Note: Descriptions are shown in the official language in which they were submitted.
1 3373 1 0
TETRAHALOPHTHALATE ESTERS AS FLAME RETARDANTS FOR
CERTAIN RESINS
Back~round of the Invention
Field of the Invention---
This invention relates to flame retardant compositions
containing at least one tetrahalophthalate ester and a
certain resin, which is selected from:
(A) Acrylonitrile-Butadiene-Styrene (ABS)
Terpolymer Resins;
(B) Polystyrene Resins;
(C) Polycarbonate Resins;
2 1 3373 1 0
(D) Polybutylene Terephth~l~te Resins; and
(E) Styrene-Maleic Arhydride (SMA) Copolymer Resins.
Additionally, the inventive composition may contain one or more bromin~tecl and/or
chlorinated compounds present in an amount effective to provide additional flame
retardancy to the resin.
Statement of Related Art
ABS resins are known in the art as a class of thermoplastics which are
characterized by excellent properties such as chemical resistance, abuse resistance, stain
resistance, etc. A discussion of typical ~,opellies of ABS resins are described on pages
1-64, 1-66, and 1-68 of Charles A. Harper's "Handbook of Plastics and Elastomers"
which is published by McGraw-Hill Book Company in 1975. ABS resins are
terpolymers which are, in general, derived from acrylonitrile, styrene, and butadiene.
Most are true graft polymers in which acrylonitrile and styrene are grafted onto a
polybutadiene or rubber phase which may further be dispersed in a rigid styrene-
acrylonitrile (SAN) matrix. Other ABS resins are mechanical polyblends of elastomeric
and rigid copolymer, e.g. butadiene-acrylo-nitrile rubber and SAN. (See G.C. Hawkins,
3 ~337310
"Condensed Chemical Dictionary", 10th Edition, p. 3, 1981 as well as U.S. Patent Nos.
4,107,232; 4,206,290; 4,487,886; 4,567,218; and 4,579,906. Hawkins, supra, defines
ABS resin as: "Any group of tough, rigid thermoplastics deriving their name from the
three letters of the monomers which produce them; Acrylonitrile-Butadiene-Styrene.
Most contemporary ABS resins are true graft polymers con~i~tin~ of an elastomeric
polybutadiene or rubber phase, grafted with styrene and acrylonitrile monomers for
compatibility, dispersed in a rigid styrene-acrylonitrile (SAN) matrix. Mechanical
polyblends of elastomeric and rigid copolymers, e.g., butadiene-acrylonitrile rubber and
SAN, historically the first ABS resins, are also marketed.
Varying the composition of the polymer by chs~nging the ratios of the three
monomers and use of other comonomers and additives results in ABS resins with a
wide range of properties."
The general chemical structure of ABS is
H- H H H H H H H
C--C --C--C=C--C C--C
H CN H H H ~
wherein x, y, and z may independently vary from about 10
4 1 3373 1 0
to about 1,500. (See U.S. Patent 4,567,218). It should be understood that analogs of
each of the monomeric components above may be substituted in whole or in part, and is
within the definition of ABS resin. For example, a-methylstyrene may be substituted
for styrene and methacrylonitrile for acrylonitrile. Descriptions of the compositions of
various ABS resins and how they are prepared may be found in U.S. Patent Nos.
2,505,349; 2,550,139; 2,698,313; 2,713,566; 2,820,773, 2,908,661; 4,107,232;
4,173,561; 4,200,702; 4,206,290; 4,289,687; 4,355,126; 4,379,440; 4,456,721;
4,487,886; and 4,581,403.
The ABS resins are useful in many commercial applications such as automotive,
business machines, telephone, etc., where high impact strength is required as well as in
the production of molded articles.
