PH26837A

PH26837A - Tetrahalophtlate tetrahalopthalate esters as flame retardants for styrene maleic amhydride copolymer (SMA) resins

Info

Publication number: PH26837A
Application number: PH40319A
Authority: PH
Inventors: Joseph Michael Bohen
Original assignee: Pennwalt Corp
Priority date: 1988-03-25
Filing date: 1990-04-03
Publication date: 1992-11-05

Description

\ } he _ ' v : a 26837 ee Cs | —. BE

TETRAHALOPHTHALATE ESTERS AS FLAME Co

RETARDANTS FOR STYRENE-MALEIC

ANHYDRIDE COPOLYMER (SHA) RESINS

BACKGROUND CF THE INVENTION

This invention relates to flame retardant compositions containing at least one tetrahaloph- : thalate ester and an SMA resin. Additionally, . tris composition may also contain one or more ; brominated and/or chlorinated compounds in an 1C amount to provide additional flame retardancy to ; the SIA resin. This invention also comprehends : the method of improving the flame retardancy and processability of the SiIA resins by using these tetrahalophthalate esters 2lone or in combination with one or more bromine and/or chlorine com- pounds.

STyrene-llaleic Anhydride (SMA) copolymers find extensive use in the manufacture of molded articles and foamed products. In general, they are prepared by copolymerizing styrene and maleic anhydride in the proper ratio and under the aporopriate conditions. The preparation and ’

’ ~ - description of SKA copolymers are described in U.S. Pat. Nos. 2,769,804; 2,971,939; 3,336,267;

Sand 3,966,843, the teachings of which are incor- porated herein by reference. .

SiA polymers burn rapidly and are generally not used in applications which require fire i : retardant polymers such as radio and television cabinets, tables, chairs, appliance housings and thé like. (See U.S. Pat. No. 4,151,218 which is incorporated by reference).

The use of brominated and/or chlorinated compounds by themselves or in combination with other materials such as organic phosphates, anti- mony compounds, etc., as flame retardants for

SMA resin compositions are well known in the art and are exemplified by U.S. Pat. Nos. 3,766,249; 3,966,843; 4,032,481; 4,038,245; 4,085,912; 1,113,672; 4,136,135; 4,151,218; and 4,323,655.

The aforesaid patents are incorporated herein by reference.

Tetrahalophthalate esters have been used as flameproofing materials. For example, U.S. .

oT Pat. No. 4,098,704 describes the use of these materials as textile finishing agents. U.S.

Pat. Nos. 4,298,517 and 4,397,977 disclose these compounds as flame retardants for halo- genated resins. However, no teachings have been found which show the use, of these com- pounds as flame retardants or processing aids for SMA resins.

SUMMARY OF THE INVENTIOCN

: 10 The present invention is directed to a composition of a styrene-maleic anhydride (SMA) resin and a flame retardant processing aid comprising: (i) a styrene-maleic anhydride (SMA) : resin having the following general formula:

H H H H H H blr bd ob deo JH } \,” ’ jm LL n \ - Lh - .

wherein m is a number from 1 to about 100 and

Co n is a number from zero to about 100; and (ii) a flame retarding effective amount of a tetrahalophthalate ester flame retardant i 5 processing aid of the formula: . A 0 oo | A — Lon oo - } A TOK ceron,o, RL - so bk 2 a : wherein : (a) R is selected from the group con- | B sisting 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 : "2 . ——CHCH,,03=—R"

where r8 is an alkyl or substituted alkyl of . i . " 1 to 18 carbons, and b is 1 to 50; (b) R! is selected from the group consis- ~~ °° ting of hydrogen, an alkyl or substituted alkyl . 5 of 1 to 30 carbons, alkenyl or substituted alke- nyl of 2 to 22 carbons, oo Co 0 | I : ’ il SE oo CR’ Co Lo Cn where Rr’ is an alkyl of 1 to 18 carbons; a poly- EEE hydroxyalkyl of 3 to 12 carbons; (COOH)1 to 3 ©

I lor 2 : o | : i c 00 , -CH-CH,

ROCC AA

: CH ROQC . 3 (8) “CHORAL (all isomers): 0 . : 0 * 3 oo Lo I :

C : oo A), - a . oO) (A) EE - I (all isomers): oo 0

Ry g* RJ RY R3 RY -CHCHNR’R™-( CHCH), NR”: and~(CHCH) SN : with the proviso that the valence of RT is equal’ to q; (e) R® is independently selected from the group consisting of H and CH; - : (d) R3, RY, RS, and RS are independently ‘selected from the group consisting of H and alkyl - of 1 to 18 carbons; ~~ .(e) p is an integer of 0 to 50; (£f) q is an integer of 1 to 6; (g) X is selected from the group consisting + of C or NH;

a (nh) A is selected from the group consisting ~ of C1 or Br; and (i) provided further that when p is zero : and X is oxygen that R and RL are other than a ‘neopentyl group. - Co

Preferably, the weight ratio of (i) to (ii) } , © is within the range of about 100:1 to about 2:1.

Co CL It is preferred that in the above tetrahaloph- Co © tfalate 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, and q is 1 to 6. More preferably ) R is oo

CH

3 . ; -CH,CH-CH, ~CHy CoH, -CoH, =C Hy Cglys g

Cglyo, Hats Tada

L

: C,H R CH CH.,H. C,H. H. Lo : 275; +S 3, 275, Lg, }

N CH, CoH, CoH), CH, “SH Hg, C121

SE C_H 0 2's, °F

I

+=C Br

CH, © [3

Ho buch, 0d Br, and q = 1.

Br Br

: In the tetrahalophthalate ester of ii, pre- ) ferably p is zero, q is one, and X is oxygen.

Even more preferred is when also R and rR: are : alkyl groups and A is Br. Most preferably, the the ester is di-2-ethylhexyl tetrahalophthalate.

