PH26591A - Tetrahalophthalate esters as flame retardants for certain resins - Google Patents

Tetrahalophthalate esters as flame retardants for certain resins Download PDF

Info

Publication number
PH26591A
PH26591A PH37760A PH37760A PH26591A PH 26591 A PH26591 A PH 26591A PH 37760 A PH37760 A PH 37760A PH 37760 A PH37760 A PH 37760A PH 26591 A PH26591 A PH 26591A
Authority
PH
Philippines
Prior art keywords
resin
composition according
styrene
alkyl
carbons
Prior art date
Application number
PH37760A
Inventor
Joseph Michael Bohen
Ronald Francis Lonvenguth
Original Assignee
Pennealt Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US07/173,343 external-priority patent/US4954542A/en
Priority claimed from US07/173,344 external-priority patent/US4912158A/en
Application filed by Pennealt Corp filed Critical Pennealt Corp
Priority to PH40319A priority Critical patent/PH26837A/en
Publication of PH26591A publication Critical patent/PH26591A/en

Links

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)

Description

BACKGROUND OF THE INVENTION Field of the Invention
This invention relates to flame retardant compositions containing at least one tetrahalo- phthalate ester and a certain resin, which is selected from: (A) Acrylonitrile-Butadiene-Styrene (ABS)
Terpolymer Resins; (B) Polystyrene Resins; (C) Polycarbonate Resins; and (D) polybutylene Terephthalate Resins.
Additionally, the inventive composition may contain one or more brominated and/or chlorinated compounds present in an amount effective to pro- vide additional flame retardancy to the resin.
Statement of Related Art
ABS resins are known in the art as a class of thermoplastics which are characterized by excellent properties such as chemical resistance, abuse resistance, stain resistance, etc. A dis- cussion of typical properties of ABS resins are described on pages 1-64, 1-66, and 1-68 of
Charles A. Harper's "Handbook of Plastics and
Elastomers" which is published by McGraw-Hill
Book Company in 1975. These pages are hereby incorporated by reference. ABS resins are ter- polymers which are, in general, drived from ’ 10 acrylonitrile, styrene, and butadiene. Most are true graft polymers in which acrylonitrile and styrene are grafted onto a polybutadiene or rubber phase which may further be dispersed in a rigid styrene-acrylonitrile (SAN) matrix.
Other ABS resins are mechanical polyblends of elastomeric and rigid copolymer, e.g. butadiene- acrylo-nitrile rubber and SAN. (See G.C.
Hawkins, "Condensed Chemical Dictionary", 10th
Edition, p. 3, 1981 as well as U.S. Patent Nos. 4,107,232; 4,206,290; 4,487,886; 4,567,218;
and 4,579,906 all of which are incorporated herein by reference. Hawkins, supra, defines ABS resin as: "Any group of tough, rigid thermoplastics deriving their name from the three letters of the monomers which produce them; Acrylonitrile-
Butadiene-Styrene. Most contemporary ABS are true graft polymers consisting of an elastomeric poly- butadiene or rubber phase, grafted with styrene and acrylonitrile monomers for compatibility, dispersed in a rigid styrene-acrylonitrile (SAN) matrix. Mechanical polyblends of elastomeric and rigid copolymers, e.g., butadiene-acrylonitrile rubber and SAN, historically the first ABS resins, are also marketed.
Varying the composition of the polymer by changing the ratios of the three monomers and use of other comonomers and additives results in ABS resins with a wide range of properties.”
The general chemical structure of ABS is: = 4m
Tu H H | H H ! - ! lcd ! - !
LTTE be y z wherein x, vy. and z may independently vary from about 10 to about 1,5000. (See U.S. Patent No. 4,567,218, the teachings of which are incorporated herein by reference.) It should be understood that analogs of each of the monomeric components above may be substituted in whole or in part, and is within the definition of ABS resin. For example, a-methylstyrene may be substituted for styrene and methacrylonitrile for acrylonitrile.
Descriptions of the compositions of various ABS resins and how they are prepared may be found in U.S. Patent Nos. 2,505,349; 2,550,139; 2,698,313; 2,713,566; 2,820,773; 2,908,66; 4,107,232; 4,173,561; 4,200,702; 4,206,290; 4,289,687;
4,355,126; 4,379,440; 4,456,721; 4,487,886; and 4,581,403, the teachings of which are incorpo- rated herein by reference.
The ABS resins are useful in many commercial applications such as automotive, business machines, telephone, etc., where high impact strength is required as well as in the production of molded articles.
Polystyrene resins find extensive use in the manufacture of packaging material, refrigerator doors, air conditioner cases; machine housings, electrical equipment, toys, clock, TV, and radio cabinets, thermal insulation, ice buckets, con- tainers, furniture construction, appliances, dinnerware, etc. The preparation and description of polystyrene and expandable polystyrene are well known in the art. They are discussed in
G. Hawley, "Condensed Chemical Encyclopedia”, 10th Edition, pp 838 and 976 (1981); Kirk-Othmer "Encyclopedia of Chemical Technology", 2nd Edition,
ivy - ; 26591
Vol. 9, pp 847-884 (1966) and Vol. 19, pp 85-134 (1969); A.E. Platt in "Encyclopedia of
Polymer Science and Technology”, Vol. 13, pp 156-189 (1970); and U.S. Patent Nos. 4,281,067; 4,298,702; 4,419,458; 4,497,911; 4,548,956; 4,596,682; and 4,618,468, the teachings of which are incorporated herein by reference.
For many applications where styrenic polymers are used, there is a need to add flame retardants since these materials are flammable.
Some of the applications which require flame retarded styrenics are radio and TV cabinets, toys, electrical equipment, furniture construct- ion, etc. (See, for example, U.S. Patent Nos. 4,341,890 and 4,548,956, the teachings of which are incorporated herein by reference.)
Polycarbonate resins are known in the art as a class of thermoplastics that are characterized by excellent properties such as electrical, dimen- sional stability, high impact strength, toughness, -]=-
and flexibility. In general, they are prepared by the reaction of a dihydric phenol with a carbonate ester, phosgene, or a bis chloro- formate ester. U.S. Patent Nos. 2,999,835; 3,169,121; 3,879,348; 4,477,632; 4,477,637; 4,481,338; 4,490,504; 4,532,282; 4,501,875; 4,594,375; and 4,615,832 describe in detail the preparation of various classes of polycarbonate resins, the teachings of which are incorporated herein by reference.
Because of their many excellent properties, polycarbonate resins are useful in many commer- cial applications as engineering thermoplastics and in the manufacture of molded articles.
Polybutylene terephthalate (PBT) resins are known in the art as a class of thermoplastics that are characterized by excellent properties such as thermal stability, good resistance to brittleness, low friction and wear, chemical resistance, etc. In general, they are prepared by the polycondensation of terephthalic acid or a diester of terephthalic acid, such as dimethyl terephthalate (DMT), with 1,4 butanediol.
U.S. Patents 2,645,319; 3,047,539; 3,953,394; and 4,024,102 describe in detail the preparation of PBT, the teachings of which are incorporated herein by reference.
The use of brominated and/or chlorinated compounds by themselves or in combination with other materials such as organic phosphates, boron compounds, etc. as flame retardants for
ABS resin compositions are well known in the art ‘and are exemplified by U.S. Patent Nos. 4,051,101; 4,051,105; 4,096,206; 4,107,122; 4,107,232; 4,173,561; 4,200,702; 4,289,687; 4,579,906; 4,355,126; 4,378,440; 4,567,218; 4,581,403; 4,581,409; and 4,600,747. The aforesaid patents are incorporated herein by reference.
Tetrahalophthalate esters have been used as . flame-proofing materials. For example, U.S. Patent
No. 4,098,704 describes the use of these materials as textile finishing agents. U.S. Patent Nos. 4,298,517 and 4,397,977 disclose these compounds as flame retardants for halogenated resins. However, no teachings have been found which show these compounds as flame retardants or processing aids for ABS resins.
SUMMARY OF THE INVENTION
- 10 This invention encompasses flame retardant plastic compositions which comprise the following ingredients in mixture: (I) a resin which is selected from among: (A) Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer Resins; (B) Polystyrene Resins; (C) Polycarbonate Resins; and (D) Polybutylene Terephthalate Resins, and
(IT) a flame retarding effective amount incorporated in the resin of (I) of a tetra- halophthalate ester flame retardant processing aid of the formula:
ROOC 0 2 0) C-X- (CHCH,0) | rl (A), 9 wherein: (a) the ring can have all possible isomeric arrangements; (b) R is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 30 carbons, hydroxyalkyl of 2 to 20 carbons, polyhydroxyalkyl of 3 to 10 carbons, and
—CHCH,0) —— RS 2°'b where Rr is an alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to 50;
(c) r! is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 30 carbons, alkenyl or substituted alkenyl of 2 to 22 carbons, i -c-R’ where rR’ is an alkyl of 1 to 18 carbons; a polyhydroxyalkyl of 3 to 12 carbons;
co Cae : ET Be Cee eT - Chee