Poly~lylt;ne resins find extensive use in the m~nllf~cture of packaging material,
refrigerator doors, air conditioner cases, m~t~hine housings, electrical equipment, toys,
clock, TV, and radio cabinets, thermal insulation, ice buckets, containers, furniture
construction, appliances, dinnerware, etc. The plepaldlion and description of
polystyrene and expandable poly~lylelle are well known in the art. They are discussed
in G. Hawley, "Condensed Chemical Encyclopedia", 10th Edition, pp 838 and 976
`''~
_ 5 l 3373 1 0
(1981); Kirk-Othmer "Encyclopedia of Chemical Technology",
2nd Edition, Vol. 9, pp 847-884 (1966) and Vol. 19,
pp 85-134 (1969); A.E. Platt in "Encyclopedia of Polymer
Science and Technology", Vol. 13, pp 156-189 (1970);
and U.S. Patent Nos. 4,281,067; 4,298,702; 4,419,458;
4,497,911; 4,548,956; 4,596,682; and 4,618,468.
For many applications where styrenic polymers are
used, there is a need to add flame retardants since these
materials are flammable. Some of the applications which
require flame retarded styrenics are radio and TV cabinets,
toys, electrical equipment, furniture construction, etc.
(See, for example, U.S. Patent Nos. 4,341,890 and
4,548,956.
Polycarbonate resins are ~nown in the art as a class
of thermoplastics that are characterized by excellent
properties such as electrical, dimensional stability,
high impact strength, toughness, and flexibility. In
general, they are prepared by the reaction of a dihydric
phenol with a carbonate ester, phosgene, or a bis chloro-
formate ester. U.S. Patent Nos. 2,999,835; 3,169,121;3,879,348; 4,477,632; 4,477,637; 4,481,338; 4,490,504;
4,532,282; 4,501,875; 4,594,375; and 4,615,832 describe
in detail the preparation of various classes of polycar-
bonate resins.
6 133:731û
Because of their many excellent properties, polycar-
bonate resins are useful in many commercial applications
as engineering thermoplastics and in the manufacture of
molded articles.
Polybutylene terephthalate (PBT) resins are known in
- the art as a class of thermoplastics that are characterized
by excellent properties such as thermal stability, good re-
sistance to brittleness, low friction and wear, chemical
resistance, etc. In general, they are prepared by the
10 polycondensation of terephthalic acid or a diester of
terephthalic acid, such as dimethyl terephthalate (DMT),
with 1,4 butanediol. U.S. patents 2,645,319; 3,047,539;
3,953,394; and 4,024,102 describe in detail the preparation
of PBT.
Styrene-Maleic Anhydride (SMA) copolymer resins find
extensive use in the manufacture of molded articles and
foamed products. In general, they are prepared by copoly-
merizing styrene and maleic anhydride in the proper ratio
and under the appropriate conditions. The preparation and
description of SMA copolymers are described in U.S. Patent
Nos. 2,769,804; 2,971,939; 3,336,267; and 3,966,843
SMA polymers burn rapidly and are generally not used
in applications which require fire retardant polymers such
7 1337310
as radio and television cabinets, tables, chairs, appliance
housings and the like. (See ~.S. Patent 4,151,218),
The use of brominated and/or chlorinated compounds
by themselves or in combination with other materials such
5 as organic phosphates, boron compounds, etc. as flame
retardants for ABS resin compositions are well known in
the art and are exemplified by U.S. Patent Nos. 4,051,101;
4,051,105; 4,096,206; 4,107,122; 4,107,232; 4,173,561;
4,200,702; 4,289,687; 4,579,906; 4,355,126; 4,378,440;
lO 4,567,218; 4,581,403; 4,581,409; and 4,600,747.
Tetrahalophthalate esters have been used as flame-
proofing materials. For example, U.S. Patent No. 4,098,704
describes the use of these materials as textile finishing
agents. U.S. Patent Nos. 4,298,517 and 4,397,977 disclose
15 these compounds as flame retardants for halogenated resins.
However, no teachings have been found which show these
compounds as flame retardants or processing aids for
ABS res ns.
Summary of the Invention
This invention encompasses flame retardant plastic
compositions which comprise the following ingredients
in mixture.
8 1 3373 1 0
(I) a resin which is selected from among:
(A) Acrylonitrile-Butadiene-Styrene
(ABS) Terpolymer Resins;
(B) Polystyrene Resins;
(C) Polycarbonate Resins;
(D) Polybutylene Terephthalate Resins;
and
(E) Styrene-Maleic Anhydride (SMA) Copolymer
Resins.