Another aspect of this invention is that . the composition may optionally also contain other oo .bromine and/or chlorine’ compounds such as those that are well known in the art.

This invention also comprehends the method : of improving the flame retardanty and processability ) of the SMA resins by incorporating in the resin the tetrahalophthalate compound as described above alone or in combination with other bromine and/or a chlorine flame retardants.. = “re oo EE

In practicing this invention, the tetra- halophthalate by itself or additionally with other brominated and/or chlorinated flame retar- dants is added to the SMA resin in any convenient , 20 manher, such as blending or extruding in order to get a uniform composition. Flame retardant syner- gists such as antimony oxide (80,04) may also be added if desired. In addition, other additives such as thermal stabilizers, ultraviolet stabi- : oo lizers, reinforcing agents, organic polymers, "mold release agents, blowing agents, colorants, and the like may also be optionally included. : A further advantage of the polyoxyalkylene tet- i rahalophthalates alone or in combination with "other brominated and/or chlorinated compounds B Co as used in this invention is their improved com- oo patibility with SMA resins.

Representative tetrahalophthalate compounds . useful in practicing this invention are as follows oo (where A is Br or Cl): Co

/)

SR . ce tale llonInELol. Lay ied. eeude. an FERS UC ’ vee pms me Be Lee Le A Le Lowa 2 ee A A : A COOH A _ COOH

A COOXCHCH;OWH A CONCH :CHOY=CH\

A A

. A A . CH

A COOH A COOCH:—CH—OH

A C= NH(CH:CHIONH A COO(CHCH;OrCH)

A 0 A

OA . Hs A 0 A

A COOCH;~CH=—0OH A COOR ROC A : A COO(CHICH ION CH) A COXXCHICHION = C A

A A OQ A

A CH A

” A COOCH;—CH=—OH A C COOCHHCH2)sCHn

A COXCH;CHORH A COOCHNCH1wCH;

A A

A COO(CH;CH;OV—CH;

A COOC Hs A A

A COO(CHICHOnCH} A A

A COOCHCH—OH

CH; }

A : COOH

A COOH A A

A COO(CHCHION CH) A A ’

A COOXCHCHOMCH;, 1

A A CH

A COOCH NCH: )10CH} A COOCH:CH—0H

A COOICH:CH OCH) A CONCH CH:01-CH:CH

A A

’ A TH A THs

A COOCH ;CH=OH A COOCH:CH=0H

A COO(CHCH0%CH) A COO(CH CH 0)soCH

A A

A CH A CH)

A COOCH;CH=0H A COOCH;CH—OH . O : 1O

A COO(CH CHO —C A }

A A

A CH § A

A COOCH;=CH=0H R=OC A ’ 1O

A COO(CH ;CH 0) sg mmm C A ' A A

A A

A COOH A COOH

A COOXCHCHOLH A COO(CH;CH;;O)sH

A : A : COOH COOH

A A A A

- A COO(CH CH ;ORH A COO(CH ;CH;OmH

A - A .

COO(CH;CHONCH; COO(CH;CHIOKCH,

A A A A

A COOH A A

A COOH

COOH

A A ? .

A COOH ~CH:

CH—OH

A A

CH;CH;O% CH,

COO(CH:CHOmH A CONCH CH0

A

’ ‘y

A ’

A COOH —CHi=CHy

TCH CH,

A COXCH;=~CH:~0x =CH:~CH,

A “

A A

A COOH A COOH gr

A COO(CH;=CH:Om—CHy=CH= N(CH; 1, A OCH ICH One CH: =(CHI—CHO

A A OH

A

A 0 i A COOH j A COOH -C = | CH; . (CHOH, i

A COXCH=CH ;0)(CH;CH 0)

A COO(CH CH 0% -¢ TOIHCH; oH

A

A ; ©

COO(CH:CHORCH CH NICH; ¥ A A

A A

COOH

A CH THs 5 A ’ A COOCH;~CH=0OH HOCH=CH;OC A “A CONCHCHOY = A

A 0 A

COOH A

A A A COOH

O 2 a A A COO(CH CH Om=—CCH;

COO(CH CHO), 3H A

A A

A COOH HOOC CA

CH CH O

A CONMICH= CHO. 11CHy—~CH—NHC Sa

A oO A

A

A COOH —CHimcHy

MCHIR Qs

A COO(CH;~CHOn.30 | =CH;—=CH;

A ! -— ’ A

A COOH

A ~_ COOH —CH, (OT Hi - = C=CyHg / A CONCH CHO W— CH; —CH vee 2

NN TCOM HCH ~ CHO 4 —~CH: hy 4 Hy)

COO(CH:CHOLCHY A

A A - A COOH ’ hai }

A A A COO(CH:CHOY-15CH ;CHIN(CH 2) CH} .- COOCHy—CH—OH A

CH3

A A

A COOC Hs A COCH

A ~~ COO(CH=CH;ONCH; A COO(CHCH OW —C (CHL 1s= CH) + A A 0

A A TH

A COOH A COOCH;=—CH=—O0H

COOH

A COOCHICHOR=C COOCHI CH=CH A CONH(CH;CH:05CH: ' A .Q A A A : __The preferred compounds are’

Br - cH Br TH . Be COOCHCH—OH Br COOCH;CH—OH

Be COOXCHICHIOW CH) Br CO=—NH(CHCH01+, CH:

Br Be

Bc COO(CH CHOY CH)

Br COOC; Hy Be Be 1 COO(CHICHIONCH) Be Be

Be COOCHICHOM

CH) : y ofr ooo 8

Be COOCHCH—OH RO—C Be or COOCH;CH—OH RO—C 8c g

Be COO(CH CHO) 4 =C Be Be COOXCH CHO o=—C Br

Br Br Be Be

Be 0 or

BL COOC ; Hy CHOC Br

QO 2

Be COOXCH CHOY oC Be > Te \ : 4 Cig 8 a } & ~ Can Cay & HC ly CoO CyHia

Sc Coocu, ex 19 My Be Coo ¢ Wig tr Cry 6r

Br ca, Br Br | 3 “Opt OB Br O 0 { ) Ne 3c cH, ~/ . 3r Br . Br Br n : . 3r

Br CH, Br BR 14 ” . | . Br men au A

TESRR LL) =< OO RCH, 0H Br O oCH.CH.0 “NN ar : ca, { -o2 2 T ’ : 3r Br Br B er } r ' Br my Br

PON SH < cy mgm a VT AN oR fRaTHIE T= $l CECE ar 2s hs ~ <8, =. . Br ’ @ : a- . ve Br oC A } ’ } ar | .