Po (COOH) 4 5 W oo ! : | Ti } : —C COOCH:—CH—CHy,
Lo ©), ol J . AA : | ROOC ROOC 0
Loo CHy (Al —¢ ; 5 CH= CH= NH—C (all 1s50men AM 5, 0 i fq. RORY © pips R Re . a | [1 . Co i : Co — CHCHNRIR®: —(CHCH), NR, and —(CHCH)N:
E10 with the proviso that the valence of R! is equal to q: k (d) R2 1s independently selected from the class to consisting of H and CH3 -; : (e) R3, RY, RS, and R6 are independently selected : from the class consisting of H and an alkyl 15¢ of 1 to 18 carbons; (f) p is an integer of 0 to 50; by (9) gq is an integer of 1 to 6; o ~ (h) X is selected from O to NH; and ) (1) A is selected from Cl or Br. : : ‘ - : Lo oo : -13- BE co Co . so, . ¢ . .
Preferably, the weight ratio of (I) to (II) is within the range of about 100:1 to about 2:1. (IIT) Brominated and/or chlorinated flame re- tardants other than (I) which optionally may be present.
DETAILED DESCRIPTION OF THE INVENTION
The above composition can also contain other brominated and/or chlorinated flame retardants.
PREFERRED RESINS
(A) In the above ABS resin, a portion or all of acrylic and styrenic monomers comprising the resin include methacrylonitrile or of- methylstyrene, or methacrylonitrile and of- methylstyrene. The preferred ABS resin is comprised of monomeric units of a vinyl aromatic monomer, a vinyl nitrile monomer, and a butadiene monomer and the number of units of each monomer is independently within the range of from about 10 to about 1500.
‘ } (B) The polystyrene resin is selected from one of the following: (a) a homopolymer of styrene having the following repeatable unit
H H
L_ n wherein n is within the range of greater than 1 to about 3,000; (b)a homopolymer of styrene as in (a) modified with rubber in which the rubber is dispersed as discrete particles into a matrix of said homopolymer and the weight ratio of rubber to homopolymer is within the range of from about 2:98 to about : 25:75; or (¢) a copolymer of butadiene and styrene in which the weight ratio of butadiene to styrene is within the range of about 2:98 to about 25:75; or (d) blends of (a) and (b); polybutadiene and/or a styrene-butadiene copolymer being preferred.
In a preferred embodiment of the invention, the homopolymer of (B) (a) above is in the form of a polystyrene foam. The foam is preferably prepared by polymerizing the repeatable homopolymer unit in the presence of a liquid or gaseous blowing agent and said agent has a boiling point that is below the softening point of the polystyrene and does not dissolve said polystyrene. The preferred blowing agents are selected from the group con- sisting of one or more of propane, butane, pentane,
, hexane, heptane, cyclohexane, methyl chloride, dichlorodifluoroethane, 1,1,2 trifluoroethane, and 1,1,2 trichloroethane. (C) The polycarbonate resin has repeated structural units of the formula: 0 - a wherein a is greater than 1 and z is a divalent aromatic radical of a dihydric phenol. (D) The polybutylene terephthalate resins : that may be used in the present invention have the following repeated structural units of the formula: 0 0
I I
OCH, CH, CH, CH, OC ~O)- C 1 + a wherein a > 1.
It is preferred that in the above tetra- halophthalate ester (II), R is an alkyl or substituted alkyl of 1 to 10 carbons, A is Br,
X is oxygen, p is 0 to 20 (most preferably 0), and q is 1 to 6 (most preferably 1). More preferably R is os ~CH,CH-OH, ~CH,, —C, Hg, —C3Ho, ~CyHgi “Cellyzr ~CyHgr ~CHgHy 3, ~CgHyqgs "CHa Car “C10f21
CoHgi r is CH3,CyHg /C Hy H, “C3Hgr Celyzr ~CgHyqr “HTC “CioM21
C,yHg, or 0
I
-C r
HE i
HO-CHCH,, 0C Br, and gq = 1.
Br Br
The invention also comprehends a method for preparing a flame retardant plastic composition having enhanced processability properties which comprises incorporating a flame retarding effective amount of one or more of the above tetrahaloph- thalate esters of (II) in one or more of the above resins.
The invention also comprehends the method of _ improving the flame retardancy, processability, . and physical properties such as impact strength of the specified resins by incorporating in the resins the tetrahalophthalate compounds as described above alone or in combination with other bromine and/or chlorinated flame retardants.
The abo we resins are sold on the basis of their impact properties. Unfortunately, when such materials have to be flame retarded with conven- tional retardants to meet code requirements, there is a significant loss of impact strength. :
- A i : hE pr. ahd : ; ¥ e or Representative tetrahalophenalacs Compounds useful p Practicing i, this invention are as follows (where A is 3r of Cl):
A A
TA COOH A 8 COOH
A COO(CHICH0)H A COO(CH, CH, 0)—CH,
A A
A A TH
A COOH A COOCH;~CH—0N
A §~ NH(CHICH OM A CONCH CHOnCH,
B A o A . 3 A FH) A q A
Ki A COOCH; —~CH—0H A coor ROC A © 3 A COO(CH,CH 0h, CH, A CONCHICH ON ~C A
A A 0 A a A Hy A . A COOCH;~CH—0H A COOCHYCH,)yCH, n A COXCHCHOnpH A COOCHKCH;)CH,
A A se
A ) COO(CHCH,0)—~CH,
A COOC; Hy A A : A CO(CH ICH 0nCH, A” A
A COOCH:CH~0H
CH) : } A : COOH : A COOH A A
A COXCHCH0n,,cH, A A
A CONCH CH10MCH,
A : A fH
A COOCHACH,)10CH, A COOCH,CH=0H ; A COO(CH,CHOnCH, A COXCH CH 01CH CHA } ; A A ; i oo =20- BN BAD ORIGINAL . ' . [I ~ y " : . | . :
ogli > j ) 0 . + gl ht . ! I — we 2, 6 r ) 1 ' (LR 4 fo : fo
Lik A COOCH,CH~OH A COOCHCH=0H er wl
A A” COO(CHCH0mCH;) A COO(CHCH:0)40CH,
A A
A TH A TH .
A COOCHCH=O0H A COOCH;CH~O0H ;
A COO(CH CH 0M —C A - A A
A Hy 2 A ’
A COOCH;~CH—OH R—0OC A
A 5
Ri A COO(CH }CH 70) gg © A ’ A A
A A
A COOH A COOH
A COO(CH;CH0MH A COO(CH;CH;0)50H
A A i
COOH COOH
A A A A
A COO(CH;CH0MH A COO(CHICH;0nH
A A
COO(CH;CHONCH, COO(CH;CHONCH,
A A A A
A COOH A aA
A COOH
COOH
A A A
A COOH —CHy
CH~OHK
A A
COO(CH,;CH CH
COO(CH CH 0m,H A OO(CHICH;ON
A 2
A ' : E ?
A COOH. CH=CH ’
NER eH 3
A CORE ~CI, —O\s gs =CRy=Ciy , : r INAL ! . RIG
BAD ©
1 gl } . 11d 3 A A i A COOH A COOH ar CH, ne + A COO(CH)— CH OR =—CHy—CH=— N(CH)» A COO(CHICH 10ne=CH;—(CHL~ CHO
A A on
A . -
A 0 n A COOH .
A COOH -C
CH, (CHOH, c i
A CH=CH 0)(CH;CH OH
A COO(CH CH 10M = oo TONCHICH Onl
A
A A)
COO(CHCHIONCHCHN(CH ,
A 8 A ’
A A
COOM
A FH FH 9 A
A COOCH;=CH=OH HOCH=—CH;0C A
A CONCHICHION gc A
A 0 A
COOH A
A A . A COOH i
A A A CO(CH;CHON~CCH,
COOICH;CH0);sH A
A A
A COOH HOOC A
Hy Th '
A CONHICH=CH1OW-)CHi—CH—NNE A
A 0 A
A .
A COOH = CH=CH
NCH. CH
A COO(CH;—~CHOX-39 | —CHy~CH;
A 3 [ A
A . : A r,s COOH
A COOH -CH; y Lo
O Semcmy ~CHy=C~L 1H, dy Ag Sa - : so AN COB EH EHO = CH ~ CHER,
A CONM{CH;—CH10%. 3¢ ~CH; A
Coke A ) . — — : : <+ .
Lo. 22 BAD ORIGINAL r ' Tg ot ail , . 9 . j r ' COO(CHCH;0)1CH) A
A A - A COOH © jo
A A A COO(CHCH 0). 23CH CH N(CH») CH) ; COOCH;—CH—OH A
CH)
A A .
A COOC;H} A COOH - A COO(CH;~CHOnCH, A COO(CH;CH;0n—C—(CH1)i.1s—CH,
A A »
A A TH ,
A COOH . A COOCH;—CH—OH
COOH
A coocnanon-g {Of ocnin=gn A CONR(CH;CH;0) CH;
A Oo A A A
The preferred compounds are:
Br CH Br THs
Be COOCHCH=-OH Br COOCHCH—OH
Be COO(CHICHON CH) Be CO=—NH(CH;CH0M,.CH)
Br Be » | COO(CHICHION CH)
Be COOC Hy ix Br
Br COOXCHCHIONLCH) Be Be
Be COOCH CHO
CH) o> he 9 be he fH 9 Bt
Be COOCHCH—OH RO—C Be Be COOCHICH~=OH RO=—C Br g g
Be COO(CHCHON 4 C Be 8 COO(CH CHO) g—C Br ] _] Be Be
Be 9 4
Br COOC Hy CHOC Br
O 0
Be COO(CH CHOW eC TT
Br Br 4 Cig o a ) 6 CoO CMI
COD City & M Cg Ry O 8 Cones, Cm Cy lly & Sam ;
Ce Cia RS oo Br Br NAL i
The R in the above formulas is -CH,~-CH-OH is or -CH-CH,-OH .
The brominated and/or chlorinated compounds that may be used in combination with the tetra- halophthalates are any of those that are well known in the art. Preferred halogenated flame retardant examples are:
EE ~24-
BAD ORIGINAL a of ? 3 i 18 ot oo z 4 Li 5
EF Tr . : 1 cx, sr or ar] 8 ~~O-+0) 3 Or 0 lS ar
Ir ar rz J, - or SH ir br -
HOCH, CH ,0 ¢ R,CR,OR 12 OCH ,CB,0 ~Or cH z Br } 8r ir : Br 2 Br Br ‘
E CH, 0 ' ox fHafncEg0 ¢ Opens
A B cK | ] 4 ; r Br Pr 3 rc Br, i
Br 3 r nL
CH,=CACR,0 c Or cE CaecE, x ’ (xs 4 tot) . 3 ; } 4 Sz "
R cx 0 ;
NN! o
Rg ! olen, O)- {Qn ashen, .
Ny 0 .
E ar “5 ir i i ¥ i : 1 Ld } ne ! or : “Cr 1 | } 4 ; 4 \" 1: . . ORG i . BAO i ‘ - - 1 -25-, a . .
AM } it
IY Pls : ge " if B . of pr .. 1 . - ° 0 ’ » sr Br 0 A ° s | Co
Xo) «oy "AOL mre TO} or,
K . N ! g | o °
Q~ : ” . 1 } Br br, v c ° . B (x + yu 85-3) Yn ! Br nen J] 2 Br : : 0
TB ° 3 Br COCR CH 0cH cH on = 4 - 0 on 5 : C,H, ’ d ir : 1 Br py s 5: 1 : il i 3r Ir . ; . : . 0 don-on Co sr, Co core on : 4 i vhere R* apg pe are 3 alkylene or Substituted 8lkylene : Ry " LE ‘ | 4 } arf dene
Ar i B
Co ~26- ~~ BAD ORIGINAL = . i . - . E .. . Cr ‘ :
alt | i 4 . " a nd ' “ a . .
Pi : > Br cH, Br Br 3r| Br - \ . I
Or Op =O) O Br ay : cH . , 3 Br Br 3 i r Br n Br i ) } Br CHy Br Br Br, . :
B : HOCH, CH ,0 Ort «Opn (Or omns —~O) : : B Fs B } 5 r r Br Br " : it : ‘ . : Ry : ; ’ Br Br . v : CH ” 5 { 3 OR ‘
R CH,CHCY,0 O Cc — OCH.,CHCR Br
E [ay icta JS 27 CH,
A Br Br Br Cr, Br 3r OH Brg
Br To }
Cen 5
CH, =CHCR, 0 <0) c OCH, CHaCH, : cH, ’
Br . .} 4 | 14
H Cty 0 i a tgon,cne 0) ¢ Hj CR 0CChacH, . 0 C 3 3c L 1 4 ¥ bo oo i . Br } . . Eo
Ope K : | J
A
. oo a) a 0 or : : 8h : . : Co Ce274
Ji 26 Ra 591
