --~ p, ,. ' ~ ~ 6 3 ~ .~ o 7 ~:
8 ~ ~ oo ~o or- ~o ~ .:
g ~ ~ ~1 ~ ~ ~ c~ o ~n ~ ~ ~ . .
~ ~ ,1 ~ ~ .
1~ ~ ~ rl ~ ,~
:, 12 ~ ~l oo ~o o~ ~ 'd o --1 0 ~ I `D ~ ~ ~ O r l ~
3 h~ C~ o ::
14 ~ h ~ . .
t~ ~ : ', ta 16 u~ ~1 ~ ' o; '~
17 u7 ¢ ~ ~ -18 a) J ~ ~ ;~
'' 19 ~ a) ~ X
" . ~ o ~
t~ P~ ~ ~ .
td bO a~ o~
2 2 ~ ~ ,h ~ ~ . .
~ ~ ~ t~ o ~ O a ~d a~ ~1 ~ V ~ ~ r~
~ E-~ ~ I O U) ~ al ~rl 07 1 ,~ ~1 ~ V ~ V V V Jl 0 ;; . ~ p~ X ~ ~ ~
24 ~ ~ 5 ~ a) '~ o ~
.~ 0 JJ ~ .~ :~
v e _~ O rl o ,_ ,~ ~
~ ~ ~ v o~ - ~ v c) ,-., ~ ~ ~ n O ~ 0 ~) X ~ ~d ~rl P- ~ v ~ ~ ~ a) ~ e ~
~, ~D ~,.,, p,,~ ~, ~ ?~ o e ~ h .C ; : :
O c~ u o t) ~ ~ ~n ~ rl ~
27 . rl ~ O ?~ ~ v ,1 ~n O
v ~ e s~ ~ ~ e ~rl ,J ~ 5 h u~ r~
~ rl ~ O aJ,~ U~ U ~ v- ~1 28 ~ u~ o s~ u~ c . ,, v ~ ~ ~ ~ ~ x~ c~
~ ~ ~i ~ ~ f~ O E~ ~3 3 0 ~ ~ X o n~
~1 c~ ~ . rd~ U
- ... ,. - , . . ~ - .
G~--459 llV1579 ,~
1 It is seen that the properties can be retained m 2 with significant cost advantages by addition of alumina 3 trihydrate. .:
4 EXAMPLES 16 - 17 ~ ;, 6 Following the procedure of Examples 1-10, the 7 listed compositions are prepared, having the properties set 8 forth in Table 4:
: 11 . ., 3 , :~
~, 16 8 .
. .
29 .
,E - 4 5 9 ~ S~3 ~:"
2 I ~ .
3 ~ .
tl .
4 r~ Q~
c)Pl r~ .
~ r~) tn 7 ~ ~d ~ ¦
8 ~ ~ ~ trl ~t t~
9 ":Q' ~rl ~1 ~ . ~ . ~4 ' ~ ~ ~a " .
~I h ~1 o o o ~ o ~ ~ ~,~
~3 ~1 '~ '~ ~ o c~ tn ~, 12 ~ o ~
13 o c~ ~u tn .: :4 ~ .,1 ~ o a ~
:-~ 15 ~ ta I oo o 0 ~ u~ u, ~IJ, ~ J I O O
.; ~ r~
~ ¢ '~
17 ~ , a)~ ~ ~
a~ ~ . -18 o tn td u~
19 ,1 td ~ 4 X
o ~ a ,~ o ~ ~n ~ tn o ,r~ ~d ~0 tl~ o o 21 c~ P~ u ~ tn ~ ~ .
~ .Q 0 ,a ~
2~ ~ ,c ~ ' ~ ~d u ~ ~,~ ^ o ~ ~ ~ d ..
"" ~1 ~ ~ U ~ ~,1 P~
, ~ ~ ~ I tU ~n h tn tn ,,1 ~n~
~a ~ ~ut~ u O ~ ~ ~ o .
. ~ ~ h tU td ~ tn .C X a ~
2l~ ~ ,~ ~ "~ tu tu p~ tn tn ~ ,~ ~ u ~ tu .~ t~ ~
~ ~i ~ O ~rJ O rJ oo ,~ tn ~ d h ~ p,tj h a~ ~u~ "~1 tJ
26 td I tu ~d ~ ~ tn ~C e ~_ ~ ,~ t~r~ ~ ta u a tu r,l ~ o ,u : ~ t ru ~ tn O e O r,~J ~ u O o ~tn ~,1 ta ,~ td 27 . .,~ ~~ tU ~ E O ~ a) ru r~ u ~ ,. O
~1 ~ E3 ~ 4 Ei~r~~ rd\~l ~U h tn ru rJ r~ ~:L O ~U ,~ ~ r~ U r~ W E3 u-28 ,~ o p~ ~a ~u '~ ~ ~ o ,~ u o ~:
n ~tu,~ .
,. ,. ta F: ~ ,~ o E~
7 X O td .J~
~ ~ ~ . td ,~
_ _.,. ... ~ . _ ~ S ~ 8CH-242~
It is seen that red phosphorus permits the incorporation of high amounts of rubber, while maintaining good flame retardant characteristics. These compositions also have the desirable feature of being free of halogen.
