PT88909B - FIRE RETARDING RESIN PREPARATION PROCESS CONTAINING, AS FLAME RETARDING AGENT, TETRA-HALOFTALATE ESTERS - Google Patents

Abstract

Tetrahalophthalate ester flame retardent processing aid (11) for thermoplastic resin (1) has formula (A) where R=H, opt. substd. 1-30C alkyl, 2-20C hydroxyalkyl, 3-10C polyhydroxyalkyl gp. or HCH2O)b-R8 where R8=opt. substd. 1-18C alkyl and b=1-50; R1=H opt. substd. 1-30C alkyl, opt. substd. 2-22C alkenyl gp. C(O)R7 where R7=1-18C alkyl gp. 3-12C polyhydroxyalkyl gp. GPs (B)-(D), etc. where 1 or 2 1 to 3 R2=H or Me; p=0-50; q=1-6; X=O or NH; A=Cl or Br. Resin compsns. opt. contain an additional Br- or CL- contg. flame retardant (111).

Description

The present invention relates to a process for the manufacture of a flame retardant resin with improved flow characteristics, comprising the mixture (I) of a resin which is selected from:

(A) acrylonitrile-butadiene-styrene resin;

(B) polystyrene resin;

(C) polycarbonate resin;

(D) poly (butylene terephthalate) resin;

(E) styrene-maleic anhydride copolymer resin; and (II) an effective flame retardant amount of at least one flame retardant tetrahalophthalate ester as an auxiliary agent.

Mr -

408 IR 50171 (08MAG48)

-2 DESCRIPTIVE MEMORY

Background of the Invention

Invention Field

This invention describes processes for preparing flame retardant compositions, containing at least one tetra-ha loftalate ester and a certain resin that is chosen from:

(A) acrylonitrile-butadiene-styrene (ABS) terpolymer resins;

(B) polystyrene resins;

(C) polycarbonate resins;

(D) poly (butylene terephthalate) resins; and (E) styrene-maleic anhydride (SMA) copolymer resins.

In addition, the composition of the invention may contain one or more brominated and / or chlorinated compounds present in an effective amount to impart additional flame retardancy to the resin.

State of art

ABS resins are already known in the art as a class of thermoplastics that are characterized by excellent properties such as chemical resistance, resistance to overuse, resistance to stains, etc. A discussion of the typical properties of ABS resins is described in pages 1-64, 1-66 and 1-68 of Charles A. Harper's Handbook of Plastics and Elastomers, published by the McGraw-Hill Book Company in 1975. These pages are cited for reference only. ABS resins are terpolymers that are generally derived from acrylonitrile, styrene and butadiene. Most are true graft polymers in which acrylonitrile and styrene are grafted onto a polybutadiene or rubber phase and can then be dispersed in a rigid styrene-acrylonitrile (SAN) matrix. Other ABS resins are mechanical poly-mixtures of elastomeric and rigid copolymers, e.g. eg, butadiene-acrylonitrile rubber and SAN. (See G. C. Hawkins, .η z

- 3 well

886,

408

IR 30171 (08MAG48)

Condensed Chemical Dictionary, 103. edition, pg. 3, 1981, by US Patent Nos. 4 107 232, 4 206 290, 4 487 4 567 218 and 4 579 906, all of which are cited here for reference only. Hau / kins, supra, defines ABS resin as: Any group of hard, rigid thermoplastics, deriving its name from three letters of the monomers that produce them: Acrylonitrile-Butadiene-Styrene. More recently, ABS resins are true graft polymers, consisting of an elastomeric rubber or polybutadiene phase, grafted with styrene and acrylonitrile monomers for compatibility, dispersed in a rigid tyrene acrylonitrile (SAN) matrix. Also on the market are mechanical mixtures of elastomeric and rigid copolymers, butadiene-acrylonitrile rubber and SAN, which have historically been the first ABS resins.

of espolip. ex.

By varying the composition of the polymer by changing the proportions of the three monomers and using other co-monomers and additives, ABS resins are obtained with a wide spectrum of properties.

they can, independently of each other, vary between x, y and z between about 10 and about 1500 (see US patent 4 567 218, whose teachings are cited here for reference only). It is understood that the monomeric components mentioned above can be replaced by analogs, in whole or in part, and the resin remains within the definition of ABS. For example, -methylstyrene can replace styrene and meta-acrylonitrile can replace acrylonitrile. You can find the description of compositions of various ABS resins and the way American N9s paints are prepared

581 403, whose teachings are cited here for reference only, in pages 505 349, 2 550 139, 2 698 313, 2 713 566, 820 773, 2 908 661, 4 107 232, 4 173 561, 4 200 702, 4 206 290, 289 687, 4 355 126, 4 379 440, 4 456 721, 4 487 886 and

-468 408

IR 30171 (08MAG48) co.

A8S resins are useful in many commercial applications such as automobiles, office machines, telephones, etc., where high impact resistance is required, as well as in the production of molded articles.

Polystyrene resins find widespread use in the manufacture of packaging materials, refrigerator doors, air conditioner boxes, machine exteriors, electrical equipment, toys, watches, TV, radio boxes, thermal insulation, ice buckets, containers, construction of furniture, instruments, tableware, etc. The preparation and description of polystyrene and expandable polystyrene are well known in the art. They are handled by G. Hawley, Condensed Chemical and Cyclopedia, 103. ed. , pp 838 and 976 (1981); Kirk-Othmer Eri cyclopedia of Chemical Technology, 22, ed., 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 US 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 cited here for reference only.

For many applications where styrenic polymers are used, there is a need to add flame retardants as these materials are flammable. Some of the applications that require styrenic flame retardants are radio and TU boxes, toys, electrical equipment, furniture manufacture, etc. (See, eg, US Patents Nos. 4,341,990 _and 4,549,956, the teachings of which are incorporated herein by reference only).

Polycarbonate resins are known in the art as a class of thermoplastics that are characterized by excellent properties, e.g. and. electrical, dimensional stability, high impact resistance, hardness and flexibility. They are generally prepared by reacting a dihydric phenol with a carbonate ester, phosgene or a bis-chloroformate ester. American patents No. 9. 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 -

6Θ 409 IR 30171 (09MAG49)

-5 classes of polycarbonate resins, their teachings being cited here for reference only.

Due to their many excellent properties, polycarbonate resins are useful in many commercial applications such as construction thermoplastics and in the manufacture of molded articles.

Poly (butylene terephthalate) resins (PBT) are known in the art as a class of thermoplastics characterized by excellent properties such as thermal stability, good resistance to breakage, low friction and wear, chemical resistance, etc. They are generally prepared by polycondensation of terephthalic acid or a terephthalic acid diester, eat dimethyl terephthalate (DMT) with 1,4-butanediol. American patents No. 9. 2 645 319, 3 047 539, 3 953 394 and 4 024 102, describe in detail the preparation of PBT, its teachings being cited here for reference only.

The styrene-maleic anhydride (SMA) copolymer resins find an extensive application in the manufacture of molded articles and foam products. They are generally prepared by copolymerizing styrene and maleic anhydride in suitable proportions and conditions. The preparation and description of SMA copolymers are described in U.S. Patent Nos. 2,769 Θ04, 2 971 939, 3 336 267 and 3 966 843, the teachings of which are cited here for reference only.

SMA polymers burn quickly and are not generally used in applications that require flame retardant polymers, such as radio and television boxes, tables, chairs, boxes of various objects and the like (see US patent 4 151 218 cited here for reference only) ).

use of brominated and / or chlorinated compounds on their own or in combination with other materials, e.g. eg, organic phosphates, boron compounds, etc., as flame retardants for ABS resin compositions, are already well known in the art and are exemplified by US patents NSs. 4 051 101, 4 051 105, 4 096 206, 4 107 122, 4 107 232, 4 173 561, 4 200 702, 4 289 6Θ7, 4 579 906, 4 355 126.4 378 440, 4 567 218, 4 581 403, 4,581,409 and 4,600,747, the aforementioned patents being incorporated herein by reference.

-668 408

IR 30171 (08MAG48)

Tetrahalophthalate esters have been used as flameproof materials. For example, US patent 4,098,704 describes the use of these materials as textile finishing agents. American patents No. 9. 4,298,517 and 4,397,977 describe these compounds as flame retardants for halogenated resins. However, there was no news of these compounds as retardants or processing aids for ABS resins.