In practicing this invention, (II) the tetra- halophthalate by itself or additionally with (III) other brominated and/or chlorinated flame re- tardants is added to (I) the resin in any con- venient manner, such as blending or extruding in order to get a uniform composition. Flame re- tardant synergists such as antimony oxide (8b,03) may also be added if desired. In addition, other additives such as thermal stabilizers, ultra- violet stabilizers, reinforcing agents, organic polymers, mold release agents, blowing agents, colorants, and the like may also be optionally included. A further advantage of the tetrahaloph- thalates alone or in combination with other © 15 brominated and/or chlorinated compounds as used in this invention is their improved compatibility with the resins.
Detailed Resin Descriptions (A) The ABS resins that may be used in this invention are, in general, drived from acrylo- nitrile,styrene, and butadiene and have the following general structure: 5 .
H H HHHH c~C 7% “=f :
H CN H H 'Q : ro xX vy Zz acrylonitrile butadiene styrene wherein x, y, and z may independently vary from about 10 to about 1,500. It is understood that analogs of each of the components above that comprise the ABS resins may be substituted in whole or in part.
The ratio of tetrahalophthalate or a mixture of tetrahalophthalate and one or more brominated and/or chlorinated compounds to ABS resins that will impart flame retardancy to the latter may vary from 1:100 to about 1:2 depending on the application. In addition, the ratio of tetra- halophthalate to other brominated and/or chlorinated compounds may vary from 100:0 to about 1:99. (B) The styrenic resins that may be used in the present invention are the following: polystyrene homopolymer, both crystalline and 16 non-crystalline forms; expandable polystyrene beads, and rubber-modified polystyrene which include medium impact polystyrene, high impact polystyrene (HIPS), and super high impact poly- styrene.
The homopolymers of styrene, both crystalline and non-crystalline, have the following repeatable unit:
H H . bol ©
H n wherein n is greater than 1 to about 2000-3000.
The non-crystalline forms are generally prepared by polymerizing styrene with peroxide catalyst such as those described in U.S. Patent No. 4,281,067 while the crystalline stereoregular isotactic form uses Ziegler-Natta catalysts (See I. Pasquon in Encyclopedia of Polymer
Science and Technology, Vol. 13, pp. 14, 19-20, and 31 (1970).
Expandable polystyrene beads are those that are prepared by incorporating a volatile ex- panding or blowing agent during the polymerization of styrene. The blowing or expanding agents that may be used to cause polystyrene to foam are well known in the art. They may be liquid or gaseous, do not dissolve the styrene polymer, and have boiling points below the softening point of the polymer (See Column 6 in U.S. Patent No. 4,618,468). Suitable blowing agents are aliphatic hydrocarbons such as propane, butane, pentane,
hexane, heptane, cyclohexane or halogen hydro- carbons such as methyl chloride, dichlorodifluoro- methane, 1,1,2 trifluoroethane, 1,1,2 trichloro- ethane and the like. Mixtures of the above may also be used. Typically, expanding agents are used in amounts of about 2 to 20% by weight.
Rubber-modified polystyrenes that are suitable include medium, high, and super high impact polystyrenes. In these compositions, the rubber is dispersed in the polystyrene matrix as discrete particles (See U.S. Patent
No. 4,341,890). Many rubber-modified styrenes are prepared by polymerizing styrene in the presence of a rubber such as polybutadiene or a styrene-butadiene copolymer (SBR). Some grafting of the styrene to the rubber takes place during polymerization. The weight ratio of the rubber to polystyrene may vary from about 2:98 to about 25:75. In general, the moderate impact polystyrene will contain about 2 to about
4% rubber, the high impact polystyrene greater than about 10% to about 25%. / See H. Keskkula in "Encyclopedia of Polymer Science and Technology"
Vol. 13, pp. 396 and 400-404 (1970)/. (C) The polycarbonate resins that may be employed in the present invention are typical dihydric phenols such as used are disclosed in
U.S. Patent No. 3,334,154, which is incorporated } herein by reference. They are as follows: Lo 2,2 bis-(4-hydroxyphenyl)-propane; hydroquinone resorcinol, 2,2 bis-(4-hydroxyphenyl)-pentane; 2,4' dihydroxydiphenyl methane; : bis- (2-hydroxyphenyl)-methane; bis-(4-hydroxyphenyl) -methane; bis- (4-hydroxy-5-nitrophenyl)-methane; 1,1 bis (4-hydroxyphenyl)-ethane; 3,3 bis-(4-hydroxyphenyl)-pentane; 2,2' dihydroxydiphenyl sulfone; 4,4' dihydroxydiphenyl ether; and 4,4' dihydroxy-2,5-diethoxydiphenyl ether.
EXAMPLE 1
To 1,392 g (3.0 moles) of tetrabromophthalic anhydride were added 1,050 g (3.0 moles) of
Methoxy Carbowax 350 in the presence of 22.0 g of sodium acetate. The mixture was heated at 90°C for 9 hours in a nitrogen atmosphere. The reaction mixture was filtered hot to remove the sodium acetate. The analytical data were consistent with the assigned structure.
Br
Br COO (CH,CH,0) 5 CH,
Br COOH r
EXAMPLE 2
To the compound of Example 1 were added : 348.0 g (6.0 moles) of propylene oxide and 2.0 liters of toluene. The mixture was heated at 60°-100°C. The solvent and residual propylene oxide were removed to give the product in almost quantitative yield. The analytical data were consistent with the assigned structure:
Br
Br COO (CH, CH, 0) 7avCi3
Br ~ C00-CH, ~CH-0K r CH,
EXAMPLE 3
To 92.8 g (0.2 mole) of tetrabromophthalic anhydride is added all at once 80 g (0.2 mole) of Carbowax 400 and the mixture heated to 120°- 130°C for 2.5 hours. The desired product is isolated in essentially quantitative yield as a clear yellow viscous liquid. Calcd. Mol. Wt., 864; found 865. Caled. % Br. 37.1; found, 38.5.
The analytical data are consistent with the assigned structure:
Br
Br COOH
Br COO (CH, CH,CH, 0) oH
Br
EXAMPLE 4
To 240 g (0.24 mole) of the compound of
Example 3 is added 45.3 g (0.24 mole) of tri- metallic anhydride and heated at 155°C under nitrogen for about 7 hours. The infrared spectrum indicated the completion of the reaction by the substantial disappearance of the anhydride absorption band at 5.65. The product was isolated in essentially quantitative yield.
Analy. Calcd.; %Br, 30.3%; Mol. Wt. 1056; neutralization equivalent, 352; Found: %Br, 29.4; Mol. Wt., 1014; neutralization equivalent, 351. The spectral data was consistent with the structure:
Br
Br COOH COOH ~~ -
Br COO (CH,CH,CH,0) ¢ CcooH 0
Br
EXAMPLE 5
To 156.3 g (0.18 mole) of the compound of
Example 3 is added 70.9 g (0.18 mole) 2, 3-dibromo- propyl trimellitate. The mixture is heated at
130°-140°C for 6 hours with stirring to give the product as a brown opaque oil. Isolation afforded the product in essentially guantitative yield and the analysis is consistent with the structure being:
Br Ce ——
Br COOH
COOH
B “coo(cH CH,0) Cc COOCH,,CH-CH t 270279 2) [2 0 Br Br
Br (and isomers)
/ . - & -
Ea - “ ol
J } . ) a
So Examples 6 to 11 Co nT
The following Preparation were carried out as in
Example 1 using the reactant set forth below. :
Tetrabromophthalic :
Example No. Anhydride Hydroxy Compound Product Structure ’
Br COOH . ; : SE
CC CE
Br ’ COO(CHCH0nH Le . a Br . : . 7 1.0 mote HO(CH,CH0MH Br Lo (Carbowax 200) ‘ i — 1.0 mote .Br COOH
Br COO(CH,CH 01H EE . Be av. ’ | te | } $ 1.0 mole HO(CH;CH0) 3H Br (Carbowax &0) 1.0 mote Br COOH
J Vg COO(CHCH;0), 3H oo . Be [AR } : { 9 1.0 mole HO(CHCH0)3H Br : ; (Carbowax 1000) C00 1.0 mole Be H \ i
Be COO(CH CHO) 3H
» . 13 nN) ' Mo —4
Tow m : <0 o - ~ Pees . jos] 8 on « 0 —_ ™~ (le)
Jan) ~ ~ o 0 oO 5 ~ Oo O L 2 0 0 S b s
R (2) =
M fis} “1 A mom 4 , —m +H
QO
3 8 ~! a M 4
A m m m 0 ~~
QQ — << s z 2 0 5 Q
Q es) | — = g nn A jae o ot <r oN ©
QO wn Q o 0 o al © mo hl a o o Be OO a4 ~ Uo 2 ~ + 3 0 oN DO 0 ~N 0 0 © 0 H mo > EB TQ g 0 he! uo ~ 0 ol 0 a \ > ; 0 © : ~ mM: OO
Q jor] O a1} Le O O * et mn = mo—~
H
— te! — [1] 0 0 . . + Q 0 151 . ~ 0 © 2 — ] = oO [Ll 0 —~ a0 © o o Hr 0 Q OH Q Q 3s 5% 4 3 od + Eq & BE
Ho oy 04 ©] [j)] 0 H o oO
Qo Ww a . .
Q Pol - ~ - + H
Joh Q + on Q o 3 a el a = [5] 0 +H — 0 — a 0 o
Yi ~ . 0
Q Q Zz ££ 0
BE +H Q 0 a 2 a a g
Ea [ol 0 » 3 fz
EXAMPLE 12
To 96.4 g (0.2 mole) of tetrabromotereph- thalic acid is added all once 160 g (0.2 mole) of Carbowax 400 and 300 g toluene containing 1.0 g P-toluene sulfonic acid. The mixture is heated to reflux until 3.6 g (0.2 mole) water was collected. The toluene is removed under reduced pressure to give a clear viscous liquid in essentially quantitative yield.
COOH
Br Br
I I
Br Br
COO (CH,CH,0) oH
EXAMPLE 13
To 86.4 g (0.1 mole)of the compound of
. 1 ' ' ¥ "26591
Example 3 is added all at once 21.8 g (0.1 mole) pyrometallitic dianhydride and the mixture heated to 120°-130°C for 2.5 hours to give the desired product. Water, 1.8 g(0.1 mole), is added to : 5 open the remaining anhydride group and the analytical data are consistent with the assigned structure:
Br
Br OOH HOO
Br 00(CH CHM 970 COOH
Br 0
COOH
EXAMPLE 14
To 86.4 g (0.1 mole) of the compound of
Example 3 is added all at once 10.9 g (00.05 mole)
. \ ! / - of pyromellitic dianhydride and the mixture heated to 120°-130°C for 2.5 hours to give the desired product. The analytical data are consistent : with the assigned structure: 0 ll
Br -C
Br COOH COOH
Pd ’ O
Br COO (CH CHI 0) HOOC v
Br i 2 0 (and isomers)
EXAMPLE 15