Obviously, other modifications and variations of the present invention are possible in the light of the above description. It is, therefore, to be understood that changes may be made in the particular embodiments disclosed herein which are within the full intended scope of the invention as defined in the appended claims.
The instant application discloses, but does not claim, subject matter disclosed and claimed in the related, commonly assigned Canadian Application Serial No. 291,790, filed November 25, 19770 ~-.
(a) a normally flammable polyphenylene ether 6 resin;
7 (b) a flame retardant aromatic phosphate plasticizer 8 in an amount at least sufficient to provide a flexibilized composition after molding; and (c) a thermoplastic elastomer comprising an A-B-A ;
11 block copolymer wherein terminal blocks A and Al are polymeric 12 units of a vinyl aromatic compound and center block B is a 13 polymer of a conjugated diene.
As employed herein, the term "flexibilized" is ~ 16 used in its art-recognized sense to clefine compositions which ; 17 are calenderable into relatively thin sheets, e.g., 1/4 inch ;~
18 or less in thickness, which can be bent without causing cracking 19 or crazing. Such thermoplastic compositions are suitable, 2p in appropriately thin forms, for products such as shower curtains 21 wall coverlngs, automotive upholstery, and the like.
23 The term "normally flammable" as used herein, des-24 cribes compositions which do not meet the V-O and V-l require-ments of the Underwriters' Laboratories Bulletin No. 94 tes~.
27 In a preferred feature, the new compositions will 2~ also include: ~ -29 (d) a minor propOrtiOn of flame retardant halogenated plasticizer based on the amount of aromatic phosphate V~ ' ''''~
!¦ 8CH-2422 j~-45~
~ p~ne~t (b). Especially preferred halogenated hydroc~rb~ns 2 are chlorinated paraffins. The amount can vary, but up to 3 equal parts by weight, 50: 50, based on the aromatic phosphate 4 are preferred, and 50:50 is most economical. A useul chlori-nated parafin is available from ICI A~erica, Inc., under the 6 designation Creclor S-45.
8 Another preferred feature is the new composition 9 which also includes:
(ej a minor proportion of alumina trihydrate, 11 sufficient to enhance the flame re~ardant capability of 12 aromatic phospha~e component (b). The amount can vary widely 13 within these limits but preferably, the amount of alumina tri-14 hydrate (which is a standard item of commerce), comprises from about 5 to about 40 parts by weight per 100 parts by weight ; 16 of components (a) and (b) combined.
18 Still another preferred feature is the new composi-l9 tion which also includes:
(f) a minor proportion of elemental red phosphorus, 21 sufficient to enhance the f'ame retardant capability of aromatic 22 phosphate component (b). Elemental red phosphorus can be used 23 in fairly broad ranges in amount but preferably, it will com-24 prise from about 1 to abou~ 10 parts by weight per 100 parts by weight of components (a), (b) and (c) combined.
27 The normally flammable polyphenylene ether resin (a) 28 is preferably of the type having the structural formula:
~ .. _ ._ __ .. _.__ _._.. ,.. ,. .. ~. _ . .. . ___~_ !, . , ~
~,E-45 ~ liO15798CH-:Z422 ~ - r n 6 . Q
' 8 . ~ ~:
9 , :-, wherein the oxygen ether atom of one unit is connected to the 11 benzene nucleus of the next adjoining unit, n is a positive 12 integer and is at least 50, and each ~ is a monovalent sub- ~ :~
13 stituent selected from the group consisting of hydrogen, halogen, : 14 hydrocarbon radicals free of a tertiary alpha-carbon atom, lS halohydrocarbon radicals having at least two carbon atoms be~ween 16 the halogen atom and the phenyl nueleus, hydrocarbonoxy radicals 17 and halohydrocarbonoxy radicals having at least two carbon atoms i8 between the halogen atom and the phenyl nucleus.
19 . ',' A more preferred class of polyphenyLene ether resins : ;
21 for the compositions of this invention includes those o~ the 2~ above formula wherein each Q is alkyl, most preferablyj having 23 irom l to 4 carbon atoms. Illustrati~ely, members of this 24 class include poly(2,6-dimethyl-1,4-phenylene~ether; poly-(2,6-diethyl-1,4-phenylene)ether; poly(2-methyl-6-ethyl-1,4-26 phenylene)ether; poly(2-methyl-6-propyl-1,4-phenylene)ether; . .
27 poly(2,6-dipropyl-1,4-phenylene)ether; poly(2-ethyl-6-propyl-1,4- ~ :
28 phenyLene)ether; and the like.
29 .
.
. . .
GE-459 ~ 8CH-2422 l Especially preferred is poly(2,6-dimethyl-1,4-2 phenylene~ether, preferably, having an intrinsic viscosity 3 o about 0.45 deciliters per gr~m (dl./g.) as measured in 4 chloroform at 30C.