Summary of the Invention

This invention encompasses the preparation of flame retardant plastic compositions comprising the following mixed ingredients.

(I) a resin chosen from (A) Acrylonitrile-Butadiene-Styrene (ABS) resins;

(0) Polystyrene resins;

(c) polycarbonate resins;

(D) poly (butylene terephthalate) resins and (0) styrene-maleic anhydride copolymer (S MA) resins.

(II) an effective, flame retardant amount, incorporated in the resin of (i), of a flame retardant processing aid, tetrahalophthalate ester, of the formula:

Where:

(a) the ring can have all possible isomeric arrangements;

(b) R is chosen from the group consisting of hydrogen, an alkyl or substituted alkyl, from 1 to 30 oar

bonos, hydroxyalkyl of 2 to 20 carbons, polyhydroxyalkyl of 3 to 10 carbons, and

408

IR 30171 (D8MAG48)

4- CHCH ₂ C9- _b R where R is an alkyl or substituted alkyl of 1 to 18 carbons and b is 1 to 50j (c) r! is chosen from the group consisting of hydrogen, a bonos alkyl, bonos alkenyl, or substituted alkyl from 1 to 30 or substituted alkenyl from 2 to 22 ca_r

-C-R where 3

R is an alkyl of a 12 carbons, carbons, a polyhydroxyalkyl

j

(all

CH-CH ₂ ;

(all isomers);

-CHCHNR ⁵ R ⁶ ;

R ³ R ⁴ r ³ r ⁴

II ₅ II - (CHCH) ₂ NR; and - (CHCHj ^ N;

with the proviso that the valence of R ^ is equal to q;

(d) R are chosen, independent of each other, from the class consisting of H and CH ^ -;

(e) R · ⁵ , r \ R ^ θ r ⁶ are chosen, independent of each other, in the class consisting of H and an alkyl of 1 to 18 carbons;

Λ.

408

IR 30171 (08MAG48)

(r) P is a number all in 0 to 50; (g) q is a number all in 1 to 6; (H) X is chosen in between 0 or NH; and (i) THE is chosen in between Cl or B r.

Preferably, the weight ratio between (i) and (II) is in the range of about 100: 1 to about 2: 1.

(III) Flame retardants, brominated and / or chlorinated, other than (I), which may optionally be present.

Detailed Description of the Invention

The aforementioned compositions can also contain other brominated, brominated and / or chlorinated flame retardants. Other favorite flame brominated donors are chosen from the group consisting of:

Preferred resins (A) In the aforementioned ABS resins, some or all of the acrylic and styrenic numbers that make up the resin include meta-acrylonitrile or ° <-methyl tyrene, or meta-acrylonitrile and

X-methylethylene. The preferred ABS resin is made up of monomeric deions of an aromatic vinyl monomer, a vinyl-nitrile monomer and a butadiene monomer, and the number of units of each monomer is, independently of each other, in the range of about 10 to about 1500.

(B) Polystyrene resin is chosen from one of the following:

(a) a styrene homopolymer with the following repeat unit ϊ Ϊ

--c -------------- _c -

where n is in the range of more than 1 to about 3,000;

408

IR 30171 (08MAG43)

(b) a styrene homopolymer as in (a), modified with rubber, in which the rubber is dispersed as discrete particles in a matrix of said homopolymer and the weight ratio between rubber and homopolymer is in the range of about 2 : 98 at about 25:75; or (c) a copolymer of butadiene and styrene, in which the weight ratio between butadiene and styrene is in the range of about 2:98 to about 25:75; or (d) mixtures of (a) and (b), with polybutadiene and / or a styrene-butadiene copolymer being preferred.

In a preferred arrangement of the invention, the homopolymer of (S) (a), referred to above, is in the form of polystyrene foam. Preferably, the foam is prepared by polymerizing the homopolymer repeat unit in the presence of a liquid or gaseous gas-producing agent, and said agent has a boiling point that is lower than the softening point of the polystyrene and does not dissolve in said polystyrene. The preferred gas-forming agents are chosen from the group consisting 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 structural repeating units, of the formula:

D - Z -

□ n a is greater than 1 and Z is a divalent aromatic radical of a dihydric phenol;

(D) The poly (butylene terephthalate) resins that can be used in the present invention, have the following structural repeating unit, of formula:

408

IR 30171 (08MAG48)

where a> 1.

(E) SMA resins that can be used in the present invention usually have the following general structural formula:

where m is from 1 to 100 and n from 0 to 100. The weight ratio of (styrene): (maleic anhydride) can be 1-19: 1.

It is preferred that in the aforementioned tetrahalophthalate ester (li), R is an alkyl or substituted alkyl of 1 to 10 carbohydrates, A is Br, X is oxygen, p is 0 to 20 (with great preference 0) eq is 1 to 6 (most preferably 1). Most preferably R is

CH,

I ³ -CH ₂ CH-OH, -CHj, -C ₂ H ₅ , -CjH ₇ , -C ₄ H ₉ ; -C ^ H,

- ^CH 6 ^H 13 '- ^C S ^H 17 - ^CH ₂ j ^HC z, ^H 9' - ^C 10 ^H 21

C ₂ H ₅ ; R ¹ is CH ₃ , C ₂ H ₅ , C ^ H ,, H, ' ^C 3 ^H 7' -C ₆ H ₁₃ , -C _to H ₁₇ , -ch ₂ -çhc _Zi h ₉ , -C _1o H _{21 <}

C ^ H ^, ^0LJ

408

IR 30171 (0BMAG4B)

The invention also comprises a process for preparing a flame retardant plastic composition, with improved processing properties, which comprises incorporating an effective flame retardant amount of one or more of the above-mentioned tetrahalophthalate esters in one or more of the resins here. mentioned.

This invention also comprises a process of improving flame retardancy, processability and physical properties, such as impact resistance, of the specified resins, by incorporating tetrahalophthalate compounds into the resins, as described above, alone or in combination with others retaj? flame, brominated and / or chlorinated donors.

The resins mentioned are sold based on their impact resistance properties. Unfortunately, when these materials have to undergo flame retardant treatment with conventional donors in order to comply with legal requirements, there is a significant loss of impact resistance.

Representative tetrahalophthalate compounds, useful for the practice of this invention, are the following (where A is Br or Cl):

-1268 408

IR 30171 (08MAG48)

COOCH „CH-OH ² I

CH ₃

COOH

COO (CH ₂ CH ₂ O) ₇ CH ₃

C00CH ₂ (CH ₂ ) _1q CH ₃

C00 (CH ₂ CH ₂ 0) _7med CH ₃

C00H

68 408 IR 30171 (08MAG48) f? S? V is “ -13-

COOH

THE

C00 (CH ₂ CH ₂ 0) ₄ H

THE

THE

COOH

O

C00 (CH ₂ CH ₂ 0) ₅₀ H

COO (CH CH_0) _z H zz □

C0O (CH ₂ CH ₂ O) ₂₃ H

COOH

60 GO 408 30171 (08MAG48) - THE THE φ: THE COOH —CH „-CH _O C00 (ch ₂ -ch ₂ - ₀ ) ₀ _ _5C /? / ^N - ^(CH 2 ^ 2-17 ^CH 3 -ch ₂ -ch ₂ - 2

THE

THE

COOH

A f ^H 3

C00 (CH ₂ -CH ₂ 0) _g -CH ₂ -CH ^ '(CH ₃ ) ₂

THE

THE

THE

COOH

THE

C00 (CH ₂ CH ₂ 0) _g

THE

THE

THE

COOÍCHjCHjOJ ^ -CHj-ÍÇhJ ^ -CHO

OH

-f (CHOH), I 4 “ί

0

Ç00 (CH ₂ CH ₂ 0) _g CH CH N (CH)

THE

COOH ch ₃ coo (ch-ch ₂ o) ₃ (ch ₂ ch ₂ o) _1q h

THE

THE

O

THE

COOH

3'2

68 TO 08 IR 30171 (08MAG48) -15-

THE

THE

COOH

C (jNH (CH ₂ -CH ₂ 0) ₀ _ _5Q

COOH

C0C (CH ₂ -CH ₂ 0)

/ ^N ^ ^CH 2 ^ 2-17 ^CH 3

-COOH

-CH ^ -CC -CH ₂

Preferred compounds are:

B r

C0C (CH ₂ CH ₂ 0) _7ned CH ₃

CH,

I 7

COOCH CH-OH

C0-NH (CH ₂ CH ₂ 0) _7med CH ₃ θ Γ r

408

IR 30171 (08MAG48)

Br C ₂ H ₅

In the aforementioned formulas R is

-ch ₂ -ch-oh or -CH-CH ₂ -OH.