N cg

EI ~~ :

TEE eC ~~ OCH CHeCH, : ' — od, = . R$ oo . a 3r SH 8r ° : i" | / 7 \ ! of

Ci. .=z" SH. z ‘ - poss Opn LOoenners, : ar 4 1 .

Br . - ’ Br Con \\ ’ : ’ Co ‘ br

The R in the above formulas 1s

CH CH

CH, -CH-CH or -CH-CH,-OH. oo - 15 - oo . hl

The brominated and/or chlorinated compounds that may be used in combination with the tetrahaloph- thalates are any of those that are well known in oo rT | the art.

Preferred halogenated £1ame retardant ) mee examples are : - 16 -

) ’ wr . ° - *s Br, : 9 fH o

MN . . 5 0 3 3 © Ty bz, o . {x - y - $-8) 2 1 0 ae

RS

2-72 (

I L = ICL : ] ° o ’ . +f

0 ch

BL COCH, CH, 0CH CH, OH

LL : ( Froconrer, Lo Co oo 0 OH 3 :

Co Pes } Co B Br iN ° ] br

Co OR"OH ~~ : g ol C-CH, Br : mi OL Fz ~~ COR'''OH, Br i

A

0 Br ' where R" and R''' are alkylene or substituted alkylene - 18 = 4

The SMA resins that may be used in the oo present invention usually have the following ) i. structural formula: BN oo . . Lo

HH H H HH

[| Fr ¢———C——C—C - C—C

E doo ©) | ii oo \ _/ 0 m n wherein m=1 to about 100 and n=0 to about 100.

The weight ratio of styrene to maleic anhydride E. oo may vary from about 50:50 to about 95:5. =

The ratio of tetrahalophthalate or a mix- ture of tetrahalophthalate and one or more bor- 18 minated and/or chlorinated compounds to SMA 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 tetrahalophthalate to other brominated and/or “chlorinated compounds may vary from 100:0 to . about 1:99. oo ~ .The compositions of this invention may also include other additives such as thermal stabilizers,

ultraviolet stabilizers, reinforcing agents, organic polymers, mold release agents, blowing , agents, colorants, etc. - In order to illustrate the present inven- tion, the following examples are presented. These - are not to be construed as limiting the scope of : . the invention. -

EXAMPLE 1 ~~ To1,392 g (3.0 moles) of tetrabromophthalic oo | - anhydride were added 1,050 g (3.0 moles) of Methoxy oo

Carbowax 350 in the presence of 22.0 g of sodium acetate. The mixture was heated at 90°C. for 8 hours in a nitrogen atmosphere. The reaction mixture was filtered hot to rémove the sodium acetate. The analytical data were consistent : with the assigned structure. :

Bp Br 00(CH,CH,0), ors oo : - B 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 Co 60°C .-100°C. The solvent and residual propy- - lene oxide were removed to give the product in almost ggantitative yield. The analytical data were consistent with the assigned structure. - Br - - : oo OX COO(CH, CH 0), ( CHy om - B CO0-CH,, ~CH-OH -L

To Br

CH : : 3

EXAMPLE 3

To 92.8 g (0.2 mole) of tetrabromophthalic - ) anhydride is added all at once 90 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. Calcd. % Br, 37.1; found 38.5.

The analytical data are consistent with the : assigned structure. | oo BN

Br

Br OCH Co

Dp 0 coo 580 5

Br : ; av,

EXAMPLE 4

To 240 g (0.24 mole) of the compound of oo oo Example 3 is added 45.3 g (0.24 mole) of trime- litic anhydride and the mixture was heated at 155° C. under nitrogen for about 7 hours. The ) 10 infrared spectrum indicated the completion of the reaction by the substantial disappearance of the anhydride absorption band at 5.65u. The product was isolated in essentially quantitative yield. Analy, Calcd.; % Br, 29.4; Mol. Vt., 1,014; neutralization equivalent, 351. The spectral data was consistent with the structure. - 22 a 4 4

Br oc COOH - | oo . Br” Tr oot) ~O)— COOH . ~ | 0 co : EXAMPLE 5 :

To 156.3 g (0.18 mole) of the compound oo

Co of Example 3 is added 70.9 g (0.18 mole) 2,3- : dibromopropyl trimellitate. The mixture is : heated at 130° - 140° C. for 6 hours with | oo © © stirring to give the product as a brown opagge Co oil. Isolation afforded the product in essen- Lo tially quantitative yield and the analysis was consistent with the structure being:

Br

N 0 ~~ COOH

Br TCO0(CH,CH,0) o-2 LO ysocsn ones

Cn “Br ;

Br Br (and isomers)

EXAMPLES 6 to 11 :

The following preparations were carried out as in Example 3 using the reactants set forth below. | Co oo SL ee -—

Tetrabromo | -

Example phthalic :

Br 6 1.0 mole HOCH ,CH, OCH CH , OH Bp COOH

B

P37 COO(CHGHO HH r : 7 1.0 mole HO(CH,CH,0),H (Carvbwak 260) B Br co . "1.0 mole r OH : oo . Br 00(CH.CH,0 rT 2 3 ’ av. 8 1.0 mole HO(CH,CH,0). H Er .0 mole 5 Br COOH (CarbBwak 606) av.