10 (II) a flame retarding effective amount incorporated in
the resin of (I) of a tetrahalophthalate ester flame
retardant processing aid of the formula:
~ C-X-(CHCH2O)p -
wherein:
(a) the ring can have all possible isomeric
arrangements;
(b) R is selected from the group consisting of
hydrogen, an alkyl or substituted alkyl of
1 to 30 carbons, hydroxyalkyl of 2 to 20
carbons, polyhydroxyalkyl of 3 to 10 carbons,
and
`_ 9 1 3373 1 0
~CHCHp~RIs
where R8 is an alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to
50;
(c) Rl is selected from the group consisting of hydrogen, an alkyl or
substituted alkyl of 1 to 30 carbons, alkenyl or substituted alkenyl of 2 to
22 carbons; O
--C--R7
where R7 is an alkyl of 1 to 18 carbons;
a polyhydroxyalkyl of 3 to 12 carbons;
t ) o 2~(COOH)1 ~O 3
--C~COOCH2--CH--CH2.
ROOC
ROOC
--CH2--CH--NH--C~ (all isomers),
o
--C (Ah
ROC ~ (all isom~rs),
IR3 l 4 IR3 l 4 IR3 IR4
--CHCHNR5R6,--(CHCH)2NR5. and--(CHCH)3N;
with the proviso that the valence of R' is equal to q,
(d) R2 is independently selected from the class consisting of H and CH3 -;
~J
1 3373 ~ O
(e) R3, R4, R5, and R6 are independently selected
from the class consisting of H and an alkyl
of 1 to 18 carbons;
(f) p is an integer of O to 50;
S (g) q is an integer of 1 to 6;
(h) X is selected from O to NH; and
(i) A is selected from Cl or Br.
Preferably, the weight ratio of (I) to (II) is within
the range of about 100:1 to about 2:1.
10 (III) Brominated and/or chlorinated flame retardants
other than (I) which optionally may be present.
Detailed Description of the Invention
The above composition can also contain other
brominated and/or chlorinated flame retardants. Preferred
15 other brominated flame retardants are selected from the
group ccnsisting of
1337310
lOa
rS ~ ~ Dr5 Hr~ ~ H2CH2 ~ - Hr~
~0~
Brx Bry O o
(x + y , 5-8~ B ~ C ~ Br
Br ~ /NCH2CH2N < ~ Br
O O O
Br4 ~JcocH2cH2ocH2cx2oE
~ ICIOCH2~CHC~3
-- O OH
J~1}5
Br Br Br5
<~
Br ~ r
Br Br
~ COR~OH
Br ' ~
I COR OH
where R~ and R~'are
alkylene or substituted alkylene
,Br
~, C,-CEE2Br
Br
Br
. : .
1337310
lOb
Br
CH3 r _ Br_
Br Br n Br
Br CH3 Br 8r Br
HOCH2CH20 ~ CH ~ H2CH20H Br ~ OCB2CB20 ~ Br
8r Br 8r Br
Br CH Br
-)' ' 3 ~ ~ OH
8r Br B ~ , ~ 2~CHCH28r ~ Br5
C82'CHCH20 ~ ~ CCH2C8-CI{2 ~ 8rX
~2 ~ ~ C ~ ~2cH20CCH=c~2 ~ ~nd
8r ~ OH
Br
- lOC 1337310
Preferred Resins
(A) In the above ABS resin, a portion or all of acryl-
ic and styrenic monomers comprising the resin include
20 methacrylonitrile or a-methylstyrene, or methacrylonitrile
and a-methylstyrene. The preferred ABS resin is comprised
of monomeric units of a vinyl aromatic monomer, a vinyl
nitrile monomer, and a butadiene monomer and the number
of units of each monomer is independently within the range
1337310
11
of ~rom about 10 to about 1500.