The brominated and / or chlorinated compounds that can be used in combination with the tetrahalophthalates are any that are already well known in the art. Preferred examples of the following are regenerated flame retardants.

68 408 IR 30171 (08MAG48) -17-

CHCHCHO

I 2 | 2

Mr Br

ch ₃ Br z - C __ < 1 © > -0CH ₂ CHCH ₂ Br Br ch ₃ 'Br ^Br

OH

H Br CH, 1 - ⁵ Br CP = CC0CH ₂ CH ₂ 0 _ ^^ _ _ Ç__ 7 0 Br CH ₃ Br

II

DCH ₂ CH OCCH = CH

OH

408

IR 30171 (08MAG48)

0

Br

0

where R and R 'substituted are alkylene or alkylene

408

IR 30171 (08MAG48)

Br CH, I -> J3r ç ^h 2ç ^h ch2U5 \ 1 - C - (I ' \ _0CH „CHCH _o Br / ^z | ^{2 Br Br} Sr- ^ 1 ch ₃ 'Br ^0r

0H

OH

Br

-2068 408

IR 30171 (08MAG48)

In the practice of this invention, tetrahalophthalate (II) alone or additionally containing other brominated and / or chlorinated flame retardants (III), is added to the resin (i) in any convenient manner, e.g. ex. by mixing or extrusion, to obtain a uniform composition. If desired, synergistic flame retardants such as antimony oxide (Sb20-j) can be added. In addition to these, other additives such as thermal stabilizers, ultraviolet stabilizers, reinforcing agents, organic polymers can also be optionally included. , mold release agents, gas producing agents, dyes and the like. Another advantage of tetrahalophthals alone or in combination with other brominated and / or chlorinated compounds used in this invention is their improved compatibility with resins.

Detailed Descriptions of Resins (A) The ABS resins that can be used in this invention are generally derived from acrylonitrile, styrene and butadiene and have the following general structure:

Η Η Η H I 1 1 1 ¹ rr ¹ 1 I ¹ rrrr L - u i i H CN X L, - ’Lz —- L * - * L 1 l Η H

butadiene

acrylonitrile styrene where x, y and z, independently of each other, can vary from about 10 to about 1500. Note that each of the previous components that make up ABS resins can be replaced in whole or in part by analogs.

The ratio of tetrahalophthalate or a mixture of tetrahalophthalate and one or more brominated and / or chlorinated compounds, to ABS resins, which will give flame retardancy, can 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 can vary from 100: 0 to about 1:99.

408

IR 30171 (08MAG48)

(θ) The styrenic resins that can be used in the present invention are as follows: polystyrene homopolymer, both in crystalline and non-crystalline form; polystyrene pearls ex. pansible and rubber modified polystyrene, which includes medium impact polystyrene, high impact polystyrene (HIP5) and super high impact polystyrene.

Styrene homopolymers, both crystalline and non-crystalline, have the following repeating unit

where n is greater than 1 and goes up to about 2000-3000. The non-crystalline forms are generally prepared by polymerizing styrene with a peroxide catalyst such as those described in US patent 4 281 067, while the isotactic regulating crystalline form uses Ziegler-Natta catalysts / see I. Pasquon in Encyclopedia of Polymer Science and Technology, Vol. 13, pag. 14, 19-20 and 31 (1970) J \

Expandable polystyrene beads are prepared by incorporating a volatile expanding or gas-producing agent during the polymerization of styrene. Expansive agents or gas producers that can be used to produce polystyrene foam are well known in the art. They can 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 4 618 468). Suitable expanding agents are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclohexane or halogenated hydrocarbons such as methyl chloride, dichlorodifluoromethane, 1,1,2-trifluoroethane, 1,1,2-trichloroethane and the like . Mixtures of those agents can also be used. Expansive agents are typically used in amounts of about 2 to 20% by weight.

The rubber-modified polystyrenes, which are suitable for

-2268 409

IR 30171 (08MAG48) dos, include medium, high and super-high impact polystyrenes. In these compositions, the rubber is dispersed in the polystyrene matrix in discrete particles (see US patent 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 (S8R). Some grafting of the styrene to the rubber occurs during polymerization. The rubber: polystyrene weight ratio can vary from about 2:98 to about 25:75. In general, moderate impact polystyrene will contain from about 2 to about 4% rubber, the high impact polystyrene will be greater than about 10% and will go up to about 25%.

See H. Keskkula in Encyclopedia of Polymer Science and Technology, Vol. 13, pp 396 and 400-404 (197θ) _ /.

(C) The polycarbonate resins that can be used in the present invention are typically dihydric phenols such as those described in U.S. Patent 3,334,154, cited here for reference. Are the following:

2.2- bis- (4-hydroxyphenyl) -propane; hydroquinone;

resorcinol;

2.2- bis- (4-hydroxyphenyl) -pentane;

2,4'-dihydroxydiphenylmethane; 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'-dihydroxydiphenylsulfone; 4,4'-dihydroxydiphenylether; and 4,4'-dihydroxy-2,5-dietoxidiphenylether.

EXAMPLE 1

To 1392 g (3.0 moles) of tetrabromophthalic anhydride was added 1.050 g (3.0 moles) of Methoxy-Carboiuax 350 in the presence of 22.0 g of sodium acetate. The mixture was heated at 90 ° C for 8 hours under a nitrogen atmosphere. The reaction mixture was filtered hot to remove sodium acetate. The analytical results were consistent with the assigned structure.

408

IR 30171 (D8MAG48)

EXAMPLE 2

To the compound of Example 1, 348.0 g (6.0 mole) of propylene oxide and 2.0 l of toluene were added. The mixture was heated to 60Θ-100Θ0. The solvent and residual propylene oxide were removed, obtaining the product in almost quantitative yield. The analytical results were consistent with the assigned structure:

C00 (CH ₂ CH ₂ 0) _{7n] and} CH ₃

EXAMPLE 3 (0.2 only, 80 mix at 1209-13050

A 92.8

add tetra-bromophthalic anhydride (g) (0.2 mole) of carbowax 400 at a time and heat for 2.5 hours. The desired product is the side with essentially quantitative yield, in the form of a clear, yellow, viscous liquid. Calculated molecular weight 864; obtained 865.% of 8r calculated 37.1; obtained 38.5. Resins consistent with the assigned structure:

analytical results

coo (ch ₂ ch ₂ ch ₂ o) ₉ h

408

IR 30171 (08MAG4B)

EXAMPLE 4

To 240 g (0.24 mole) of the compound of Example 3, 45.3 g (0.24 mole) of trimellitic anhydride are added and heated at 155 ° C under nitrogen for about 7 hours. The infrared spectrum indicated the end of the reaction by the substantial disappearance of the anhydride absorption band at 5.65. The product was isolated in essentially quantitative yield. Calculated analysis:% Br 30.3; molecular weight 1056; neutralization equivalent 352; obtained:% Br 29.4; molecular weight 1014; neutralization equivalent 351. The spectral results were consistent with the structure:

COOH

COOH

EXAMPLE 5

To 156.3 g (0.18 mole) of the compound of Example 3, 70.9 g (0.18 mole) of 2,3-dibromopropyl trimellitate are added. The mixture is heated to 130- 140 ° C for 6 hours, with stirring, obtaining the product as a brown opaque oil. The insulation provided the product with an essentially quantitative yield and the analysis was consistent with the structure:

(and isomers)

408

IR 30171 (08MAG48) -25- / . .-•"'THE'* EXAMPLES 6 to 11

The following preparations were carried out as in Example 1 using the reagents listed below.

Exem Anhydride Compound with hydroxy tetrabromo xyl

At. phthalic

Product Structure

1.0 mole H0CH ₂ CH ₂ 0CH ₂ CH ₂ 0H

1.0 mole

COOH coo (ch ₂ ch ₂ o) ₂ h

7 1.0 mole ho (ch ₂ ch ₂ o) ₄ h (Carbowax 200) 1.0 mo 1 e 8 1.0 mole ho (ch ₂ ch ₂ o) ₁₃ h (Carbowax 600) 1.0 mole 9 1.0 mole ho (ch ₂ ch ₂ o) ₂₃ h (Carbowax 1000) 1.0 mole 10 1.0 mole H0 (CH ₂ CH ₂ 0) ₄₅ H

(Poly-glycol

COOH

COOH

C00 (CH ₂ CH ₂ D) ₁₃ H med.