Br 9 1.0 mole HO(CH,CH,0), H Br. COCH (Carbivak 1680) : 1.0 mole B r 00 (CH CH, 0H av. . Br ©. 10 1.0 mole HO(CH,CH,0), H B COCH : (Polyly&olE-2000) 0) Co 8r av.

B or HOOC Br r B 11 2.0 mole HO(CH,CH,0).H OOH 0) (Carvawal 180) Br 1.0 mole . Br 00(CH,CH,0) o-C BY

Br il 0. av.

EXAMPLE 12

To 96.4 g (0.2 mole) of tetrabromoter- on oo a phthalic acid is added all at ance 160 g (0.2 Ea mole) of Carbowax 400 and 300 g of toluene con- . taining 1.0 g P-toluene sulfonic acid. The mixture is heated to reflux until 3.6 g (0.2 a mole) water was collected. The toluene is removed under reduced pressure to give a clear viscous liquid in essentially quantitative yield. - oo oo Co COOH | SS

SE Br Br ST 10x )

Br Br 00(CH,CH,0) 4 ori

EXAMPLE 13

To 86.4 g (0.1 mole) of the compound of SE

Example 3 is added all at once 21.8 g (0.1 mole) ~ ; pyromellitic dianhydride and the mixture to 120° Z 130° C. for 2.5 hours to give the desired product. Water, 1.8 g (0.1 mole), is added to open the remaining anhydride group and the ana- lytical data are consistent with the assigned structure.

Br

HOOC

Br 00(CH_CH,_0) .=C OOH 27279 Ce _ Br i - Co = COOH ‘

EXAMPLE 14

To 86.4 g (0.1 mole) of the compound of

Example 3 is added all at once 10.9 g (0.05 mole) of pyromellitic dianhydride and the mixture : : heated to 120° - 130° C. for 2.5 hours to give oo © the desired product. The analytical data are Ln consistent with the adsigned structure. oo + 0

Co I =C

Br COOH ‘Br, COOH : © OH

B COO(CH,CH,0) HOOC 4 oo . Br : Il - ave 0 . (and isomers) - 26 - oo

EXAMPLE 15

To 86.4 g (0.1 mole) of the compound of B - Example 3 is added all at once 21.8 g (0.1 mole) of phthalic anhydride 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.

B COOH HOOC

_ Br COO(CH,CH,0) ,C BE on)

Br/ Br 0

EXAMPLE 16

To 139.2 g (0.3 mole) 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 COOH - 2 Co : -CH—C—C_H : 2, 25 :

Bp B 00(CH,CH,0) CH, :

B . r 3 ’ EXAIPLE 17

To 139.2 g (0.3 mole) 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 a. | :

By COOH CH,

CH, 2 : © CHz—C—C Ha

Br COC(CH , (CH,CH,0) gay on’

Br “ 3 oo EXANPLE 18 ’ To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 350.0 g (1.0 mole) of llethoxy

Carbowax 350 in presence of 7.0 g of sodium ace- tate. The mixture is heated at 90°C. for 8 hours in a nitrogen atmosphere. The reaction mixture : ig 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

C1 ¢Co(CH, CHC), CH : (CH,CH, Poavt3 i} C COOH 2 : EXAMPLE 19 . :

To 634.0 g (1.0 mole) of the composition of Example 13 is added 116 g (2.0 moles) of propylene oxide in 200 ml of toluene. The reaction mixture is heated fron 60°-100°C. for =29-

Co a

3-5 hours, and then concentrated to give the } product in nearly quantitative yield. ‘The . analytical data are consistent with the assigned oo ee structure.

Ci . cl CO0(CH,GH,0) CH oo > oo

Cl CO0CH, OH -OR : oc CH,

EXAMPLE 20 ) | :

To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 200.9 g (1.0 mole) of Carsowax 200 in the precence of 7.0 £ of sodium acetate. } 10 The mixture is heated at 90°C. for 2 hours in a nitrogen atmosphere. The reaction mixture is : filfered hot to remove sodium acetate to generate oo the expected product in nearly quantitative yield.

The analytical data are consistent with the assigned oo . structure. : : cL

OX COO(CH,CH,0), KH

Cl: COOH : =

EXANPLE 21

Co To L84,0 g (1.0 mole) of the product of cee” : Example 20 is added 116.0 gz (2.0 moles) of pro- : - pylene oxide in 200 ml of toluene. The reaction . | . ’ 8 , mixture is warned at 60°-100°C, for 3-5" hours, and ther concentrated to give the product in . necrly quantitative yield. The analytical data i are consistent with the assigned structure. ' ’ © Cl Co a COO(CH,CH,0),, H . 6 COCCH,, -CH-OH . A

Ci CH,

EXALPLE 22

To 284.0 g (1.0 mole) of tetrachlorophthalic . anhydride is added 400.0 g (1.0 mole) of Cariowax : LOO 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 oo . - 31 ~- .

. - * . Ce the expected product in nearly quantitative } vield. The analytical data are consistent with the assigned structure.’ SE me . ’ ] 3 eS : Cl ¢€1 oo : : C C | : : -

C1 C00(CH,CH,0), H | Lo

C COOH . g EXAMPLE 23 oo | "To 46.4 g (0.1 mole) of tetrabromophthalic "anhydride is added all at once 44.1 g (0.1 mole) oo

Co CT ; of polyoxyethylated dimethylamine (CH,) N(CH,CH,0) : : av H) dissolved in 100 ml of toluene. The mixture was heated at 100°-110°C. for 4-5 hours and then . concentrated to give the desired product in essen- - tially quantitative yield. The analytical data oo are consistent with the assigned structure, . oo HOC _ _Br co : - (C3) N(CH CHRO) ge | Q Br oo : : 0 Br : 1X ) - 32 _ . o- . ’ . “%

EXAMPLE 24

To 92.8 g (0.2 mole) of tetrabromophthalic : anhydride is added 80.0 g (0.2 mole) of i Ths

H,N-CH-CH, ( (OCH, -CH-) . Gavi io (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 COCH : CH CH 13 [3

B I 7 T = - HA r CONHCH CH, (CCH, CH )s bavi Hy

Br :

EXALPLE 25

Poly(ethylene glycol 300}, 204.5 3 (0.67 _ mole) was refluxed (T=117°C.) with 600 ml of toluene for 1.5 hours in order to remove a snall i amount of water present in the glycol. The mix- ture was cooled to about 100°C. and tetrabromoph- on thalic 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 diatomaceus earth and decolorizing charcoal. The filtrate was dis- tilled to remove the solvent to give 904.1 g of product as.a viscous liquid.