To 86.4 g (0.1 mole) of the compound of
Example 3 is added all at one 21.8 g (0.1 mole)
of phthalic anhydride and the mixture heated to 120°C-130°C for 2.5 hours to give the desired product. The analytic data are consistent with the assigned structure:
Br COCH HOOC
Br TCO (CH CH 0) ok av 0
Br Br
EXAMPLE 16
To 139.2 g (0.3mole) of tetrabromophthalic anhydride is added all at once 122.9 g (0.1 mole) polyoxyethylated trimethylol propane of molecular weight 1229 and the mixture heated to 120°-130°C for 2.5 hours to give the desired product. The analytical data are consistent with the assigned structure:
Br
Br COOH — cH,
NN
—CH,— C —C,H 2 275 0 ~~
Br COO (CH, CH, ) 9a% CH,
Br 3
EXAMPLE 17
To 139.2 g (0.3mole) of tetrabromophthalic anhydride is added all at once 156.8 g (0.1 mole) polyoxypropylated trimethylol propane of molecular weight 1568 and the mixture heated to 120°-130°C for 2.5 hours to give the desired product. The analytical data are consistent with the assigned structure:
Br
Br COOH — CH, ~N
CH — CH,— C— C,H 3 2 25 [ yd
Br COO (CH, CH, 0) g== CH,
Br 3
EXAMPLE 18
To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 350.0 g (1.0 mole) of Methoxy
Carbowax 350 in presence of 7.0 g of sodium acetate. The mixture is heated at 90°C for 8 hours in a nitrogen atmosphere. The reaction mixture is filtered hot to remove sodium acetate to give the expected product in nearly quantitative yield. The analytical data are consistent with the assigned structure:
Cl cl COO (CH, CH, 0) 7avCii
Cl - COOH
Cl
EXAMPLE 19
To 634.0 g (1.0 mole) of the composition of
Example 18 is added 116 g (2.0 moles) of propylene oxide in 200 ml of toluene. The reaction mixture is heated from 60°-100°C for 3-5 hours, and then concentrated to give the product in nearly guan- titative yield. The analytical data are con- sistent with the assigned structure:
Cl
Cl COO (CH, CH, 0) 5 ,CH4
Cl COOCH, CH — OH
C1 CH,
EXAMPLE 20
To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 200.0 g (1.0 mole) of Carbowax 200 in the presence of 7.0 g of sodium acetate.
The mixture is heated at 90°C for 8 hours in a nitrogen atmosphere. The reaction mixture is . filtered hot to remove sodium acetate to generate the expected product in nearly quantitative yield. The analytical data are consistent with the assigned structure:
Cl
Cl _~COO(CH,CH,0) , H
Cl COOH
Cl
EXAMPLE 21
To 484.0 g (1.0 mole) of the product of
Example 21 is added 116.0 g (2.0 mole) of propylene oxide in 200 ml of toluene. The reaction mixture is warmed at 60°-100°C for 3-5 hours, and then concentrated to give the product in nearly quantitative yield. The analytical data are consistent with the assigned structure:
Cl
Cl COO (CH,CH, 0), H
Cl COOCH,,~CH-OH
C1 CHy
EXAMPLE 22
To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is- added 400.0 g (1.0 mole) of Carbowax 400 in the presence of 7.0 g of sodium acetate.
The mixture is heated at 90°C for 8 hours in a nitrogen atmosphere. The reaction mixture is filtered hot to remove sodium acetate to generate : the expected product in nearly quantitative yield.
The analytical data are consistent with the assigned structure:
cl Cl <0 COO(CH,CH,0) 4 JH cl COOH
EXAMPLE 23
To 46.4 g (0.1 mole) of tetrabromophthalic anhydride is added all at once 44.1 g (0.1 mole) of polyoxyethylated dimethylamine /CH3) JN (CH,CH,0) gH_/ dissolved in 100 ml of toluene.
The mixture was heated at 100°-110°C for 4-5 Ipurs and then concentrated to give the desired product in essentially quantitative yield. The analytical data are consistent with the assigned structure:
0 Br ii
HOC Br (CH3) N (=CHCH,0) govt Br 0 Br
EXAMPLE 24
To 92.8 g (0.2 mole) of tetrabromophthalic anhydride is added 80 g (0.2 mole) of 3 Ps
H,N-CH-CH,/ (OCH,-CH-_/ oc. NH, (Jeffamine D-400) and the mixture heated to about 120°C. The final product is obtained in almost quantitative yield. The analytical data are consistent with the assigned structure:
Br
Br COOH
Hs 3
Br CONHCH-CH,, (OCH, -CH-) 5. gaviHy
Br . . “
EXAMPLE 25
Poly (ethylene glycol 300), 204.5 g (0.67 mole) was refluxed (T = 117°C) with 600 ml of toluene for 1.5 ours in order to remove a small : amount of water present in the glycol. The mixture was cooled to about 100°C and tetra- bromophthalic anhydride, 614.5 g (1.35 moles) and sodium acetate, 1.62 g were added and the mixture was reheated to reflux and held for 25 hours. After the mixture was cooled to 50°C, propylene oxide, (156.4 g, 2.69 moles, 100% excess)
was added and the mixture heated to and held at 100°C for 2.5 hours. When the solution cooled to about 50°C, it was filtered through a bed or diatomaceous earth and decolorizing charcoal.
The filtrate was distilled to remove the solvent to give 904.1 g of product as a viscous liquid.
Cala. % Br, 47.4. Found % Br, 46.5. Analytical data is consistent with the assigned structure.
Br 0 H H 0 Br i | I
Br CO0CH TH; CHafH, coc Br
OH OH
B fo (CH CH 0 gg —— ; Br 0 0 B
Br r
EXAMPLE 26
This compound was prepared by the procedure described in Example 25 except. that poly- (ethylene glycol 200) was used in place of poly (ethylene 300). Product is viscous liquid. calcd. % Br, 51.0. Found % Br. 49.3.
Analytical data was consistent with the assigned structure. oo Br 0 H H 0 ‘By 1 foc
Br OCH.,CCH, - CH,CH,COC Br 2] 3 3 2
OH OH
Br CO (CH,CH,0) ,—&/— c” Br 277°2774-5
I I
Br 0 0 Br
EXAMPLE 27
This compound was prepared by the procedure described in Example 25 except that poly (ethylene glycol 600) was used in place of poly (ethylene glycol 300). Product is a viscous liquid.
t 4
Calcd. % Br. 39.5. Found % Br. 39.3.
Analytical data is consistent with the assigned structure.
Br 0 - H H 0 Br [I CL
Br cota Hac Br
OH OH
Br CO— (CH,CH,0) 45 qy—— i “Br
I
Br 0 0 r
EXAMPLE 28 :
This compound was prepared by the procedure described in Example 25 except that poly(ethylene glycol 400) was used in place of poly(ethylene glycol 300). Product is a viscous liquid.
Calcd. %Br. 44.2. Found % Br. 44.9.
Analytical data is consistent with the assigned structure.
Br 0 H H 0 Br
Foo [
B OH CHT c0c Br
OH OH
: Br CO — (CH,CH,0) 89 Cc Br
I
Br 0 Br
EXAMPLE 29
Methanol (54.1 g, 1.5 mole), tetrabromoph- thalic anhydride (695.6 g, 1.6 moles), and potassium acetate, 2.73 g were refluxed for 4 hours with 500 ml of toluene. After cooling the reaction mixture to room temperature, propylene oxide (87.12 g, 1.5 moles) were added and the mixture reacted at 80°C for 2.5 hours. Product was obtained as a viscous liquid after dis- tilling out the toluene. Calcd. % Br. 57.7.
Found % Br, 57.2. Analytical data is consistent with assigned structure.
Br 0
Br COCH,
H
Br ie
Br 0 OH
EXAMPLE 30
This compound was prepared by the procedure similar to that descriled in Example 29 except that methoxycarbowax 350 was used in place of methanol and ethylene oxide in place of propylene oxide. Caled. % Br, 37.8. Found % Br, 37.2.
Analytical data is consistent with assigned structure. } Br 0
Br CO —~— CH,CH,0) ;CH,
Br i
Br 0
EXAMPLE 31
This compound was prepared by the procedure in Example 29 except that 2-methoxyethanol is used in place of methanol. Product is viscous liquid. Caled. % Br, 53.6. Found % Br, 52.0.
Analytical data is consistent with the assigned a 6 O) i 1 “Ls YD structure.
Br I H
Br COCH,, CCH 4
OH
~~
Br |e
Br !
EXAMPLE 32
This compound was prepared by the procedure outlined in Example 29 except that methoxycarbowax 350 was used in place of methanol and epoxybutane in place of propylene oxide. Product is a viscous liquid. Calcd. % Br, 36.5. Found % Br, 37.2. Analytical data is consistent with the assigned structure.
.
Br 0 H
Br cota 2"
OH
Br CO(CH,CH,0) CH
I
Br 0
EXAMPLE 33
This compound was prepared by the procedure outlined in Example Example 29 except that 2-ethylhexanol-1 was used in place of methanol. Product is a viscous liquid. Calcd. % Br, 50.0. Found % 52.7.
Analytical data is consistent with the assigned structure.
Br i H
Br OCH TMs
OH
B jC] Cat
Br 0 Cols
' . ' »
EXAMPLE 34
This compound was prepared by the procedure described in Example 29 except that stearyl alcohol was used in place of methanol. Product is a viscous liquid. Calcd. % Br, 41.0. Found % Br, 43.0. Analytical data is consistent with the assigned structure.
Br 0 H . :
Br Oa
OH
Br O12) 173
Br 0
EXAMPLE 35
This compound was prepared by the procedure described in Example 29 except that 2,3-dibromo- propanol-1 was used in place of methanol. Product is a viscous liquid. Calcd. % Br, 64.8. Found $ Br, 61.9. Analytical data is consistent with the assigned structure.
Br i H
Br. os
OH
Br EI
Br 0 Br
EXAMPLE 36
This compound was prepared by the procedure outlined in Example 29 except that epichlorohydrin was used in place of propylene oxide. Calcd. % Br, 35.7. Found % 35.4. Analytical data is consistent with the assigned structure.
Br | H
Br Coon
OH
Br CO (CH, CH, 0) ,CH
I
Br 0
EXAMPLE 37
To a solution of methoxycarbowax 350 (300.0 g, 0.89 mole) in dry toluene (184 ml) was added sodium methoxide (48.0 g, 0.90 mole) in methanol. The methanol was then distilled off atmospherically. Tetrabromophthalic anhydride was then added (442.2 g, 0.89 mole) along with an additional 50 ml of toluene. The reaction mixture was refluxed for 2 hours and after cooling to room temperature, epichlorohydrin (106.94 gq, 1.16 moles) was added. The mixture was refluxed for 20 hours. After the solvent and excess epi- chlorohydrin were distilled, a viscous dark product was obtained. Caled. % Br, 37.2. Found $ Br, 40.4. Analytical data is consistent with assigned structure.