E-2000)

1.0 mole

Sr coo (ch ₂ ch ₂ o) ₄ h med.

COOH coo (ch ₂ ch ₂ o) ₃₃ h med.

COOH coo (ch ₂ ch ₂ o) ₄₅ h med.

408

IR 30171 (08MAG48)

-26EXEMPL05 6 to 11 - continued

Exem Compound Anhydride with droxyl tetrabromjo

N2. phthalic

2.0 mole HO (C 0) _g H (Carbowax 400)

1.0 mole

Product Structure

EXAMPLE 12

96.4 g (0.2 mole) of tetrabromophthalic acid are added in one go, 160 g (0.2 mole) of Carbou / ax 400 and 300 g of toluene containing 1.0 g of p-toluenesulfonic acid . The mixture was heated to reflux until 3.6 g (0.2 mole) of water was collected. Toluene was removed under reduced pressure to obtain a clear viscous liquid with essentially quantitative yield

C0O (CH ₂ CH ₂ O) _9med H

EXAMPLE 13

To 86.4 g (0.1 mole) of the compound of Example 3, 21.8 g (0.1 mole) of pyromelitic dihydride are added in one go and the mixture is heated to 120-130 ° C for 2.5 hours, obtaining the desired product. Water, 1.8 g (0.1 mole) is added to open (open) the remaining anhydride group; the analytical results were consistent with the assigned structure:

408

IR 30171 (0BMAG48)

EXAMPLE 14

To 86.4 g (0.1 mole) of the compound of Example 3, 10.9 g (0.05 mole) of pyromelitic di-anhydride are added all at once and the mixture is heated to 1209-13090 for 2.5 hours to obtain the desired product. The analytical results were consistent with the assigned structure:

COOH coo (ch ₂ ch ₂ o) med

COOH

(and isomers)

EXAMPLE 15

To 06.4 g (0.1 mole) of the compound of Example 3, 21.8 g (0.1 mole) of phthalic anhydride are added in one go and the mixture is heated to 120-130 ° C for 2 , 5 hours, obtaining the desired product. The analytical results are consistent with the assigned structure:

408

IR 30171 (08MAG48)

-28EXAMPLE 16

To 139.2 g (0.3 springs) of tetrabromophthalic anhydride are added, in one go, 122.9 g (0.1 moles) of polyoxy trimethylolpropane. molecular weight 1229 and the mixture is heated to 1209-130 ° C for 2.5 hours to obtain the desired product. The analytical results are consistent with the assigned structure:

COOH ^CD0 < ^CH 2 ^CH 2 ^{0) 9} month

-ch ₂

-CH \ -C H /

-ch ₂

EXAMPLE 17

To 139.2 g (0.3 mole) of anhydride at once, 156.8 g (0.1 mole) of tetrabromophthalic add polymethylmethylolpropane of molecular weight 1568 and the mixture is heated to 120-130 ° C for 2.5 hours, obtaining the desired product. The analytical results are consistent with the assigned structure:

COOH ch ₃ coo (ch ₂ ch ₂ o) ₉ - ^c x

-CH -C-C H /

-ch ₂

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 the presence of 7.0 g of sodium acetate. The mixture is heated at 90 ° C for 8 hours under a nitrogen atmosphere. The reaction mixture is filtered hot to remove sodium acetate, obtaining the expected product, with an almost quantitative yield. The analytical results are consistent with the assigned structure:

& T

3 _{: fc}

409

IR 30171 (08MAG48)

EXAMPLE 19

To 634.0 g (1.0 mole) of the composition of Example 18, 116 g (2.0 mole) of propylene oxide in 200 ml of toluene are added. Heat the reaction mixture at 60-100 ° C for 3-5 hours, then concentrate, yielding the product in almost quantitative yield. The analytical results are consistent with the assigned structure:

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 to 90 ° C for 8 hours under a nitrogen atmosphere. The reaction mixture is hot filtered to remove the sodium acetate, obtaining the expected product, in almost quantitative yield. The analytical results are consistent with the assigned structure:

4med ^

EXAMPLE 21

484.0 g (1.0 mole) of the product of Example 20 are added

408

IR 30171 (08MAG48)

116.0 g (2.0 mole) of propylene oxide in 200 ml of toluene. The reaction mixture is heated to 60-100 ° C for 3-5 hours and concentrated, yielding the product in almost quantitative yield. The analytical results are consistent with the assigned structure:

4med

EXAMPLE 22

To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 400.0 g (1.0 mole) of Carbou / ax 400 in the presence of 7.0 g of sodium acetate. The mixture is heated to 90 ° C for 8 hours in a nitrogen atmosphere. The reaction mixture is filtered hot to remove sodium acetate, obtaining the expected product in almost quantitative yield. The analytical results are consistent with the assigned structure:

EXAMPLE 23

To 46.4 g (0.1 mole) of tetrabromophthalic anhydride, 44.1 g (0.1 mole) of polyoxyethylated dimethylamine (CH-P ^ NICH ^ CH ^ OjgH— / dissolved in 100 ml of toluene The mixture is heated at 1009-110 ° C for 4-5 hours and concentrated, obtaining the desired product with essentially quantitative yield.The analytical results are consistent with the assigned structure:

6Θ 408

IR 30171 (08MAG48)

(ch ₃ ) ₂ n (-ch ₂ ch ₂ o-)

EXAMPLE 24

To 92.8 g (0.2 mole) of tetrabromophthalic anhydride is added 80 g (0.2 mole) of

CH, CH ₇ i ^} | ³ h ₂ n-ch-ch _{2 /} T (0CH ₂ -CH-_7 _5t6med NH ₂ (Jeffamine 0-400) and the mixture is heated to about 120 ° C. The final product is obtained in almost quantitative yield. analytical results are consistent with the assigned structure:

Br B r ú COOH CH, 1 CH, | ⁵ Br Br CONHCH-CH ₂ (° CH ₂ -CH-) _5i6med NH ₂ EXAMPLE 25 Submitted reflux polyethylene glycol 300, 204.5 g

(0.67 mole) (T = 11750) with 600 ml of toluene for 1.5 hours in order to remove a small amount of water present in the glycol. The mixture was cooled to about 100 ° C and tetrabromophthalic anhydride, 614.5 g (1.35 mole) and sodium acetate, 1.62 g, were added and the mixture was reheated to reflux and kept for 25 hours. The mixture was then cooled to about 5050, propylene oxide (156.4 g; 2.69 mole, 100% excess) was added and the mixture was heated to 100 ° C and maintained at this temperature for 2.5 hours. When the solution cooled to about 50 ° C, it was filtered through a bed of diatomaceous earth and decolorizing coal. The filtrate was distilled to remove the sun.

product, obtaining 904.1 g of product in the form of a liquid

408

IR 30171 (08MAG48)

-32% Br, calculated, 47.4. Br $ obtained, 46.5. The viscous ones.

assigned structure results:

analytical are consistent with the

EXAMPLE 26

This compound was prepared by the procedure described in Example 25, with the exception that polyethylene glycol 200 was used in place of polyethylene glycol 300. The product is a viscous liquid. % calculated from Br, 51.0. % obtained from Br, 49.3. The analytical results are consistent with the assigned structure:

EXAMPLE 27

This compound was prepared by the procedure described in Example 25 except that polyethylene glycol 600 was used in place of polyethylene glycol 300. The product is a viscous liquid. $ calc. of Br 39.5. % obtained from Br 39.3. The analytical results are consistent with the assigned structure:

408

IR 30171 (08MAG4B)

EXAMPLE 28

This compound was prepared by the procedure described in Example 25, with the exception that polyethylene glycol 400 was used in place of polyethylene glycol 300. The product is a viscous liquid. % calc. by Sr 44.2. % obtained from Br 44.0. The analytical results are consistent with the assigned structure.