Calcd. % Br, 47.4. Found 7% Br, 46.5. Analy- tical data is consistent with the assigned structure.

Br i A i i Br

Br. Q0CH, CCH, CH.CH.C Br 21 3 Ih”

H H

3 N00 —(CH,CH,0) 4 _,—0C Br

Br I -7 I B r o

EXAMPLE 26

This compound was prepared by the procedure

Ce described in Example 25 except that poly(ethylene glycol 200) was used in place of poly(ethylene 300). Product is viscous liquid.

Caled. % Br, 51.0, Found % Br, 49.3. Analy- : tical data was consistent with the assigned structure. ’ i 0 ]

Br | i H 0 Br - r COCH,CCH CH.CH, COC r 31 2 : = CH CH or ; Br

CQ—(CH,CH,O) —_C

Br I 272m m= | Br 0 0

EXALFLE 27

This compound was prepared by the procedure described in Example 25 except that poly(ethylene zlycol 600) was used in place of poly(ethylene glycol 300). Product is a viscous liquid.

Caled. % Br, 39.5. Found & Br, 39.3. Analy- ticzl data is consistent with the assigned structure.

< C loos don cH oy be CH

CO— (CH, CH, 0). ,_4+—C Br 0

EXANPLE 28

This compound was prepared by the procedure described in Example 25 except that poly(ethylene 5 glycol 00) was used in place of poly(ethylene glycol 300). Product is a viscous liquid. ’ Calcd. % Br, LL4.,2, Found 4% Br, 44,0. Analy- ticzl data is consistent with the assigned structure. v 0 H H 0 § lees | CH Le )

Br, : 20% 2 5C0C Br - OH Gil

Br ~~ c Br

Bh joe 5 . - oo : - 36 -

EXALPLE 29

Methanol (54.1 g, 1.5 mole), tetrabromo-

Ce phthalic anhydride (695.6 z, 1.6 moles), and i potassium acetate, 2.73 g wviere refluxed for 4 hours with 500 nl of toluene. After cooling the reszction mixture to room temperature, Dro- pvlene oxide (87.12 g, 1.3 moles) were added . . o and the mixture reacted at 80°C. for 2.5 hours.

Product was obtained as a viscous licuid after ‘ 10 distilling out the toluene.

Caled. % Br, 57.7. found % Br, 57.2. #naly- tical data is consistent with assigned structure. .

Br i : Br CCCH 5 ; r . .

COCH,CCH . 3 I 2 3 : r OH

EXANPLE 30 ‘

This compound was prepared by the procedure similar to that descrived in Example 29 except : . that methoxycarvowax 350 was used in place of , - 37 - hl methanol and ethylene oxide in place of propy- lene oxide. . ‘Calcd. % Br, 37.5. Found -% Br, 37.2. Analy- . - tical data is consistent with assigned structure. 0

Br Il

Br COt—CH,CH,0) CH 4 3 H 1 ’ r joc EH

Br 0

EXAIIPLE 31 : This compound was prepared by the procedure in Excnnle 29 except that 2-methoxyethanol is used in place of methanol. Product is viscous liquid.

Calcd. % Br, 53.6. found % Br, 52.0. &naly- tical data is consistent with the assizned structure.

Br 0 H l

Br COCH CH

OH

Br ’ a1

RE

CF

- 38 -

EXANELE 32 : This compound was prepared by the procedure - outline 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. Analy- tical data is consistent with the assigned structure.

Br 3

B

Q POC Cos ’ B ~ Fiat .CH vr o(<c I I i ( H CH, 0) CH,

Br 0 * ~1C EXAMPLE 33 . } This compound was prepared ty the procedure outlined in Examnle 29 except that 2-ethylhexa- nol-1l was used in place of methanol. Product is a viscous liguid. ’ Caled. # Br, 50.0. Found % 52.7. Analytical date is cosnsistent with the assigned structure.

Bp 0 } x : Br A__COCH, CCH,

Z| Pb)

CH

Br Il 5 Hq 7 i! oY; 2 5

: EXALFLE 34

This compound was prepared by the procedure a described in Example 29 except that stearyl alco- . nol was used in place of methanol. Product is a viscous liquid.

Caled. % Br, 41.0. Found % Br, 43.0. Analy- tic2l data is consistent with the aszigned structure. 0 H 5 Br I r COCH.,CCH 2) 3

Br CO(CH,), CH

I 2)17 3 . Br 0 : EYALPLE 35 - 10 This compound was prepared BY the procedure described in Example 29 except that 2,3-dibromo- propanol-l was used in place of methanol. Product is a viscous liguid.

Calcd. % Br, 64.8. Found % Br, 61.9. Analy- tical data is consistent with the ascigned structure.

Br 0 i

Br docu cox : 213 - OH : er ~~ GOCH,GHCH, Br = . r . - LQ =~

EXAMLFLE 36

This compound was prepared by the procedure pe outlined in Example 29 except that epichloro- hydrin was used in place of propylene oxide.