6 The choice of an aromatic phosphate plasticizer can vary broadly.
The phosphate plasticizer is preferably a compound o the formula:
~ 11 .
16 oR2 17 . -wherein Rl, R2 and R3 are the same or different and are aryl, 19 alkyl substituted aryl, or hydroxyalkyl. To keep the amount of halogen low, it is preferred that no halogen be present 21 in component (b).
2~
23 Examples include cresyl diphenyl phosphate, tri-24 cresyl phosphate, triiosopropylphenyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, or mixtures thereof.
26 Especially preferred is triphenyl phosphate.
28 Commercially available aromatic phosphates which 29 have been found to be particularly useful are FMC Corporations's Kronitex 50 and ~ronitex 300, which are isopropylated triphenyl 31 phosphate compounds.
GE-459 ¦¦
~ :, 1 The plasticizer (b) is added in amounts which will 2 be sufficient to provide a flexibilized composition within the ,i 3 meaning of the term described above. In general, the plasticizer 4 i9 present in amounts ran~ing from at least about 10 to 100, pre-S ~erably from about 15 to about 65 parts by weight of plasticizer, 6 per 100 parts of resin component (a).
7 The present compositions also include thermoplastic :~
8 elastomers ~c), which are A-B-Al block copolymers. In general, these resins comprise a polymerized center block B which is derived from a conjugaced diene, e.g., butadiene, isoprene, 11 1,3-pentadiene, and the like, and polymerized terminal blocks 12 A and Al which are derived from vinyl aromatic, e.g., styrene ;
13 compounds, such as styrene, e~~methyl styrene, vinyl toluene, 14 vinyl xylene, vinyl naphthalene, and the like. Preferably, the A-B-Al block copolymer will have terminal blocks A and Al 16 comprised of polystyrene and a center block comprised of poly-17 butadiene.
19 The linear A-B-Al block copolymers are made by an -~
organometallic initiated polymerization process using, for ;~ 21 example, sodium or lithium metal or an organic derivative 22 thereof. The diene menomers can be polymerized with a mono-23 functional or difunctional initiator, as is described in 24 Kennedy et al, Interscience Publishers, Vol. 23, Part II (1969), - .!5~-.~9 .
'~ pages ~ Other methods of preparing these block copolymers 26 are described in Zelinski, U.S. 3,251,905 dated May 17,1966 27 and Holden et al, U.S. patent No. 3,231,635 dated 28 January 25, 1966. ~
~ 2g .
;
,, .. , . ,, ., "~, ", . ....... . .. . .
L57~ :
~E-459 1 1 Commercially available A-B-A block copolymers include 2 Kraton~ 411g, poly(styrene-butadiene-styrene) with 20% mineral oil 3 and the Kratons designated as K-1101 (polystyrene-polybutadiene-1 4 polystyrene), K-1102 (polystyrene-polybutadiene-polystyrene), and K-1107 (polystyrene-polyiso~rene-polystyrene), all from Shell 6 Chemical Company, Polymers Division. .
; 8 Hydrogenated A~B-A block copolymers can also be used as thermoplastic elastomers in the present compositions. These are prepared by techniques which are well known in the art. Seet ;;
11 for instance, the disclosure in Jones, U.S. 3,431,323, dated 12 March 4, 1969. A preferred commercially available copolymer 13 of this type is Shell Chemical's KG-6521 resin.
14 :-I The thermo~lastic elastomer (c) ean vary broadly in 16 amount, but generally is present in amounts from about 10 to about 17 10~, more preferably from about 15 to about 65 parts by weight of 18 thermoplastic elastomer per 100 parts of polyphenylene ether (a).
19 :
Other ingredients, such as fillers, reinforcements, 21 pigments, stabili.zers, lubricants, and the like, m~y be added 22 for their conventional purposes.
24 The manner in which the present compositions are prepared is not critical and conventional methods can be employed.
26 ¦ Preferably, however, each of the ingredients is added as part of 27 ¦ blend premix, and the latter is passed through an extruder, e.g , :
28 a 28 mm WP twin screw extruder, at a~ extrusion temperature of 29 from about 350 to about 550F., dependent on the needs of the particular composition The strands emerging from the extruder . ., ~ ,_ J-459 l 1 ~ may be cooled, chopped into Pellets, and molded or calendered to 2 any deslred shape.
4 Description of the Preferred Embodiments - The _ .
following examples are illustrative of the compositions of this invention. They are not intended to limit the invention in any 8 manner. -9 EXAMPLES 1-10 . : -1~ . ,, ~
11 The ollowing blends were prepared in a 28 mm Werner 12 Pfleiderer twin screw extruder and tested for physical properties 13 and flame retardancy by the Underwriters' Laboratory U.L. 94 test 14 and the GE Oxygen Index Test, with results set forth in Table 1:
7 ~ - ;-~
,~ 19 I . '. ~ :, 20 ~ :~
22 1 ~`~
2g ~ , ' .' '. ''' '_ -10- ::
.,, .~
. _ . - ~
E-459 S 75~ :, . , .~
O u~ 0 r~
~ ~ ~ `I o 1~ ~
~o " ~ , .