EXAMPLE 29

Refluxed for 4 hours with 500 ml of toluene, a mixture of methanol (54.1 g, 1.5 mole), tetrabromophthalic anhydride (695.6 g, 1.6 mole) and potassium acetate 2 , 73 g. After cooling the reaction mixture to room temperature, propylene oxide (B7.12 g; 1.5 mole) was added and the mixture was reacted at 8090 ° C for 2.5 hours. The product was obtained as a viscous liquid, after toluene was distilled off. $ calc. of Br 57.7. $ obtained from Br 57.2. The analytical results are consistent with the assigned structure:

II

COCH-j

H

C0CH _or CCH, (I 2 | ³

0H

EXAMPLE 30

This compound was prepared by a procedure similar to that described in Example 29, except that methoxy-ca_r bowax 350 was used instead of methanol, and ethylene oxide in place of propylene oxide. % calc. of Br 37.8. % obtained from Br 37.2. The re68 408

IR 30171 (08MAG48)

are consistent with the assigned structure:

analytical results

C0CH „CH„ 0H

H ^{2 2} o co - (- ch ₂ ch ₂ o) ₇ ch ₃

EXAMPLE 31

This compound was prepared by the procedure of the Example with the exception that 2-methoxyethanol was used instead of methanol. The product is a viscous liquid. % calc. of Br 53.6. % obtained from Br 52.0. The analytical results are consistent with the assigned structure.

H

II I

CCCHCCH ² I ³

OH

COCH „CH„ OCH

II ^{2 2}

EXAMPLE 32

This compound was prepared by the procedure outlined in Example 29 except that methoxycarbou / ax 350 was used in place of methanol and epoxybutane in place of propylene oxide. The product is a viscous liquid. % calc. of Br 36.5. % obtained from

Br 37.2. The analytical results are consistent with the assigned structure:

408

IR 30171 (08MAG48)

EXAMPLE 33

This compound was prepared by the procedure outlined in Example 29, except that 2-ethylhexanol-1 was used instead of methanol. The product is a viscous liquid. % Br calc. 50.0. % obtained 52.7. The analytical results are consistent with the assigned structure:

H

II I

C0CH ₉ CCH, ² 1

OH

COCH „CHC, H

II ² | ⁴

C ₂ H ₅

EXAMPLE 34

This compound was prepared by the procedure described in

Example 29 except that stearyl alcohol was used instead of methanol. The product is a viscous liquid. % calc. of Br 41.0. % obtained from Br 43.0. The analytical results are consistent with the assigned structure:

0H co (ch ₉ ) ch., L | 2 17 3

COCH ₉ CCH ₇

I J

EXAMPLE 35

This compound was prepared by the procedure described in Example 29 with the exception that 2,3-dibromo-propanol-1 was used instead of methanol. The product is a viscous liquid. % calc. of Br 64.8. % obtained from Br 61.9. The analytical results are consistent with the assigned structure:

408

IR 30171 (08MAG48)

EXAMPLE 36

This compound was prepared by the procedure outlined in Example 29 with the exception that epichlorohydrin was used instead of propylene oxide. / 6 calc. of Br 35.7. % obtained 35.4.

The analytical results are consistent with the assigned structure.

gives:

EXAMPLE 37

To a solution of methoxycarbouax 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 to the atmosphere. Then tetrabromophthalic anhydride (442.2 g; 0.89 mole) was added simultaneously with an additional 50 ml of toluene. The reaction mixture was refluxed for 2 hours and, after cooling to room temperature, epichlorohydrin (106.94 g; 1.16 mole) was added. The mixture was refluxed for 20 hours. After distillation of the solvent and excess epichlorohydrin, a dark, viscous product was obtained. % calc. of Br 37.2. % obtained from Br 40.4. The analytical results are consistent with the assigned structure:

409

IR 30171 (0BMAG48)

EXAMPLE 38

5 Methoxycarbowax 350 and toluene were refluxed for an hour to distill a small amount of water. Tetrabromophthalic anhydride (molar ratio 1: 1 to methoxycarbowax 350) and sodium acetate were added and the mixture was refluxed for 17 hours. After cooling to room temperature, an excess of diazomethane (prepared from the decomposition of N-methyl-N-nitrous-p-toluenesulfonamide by sodium hydroxide) in ethyl ether was added and left to mixture stand overnight. The excess diazomethane was decomposed by the addition of acetic acid and the solvent was removed by distillation. The product is a viscous liquid. % calc. of Sr 39.2. % obtained from Br 37.4. The analytical results are consistent with the assigned structure:

II

C0CH ₃ co 4- ch ₂ ch ₂ o) ₇ ch ₃

EXAMPLE 39

Di- (2-ethylhexyl) tetrabromophthalate was prepared by the process described by Spatz et al. (I ά EC Product Research and Development, Vol. 8, NS, 4, 395 (1969).

-3868 408

IR 30171 (08MAG48)

II coch _q chc.h _q

ZI 4 / ^C 2 ^H 5

COCH-CHC. H _o

II ^{2 | 4 9 0 C} 2 ^H 5

EXAMPLE 40

In a glass-lined one-gallon (3.75 1) reactor, polyethylene glycol 600 (835.4 g; 1.40 mole), tetrabromophthalic anhydride (1298.4 g; 2.80 mole) was introduced, potassium acetate (1.35 g) and toluene (1000 g) and heated to 12 ° C. After 4 hours at this temperature, ethylene oxide (246.68 g; 5.60 mole) was pumped into the reactor for 3/4 hours while maintaining the temperature at 120 ° C. After more than one hour of heating, the mixture was cooled to room temperature, the excess ethylene oxide was removed and the product was collected. After removing toluene, 2250 g of the product was isolated, with a yield of 99%, in the form of a viscous liquid. % calc. of Br 39.2. % obtained from Br 38.8. The analytical results are consistent with the assigned structure:

II

II

COCH ^ H 0H

CO (CH_CH _o O) ll 2 2

Br

EXAMPLE 41 The product of Example 3, 453.8 g (0.27 typical 83.4 g (0.82 mole), potassium acetate mole), acetic acid anhydride and toluene 400 ml, were refluxed for 8 hours. After cooling to room temperature, the reaction mixture was transferred to a separating funnel and was extracted first with 100 ml of a 16% solution of potassium bicarbonate and then with 100 ml of water. After removing the solvent by distillation afforded 335.0 g (64% yield) of product as _D f rm of

a viscous liquid. % calc. of Br 36.8. % obtained from Br 32.9. The

408

IR 30171 (08MAG48) analytical results are consistent with the assigned structure:

HO

II I II

COCH ₂ COCCH

CO (CH CH 0)

II ^{2 2} 0

EXAMPLE 42

Tetrabromophthalic anhydride (231.9 g; 0.50 ml), 2-ethylhexanol (130.2 g, 1.0 mole) and potassium acetate (0.24 g) were heated and the mixture was maintained at 120 ° C for 4 hours. The mixture was cooled to 60 ° C and potassium carbonate (35.9 g; 0.26 mole) was added. The mixture was reheated to 80 ° C and maintained at this temperature for 2 hours. The mixture was cooled to 60 ° C and triethylamine (14.2 g; 0.14 mole) was added. The mixture was reheated to 70 ° C and methyl iodide (113.6 g; 0.8 mole) was added over 20 minutes. The mixture was heated to 70-75 ° C and held at this temperature for 2/2 hours. The mixture was cooled to room temperature and filtered to remove the potassium iodine by-product. The filtrate was distilled to remove toluene, obtaining 290 g of the crude product as a light yellow liquid. This product was extracted with 3 x 100 ml of a 6.5% solution of potassium carbonate, followed by 2 x 100 ml of water and once with a 30% solution of sodium chloride. The organic phase was dried over anhydrous magnesium sulfate, overnight. The magnesium sulphate was filtered off and after distilling off the solvent from the filtrate, 204 g of the product (67% yield) were obtained as a light yellow liquid. % calc. of Br 52.6. % obtained from Br 52.2. The analytical results are consistent with the assigned structure:

l |

408

IR 30171 (08MAG48)