Calcd. % Br, 35.7. Found % 35.4. Analy- tical data is consistent with the assizned structure. o H 2 {r Loon ! H =n o Y Cot ~

CH Gum CL : OH - Br CO(CH,CH.0), CH

Br I 27277773

ELAMPLE 37

To a solution of nethoxzycarbowax 350 (300.0 z, 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. Petrabromophthalic anhydride was then added (4£2.2 g, 0.89 mole) along with an additional 50 ml of toluene. The reaction mivture was refluxed for 2 hours and after cool- ing to room temperature, epichlorchydrin (106.94 : Th %

g, 1.16 moles) was added. The mixture was reflused for 20 hours. After the solvent and excess epichlorohydrin were distilled, a vis- a cous dark product was obtained. oo oo

Calcd. % Br, 37.2. Found % Br, LO. Lb,

Analytical data is consistent with assigned structure.

Br ©

I i.

Br CHIT 0

SOUT

, Br 0 . ) EXAMPLE 38 oo

Methoxycarvowax 350 and toluene viere refluxed for 1 hour in order to distill out a small anount of water. Tetrabromophthalic anhydride (1:1 mole ratio with methoxycar- Lo bowax 350) and sodium acetate were added and the niiture feflhi®ed for 17 hours. After coocl- ing to room temperature, an excess of diazome- thane (prepared from the decomposition of H-methyl-

F-nitroso-ptoluene’ sulfonamide by sodium hydroxide)

CL - Lo - :

in ethyl ether was added and the mi:iture allowed to stend overnight. The excess diazomethane was decomposed by adding acetic acid and the solvent = removed by distillation. Product is viscous liquid. = : Calcd. % Br, 39.2. Found % 3r, 37.4. Analy- tical data is consistent with the assigned structure. : Br © 5 2 or - 3

Br

OCR C0008

Br - EXALNPLE 39

Di(2-ethylhexyl) tetrabromophthalate was : nrepared by the procedure dezcrived by Spatz et.al (I & EC Product Research and Development), Vol. 8,

To. 4,395 (1969). 0

Br

B VOC

B Z"3

COCH,CHC, H

So CoH :

E{ALFLS 40 .

Poly(ethylene glycol 600) 885.4 g (1.40 - moles), tetrabromophthalic anhydride, 1298.4 gz (2.80 moles), potassium acetate, 1.35 g, and 3 toluene (1000 g) were charged into a one-gallon zlass-lined reactor and heated to 120° C. After

L hcurs at this temperature, ethylene oxide, 216,58 z (5,60 moles) was pumped into the reac- “tor in 3/4 hour while maintaining the temperature

So 10 at 120°C. After one hour longer of heating, the © mixture was cooled +o room temperature, the ecess ethylene oxide was then vented, and the preduct collected. After stripping off the toluene, 2250 g of the product was isolated in 997% yield as a viscous liquid.

Caled. % Br, 39.2. Found % Br, 38.8. Analy- : tical data is consistent with the assigned structure. 0 9

Boer c on TOCHOHC br, ON 2% TOF, jo 25 : - Bi -

ELALFLE 41

To the product of Example 3, b53.8 g - (0.27 mole), acetic anhydride, 83.4% g (0.82 mole), potassium acetate, ‘1.0 g, and toluene, LGO ml, were refluxed for 8 hours. After cooling to room tem=- perature, the reaction mixture was transferred to a separatory funnel and extracted first with 100 ml of a 165 potassium bicarbonate soluticn and then with 100 ml of water. After distilling . : 10 off the solvent, 335.0 g (647 yield) of product was obtained as a viscous liquid. j Calcd. % Br, 356.8. Found % 3r, 32.9. Analy- tical data is consistent with the assigned structure. : 0 HO OH I

Soc LA. CH } Los n

Br QI 2Ly 3 3 bi 2 JO 4 =a 3 Br), i gC pa]

SE | ° : EXAMPLE 42

Tetrabromophthalic anhydride, 231.9 g (0.50 mole), 2-ethylhexanol, 130.2 g (1.0 mole),

and potassium acetate, 0.24 £ 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 80°C, and kept it at this temperature for 2 hours.

Cooled mixture to 60°C. and added tri- ethylamine, 14.2 g (0.1% mole). Reheated mix- ture to 20°C, and added methyl iodide, 113.6 g oo (0.8 mole) in 20 minutes.

Cooled mixture to room temperature and filtered it in order to remove by-product potassium sodide.

The filtrate was distilled . to remove toluene and 290 Z of crude product was collected zs a pale yellow liquid.

Extreac- ted 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 : - LE -

product was obtained in 67% yield as a pale yellow ligmid.

Calcd. % Br, 52.6. Found % Br, 52.2. #naly- - tical data is consistent with the assigned structure. {oc > 5, OL ay cocH $C, ig

Co | CoH : EXAMPLE 43 : Tetrabromophthalic anhydride, 231.9 g (0.5 mole), 2 -(2-methoxyethoxy)-ethanol, 360.5 g (3.0 moles), stannous oxalate; 2.32 gz, and xylene, 2CC ml, were refluxed (temp. 160°C.) for 18 hours during which time, theory water was collected. The xylene and excess 2-(2-me- thoxyethoxy)-ethanol were distilled under reduced vressure to give 232 3 of crude product as a wet white solid. Redissolved 256 g of this material oo in toluene (1000 ml) and extracted it with 3 times -L7 -

200 ml of 2 7.5/5 potassium bicarbonate solution followed by one extraction with 200 ml of water. :

Dried the organic phase with anhydrous magne- - sium sulfate overnight. After removing the magnesium sulfate by filtration, toluene was removed by distillation to give 45 g of a yellow : liquid product. Overall y®ld is 17%.

Calcd, % br, L5.6. Found % Br, 45.7.