J rl u~ O r~
u~ cr I lt- ~J I I I C'`l l O l ~ ~ "l 4 h ~ ~--1 ..
. ~
o u~ o r~ ~ ,~
.,J C~ 00 1 u~ ~ I I ~ I I O u~ ~.
6 u~to ,~ ,1 ~: h .
o a~ ., u~ O u~ ~ ., 7 ~ ~ t~ o~o ~
,~ o ,~
U~ o C~l 8 ~ 0 O O o o ll~ .14 .
-. 9 o ~ ~t I o I ~ o ~) h I "
t~ ,~
~0 , ~ ~ ~q O O O O O~ p~
h ~r)l ~ I ~ O ~ I I O u) rl I
11 J_l ¢~ ,-1 ~ ~ : .
12 a~ u~
., a~ I o o o o ,~ ~1 :
~¢ ~1 ~ o~ u~ I
14 o ~ o o o ~ c~l .c ~ ~: .
,~ ta :
o~ o P~ ~ o o o o r~ r~ ~.
1~ ~a o ~1 ~o I ~ ~ I II ol~ I ' -'~ ' a~ ~ c~ , :
17 N 1:4 .
r~ ~ O O O O O ~
18 ,n ~ ,~ o~o I -rl r~ I~ ,~
X ~ ~ ., 19 ~ o .,1 o o o~ sl :.
¢ ¢ ~ I ~ I I I I O ~D ~ I . .
~ ,~
. Q) I b~
21 ,~ o ~
,~ ~ (U ~ ~ I a) ~1 ~ i ,. . .
22 ~ ,~, ~ 0 ~ ~ ,~ o ~ . ~
~ ~ ~ ~ o ~ ~ U~ ~ :: , .E-1 ~J h-rl ~ u~ O u rl rl 23 ,~:
bC ~ q 0 1 1 O ~
~1 G ~ OC) a) 1: ~. .
~ ~ r' '1 ~
24 3~ 1 a) o u~ D o a~~ ~J u ~ 0 .:
X O ~ :
~ ~ h 0 0 1--I aJ ~ ~ O ~ ]J ~O ~C r .~ ,s:: a) ~ ~ 0 1~ JJJ-) ~1 ~ ,CL, I u~ ,c:~ O O ~I
~ Q p ~ a~ tn O O 1~
0 ~ ~ e~ elJ 51 ~ ~ ~ E~ - r-l r-l ~D
~: u ~ o o ~ a~ u~r~ X X r-l r l r~ C~
v S-I rl ~ ~ U U~:) r-lal~1 al I r~ O X S~ a, al ea e~ ~ aJ ~ U~ ~ 0 .~~. 0 _ U C) U ^ U~ ~ ~ U U U C 1 ~
P I 1 0 ~-- (U Q~ U C)~ 0 0 ~ rl a ~ ~ ~-,1 rl r~ 0 ~ 7 ~_~ ~ o u r~ O 1 0 ~ ~ a) ~ O E3 ^ ~; X ~ C E¦ U U U
t:~r-l rl rl C~l aJ tJ ~ J 0 0 h ~ ~rl e~ tq rl ~1 0 0 aJ e~ e~
OC~J ~,U J~ O O S~ ~ S~ O U ,1, a S~ S~ ,~ S~ SJ
2 8 rl ~ ~ td e~ O U ~ ~ e~ ~
u P 0 Z El s-l 0 U u U u u S-l u~ rl rl W rl ~1 O
aJ rl r~l (~ 0 0 0 U U) 0 la 0 U~ ~ ~ U u~ a u ~1 s~ u, u~ r-l r-l r-l r~
29 ~ cq o c s~ s~ ~ ~ h ~ O ~1 ~ U - - ~ r l r-l r-l P~ O P~ d U D ~ .~: aJ a~ r-l X ~ ) C) al C~ C~
~ ~ ~ E~ O o~::X~
~ O ~ ~ ~ O ~) h 1~
~ r~ ~ 0 D U ~ a~ e~ b4 ~ ' .
.
, ~ v' _ .. ... . , .... ... _ _, _ . . _, . . _ , _ _ _ . ., . , . _ . _ _ . . . . _ ~E-459 li 1 It is o~ particular interest to note that in the 2 above flexible blends which contain an aromatic phosphate as the 3 plas~icizer, good self-extinguishing properties are obtained.
4 Thus, the present compositions, particularly those containing between 20 and 80 parts by weight of A-B-Al block copolymer 6 per 100 parts by weight of polyphenylene ether and aromatic 7 phosphate, are flame retardant without the chance to produce l~
8 toxic and corrosive halogen-derived products on incineration.
EXAMPLES 11 and 12 . ~ .
:
11 Following the procedure of Examples 1-10, the 12 listed compositions are prepared, having the properties set '6 forth i able 2: ;
221 . ' .
22 . . :' .
24 .
~8 ~
29 .