EXAMPLE 43

Refluxed tetrabromophthalic anhydride (231.9 g; 0.5 mole), 2- / ^- 2-methoxyethoxy-7-ethanol (360.5 g; 3.0 mole), stannous oxalate (2.32 g) and xylene (200 ml), (temp. 160 ° C) for 18 hours during which the theoretical water was collected. The xylene and the excess 2- / 2-methoxyethoxy-7-ethanol were distilled under reduced pressure, obtaining 332 g of crude product, as a white, moist solid. 256 g of this product were redissolved in toluene (1000 ml) and extracted with 3 x 200 ml of a 7.5% solution of potassium bicarbonate, followed by an extraction with 200 ml of water. The organic phase was dried over anhydrous magnesium sulfate, overnight. After removing magnesium sulfate by filtration, toluene was distilled off, yielding 45 g of a yellow liquid product. Total yield 17%. % Cal, from Br 46.6. % obtained from Br 45.7. The analytical results are consistent with the assigned structure:

II

EXAMPLE 44

This compound was prepared by the procedure outlined in Example 43, with the exception that 2- / ~ 2-ethoxyethoxy-7-ethanol was used:

Br

COCH ₂ CH ₂ OCH ₂ CH ₂ OC ₂ H ₅

II

C0CH ₂ CH ₂ 0CH ₂ CH ₂ 0C ₂ H ₅

408

IR 30171 (08MAG48)

EXAMPLE 45

This compound was prepared by the procedure outlined in Example 1, with the exception that docosyl alcohol (ol-behenylene alcohol) was used instead of polyethylene glycol 600, and propylene oxide instead of ethylene oxide. The product is a vile liquid. case. % calc. of Br 37.7. % obtained from Br 36.5. The analytical results are consistent with the assigned structure:

HI! ¹

COCH „COH ² I CH ₃

EXAMPLE 46

This compound was prepared by the procedure outlined in Example 1, with the exception that tricontyl alcohol was used instead of polyethylene glycol 600, and propylene oxide instead of ethylene oxide. The product is a viscous liquid.

H

II l

EXAMPLE 47

This compound was prepared by the procedure outlined in

Example 4, with the exception that methoxycarbowax 550 was used instead of 2 - / ”2-methoxyethoxy_7-ethanol

8 4 08

IR 30171 (08MAG48)

II

C0 (CH ₂ CH ₂ 0) ₁₁ CH ₃

C0 (CH „CH 0) .CH, l | 2 2 11 3

EXAMPLES 48-58 --- Compositions with ABS Resins

In the following examples, the flame retardancy of the compounds of this invention is demonstrated for ABS resins. The compositions were prepared by mixing the flame retardants, antimony oxide, and ABS together in a cylinder mixer, until the compounds are completely mixed. The compos. The pellets were pelletized at 230-245 ° C and then injection molded into test samples at 230 ° C. The UL-94 vertical burning test was performed and compared to a control consisting only of ABS.

ABS = acrylonitrile-styrene-butadiene terpolymer

DTBPE = 1,2-bis (2,4,6-tribromophenoxy) ethane (70% bromine)

OOTBP = Tetrabromophthalate dioctyl (45% bromine)

AO = antimony oxide

TABLE I (A)

Example No. 48 ^{(a) (b) (c)} ₄₉ (c) 50 £ 1 · - ABS 100 100 100 100 DTBPE - 22 11 5.5 DOTBP - - 17 25.7 A0 - 4 4 4 UL-94 (ò 0.125 Failed V-0 V-0 V-0 O 0.06 2 Failed U-l U-l V-l

(a) Cycolac T, a product of Borg-Warner Co., USA (b) control (100% ABS) (c) comparison (without tetrahalophthalate ester)

408

IR 30171 (08MAG48)

-430 The preceding table clearly demonstrates the flame retardancy of the ABS compositions of this invention, relative to the control. These compositions have at least a flame retardancy equivalent to the conventional flame retardancy (DTBPE) used in ABS.

EXAMPLE 52-55

The impact resistance of the various materials was determined according to ASTM D256.

TABLE II (A)

Example N9. ABS 54 55 100 100 100 100 DTBPE - 22 11 5.5 DOTBP - - 17 25.7 TO - 4 4 4 IMPACT ON GROOVE IZOD (foot-pounds / inch of groove) 3.34 1.26 1.98 1.66 (a) Cycolac ^? -) T, a product from Borg- Warner Co., U.S.A. (b) control (100% ABS) (c) comparison (without tetrahalof ester 'talato)

As can be seen from the previous results, the conventional flame retardant, DTBPE, greatly reduces the impact resistance of ABS when compared to the examples in which a portion of the DTBPE is replaced by the flame retardant compositions of this invention containing ABS.

EXAMPLE 56-58

The heat deflection temperature (HDT) of the various materials was determined according to ASTM D648

408

IR 30171 (08MAG4B) ¢ // Λ '. · »- *' -« M! '· »* ® · *>

/ jtí / *>.:. _ v> <

>' _f

-44 TABLE III (A)

Example N9. 56 ^(b) 5 ^ (c) 58 ABS ^ ³ ) 100 100 100 DTBPE - 22 11 DOTBP - - 17 TO - 4 4

TEMP. HEAT DEFLECTION (HDT) (3,264 psi (9F) 182 167 166

ÍR ^) (a) Cycolac T, a product of Borg-Wagner Co., USA (b) control (100% ABS) (c) comparison (without tetrahalophthalate ester)

The previous results show that there is an insignificant variation in HDT when part of the conventional flame retardant, DTBPE, is replaced by the esters disclosed by this invention.

EXAMPLE 59-64 --- Polystyrene Resin Compositions

The following examples demonstrate the flame retardancy of the compositions of this invention. The compositions were prepared by mixing the flame retardants, antimony oxide and high impact polystyrene together in a cylinder mixer until the compounds were completely mixed. The compounds were pelletized at 200-260 ° C and then injection molded into test samples at 230 ° C. The UL-94 vertical burning test was performed and compared with a control consisting only of high impact polystyrene.

HIPS = High impact polystyrene *

DBDPO = Decabromodiphenyl oxide (83% bromine) DOTBP = Dioctyl tetrabromophthalate (45% bromine) AO = Antimony oxide

408

IR 30171 (08MAG48)

-45 TABLE I (B)

Example N9. ₅₉ (b) 60 ^ ^c ) 61 62 63 64 HIPS ^ ³ ) 100 84 81.5 73.9 83 80.8 DBDPO - 12 9 - 9 - DOTBP - - 5.5 22.1. A, 3 16.4 A0 - 4 4 4 3.7 2.8 UL-94 Q 0.125 Failed V-0 V-0 V-0 V-0 V-0 <30,062 Failed V-2 V-0 V-0 V-0 V-2 (a) Polysar ^ - '525, a product of Polysar, Inc., (b) control (100% polystyrene) (c) comparison (without tetrahalophthalate ester) USA

The previous results clearly demonstrate a higher flame retardation of the flame retardant composition of this styrene-containing wind, compared to the conventional flame retardant (DBDPO) used in polystyrene.

Examples 60 through 62 are all performed with the same levels of bromine. A partial or total replacement of the conventional flame retardant (DBDPO) by the esters disclosed in this investment, improves the flame retardancy of polystyrene, as can be seen by the pios 63 and can be this invention and still produce an identical or better flame retardancy .

UL-94 results for 0.062 samples. The Examples64 clearly demonstrate that the total levels of bromine reduced when using the compositions prepared by

EXAMPLES 65-70

The impact strengths of various materials have been determined in accordance with ASTM D2463.

TABLE II (B)

408

IR 30171 (08MAG48)

Example N θ. 66 ^(c) 67 68 69 70 HIPS 100 84 81.5 76.4 73.9 8 0.8 DBDPO - 12 9 3 - - DOTBP - - 5.5 16.6 22.1 16.4 A0 - 4 4 4 4 2.8

Gardner's impact inch. -lb / mil (1 ril = 1/100 inch)

0.067

0.070

0.084

0.115

0.095 (a) Polysar® 525, from Polysar, Inc.

(b) control (100% polystyrene) (c) comparison (without tetrahalophthalate ester)

As can be seen from the previous results, the conventional flame retardant, DBDPO, greatly reduces the impact resistance of polystyrene (see Example 66). Compositions containing the material of the invention markedly improve impact resistance to the point of being better than that of the comparison example.

EXAMPLE 71-74

The extrusion speeds were measured during pelletizing to determine the processing characteristics of the composites.