Argl:otical data is consistent with the assigned structure. : : Loon CH oo ; 5 OCH, CH, OCH

Ti

CCCH_C i 5 H, OCH, CH, OCH , 0 :

EXAMPLE 44 oo J : § oo

Co coc

H,CH,O0CH,CH,0C Hy

Br),

COCH

Bh CH, OCH CH, CCH,

EXLAVEPLE 45

This compound was prepared by the procedure ot outlined in Example 1 except that docosyl alcohol (vehenyl alcohol) was used in place of poly(ethy- ene glycol 600) and propylene oxide in place of ethylene oxide. Product 1s a viscous liquid.

Calcd. % Br, 37.7. Found % Br, 356.5.

Anal:rtical data 1s consistent with the assigned structure. ‘ i H or

Bry; 3 [en

EXAMPLE 46 : This compound was prepared by the procedure outlined in Example 1 except that tricontyl alco- hol was used in place poly(ethylene glycol 600) and propylene oxide in place of ethylene oxide.

Product is a viscous liquid.

Choo

0 H no

COCH,,COH ~

Br, Cd,

AC

0 or EXAMPLE 47 ‘This compound was prepared by the procedure out- . SO lined in Example 4 except that methoxycarbowax 550 was used in place of 2-(2-methoxyethoxy)-ethanol. 0

I

CO(CH,CH,0),,CH4 | Th or cree 0 } EXAMPLES 48-52

In the following examples, the flame retardancy of the compounds of this invention are demomstrated,

The compositions were prepared by mixing together the the flame retardants, antimony oxide, and SMA on a roller until the compounds were blended throughly. The : ’ compounds were pelletized at 95°-245°C. and then injec- tion molded into test specimens at 190°-204°C. The

UL-94 vertical burn test vas run and compared to a control consisting of SMA itself. Melt flow of the various materials were determined according to ASTM

D=1238.

SMA- Styrene-Maleic Anhydride Polymer

DBDPO- Decabromodiphenyl Oxide (83% Bromine)

DOTBP- Dioctyl Tetrabromophthalate (45% Bromine)

AO~ Antimony Oxide

TABLE 1

Example Noe. 58 Lg 50 51 52 sale) 100.0 82.7 81.5 80.4 76.8 . DBDPO - 13,8 12.4. 11.0 6.9

DOTBP : - - 2.6 5.1 1208

Antimony Oxide - 3.5 3e5 3e5 3e5 . 15 UL .94 Rating : @ 0.0125" Failed V-0 V-0 V=0 V=0 : @ 0.63" _ Failed V-0 V-0 V-0 V=0

Melt Flow - 1.16 1.84 2,08 3.32 6.76 (g/10 min.) 2 (Bares Chemicals Dylark R 250

The above clearly demonstrates the flame retardancy of the composition of this invention relative to the : contnle

These composition have at least equal flame retardancy to a common commercial conventional flame retardant, «+ DBDPO.

Example 49-52 are all run at equal bromine levels.

Partial replacement of DBDPO with the compositions

B of this invention results in enhanced flow characte- ristkcs as shown by the improved melt flow properties measured according to ASTM D=1238. ~~

EXAMPLES 53=56

The following tests were performed on the various materials according to the appropriate ASTM method. } 1. Impact Strength-ASTM D-256 5, Tensile Strength~ASTM D=638 : 3. Heat Deflection Temperature (HDT)=-ASTM

D-648 : 4, Melt Flow-ASTM D-1238 osm s ‘ .

TABLE II

} Example No. — 53 54 55 56

SMAC®) 100.0 82.7 81.5 80.4

DBDPO - 13.8 | 12.b 11.0 DOTBP - - 2.6 5.1

Antimony Oxide - 3e5 3e5 365

Co LoI 18.7 27.6 28.6 2301

UL/94 Rating _ } @0.0125" ’ Failed V.0 ¥.0 V.0 @ 0.063" Failed V.0 V.0 ¥.0

Notched Izod 2.3 1.02 1.56 1.96 (1bs/inch)

Tensils Strength + 3950 3880 3830 3700 } (Yield) (PSI) : % Elongation 8.7 Tek 77 831

HDT (°F.) 197 197 191 192

Melt Flow 1.16 1.84 2.08 3.32 - {g/10min) | | _ ‘8/ Arco Chemicals Dylark @ 230

As can be seen from the data above, compositions : containing the flame retarddints of this invention greatly improve the impact strenght relative to the commercial flame retardant, DBDPO, while maintaining both tensile strenght and percent elongation properties. Also the em heat distortion temperature (HDT) of the compositions of this invention are comparable to both the control and to DBDPO.

The data above clearly demonstrates the improved processability of the compositions containing the materials of this invention. © - 54 a

Claims

: I claim: } Te A uniform flame rejardant composition comprising (i) a resin consisting essentially of styrene-~ oo — maleic anhydride having the following general

5 . formula: : H H H H H H I I c—C——C¢—¢C CT out bo | H No” . n m . wherein m is a number from 1 to about 100 and n is a number from zero to about 100; and (ii) a flame retarding effective amount of a tetrahalophthalate ester flame retardant processing aid of the formula: Ao A I COR A CX(CHCH_0) rt 2""p A rR q i wherein (a) R is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 9 carbons, hydroxyalkyl of 2 to 20 carbons, : 5 polyhydroxyalkyl of 3 to 10 carbons, and i —CHCH 03=R 2b oo where RC is an alkyl of substituted alkyl of 1 to 18 carbons, and b is 1 to 50; ‘ 10 (v) R is selected from the group consisting of = hydrogen, an alkyl or substituted alkyl of 1 : to 9 carbons, alkenyl or substituted alkenyl ~~ of 2 to 22 carbons, o -C - RY where R/ is an alkyl of 1 to 18 carbons; a polyhydroxyalkyl of 3 to 12 c,rbonsj c (COOH), to 3 :