. ~ ' ~ , __. __ ~ _ ..
q~
J~-459 1~
2 ~ c 4 ~ ~ . ~ ~
~ .~ ., 6 c~ ~ ~ ~
8 ~0 ~ `
¢ ~a h O ~ : -~ u a) o~') o oo ~ ~ .1 p, , n u~ Op::l ~ I ~ ~ O ~ ~1 h ,1 .:
7 ~ ~1 0 .~
rC ~ C~ ~ , 11 C) aJ u7 C ~ ,~ h ,. .~ ~ ~
L .~: ~ ~ ~ O .: :
~ b~C`J 00~') O O ~ C~
a~ o ~ ~ I O U~ O
13 ~ ~ c~ ~ co ~ ~ o ~
P~ ~d ~ ~
?~:~ , ~ C
14 'o' ~ ~
~:4 C ~ ~d o C S~ ~ ~
1 6 tn E~ ~d I ~ ~ td : ~ h ,~~1 0 o ~ o o ~ t~ .,~
~'17 ~ ~1 ~ ~ or~ ~t~
O O ,~ 1 td ,~
1~3 ~ ~) ~ o ~,1 .
~n .~: ~d u~ ~
19 ~o o ~ X ~ .
V :q ~
2 0 tn,l , ~n~;
O ¢ ~ a)o ~ ~
21 ~ ,~ t~ ~ tn~ O
O I ~ ~ 1 0 ~ ¢ ~1 ~ n .
q ~ ~ I a) ~ ~1 ~ ~
., . ~ ~ ~ td ~ :~ d O aJ
. ~ O v ~ ~ ~ a) ,s~ v " t~ a) ,~ td J~ ~ V p~ td .) ~ I a) tn ~ 4J'~ td ~n ,~1 O ~ d I 4~~) ~ ,s; o ~4 tn J
~-1 ~ ~ q) td ,~ tU ~ X ~ C ~
24 D r~ S ~: S tD P h tn tD tD tD tn ~ tn tU
cd V U p. t~ cd ~, I tn ~ O - O ~
E~ tn (D tU tn o h C~ 4~ ~~ ~ S~ tU ,~ p ~rl ~ ~ O r~ ~ ^ ~ ~ r~ trJ ~ r~.~
~ ~r~ tU S~ U UL~ ~ ~ ~ tU t~ ~ tD V C) (D
I td ~ C P. tn tn ~ tu ,_1 cn tU X ~ o cd rl ~d P-26 ¦ * ~ o " ,~ td ~ p (U ~ ~ V o tD~ W
I P ~ p~ ti ~ ~ O E3 ^ 'P cd 1~ S~ h O ~ p V o o ,~ tn ,~ 0 tn ~1 ~ ta ~ tU ,~
2 7 ,~ --~ tu td El ~L ~ h tU (D ~ H tU O O E3 O
~ ~,s:: Ei h o IJ o rl ~1 td '~ ~E3 P ~ h tn ,~ ¢ rl ~U ,1 ~J ~ tU ~ tn ._ ~ ." ~ ~rl tu J- td Q ,~tn O ~ S S ~ tn ~, ~ J bO ~ t~ cU H 5 C!~ O ~1, td ~ ~J tU C O ,~ ~ O ~ .C C 7 0 . ~ ~ Q ~ tU ,~ , t~ ~ t~ H ~
'ir~A tdE~ , ~ O E~ ~Ll ~ O
X O td ,L~ o ~ S I
W C) ~ td ,Q t~ ~ tD
.
~ .. .,---- . . ., ... , -- . .---- ~-- .
,E-459 ~ 5~ ~
l I~ is noteworthy that in these compositions, comple~e~
2 replacement of the aromatic phosphate by chlorinated paraffin 3 is catastrophic to the flame resistance, whereas up to 50% ,' replacement is only slightly detrimental.
7 Follo~ing the procedure of Examples 1-10, the ,, listed compositions are prepared, having the properties set . ,' forth in Table 3: ,~
2 , , .''. '~
' 17 . . ' ~' ' .
1~ . ' ~'':' ' . . :'' ' ~24 . ~ :
"
26 ~ :
29 .
~ ~ :
l :
3 .
4 tJ ~, N
S ~ n I o c~ ~7 o o ~ ,,5 ' E~ ~ OLn --~ p, ,. ' ~ ~ 6 3 ~ .~ o 7 ~:
8 ~ ~ oo ~o or- ~o ~ .:
g ~ ~ ~1 ~ ~ ~ c~ o ~n ~ ~ ~ . .
~ ~ ,1 ~ ~ .
1~ ~ ~ rl ~ ,~
:, 12 ~ ~l oo ~o o~ ~ 'd o --1 0 ~ I `D ~ ~ ~ O r l ~
3 h~ C~ o ::
14 ~ h ~ . .
t~ ~ : ', ta 16 u~ ~1 ~ ' o; '~
17 u7 ¢ ~ ~ -18 a) J ~ ~ ;~
'' 19 ~ a) ~ X
" . ~ o ~
t~ P~ ~ ~ .
td bO a~ o~
2 2 ~ ~ ,h ~ ~ . .