Br 0
Br - — CH, oo \. yd 0
Br 0 oo CH, 0) CH
I 277277773
Br 0
EXAMPLE 38
Methoxycarbowax 350 and toluene were refluxed for 1 hour in order to distill out a small amount of water, Tetrabromophthalic anhydride (1:1 mole ratio with methoxycarbowax 350) and sodium acetate were added and the mixture refluxed for 17 hours.
Ey os -
LA me
After cooling to room temperature, an excess of diazomethane (prepared from the decomposition of
N-methyl-N-nitroso-p-toluene sulfonamide by sodium hydroxide) in ethyl ether was added and the mixture allowed to stand overnight. The excess diazomethane was decomposed by adding acetic acid and the solvent removed by distillation. Product is viscous liquid. Caled. % Br, 39.2. Found %
Br, 37.4. Analytical data is consistent with the assigned structure.
Br 0 5 I r COCH 4
Br 0 —f CH, CH, 0) 7CH3 or}
EXAMPLE 39
Di (2-ethylhexyl) tetrabromophthalate was prepared by the procedure described by Spatz et. al (I & EC Product Research and Development,
Vol. 8, No. 4, 395 (1969).
Br 0
I
Br COCH,CHC ,H ~ 2] 49
Sf
Br 2 Cat
Br 0 C,H 275
EXAMPLE 40
Poly (ethylene glycol 600) 835.4 g (1.40 moles), tetrabromophthalic anhydride, 1298.4 g (2.80 moles), potassium acetate, 1.35 g, and toluene (1000 g) were charged into a one-gallon glass-lined reactor and heated to 120°C. After 4 hours at this temperature, ethylene oxide, 246.68 g (5.60 moles) was pumped into the reactor in 3/4 hour while maintaining the temperature at 120°C. After one hour longer of heating, the mixture was cooled to room temperature, the excess ethylene oxide was then vented, and the product collected. After stripping off the toluene, 2250 g of the product was isolated in 99% yield as a viscous liquid. Calcd. % Br, 39.2.
Found % Br, 38.8. Analytical data is consistent with the assigned structure. 0 0
I
COCH,, CH, OH HOCH, CH, 0C
CO(CH,CH,0) 15 15 C : I I 0
EXAMPLE 41
To the product of Example 3, 453.8 g (0.27 mole), acetic anhydride, 83.4 g (0.82 mole),
potassium acetate, 1.0 g, and toluene, 400 ml, were refluxed for 8 hours. After cooling to room temperature, the reaction mixture was transferred to a separatory funnel and extracted first with 100 ml of a 16% potassium bicarbonate solution and then with 100 ml of water. After distilling off the solvent, 335.0 g (54% yield) of product was obtained as a viscous liquid. calc. % Br, 36.8. Found % Br, 32.9. Analytical data is consistent with the assigned structure. 0 H 0H 0 ii i]
COCH,(OCCHs CH3COGCH0 £0) CH CH TOF
HO (CHaCHR0) 12-13 i to 0 0
EXAMPLE 42
Tetrabromophthalic anhydride, 231.9 g
(0.50 mole), 2-ethylhexanol, 130.2 g (1.0 mole), and potassium acetate 0.24 g were heated to and kept at 120°C for 4 hours. The mixture was cooled to 60°C and potassium carbonate, 35.9 g (0.26 mole), was added. Reheated mixture to a 80°C and kept it at this temperature for 2 hours.
Cooled mixture to 60°C and added triethylamine, ’ 14.2 g (0.14 mole). Reheated mixture to 70°C and added methyl iodide, 113.6 g (0.8 mole) in 20 minutes. Heated mixture to 70-75°C and kept it at this temperature for 2-1/2 hours. Cooled mixture to room temperature and filtered it in order to remove by-product potassium iodide.
The filtrate was distilled to remove toluene and 290 g of crude product was collected as a pale yellow liquid. Extracted this product with 3 times 100 ml of a 6.5% potassium carbonate solution followed by 2 times 100 ml of water and once with a 30% sodium chloride solution. Dried the organic phase over anhydrous magnesium sulfate overnight.
Filtered off magnesium sulfate and after removing the solvent from filtrate by distillation, 204 g of product was obtained in 67% yield as a pale yellow liquid. Calcd. % Br, 52.6. Found % Br, 52.2. Analytical data is consistent with the assigned structure. 0 - 3
OJ
§0CH2] Cat 0 C, He
EXAMPLE 43
Tetrabromophthalic anhydride, 231.9 g (0.5 mole), 2-/2-methoxyethoxy/-ethanol, 360.5 g (3.0 moles), stannous oxalate, 2.32 g, and xylene, 200 ml, were refluxed (temp. 160°C) for 18 hours during which time, theory water was collected.
The xylene and excess 2-/2-methoxyethoxy/-ethanol were distilled under reduced pressure to give 332 g of crude product as a wet white solid.
Redissolved 256 g of this material in toluene (1000 ml) and extracted it with 3 times 200 ml of a 7.5% potassium bicarbonate solution followed by one extraction with 200 ml of water.
Dried the organic phase with anhydrous magnesium sulfate overnight. After removing the magnesium sulfate by filtration, toluene was removed by distillation to give 45 g of a yellow liquid product. Overall yield is 17%. Calcd. % Br, 46.6. Found % Br, 45.7. Analytical data is consistent with the assigned structure.
OCH, CH, OCH, CH, OCH 5
GX jj C2 20H HO 0
EXAMPLE 44
This compound was prepared by the procedure outlined in Example 43 except using 2-/2-ethoxy- ethoxy/-ethanol. 0 l
COCH,,CH, OCH, CH, 0C, Hg
I
(OCH CHa OCH CHOC s 0
EXAMPLE 45
This compound was prepared by the procedure outlined in Example 1 except that docosyl alcohol (behenyl alcohol) was used in place of poly- (ethylene glycol 600) and propylene oxide in place of ethylene oxide. Product is a viscous liquid. Calcd. % Br, 37.7. Found % Br, 36.5.
Analytical data is consistent with the assigned structure. 0 H hi
COCH,,COH 2 : §01C2 21% ; 0
EXAMPLE 46
This compound was prepared by the procedure outlined in Example 1 except that tricontyl alcohol was used in place of poly (ethylene glycol 600) and propylene oxide in place of ethylene oxide. Product is a viscous liquid. 0 H
I
COCH,COH ?
OJ CH,
G0 (C12) 20%H3 0
EXAMPLE 47
This compound was prepared by the procedure outlined in Example 4 except that methoxycarbowax 350 was used in place of 2-/2-methoxyethoxy/- ethanol. 0
I
CO (CH, CH, 0) 11CH3 x jo (CH2CH, 0) 11CH3 0
EXAMPLES 48-58
Compositions With ABS Resins
In the following examples, the flame retar- dancy of the compounds of this invention are demonstrated with respect to ABS resins. The compositions were prepared by mixing together the flame retardants, antimony oxide, and ABS on a roller until the compounds were blended thoroughly. :
The compounds were pelletized at 230-245°C and then injection molded into test specimens at 230°C. The UL-94 vertical burn test was run and compared to a control consisting of ABS itself.
ABS = Acrylonitrile-styrene-butadiene terpolymer
DTBPE = 1,2-bis (2,4, 6-tribromophenoxy) -ethane : (70% Bromine)
DOTBP = Dioctyl tetrabromophthalate (45% Bromine)
AO = Antimony Oxide - 15 un ~~ 2 oO mn wun vv oo wn o oN — > > 2 © ~~ = Qo — 1n oO =H oo i 1 . wl > > « 19}
D
© -
J co 1 + oO of . aN [=] ol 1 | Q <¢ — > > |&]
H HH
0} Q . g PD 0 i] Qo = T 0 ~ oh +
HH «
HH Q — m a
Ke] a 9 w 5 —_ Q Q oO
Q - fo} [= ~ o + oH $2 0 co Oo [0 [ul 0 — < — ! | I BR 3 o
J g 0 [o] ~ M 2 ~ « 8 8 ~ 0 = oe a oO — = = oO no 1 a - oo 0 n . . . [14] — rr 0 oo oO — oO MH 2 S 5g
Qy @ Vv g E 3 ~ © © 5 0 0 [1s] Mm Ay <r QO 0 0 3 wu om 8 7 » a Ed Oo Oo = Q Q 0 mn 0 0 IaH - ~ ~ ~
The above clearly demonstrates the flame retardancy of the ABS compositions of this invention relative to the control. These compositions have at least equivalent flame retardancy to the conventional flame retardant ‘used in ABS (DTBPE).
Lo el : EXAMPLES "5 428k CEE ee ne pa. OY ie KANE Heghtr Ceo vos
Impact strength of the various materials were determined according to ASTM D256.
i 1 © n> 0 9 o nn nx — un < oN 0
Nn = oo +H ~ = un a — < wn 0D wo — ~ ~
U . J ~ oc ) i 0 — ™ o o~ 0 H
Ln — [0]
H +
Q 0 js Q 1S od Q = 2 1 [Ly] — 2) —~ « ~ m ~ 0 =
H Mm 4+ — <p Ko —_ © 44 Qu jc3| Q . Oo 0 — ~ o 1 I ) ™ — a oN o + [i] un — 0 <
Ee 3 © od - 0 + a 3 8
EB 2
OQ © 0 « 00 = - oO — 2 | 58 ~ 0 4 |® 0 . oO 0 — rf 0 3) i] O = 2 HH —~ H js) 0 + Qu
Q n 3 o g = ~~ x] > 0 0 [u] =] ~ jar} 0 0 0 :
E ~ A m QO
I] 0 mM 5 |= — — —_ » 9 EB QO Oo Ly] Q 0
Mm oO No « = ~~
As can be seen from the data above, the conventional flame retardant, DTBPE, greatly reduces the impact strength of ABS compared to those examples where a portion of the
DTBPE is replaced by the ABS-containing flame 0 "retardant compositions &f this invention. 7 : Le Lo EXAMPLES" 56-5 8 pp, gt Am it PA tow oe. A a
Heat Deflection Temperature (HDT) of the various materials were determined according to
ASTM D648. - 15 v «J ®l gg 4 85 © 0 nl oo «HA A Oo part — ~~ oo oo 1 = ™~ ~~ oo oN \o nl A ~ << 0) oD oO — oO M
Q a Q -
Zl oor 1 ~ o i] w| © 0 H 2g har © Q = + « lo) — < 0 q ~~ fm = < n wy jolt
Hi 0 Oo 4 2 CR 0 0 <q 2 = gh - o H & 8 oo . 4 ww 0 & og = od oO [3 de oO : s 8 5oL |® = 8 o —
BH — 0 . OU Oo ~<A A 0 ng oH ge OO HM > HG I) ~ HH © mm oO PY 0 [3 0 2 E a ~~ n << >» 0 0 8 mo, \O o © ©
Bu 4 8 HW 8» 8 8 o 5 © a ou 3 2 8 a < ZG - =
The data above shows that there is negligible charge in HDT when a portion of the conventional flame retardant, DTBPE, is replaced by the esters disclosed in this invention.
EXAMPLES 59-64
Compositions With Polystyrene Resins