TABLE III (B)

Example N9. _7i (c) 72 73 74 ΗΙΡδ ^ ³ ) 84 81.5 79 76.4 DBDPO 12 9 6 3 DOTBP - 5.5 11 16.6 A0 4 4 4 4 Extruder flow (1 lb / h) 3.4 3.7 4.2 7.9 (a) Polysar® 525, a product from Polysar, Inc., USA

(c) comparison (without tetrahalophthalate ester)

408

IR 30171 (08MAG48)

The above results clearly demonstrate the best processing of the flame retardant of this invention containing styrene.

EXAMPLES 75-79 --- Compositions with Polycarbonate Resins

In the following examples, the flame retardancy of the compositions of this invention is demonstrated for polycarbonate resins. The compositions were prepared by mixing the flame retardants, antimony oxide and polycarbonate resin together in a cylinder mixer until the compounds were completely mixed. The compounds were pelletized at 160-30530 ° C and then molded by injection into test samples at 27 ° C. The UL-94 vertical burning test was performed and compared to a control consisting only of polycarbonate resin. The following tests were carried out on the various materials according to the appropriate ASTM method.

1. Limited Oxygen Index (LOl) - ASTM D-2863

2. Fusion Flow - ASTM D-1238

3. Tensile Strength - ASTM D-638

PC = Polycarbonate polymer

BPC = brominated polycarbonate oligomer (58% Br)

DOTBP = Dioctyl tetrabromophthalate (45% Br)

408

IR 30171 (08MAG48) -48 - PAINTING I (C) Example N9. ₇₅ (b) 7 ₆ ( ^c ) 72 78 79 pg ( ^a ) 100.0 87.5 86.6 B4.9 Θ4.0 BPC - 12.5 9.4 3.1 - DOTBP - - 4.0 12.0 16.0 L0I 28 39 37 37 37 Fusion Flow 26.8 19.1 37.5 > 100 > 100 (g / 10 min) Stress Resistance on the Limit (PSI) 9210 10220 10010 10100 10300 % Stretching on the edge 17.9 1, 8 17.4 14.3 15.9

(a) Lexan 141, a product of General Electric, USA (b) control (100% polycarbonate) (c) comparison (without tetrahalophthalate ester) (d) PS I = pounds per square inch. 1 PSI = 0.0145 g / cm ³

The above table clearly demonstrates the significant improvement in flame retardancy of the compositions of this invention containing polycarbonate resins, compared to controls. These compositions containing polycarbonate resin have a flame retardancy at least comparable to that of the conventional flame retardant, BPC, used in polycarbonates.

Examples 76-79 were all performed with equal levels of bromine. The partial or total replacement of the conventional flame retardant BPC by the esters disclosed in this invention results in a great improvement of the flow characteristics, as shown by the better melt flow properties, measured according to ASTM D-1238.

The compositions of this invention containing polycarbonate resin, show greater resistance to stress, when compared to the control and is comparable to that of the conventional flame retardant, the

408

IR 30171 (08MAG48)

-A 9- '"

BPC. In addition, the compositions of this invention containing polycarbonate resin maintain the same percentage of elongation.

The foregoing results clearly demonstrate the greater ease of processing of the compositions of this invention containing polycarbonate resins.

EXAMPLES 80-86 --- Compositions with PBT Resins

The following examples demonstrate the flame retardancy of the compounds of this invention. The compositions were prepared by mixing the flame retardants, antimony oxide and poly (butylene terephthalate) (PBT) together in a cylinder mixer until the compounds were thoroughly mixed. The compounds were pelletized at 150-2163C and then injection molded in test samples at 2359C. The UL-94 vertical burn test was performed and compared to a control consisting only of PBT. The melting flows of the various materials were determined according to ASTM D-1238.

PBT = Poly (butylene terephthalate)

BPC - Brominated polycarbonate oligomer (58% bromine)

DOTBP = Dioctyl tetrabromonaphthalate (45% bromine) z

AO = Antimony Oxide

68 408 Λ & IR 30171 (08MAG48) / t. 3 __ _r ►> · * -. · '' ' - 5 0- PAINTING I I21 Example N2. 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 fee Q 0.125 V-2 grandfather V-0 V-0 Φ 0.06 3 V-2 grandfather V-0 V-0 Fusion Flow 27.6 36.2 55.1 72.6 (g / 10 min) (a) Celanex 2000, a product gives Hoec hs t- Celanese Corp . , USA

(b) contraction (100% poly (butylene terephthalate)) (c) comparison (without tetrahalophthalate ester)

The above table clearly demonstrates the flame retardancy of the compositions of this invention, relative to the control. These compositions have at least the flame retardancy equivalent to that of the conventional flame retardant, the BPC used in PBT (Example 81).

Examples 81-83 were all run at equal levels of bromine. The partial or total replacement of the conventional flame retardant (BPC) by the compositions of this invention results in better flow characteristics as shown by the flow properties measured according to ASTM D-1238.

EXAMPLES 84-86

The following tests were carried out on various materials according to the appropriate ASTM method.

1. Impact resistance - ASTM D-256

2. Resistance to tension - ASTM D-638

3. Heat Deflection Temperature (HDT) - ASTM D-648

4. Fusion flow - ASTM D-123B

68 408 IR 30171 (08MAG48) -51- TABLE II (D) Example NQ. 84 ^{(a) (b) (c) (d)} => 86 PBT ^ ³ ) 100 85.0 83.8 BPC - 15.0 11.3 DOTBP - - 4.9 Antimony Oxide - 5.0 5.0 L0I 25 32 32 UL-94 fee Q 0.125 V-2 V-0 V-0 Q0,063 V-2 V-0 V-0 Izod Groove 0.45 0.33 0.60 (pounds / inches) Tensile strength (psi / ^d ) 7320 8 04 0 7750 % Stretching 10.9 10.3 11.8 HDT (9F) / (eC) 127/53 149/65 135/57 Fusion Flow 27.6 36.2 61.9 (g / 10 min)

(a) Celanex 2000, a product of Hoechst-Celanese Corp., USA (b) control (100 / poly (butylene terephthalate)) (c) comparison (without tetrahalophthalate ester) (d) PSI = pounds per inch square. 1 PSI = 0.145 g / cm

As can be seen from the previous Table, the compositions of poly (butylene terephthalate) resins, containing the flame retardants of this invention, have much greater impact resistance, compared to the controls (Example 84) and the conventional flame retardant , BPC (Example 85), used in PBT, while maintaining the properties of both tensile strength and percentage of elongation.

In addition, the flame retardants of this invention improve

IR 30171 (08MAG48)

-52 the heat distortion temperature (HDT) and flow properties significantly compared to the controls.

The above results clearly demonstrate the best processability of the compositions according to this invention, containing poly (butylene terephthalate).

EXAMPLES 87-91 --- Compositions with SMA resins

In the following examples, the flame retardancy of the compounds of this invention is demonstrated. The compositions were prepared by mixing the flame retardants, antimony oxide and SMA together in a cylinder mixer until the compounds were completely mixed. The compounds were pelletized at 95-245 ° C and then injection molded into test samples at 190-2049 ° C. □ UL-94 vertical burning test was performed and stopped with a control consisting only of SMA. The melt flow of the various materials was determined according to ASTM D-1238.

SMA = Styrene-maleic anhydride polymer DBDPO = Decabromodiphenyl oxide (83% bromine) DOTBP = Tetrabromophthalate dioctyl (45% bromine) z

AO - Antimony oxide

408

IR 30171 (08MAG48)

-53- Example ΝΘ. S MA ^a ) TABLE I (E) 90 80.4 87 ^) 100.0 88 82.7 89 81.5 DBDPO - 13.8 12.4 11.0 D0T8P - - 2.6 5.1 Antimony Oxide - 3.5 3.5 3.5 UL-94 fee fZ 0.125 Failed V-0 V-0 V-0 CS 0.063 Failed V-0 V-0 V-0 Fusion Flow 1.16 1.84 2.08 3.32 (g / 10 min) (a) Dylark 250, a product from Arco Chemicals, USA

(b) control (100% styrene-maleic anhydride copolymer) (c) comparison (without tetrahalophthalate ester)

The previous table clearly demonstrates the flame retardancy of the compositions of this invention, in relation to the controls. These compositions have a flame retardancy at least equal to that of the conventional flame retardant, the commercial DBDPO, used in SMA (Example 87).

Examples 88-91 are all run at equal levels of bromine. The partial replacement of the conventional flame retardant (DBDPO) by the compositions of this invention, results in better flow characteristics as shown by the melt flow properties measured according to ASTM D-1238.