~ ~ ~ t~ o ~ O a ~d a~ ~1 ~ V ~ ~ r~
~ E-~ ~ I O U) ~ al ~rl 07 1 ,~ ~1 ~ V ~ V V V Jl 0 ;; . ~ p~ X ~ ~ ~
24 ~ ~ 5 ~ a) '~ o ~
.~ 0 JJ ~ .~ :~
v e _~ O rl o ,_ ,~ ~
~ ~ ~ v o~ - ~ v c) ,-., ~ ~ ~ n O ~ 0 ~) X ~ ~d ~rl P- ~ v ~ ~ ~ a) ~ e ~
~, ~D ~,.,, p,,~ ~, ~ ?~ o e ~ h .C ; : :
O c~ u o t) ~ ~ ~n ~ rl ~
27 . rl ~ O ?~ ~ v ,1 ~n O
v ~ e s~ ~ ~ e ~rl ,J ~ 5 h u~ r~
~ rl ~ O aJ,~ U~ U ~ v- ~1 28 ~ u~ o s~ u~ c . ,, v ~ ~ ~ ~ ~ x~ c~
~ ~ ~i ~ ~ f~ O E~ ~3 3 0 ~ ~ X o n~
~1 c~ ~ . rd~ U
- ... ,. - , . . ~ - .
G~--459 llV1579 ,~
1 It is seen that the properties can be retained m 2 with significant cost advantages by addition of alumina 3 trihydrate. .:
4 EXAMPLES 16 - 17 ~ ;, 6 Following the procedure of Examples 1-10, the 7 listed compositions are prepared, having the properties set 8 forth in Table 4:
: 11 . ., 3 , :~
~, 16 8 .
. .
29 .
,E - 4 5 9 ~ S~3 ~:"
2 I ~ .
3 ~ .
tl .
4 r~ Q~
c)Pl r~ .
~ r~) tn 7 ~ ~d ~ ¦
8 ~ ~ ~ trl ~t t~
9 ":Q' ~rl ~1 ~ . ~ . ~4 ' ~ ~ ~a " .
~I h ~1 o o o ~ o ~ ~ ~,~
~3 ~1 '~ '~ ~ o c~ tn ~, 12 ~ o ~
13 o c~ ~u tn .: :4 ~ .,1 ~ o a ~
:-~ 15 ~ ta I oo o 0 ~ u~ u, ~IJ, ~ J I O O
.; ~ r~
~ ¢ '~
17 ~ , a)~ ~ ~
a~ ~ . -18 o tn td u~
19 ,1 td ~ 4 X
o ~ a ,~ o ~ ~n ~ tn o ,r~ ~d ~0 tl~ o o 21 c~ P~ u ~ tn ~ ~ .
~ .Q 0 ,a ~
2~ ~ ,c ~ ' ~ ~d u ~ ~,~ ^ o ~ ~ ~ d ..
"" ~1 ~ ~ U ~ ~,1 P~
, ~ ~ ~ I tU ~n h tn tn ,,1 ~n~
~a ~ ~ut~ u O ~ ~ ~ o .
. ~ ~ h tU td ~ tn .C X a ~
2l~ ~ ,~ ~ "~ tu tu p~ tn tn ~ ,~ ~ u ~ tu .~ t~ ~
~ ~i ~ O ~rJ O rJ oo ,~ tn ~ d h ~ p,tj h a~ ~u~ "~1 tJ
26 td I tu ~d ~ ~ tn ~C e ~_ ~ ,~ t~r~ ~ ta u a tu r,l ~ o ,u : ~ t ru ~ tn O e O r,~J ~ u O o ~tn ~,1 ta ,~ td 27 . .,~ ~~ tU ~ E O ~ a) ru r~ u ~ ,. O
~1 ~ E3 ~ 4 Ei~r~~ rd\~l ~U h tn ru rJ r~ ~:L O ~U ,~ ~ r~ U r~ W E3 u-28 ,~ o p~ ~a ~u '~ ~ ~ o ,~ u o ~:
n ~tu,~ .
,. ,. ta F: ~ ,~ o E~
7 X O td .J~
~ ~ ~ . td ,~
_ _.,. ... ~ . _ ~ S ~ 8CH-242~
It is seen that red phosphorus permits the incorporation of high amounts of rubber, while maintaining good flame retardant characteristics. These compositions also have the desirable feature of being free of halogen.
Obviously, other modifications and variations of the present invention are possible in the light of the above description. It is, therefore, to be understood that changes may be made in the particular embodiments disclosed herein which are within the full intended scope of the invention as defined in the appended claims.
The instant application discloses, but does not claim, subject matter disclosed and claimed in the related, commonly assigned Canadian Application Serial No. 291,790, filed November 25, 19770 ~-.
Claims (17)
1. A flame retardant, flexibilized thermoplastic composition which comprises, in admixture:
(a) a normally flammable polyphenylene ether resin;
(b) a flame retardant aromatic phosphate plasticizer in an amount at least sufficient to provide a flexibilized composition after molding; and (c) a thermoplastic elastomer comprising an A-B-A
block copolymer wherein terminal blocks A and A1 are polymeric units of a vinyl aromatic compound and center block B is a polymer of a conjugated diene.