In the following examples, the flame retardancy of the compositions of this invention are demonstrated. The compositions were prepared by mixing together the flame retardants, antimony oxide, and high impact polystyrene on a roller until the compounds were blended thoroughly. The compounds were pelletized at 200-260°C. and then injection molded into test specimens at 230°C.
The UL-94 vertical burn test was run and compared to a control consisting of the impact polystyrene itself.
HIPS = High Impact Polystyrene
DBDPO = Decabromodiphenyl Oxide (83% Bromine)
DOTBP = Dioctyl Tetrabromophthalate (45% Bromine)
AO = Antimony Oxide
. oo ho 0 oO oy e . . | i <¥ o I wo oN > > 0 a 00 — 0 ~ » ol mn ~ oo © n . . 1 i ™ 0 ™ oy ™ > > 0 [oN] 0 .
Eg <L 0 . 0 wn o 2 oN oO aN —
Xe) © . | . ~
Pm No oc © . a ~ ~ I | 3)
Q > > = ~~ 0 a] 3]
Hon wn u — Q . . ~ + 0 ny — aN Ln < o o ~ 0 [oe] { 1 LY Q “ » - > > a : > o — + 0 iv} ~~ —_ [oH — m 0 o ~ ~ U4 Ko
H o <¥ N 1 ho oO oN 0 ~~ + 0 0 — 1 1 Q fe i > > + a jor 0 Q 0 9 3 ~ — oT > q &e — Tg 0 + ©
Qa a Q a 0n H ~ o | 1 I ~ [a Q > oN oO r Ka! — Q wn —t fd [i] [0] Q + < Fx 2, ~ Q tn 00 a oN oo ~ = nn 3 a un oN ~N \O ~ Oo vg |® 3 . . . 19] ri — 0 © Qo Q oO H 2 yg o — QQ) — a g — © ® 0 0 0 ~~ le) ny <x ny 0 0 g wn By m Nn » H m QO Oo o us] Q 0 m won AA ~~ =
The above results clearly demonstrate the superior flame retardancy of the styrene- containing flame retardant composition of this invention over the conventional flame retardant used in polystyrene (DBDPO).
Examples 60 through 62 are all run at equal bromine levels. Partial or total replacement of the conventional flame retardant (DBDPO) with the esters disclosed in this invention improves the flame retardancy of the polystyrene as can be seen by the UL-94 results for the 0.062" specimens. Examples 63 and 64 clearly demonstrate that the total bromine levels can be reduced when the compositions of this in- vention are used and still yield comparable or better flame retardancy.
EXAMPLES 65-70
Impact strength of the various materials were determined according to ASTM D2463.
© << © wn . . . aN o o 1 oN o ~ © ~— * © aN — uw . * — oN ™ 1 SH — © r~ ~N : o - © = » . «© © 0 mM 0 <r o 0 ~ ~t : oO tn un o . . ~~ ~ 1 aN nn <3 o 0 © : o
H
Q
+ _ 0 0 ~~ Q - T 1 < 0 0 © © 9
O . » . +H o 0 Lo} co — a Sd — ~ +
H 4 oo 4 n nd Q jo un a O z _ >» oo 0 a 0 — H i} nn o o n + oe © a o 0 HH o g > 0 4 Q
H oO ¥ 44 Q 0 wn oe o
NO
D 0 3 a 0 ~ 0 0 @ S . QF ~~ “ — ial o g J 0 H = — “+ n HH © & > oP oh 0 HO ~~ gg EB 9 0 AQ oO 0 © o 5 7 Aa 0 © g wn A Mm ! nn AO OH H oo = 3 0
H m © © gd ts Qo 0
[8] oma A A v - = =
As can be seen from the data above, the conventional flame retardant, DBDPO, greatly reduces the impact strength of the polystyrene (see Example 66). The compositions containing the material of the invention clearly improve the impact strength to a point where it is better than the comparison example.
EXAMPLES 71-74
The extrusion rates were measured during pelletization to determine the processing characteristics of the compounds.
TABLE III (B)
Example No. 71(c) 72 73 74
HIPS 84 81.5 79 76.4
DBDPO 12 9 6 3
DOTBP - 5.5 11 16.6
AO 4 4 4 4
Extruder Flow Rate (1bs/hr) 3.4 3.7 4,2 7.9
(a) polysar ® 525, a product of Polysar, Inc., US.A. (c) comparison (no tetrahalophthalate ester)
The data above clearly demonstrates the improved processability of the styrene-containing flame retardant of this invention. : EXAMPLES 75-79
Compositions With Polycarbonate Resins
In the following examples, the flame retardancy of the compositions of this invention are demonstrated with respect to polycarbonate resins. The compositions were prepared by mixing together the flame retardants, antimony oxide, and polycarbonate resin on a roller until the compounds were blended thoroughly. The compounds were pelletized at 160-305°C and then injection molded into test specimens at 271°C. The UL-94 vertical burn test was run and compared to a control consisting of the polycarbonate resin itself. The following tests were performed on the various materials according to the appro- priate ASTM method. 1. Limited Oxygen Index (LOI) - ASTM D-2863 2. Melt Flow - ASTM D-1238 3. Tensile Strength - ASTM D-638
PC = Polycarbonate polymer
BPC = Brominated Polycarbonate Oligomer (58% Bromine) : DOTBP = Dioctyl Tetrabromophthalate (45% Bromine)
o o o . » oO oO RN : on ASN t 0 ~ Oo a . ~ 0 — ™ — o nn
Hh — o o » . . je] [eo] ™M © ™m oN ~ o — . . ~ oo — ™ —! © = — /\ wo «TO wn o . . * . i <3 ~ 0 oN < r~ ~~ o * ~ 00 om ™ o ~ — —
Oo vw wn — o ~ . . * ol ee] 0 ~~ oN f [0] aN oy . ~ oo ™ —t o 0 [= — —_ o ow © a
Q - . i . —_ = o 1 1 © 0 oN ~
Q Ln o oN ol RN La = ~ —
HH i" i
BE a © +P ~— on —~ . ac HH
Q wn a . 5M 0 2 : Fo B 0 ie © Oo — fr ~ ao o [4] — 0 oO rd Nal 0 rd £ fo m 3» — wn > — > od — @) = + — ~ o Mm ¥ oo Aa © Q 9 © 0 + + 2) A om A A = —- BH © sw ©
J — (a) "Lexan" 141, a product of General Electric, U.S.A. (b) control (100% polycarbonate) (c) comparison (no tetrahalophthalate ester) (d) PSI = pounds per square inch. 1 PSI = .0145 g/cm2
The above clearly demonstrates the significant improvement in flame retardancy of the polycarbonate resin containing compositions of this invention relative to the control. These polycarbonate resin containing compositions have at least comparable flame retardancy to the conventional flame retardant, BPC, used in polycarbonate.
Examples 76-79 are all run at equal bromine levels. Partial or total replacement of the conventional flame retardant, BPC, with the esters disclosed in this invention results in greatly enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238,
The polycarbonate resin containing compo- sitions of this invention show improved tensile properties when compared to the control, and comparable to that of the conventional flame retardant, BPC. Furthermore, the polycarbonate resin containing compositions of this invention maintain percent elongation.
The data above clearly demonstrates the improved processability of the polycarbonate resin containing compositions of this invention.
EXAMPLES 80-86
Compositions With PBT Resins
In the following examples, the flame retar- dancy of the compounds of this invention are demonstrated. The compositions were prepared by mixing together the flame retardants, antimony oxide, and polybutylene terephthalate (PBT) on a roller until the compounds were blended thoroughly. The compounds were pelletized at 150-216°C and then injection molded into test specimens at 235°C. The UL-94 vertical burn test was run and compared to a control consisting of PBT itself. Melt flow of the various materials were determined according to ASTM D-1238.
PBT = Polybutylene Terephthalate
BPC = Brominated Polycarbonate Oligomer (58% Bromine)
DOTBP= Dioctyl Tetrabromophthalate (45% Bromine)
AO = Antimony Oxide
TABLE I (D)
Example No. 80(b) 81(c) 82 83
PBT (a) 100.0 85.0 82.8 80.7
BPC - 15.0 7.5 -
DOTBP - - 9.7 19.3
Antimony Oxide - 5.0 5.0 5.0
UL-94 Rating @ 0.125" v-2 v-0 v-0 v-0 @ 0.063" v-2 v-0 v-0 v-0
Melt Flow 27.6 36.2 55.1 72.6 (g/10 min) (a) "Celanex" 2000, a product of Hoechst-Celanese
Corp., U.S.A. (b) control (100% polybutylene terephthalate) (c) comparison (no tetrahalophthalate ester)
The above clearly demonstrates the flame retardancy of the compositions of this invention relative to the control. These compositions have at least equivalent flame retardancy to the BPC conventional flame retardant used in
PBT (Example 81),
Examples 81-83 are all run at equal bromine levels. Partial or total replacement of the conventional flame retardant (BPC) with the compositions of this invention results in enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTMD-1238.
EXAMPLES 84-86
The following tests were performed on the various materials according to the appropriate
ASTM method. 1. Impact Strength - ASTM D-256 2. Tensile Strength- ASTM D-638 3. Heat Deflection Temperature (HDT) - ASTM D-648 4. Melt Flow - ASTM D-1238
~ ® Mm oo oO o o © In
LO EE oo OO Ww wn «NN OY gl 8 ov ov rr. ~ wn ool oo o > > oO r~ A ™m aR) nN — © v| o o o ™ o Mm NNN ~~! ee . oo oO mM <3 rs» OY.
Jaz. 3, rr. oO oOo = © of © 0 > > Oo © aH +H ™m ™ nN —_ un o oO Nw
Q NN Nw ~N I~. ~~ oo 1 1 1 un Te ™ oOo oN I~ 2 o~ >> oO r~ ~~ 4 «~ wo al
H
—
BE nn o
NW
— oO se 0» 0 oo oo 4) 3 Zz 2 S ri oo (d Tg OO oo YW ag O 4 . 9 TQ RT 2 92 5 E oO O | N OHA OD ol ~ z H H ~~ nn ~ PN 3 oO
D> Jo} 0 H ©8 —~ 0 o mM TT 9 0 vu oo km HA ON al ~ 0 Qo A ~<A Mm g o°o mu
Ly] NE hd 5 — +4 ~~ 0 ~~ ~ 2s 083 ad 8 Tm Tod el m An OQ Q 4 OQ @ a Q le BBB 2 8 8 = Ee de mm =
(a) "Celanex" 2000, a product of Hoechst-Celanese
Corp., U.S.A. (b) control (100% polybutylene terephthalate) (c) comparison (no tetrahalophthalate ester) (d) PSI = pounds per inch. 1 PSI = .0145 g/cm2
As can be seen from the data above, poly- butylene terephthalate resin compositions containing the flame retardants of this invention greatly improve the impact strength relative to the control (Example 84) and the BPC conventional flame i retardant, (Example 85) used in PBT while: maintaining both tensile strength and percent elongation properties.
In addition, the flame retardants of this invention significantly improve the heat distortion temperature (HDT) and flow properties relative to the control.
The data above clearly demonstrates the improved processability of the polybutylene terephthalate containing compositions according to this invention.