EXAMPLES 92-95

The following tests were carried out on the various materials, according to the appropriate ASTM method.

1. Impact resistance - ASTM D-256

2. Tensile Strength - ASTM D-63B

3. Heat Deflection Temperature (HDT) - ASTM D-648

4. Fusion flow - ASTM D-1238.

6B 408 IR 30171 (08MAG48) f «« * ’ 5 - 5 - ·> * -54- TABLE II (E) Example NS. 92 ^ 94 95 SMA ^ ³ ) 100.0 82.7 81.5 80.4 DBDPO - 13.8 12.4 11.0 DOTBP - - 2.6 5.1 Antimony Oxide - 3.5 3.5 3.5 L0I 18.7 27.6 28.6 23.1 UL-94 fee Q 0.0125 Failed V-0 V-0 V-0 Dog 0.063 Failed V-0 V-0 V-0 Izod Groove (pounds / inches) 2.34 1.02 1.56 1.96 Stress Resistance (Limit) 3950 3880 3830 3700 (psi) % Elongation HDT (SF) 8.7 197 7.4 197 7.7 191 8.1 192 Fusion Flow (g / 10 min) 1.16 1.84 2.08 3.32 (a) Dylark 250, a product Arco Chemicals, USA

(b) control (100% maleic anhydride styrene copolymer) (c) comparison (without tetrahalophthalate ester) (d) PSI = pounds per square inch, 1 PSI = 0.0145 g / cm ^

As can be seen from the previous results, the SMA resin compositions containing the flame retardants of this invention, greatly improve the impact resistance, in relation to the control (Example 92) and the flame retardant, the commercial DBDPO, with PST ( Example 93), still maintaining the properties of both tensile strength and percentage of elongation.

In addition, the heat distortion temperatures (HDT) of the compositions of this invention are comparable to both those of con68 403

IR 30171 (08MAG48)

-55 controls like those of OBDPO.

The above results clearly demonstrate the best processability of the compositions of this invention containing maleic non-anhydrous stretch copolymer resins.

408

IR 30171 (08MAG48)

Claims (19)

1 - Process for the manufacture of a flame retardant resin with improved flow characteristics comprising the mixture (I) of a resin that is selected from: (THE) resin in acrylonitrile-butadi eno-es tyrene; (B) resin in polystyrene; (ç) resin in polycarbonate; (D) resin in poly (terephthalate butylene); (AND) resin in styrene copolymer maleic anhydride; (II) a amount effective retardant flame of at minus a flame retardant adjuvant, tetrahalophthalate ester. Process according to claim 1, characterized in that said tetrahalophthalate ester has the formula: in which: The) B) c) ring can have all possible isomeric arrangements; is selected from the group consisting of hydrogen, an alkyl or an alkyl substituted with 1 to 30 carbon atoms, hydroxyalkyl with carbon, polyhydroxyalkyl with 3 bano and 2 to 20 atoms of to 10 atoms of carI ² _and -4- CHCH „O -) - R ° 2 D θ in which R is 18 atoms of r1 is selected from the group consisting of hydrogen, an alkyl or alkyl substituted with 1 to 30 atoms of an alkyl or carbon alkyl and b is 1 to 50; replaced with 1 a 68 408 IR 3071 (08MAG48) -57carbon, alkenyl or substituted alkenyl, with 2 to 22 carbon atoms, in the R is alkyl with 1 to 18 carbon atoms; a polyhydroxyalkyl having 3 to 12 (cooh) carbon atoms; COOCH -CH-CH; ² II ² A A II ^(fl) 4 (all isomers); (A ^ 4 (all isomers); -CHCHNR ⁵ R ⁶ ; - (CHCH) ₂ NR ⁵ ; and - (CHCH) N; with the proviso that the valence of R is equal d) R is independently selected from the class consisting of H and CH ^ -; e) r \ R ⁴ , R ^ and R ^B are independently selected from the class consisting of H and an alkyl of 1 to 18 carbon> mos in f) P is one whole number in 0 at 50; g) what is it one whole number in 1 to 6; h) X is selected from 0 or NH; and i) A is selected from Cl or Br. Process according to claim 2, characterized in that p is zero, q is one and X is oxygen. featurecharacterize68 408 IR 30171 (08MAG48) Process according to claim 3, by R and r! being alkyl groups and A being Br. Process according to claim 4, in that the ester is di-2-ethylhexyl tetrabromophthalate. Process according to any of claims 1 to 5, characterized in that the weight ratio between (i) and (li) is between 100: 1 and 2: 1. Process according to claim 2, characterized in that R is alkyl or alkyl substituted with 1 to 10 carbon atoms, A to be Br, X to be oxygen, p to be 0 to 20 and q to be 1 to 6. 8 - Process for R to be chosen according to claim 2, featuring re ^_C 6 ^H 13 ' ^-C 8 ^H 17' -ch ₃ , ~ ^C 2 ^H 5 '~ ^C 3 ^H 7' ~ ^C 4 ^H 9 '^ 6 ^ 3 ^{1 -C} 4 ^H 9 - ^C 3 ^H ₇ '~ ^C 6 ^H 13' ~ ^C 8 ^H 17 ' II Process according to one of the preceding claims, characterized in that (II) additionally includes flame retardants, chlorinated or brominated, or mixtures thereof, other than said ester. Process according to claim 5, characterized in that said additional flame retardants are chosen -59Ioved among those in the group essentially made up of 68 408 IR 30171 (08MAG48) II _D .C0CH _o CH „0CH_CH„ 0H ^Br 4 ^ -Z 2 2 2 2 (if)> - COOH CHCH, v ^ / II ² 1 ³ 0 OH Br < ^Br / \ / \ Br Br Br 0 11 COROH ^Br / ~ íC GOR 'OH II 0 where R and R 'are alkylene or substituted alkylene 68 408 IR 30171 (08MAG48) -60- ο II 0CH ₂ CH ₂ OCCH = CH ₂ Process according to one of Claims 1 to 10, characterized in that the resin is (A) acrylonitrile-butadiene and non-styrene of formulas 68 408 IR 30171 (08MAG48) C-C-1 I H CN x Η Η Η H I I I I C-C = C-C -I I Η h y acrylonitrile butadie in styrene where x, y and z can, independently of each other, vary between 10 and 1500. Process according to claim 11, characterized in that part or all of the acrylic and styrenic monomers comprised in the resin include methacrylonitrile or oC-methylstyrene, or methacrylonitrile and c <-methylstyrene. Process according to claim 12, characterized in that the resin comprises monomeric units of a vinilaromatic monomer, a vinyl-nitrile monomer and a butadiene monomer. Process according to one of Claims 1 to 10, characterized in that the resin is (B) polystyrene and one of (a) a styrene homopolymer having the following repetition unit: H I c I H n where n is greater than 1 and can go up to about 3000; (b) a styrene homopolymer as in (a) modified with rubber, in which the rubber is dispersed in the form of discrete particles in a matrix of said homopolymer, with the rubber: homopolymer weight ratio in the range of about 2:98 and about 25:75; or (c) a copolymer of butadiene and styrene, the 6 8 4 03 IR 30171 (08MAG4B) portion by weight butadiene: styrene in the range of about 2:98 to about 25:75; or (d) mixtures of (a) and (b); with those of polyadiene and / or styrene-butadiene copolymer being preferred. Process according to claim 14, characterized in that the polystyrene resin is (B) (a) and is in the form of a foam. Process according to any of claims 1 to 10, characterized in that the resin is (c) polycarbonate which has structural repeating units of formula: a where a is greater than 1 and Z is a divalent aromatic radical of a dihydric phenol. Process according to any of claims 1 to 10, characterized in that the resin is (D) poly (butylene terephthalate) which has structural repeating units of formula where a> 1. Process A to 10, characterized in that maleic non-anhydride according to any one of claims 1, the resin is (E) a copolymer of the formula ~ Η Η Η H II II Γ Γ Γ Γ. Η H 1 1 ¹¹ 1 ¹ 0 = 0 C = 0 1 H (ô) m L - L n 68 ζΟΘ IR 30171 (08 ΜΑG48) -63 where m is υη number from 1 to about 100 and n is a number from zero to about 100 19 - Process by 1-19: 1. the proportion according to claim 18, characterized by weight (styrene): (a. maleic anhydride) being Lisbon,