(a) a normally flammable polyphenylene ether resin;
(b) a flame retardant aromatic phosphate plasticizer in an amount at least sufficient to provide a flexibilized composition after molding; and (c) a thermoplastic elastomer comprising an A-B-A
block copolymer wherein terminal blocks A and A1 are polymeric units of a vinyl aromatic compound and center block B is a polymer of a conjugated diene.
2. A composition as defined in Claim 1 which also includes:
(d) a minor proportion of a flame retardant halogenated hydrocarbon plasticizer based on the amount of aromatic phosphate component (b).
(d) a minor proportion of a flame retardant halogenated hydrocarbon plasticizer based on the amount of aromatic phosphate component (b).
3. A composition as defined in Claim 1 wherein said halogenated hydrocarbon is a chlorinated paraffin and comprises a 50:50 admixture by weight with said aromatic phosphate.
4. A composition as defined in Claim 1 which also includes:
(e) a minor proportion of alumina trihydrate, sufficient to enhance the flame retardant capability of aromatic phosphate component (b).
(e) a minor proportion of alumina trihydrate, sufficient to enhance the flame retardant capability of aromatic phosphate component (b).
5. A composition as defined in Claim 4 wherein the amount of alumina trihydrate comprises from about 5 to about 40 parts by weight per 100 parts by weight of components a) and (b) combined.
6. A composition as defined in Claim 1 which also includes:
(f) a minor proportion of elemental red phosphorus, sufficient to enhance the flame retardant capa-bility of aromatic phosphate component (b).
(f) a minor proportion of elemental red phosphorus, sufficient to enhance the flame retardant capa-bility of aromatic phosphate component (b).
7. A composition as defined in Claim 6 wherein the amount of elemental red phosphorus comprises from about 1 to about 10 parts by weight per 100 parts by weight of compo-nents (a), (b) and (c) combined.
8. A composition as defined in Claim 1 wherein the polyphenylene ether resin (a) has 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 sub-stituent 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.
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 sub-stituent 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.
9. A composition as defined in Claim 8 wherein the polyphenylene ether resin (a) is poly(2,6-dimethyl-1,4-phenylene ether.
10. A composition as defined in Claim 1 wherein the flame retardant aromatic phosphate plasticizer (b) is a compound of the formula:
wherein R1, R2 and R3 are the same or different and are aryl, alkyl substituted aryl, or hydroxyaryl.
wherein R1, R2 and R3 are the same or different and are aryl, alkyl substituted aryl, or hydroxyaryl.
11. A composition as defined in claim 5 wherein said aromatic phosphate is triphenylphosphate.
12. A composition as defined in claim 1 wherein aromatic phosphate component (b) is present in an amount of from about 10 to about 100 parts by weight per 100 parts by weight of component (a).
13. A composition as defined in claim 12 wherein aromatic phosphate component (b) is present in an amount of from about 15 to about 65 parts by weight per 100 parts of (a).
14. A composition as defined in claim 1 wherein said A-B-A1 block copolymer is a styrene-butadiene-styrene block copolymer.
15. A composition as defined in claim 1 wherein thermoplastic elastomer component (c) comprises from about 5 to about 100 parts by weight per 100 parts by weight of components (a) and (b) combined.
16. A composition as defined in claim 15 wherein thermoplastic elastomer component (c) comprises from about 15 to about 50 parts by weight of (a) and (b).
17. A flame retardant, flexibilized thermoplastic composition which comprises, in admixture:
(a) a normally flammable polyphenylene ether resin;
(b) from about 10 to about 100 parts by weight per 100 parts of (a) of a flame retardant aromatic phosphate plasticizer which provides a flexibilized composition after molding;
(c) a thermoplastic elastomer comprising an A-B-A1 block copolymer wherein terminal blocks A and A1 are polymeric units of a vinyl aromatic compound and center block B is a polymer of a conjugated diene; and
17. A flame retardant, flexibilized thermoplastic composition which comprises, in admixture:
(a) a normally flammable polyphenylene ether resin;
(b) from about 10 to about 100 parts by weight per 100 parts of (a) of a flame retardant aromatic phosphate plasticizer which provides a flexibilized composition after molding;
(c) a thermoplastic elastomer comprising an A-B-A1 block copolymer wherein terminal blocks A and A1 are polymeric units of a vinyl aromatic compound and center block B is a polymer of a conjugated diene; and
Claim 17 continued:
(d) a minor proportion of a second flame retardant agent, sufficient to enhance the flame retardant capability of aromatic phosphate component (b), said second flame retardant agent being selected from among (i) a flame retardant halogenated hydrocarbon plasticizer, (ii) aluminum trihydrate and (iii) elemental red phosphorus.