Claims (1)

  1. WE CLAIM:
    1. A flame retardant plastic composition with improved flow characteristics comprising the mix- ture of: (I) a resin which is selected from the group consisting of: (A) Acrylonitrile-Butadiene-Styrene resin of the formula H H H H H H H H rrr c-C c-c=¢-2¢C ¢ ——C H CN H H H 2 xX Y acrylonitrile butadiene styrene wherein x, y and z may independently vary from 10 to 1,500; (B) Polystyrene resin and is one of:
    (a) a homopolymer of styrene having the following repeatable unit: H H Cc 7 © in : wherein n is within the range of greater than 1 to about 3,000; (b) a homopolymer of styrene as in (a) modified with rubber in which the rubber is dispersed as discrete particles into a matrix of said homopolymer and the weight ratio of rubber to homopolymer is within the range of from about 2:98 to about
    25:75; or (c) a copolymer of butadiene and styrene in which the weight ratio of butadiene to styrene is within the range of about 2:98 to about 25:75; or (d) blends of (a) and (b); (c) Polycarbonate resin which has repeated structural units of the formula: . | 0 . 0 -2Z -o0C -— a wherein a is greater than 1 and Z is a divalent aromatic radical of a dihydric phenol; and (D) Polybutylene Terephthalate resin and has repeated structural units of the formula:
    0 0 I I OCH, CH, CH, 0C- —C a wherein a > a; and (II) a flame retarding effective amount of a tetrahalophthalate ester flame retardant processing aid and has the formula: 0 R I | 2 L Cc -X - (CHCH, 0) 5 R
    (a) 4 COOR qd wherein: : (a) R is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 9 carbons and 2 —+—CHCH, 03—— r® where r8 is an alkyl or subs- = , tituted alkyl of 1 to 18 carbons, and b is 1 to 50; (b) rY is selected from the group consisting of an alkyl or substituted alkyl of 1,to 9 carbons, alkenyl or substituted alkenyl of 1 to 22 carbons; 0 -c- =r’
    where Rr’ is an alkyl of 1 to 18 carbons; —f~c (COOH) |,
    [ . 0 1 or 2 0 - C Co0CH ym TH a? . A A ROOC i ROOC - C, CH, (8) 4 (A) 4 . CH,- CH - NH - C ! ol i 0 (all isomers) (all isomers)
    r3g? rir? r3g* is, da NR and dn . 5 with the proviso that the valence of rt is equal to 4g: (c) Rr? is in é&pendently selected from the class consisting of H and CH,-i (d) r3, RY, R> and Rr® are independently selected from the class consisting of H and an alkyl of 1 to 18 carbons; (e) p is an integer of 0 to 50; (£) g is an integer of 1 to 6; (g) X is selected from 0 to NH, and (h) A is selected from Cl or Br.
    2. A method for imparting flame retardant and improved flow characteristics to a resin according to claim 1 comprising mixing with said resin a flame retardant effective amount of at least one tetrahalophthalate ester flame retardant aid according to claim 1.
    5 . 3. A method for manufacturing a flame retardant resin with improved flow characteristics comprising mixing a resin according to claim 1 and a flame retarding effective amount of at least one tetrahalophthalate ester flame retardant aid according to claim 1.
    © 4. A composition according to claim 1 wherein p is zero, q is one and X is oxygen.
    / 5. A composition according to claim 6 wherein R and rl are alkyl groups and A is Br.
    6. A composition according to claim 5 wherein the ester is di-2-ethylhexyl tetrabromophthalate.
    , 1. A composition according to claim 1 wherein the weight ratio of (I) to (II) is within the range of 100:1 to 2:1.
    _ 8. A composition according to claim 1 wherein R is an alkyl as substituted alkyl of 1 to 9 carbons, A is Br, X is oxygen, p is 0 to 20, and q is 1 to 6.
    © 9. A composition according to claim 1 wherein R is selected from among “CH3, —CHgs -C3Hy, —CgHyas —Cyhly —CHCH, 3, ~CgH 50 “2 Cas 1 CyHgs R™ is CHy, CyoHe, CyHgr “C3Hyr “Cele ~CgHyqe Pe
    C,H., or 275
    0 il -C Br HO=TH 0 CHCH,0C Br, and q = 1. Br Br 7 10. A composition according to claim 1 wherein (II) includes additional brominated or chlorinated flame retardants or mixtures thereof other than said ester.
    11. A composition according to claim 10 wherein said additional flame retardants are selected from the group consisting essentially of ao J Hi 0 oe 0 0 . Brg Bre " . , 0 re fOT yensena, OF Br, 7, C ’ o n 0 o : 4 “ 7H 3 O)-<O) ; i ’ Br Br 0 7 x Y 9 il nn (x + y = 5-8) B Q c Br - . TOL rene B@ x ; : 4 Cc Cc Br | . 0 Il ) Q 0 0 1} or, CCCH CH, OCH, TH ,OH ) - rr - (0) sooner, 0 OH . Cafls a Br 8r Br 3 Br Br : 0 1} BY COR"OH on 8ry nD ] COR*®' OH i . Cc where R* and R*' ars alkylene or substicuced alkylene : Br C—CH,Br - . H : }
    8r . . 8r CR . + ’ -107- o" ' . } . .
    gi ne on A A re = A wh ya i Br CH, Br Br >] Br i he oi HO c— O oH Br O)-o Oo OO) Br
    Cy . {ss 4 A
    3r . Br r Fn ar ¥ Br cH, Br Br Br i =A : - HocH,IH,0 O < (O)-ocH cn on Br O OCH,CH,0 Oper Cn CH, / ¥ Br Br Br Br aE
    [I . b : EE 3r cu Br iE re \ } 3 ; OH ! AY : i . ” —_ | se : . CryTHCE,0 ~<O7 c Oe no Br Br ’ cay Br Br 8rg Tv Sr 8 CH, . . i / \ . Br, SH,=CHCH 0 c <Q OCH, CH=CH, ‘ CHy (x= 4 to 6) }
    8r . Sr Br n cH HO ‘ 0 a / \ 1 3 0 Jd 2 ~~ ~ / — ~ - - fpeCToCy, cA, of OO) c OO R CH,0CTHCH, , an — cn : Br J] Br Br ‘ - Co Br ON OH } he ; Br > hE : oo SE * -108- CE
    \ - 26591
    12. A composition according to claim 1 wherein the resin is acrylonitrile-butadiene-styrene and a portion or all of acrylic and styrenic monomers comprising the resin include methacrylonitrile or o(- methylstyrene.
    13. A composition according to claim 12 where the resin comprises monomeric units of a vinyl aromatic monomer, a vinyl nitrile monomer, and a butadiene monomer. 7
    14. A composition according to claim 1 wherein the Polystyrene resin is (B) (a) and is in the form of a foam. ‘ Co JOSEPH M. BOHEN RONALD F. LOVENGUTH Inventors
PH37760A 1988-03-25 1988-11-02 Tetrahalophthalate esters as flame retardants for certain resins PH26591A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PH40319A PH26837A (en) 1988-03-25 1990-04-03 Tetrahalophtlate tetrahalopthalate esters as flame retardants for styrene maleic amhydride copolymer (SMA) resins