I . 0 1l or 2 0 h O00RH =H { 2’ ROOC AA - ROOC oo rr CH Lim Cc " : } 0 270" I (all isomers); ll o -C - (4) 4 ROC : {Or (all isomers); 0 To * ! Ror RJR" RR" 5 _6 5 ~-CHCHNR”R -(CHCH) ,NR ; and - (CHCH) ;N; : with the proviso that the valence of R] is equal to qj (e) R% is independently selected from the group consisting - of H and CHz3 3 Jb 05 6 . (d) Ry R, R”y and R™ are independantly selected from the group consisting of H and an alkyl of 1 to 18 carbons; (e) p is an integer of O to 50; - 57 = s “

(f) q is an integer of 1 to ; - (g) X is selected from the group consisting of O or NH; (h) A is selected from the group consisting of Clor Br; and © (i) provided further that when p is zero and X is oxygen that R and R' are other than a neopentyl me group. oo 2. The composition of claim 1 wherein p is zero, and q is hE one and & is oxygen. . 10 3. The composition of claim 2 wherein R and R’ are alkyl groups and A is Br, : ] Lb, The composition of claim 3, di-2-ethylhexyl tetra- bromophthalate. ‘ : 5. The composition of claim 1 wherein the weight ratio = of (i) to (ii) is within the range of about 100:1 to - about 2:1.

6. The composition of claim 1 wherein said tetrahalophthalate ester of (ii) R is an alkyl or substituted alkyl of 1 to 9 carbons, A is Br, X is oxygen, p is © to 20, and q is 1 to 6.

7. The composition of claim 6 wherein RB is selected from the group consisting of .

1 to i ) A : “Be . Be Be Br } i OH B 0 - Be bus eo . ir : Be © Be ©. Br J, Br - Cen Br } Br.

B Br . O e-= —OCH;CHiOH Br OCH; CHO Br CH) i } : Br Br Br 3 Be : Br OH . i Hh 1CHCH $ OCH CHCH;Br Bry Br CHj Br ’ : Be Be . Br . CH CH= CHCH $ OCH;CH= CH; ’ CH;j : : - Br : ’ Be Br ed Ro fr g Cil;mCCOCH;;CHO O OCH; ;CH;0CCH= CH; i CH) ] Br Be i} Be Op Be 0 oO - i > Bry wen CH N B t 0 ¢ / ICH \ 4 . [ C i 1 0 0 0 0 Br, ’ & : : B : crc ICH ) - J \, . , - ‘ Tee 4 Lo. i . . . t : Bre . Bey : ~ } o 0 G+ymi-D - } . ) ot ; RIGINAL > . - 60 = Lo

0 Br docs cit oom cro L CoH Lo SOCH.

CHCH ES | 2 3 OH \y Tg Br Br . Br <o.

Br Br 0 Br J ore ox —CH, Br

Br [

om COR'''OH Br I Br where R" and R''' are alkylene or substituted alkyléne

- 61 [ N

10. A method for preparing a flaae retar- Co dant composition having enhanced processability properties which comprises incorporating a flame pe retarding effective amount of the tetrahalophtha- jate ester of claim 1 (ii) in a resin consisting essentially of styrene-maleic anhydride. :

11. The method of claim 10 wherein the weight ratio of styrene-maleic anhydride resin to the tetrahalophthalate ester is within the range of 100:1 to about 2:1. © 12. The method of claim 10 wherein in said tetrahalophthalate ester of claim 1(ii) R : is an alkyl or substituted alkyl of 1 to 9 carbons, A is Br, £ is oxygen, DP is 0 to 20, and g is 1 to 6.

13. The method of clain 10 wherein in said tetranalopnthalate ester of clain 1(ii) p ig zero, and gq is one and £ 1s oxygen.

14. The.nmethod of claim 10 wherein in said tetrahalophthalate ester of claim 1 (ii) R and rl are alkyl groups and A is Br.

15. The method of claim 10 wherein said ester is di-2-ethylhexyltetrabromophthalate.

16. The method of claim 12 wherein R - is selected from the group consisting of CH 3 H CHy ~ ’ lo - y = ’ ~CH,CH-CH, CH, Cols, CHa Cu 9 3 ! =O - : gtiy 7s and “Tu; Cole .

-C.H,, -C Ry is Cig, OZ.’ Cyfigs Hy Coflys glly3 Coins “CHa: or Cote

0 . (i ~ gm, oo 13 0 HO-CHCH, CC Br; and q = 1. : Br Br

17. The method of claim 10 wherein the resin includes other wrominated or chlorinated flame retardants or mixtures thereof. a 18.“ The method of claim 17 wherein said brominated flame retardants are selected from the group consisting essentially of Br Br

CH . | 2 H C OH - CH } Br 3 or or Br B Br 0 ~- 0 Br Br Br ar n

Br Br CH 3 1 HOCH,,CH,0 c OCH,CH., 0H CH Br 3 Br br Br B Br Br : Br CH Br { 3 CF AC, © OCH HCH Br Br Br By Cit, Br Br OH Or -.

a or TT - - ST . \ , fH } . CH) Co To. ’ Co . Br ‘ . © Be - Br : : CCOCH,CH O ¢ OCH;CH,0CCH™=CH; : CHy" ".CHy Lo Br Be : : a= ETE : Co

- . } Br, © Loo nN T : ol ) i : B wo ‘fo Te we : B CL Best Aa dl rs : Brg © \ a) . Bry NCH;CH;N Brs . / \ a c C . I i . ’ 0 o } o o . i -- i it Be, [o] C Br . \ / . NCH;CH;N } - / \ : Be” 5 i Br . , Bey . Bey . o o . Co tyes no . : 2 CO o Ce

-. : COCH;CH;0CH;CH;0H CH; . Be i . ] . COCHCHCH; 0 OH : Bry . : Be Br . . o

- . - i - COR"OH C-

- . wt OL S Be Br COR"OH Br Br ’ . ‘ 0 n . i C—~CH;Br _ SE 6 | Io : . : .. . H - 3 . . . Co : Be LL TTT : Br } where R” and R" are alkylene or substituted alkylete, ¢s : and ~ « 8 8 9 BE 266 -