(d) a minor proportion of a second flame retardant agent, sufficient to enhance the flame retardant capability of aromatic phosphate component (b), said second flame retardant agent being selected from among (i) a flame retardant halogenated hydrocarbon plasticizer, (ii) aluminum trihydrate and (iii) elemental red phosphorus.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75273176A | 1976-12-21 | 1976-12-21 | |
| US752,731 | 1976-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1101579A true CA1101579A (en) | 1981-05-19 |
Family
ID=25027573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,795A Expired CA1101579A (en) | 1976-12-21 | 1977-12-09 | Flame-retardant flexibilized polyphenylene ether compositions |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5379945A (en) |
| AU (1) | AU517478B2 (en) |
| BR (1) | BR7708512A (en) |
| CA (1) | CA1101579A (en) |
| DD (1) | DD134538A5 (en) |
| DE (1) | DE2751496C2 (en) |
| FR (1) | FR2375293A1 (en) |
| GB (1) | GB1575457A (en) |
| IT (1) | IT1088919B (en) |
| MX (1) | MX146037A (en) |
| NL (1) | NL7713133A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2752383A1 (en) * | 1976-12-28 | 1978-06-29 | Gen Electric | PLASTIC REINFORCED COMPOSITIONS OF A POLYPHENYLENE ETHER RESIN |
| JPS55500472A (en) * | 1978-06-02 | 1980-07-31 | ||
| EP0043836A4 (en) * | 1980-01-14 | 1982-04-29 | Gen Electric | Improve polyphenylene plasticizer blends. |
| NL8301569A (en) * | 1983-05-04 | 1984-12-03 | Gen Electric | POLYMER MIXTURE WITH FLAME-RESISTANT PROPERTIES, SUITABLE FOR WIRE COAT EXTRUSION, BASED ON POLYPHENYLENE OXIDE AND ELECTRICALLY CONDUCTIVE WIRE. |
| DE3628577A1 (en) * | 1986-08-22 | 1988-03-03 | Basf Ag | HALOGEN-FREE, SELF-EXTINGUISHING, IMPACT-RESISTANT, THERMOPLASTIC MOLDING |
| EP0389837A1 (en) * | 1989-03-07 | 1990-10-03 | Mitsubishi Cable Industries, Ltd. | Phenylene oxide polymer composition |
| US5118748A (en) * | 1989-03-07 | 1992-06-02 | Mitsubishi Cable Industries Ltd. | Phenylene oxide polymer composition |
| GB9119795D0 (en) * | 1991-09-17 | 1991-10-30 | Albright & Wilson | Flame retardant plastics material |
| JPH08134346A (en) * | 1994-11-14 | 1996-05-28 | Sumitomo Chem Co Ltd | Polypheylene ether resin composition |
| US6797754B2 (en) | 2002-05-06 | 2004-09-28 | Cheil Industries Inc. | Flame retardant styrenic compositions containing oxaphospholane compound as flame retardant |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663654A (en) * | 1969-02-24 | 1972-05-16 | Gen Electric | Flame retardant composition of polyphenylene ether,styrene resin and phosphorus |
| US3660531A (en) * | 1969-06-04 | 1972-05-02 | Uniroyal Inc | Thermoplastic resin blend of polyphenylene oxide with butadiene-containing polymers |
| US3890406A (en) * | 1971-09-09 | 1975-06-17 | Sumitomo Chemical Co | Modified polyphenylene oxides containing phosphoric acid ester-antimony trioxide flame retarding additives |
| DE2434848C2 (en) * | 1973-08-13 | 1986-09-04 | General Electric Co., Schenectady, N.Y. | Thermoplastic mass |
-
1977
- 1977-11-18 DE DE2751496A patent/DE2751496C2/en not_active Expired - Lifetime
- 1977-11-29 NL NL7713133A patent/NL7713133A/en not_active Application Discontinuation
- 1977-12-08 FR FR7737039A patent/FR2375293A1/en active Granted
- 1977-12-09 CA CA292,795A patent/CA1101579A/en not_active Expired
- 1977-12-14 GB GB51974/77A patent/GB1575457A/en not_active Expired
- 1977-12-15 IT IT30749/77A patent/IT1088919B/en active
- 1977-12-16 MX MX171785A patent/MX146037A/en unknown
- 1977-12-19 JP JP15281877A patent/JPS5379945A/en active Pending
- 1977-12-19 DD DD77202763A patent/DD134538A5/en unknown
- 1977-12-20 BR BR7708512A patent/BR7708512A/en unknown
- 1977-12-20 AU AU31792/77A patent/AU517478B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2375293B1 (en) | 1984-09-07 |
| JPS5379945A (en) | 1978-07-14 |
| FR2375293A1 (en) | 1978-07-21 |
| MX146037A (en) | 1982-05-04 |
| GB1575457A (en) | 1980-09-24 |
| DD134538A5 (en) | 1979-03-07 |
| DE2751496C2 (en) | 1994-09-22 |
| AU517478B2 (en) | 1981-08-06 |
| AU3179277A (en) | 1979-06-28 |
| DE2751496A1 (en) | 1978-06-22 |
| BR7708512A (en) | 1978-08-22 |
| NL7713133A (en) | 1978-06-23 |
| IT1088919B (en) | 1985-06-10 |
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| MKEX | Expiry |