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11521188A 1988-03-25 1988-03-25
US11568888A 1988-03-25 1988-03-25
US07/173,343 US4954542A (en) 1988-03-25 1988-03-25 Tetrahalophthalate esters as flame retardants for polybutylene terephthalate resins (PBT)
US07/173,344 US4912158A (en) 1988-03-25 1988-03-25 Tetrahalophthalate esters as flame retardants for polycarbonate resins

Publications (1)

Publication Number Publication Date
PH26591A true PH26591A (en) 1992-08-19

Family

ID=27493998

Family Applications (1)

Application Number Title Priority Date Filing Date
PH37760A PH26591A (en) 1988-03-25 1988-11-02 Tetrahalophthalate esters as flame retardants for certain resins

Country Status (1)

Country Link
PH (1) PH26591A (en)

Similar Documents

Publication Publication Date Title
DE19681298B4 (en) A flame retardant resin composition and process for producing an organic phosphorus compound
DE60320372T2 (en) PENTABROMBENZYL ALKYL ETHERS AND THEIR USE AS FIRE-INHIBITING AGENTS
US3207731A (en) Self-extinguishing alkenyl aromatic polymeric compositions containing polybromophenyl acrylates and dibromocyclopropyl styrenes
US4764550A (en) Tetrahalophthalate esters as flame retardants for polyphenylene ether resins
CA2217815A1 (en) Benzoates as flame retardants and/or plasticizers
JPS58201834A (en) Stabilization of vinyl chloride polymer, stabilizing composition and stabilized polymer
CA1337310C (en) Tetrahalophthalate esters as flame retardants for certain resins
US4762861A (en) Tetrahalophthalate esters as flame retardants for polystyrene resins
US4954542A (en) Tetrahalophthalate esters as flame retardants for polybutylene terephthalate resins (PBT)
DE3241542A1 (en) POLYPHENYLENE ETHER RESIN AND MASS HEAT-STABILIZED WITH PHOSPHITE COMPOUNDS
DE2757558C2 (en)
US4923916A (en) Tetrahalophthalate esters as flame retardants for polystyrene resins
US4683255A (en) Polyphenylene ether resin composition having excellent fire retardancy
PH26591A (en) Tetrahalophthalate esters as flame retardants for certain resins
US4912158A (en) Tetrahalophthalate esters as flame retardants for polycarbonate resins
US4016138A (en) Plastic compositions
JPS61235453A (en) Polyacetal resin composition
US4938894A (en) Tetrahalophthalate esters as flame retardants for ABS (acrylonitrile-butadiene styrene terpolymer) resins
WO1988003542A1 (en) Flame retarded modified polyphenylene esters having improved flow characteristics
US4923917A (en) Tetrahalophthalate esters as flame retardants for styrene-maleic anhydride copolymer (SMA) resins
EP1861458B1 (en) Flame retardants and flame retarded polymers
EP0098109B1 (en) Phosphorus-containing compounds, their production and their use as anti-oxidants
AU2785489A (en) Tetrahalophthalate esters as flame retardants for certain resins
US6503992B2 (en) Phosphorous-containing monomers and flame retardant high impact monovinylidene aromatic polymer compositions derived therefrom
CA1336635C (en) Halophenyl ester flame retardants for polyphenylene ether resins