(B) The polystyrene resin is selected from one
of the following:
(a) a homopolymer of styrene having the following
5 repea~able unit
H H
C C
~ H
wherein n is within the range of greater than 1 to
about 3,000i
(b) a homopolymer of styrene as in (a) modified with
rubber in which the rubber is dispersed as discrete
15 particles into a matrix of said homopolymer and the
weight ratio of rubber to homopolymer is within the
range of from about 2:98 to about 25:75; or
(c) a copolymer of butadiene and styrene in which the
weight ratio of butadiene to styrene is within the range
20 of about 2:98 to about 25:75; or
(d) blends of (a) and (b); polybutadiene and/or a styrene-
butadiene copolymer being preferred.
In a preferred embodiment of the invention, the homo-
polymer of (B)(a) above is in the form of a polystyrene
25 foam. The foam is preferably prepared by polymerizing
the repeatable homopolymer unit in the presence of a
liquid or gaseous blowing agent and said agent has a
boiling point that is below the softening point of the
12 l 3373 1 0
polystyrene and does not dissolve said polystyrene.
The preferred blowing agents are selected from the group
consisting of one or more of propane, butane, pentane,
hexane, heptane, cyclohexane, methyl chloride, dichloro-
5 difluoroethane, 1,1,2 trifluoroethane, and 1,1,2 tri-
chloroethane.
(C) The polycarbonate resin has repeated struc-
tural units of the formula:
o
11
~ Z OC--
wherein a is greater than 1 and z is a divalent
aromatic radical of a dihydric phenol;
lS (D) The polybutylene terephthalate resins that may
be used in the present invention have the following re-
peated structural units of the formula:
O O
- OCH2CH2CH2CH2OC ~ C -
wherein a > 1.
(E) The SMA resins that may be used in the present
invention usually have the following general structural
25 formula: H H H H H H
--C ~ C -C C -C
O=C C=O ¦ H ¦ H
n
13 1 3373 1 0
wherein m is 1 to 100 and n is 0 to 100. The weight ratio
of (styrene):(maleic anhydride) may be 1-19:1.
It is preferred that in the above tetrahalophthalate
ester (II), R is an alkyl or substituted alkyl of 1 to 10
5 carbons, A is Br, X is oxygen, p is 0 to 20 (most prefer-
ably 0), and q is 1 to 6 (most preferably 1). More pre-
ferably R is
ICH3
-CH6Hl3 -2C3HOH~-cHHcHc;H2Hs~c;cHH7~ -C~Hg; -C~Hl3, -C~Hg
C2Hs; Rl is CH3, C2Hs, C4Hg, H,
-C3H~, -C~Hl3, -C8Hl~, -CH~ CHC~Hg, -CloH2l,
C2Hs, or
-
14 l 3373 1 0
~C Br
CH3 1l _~ ~r, and q = 1.
Br Br
The invention also comprehends a method for preparing a flame retardant plastic
composition having enhanced processability properties which comprises incorporating a
flame re~dillg effective amount of one or more of the above tetrahalophth~ te esters
of (II) in one or more of the above resins.
This invention also comprehends the method of improving the flame retardancy,
processability, and physical properties such as impact strength of the specified resins by
incorporating in the resins the tetrahalophth~l~te compounds as described above alone or
in combination with other bromine and/or chlorinated flame retardants.
The above resins are sold on the basis of their impact properties. Unfortunately,
when such materials have to be flame retarded with conventional retardants to meet
code requirements, there is a significant loss of impact strength.
~.
.,
1 3373 1 0
Representative tetrahalophth~l~te compounds useful in practicing this invention
are as follows (where A is Br or Cl):
A A
A~CooH A~COOH
A COO(CH2CHp)9H A~COO(CH2CHp)~CH3
A A
A~COOH A~T~COOCH2--CH--OH
A ~ C--NH(CH2CHp)9H A ~ COO(CH2CHp)7CH3
A O A
A~COOCHI--CH--OH A~COOR A
A COO(CH2CHlha~CH3 A COO(CH2CHp)~ CI A
A O
A fH3 A
A ~ ~ X cOOcH2--CH--OH A ~ COOCH2(CHz)6CH3
A COO(CH2CHp)2H A COOCH2(CH2)6CH3
A A
A Coo~cH2cH2o)~cH3
A~COOC2H5 A~A
A ~COO(CH2CHp)7CH3 A f A
A COOCH2 ~CH--OH
CH3
A COOH
A ~ COO(CH2CHpho~cH3 A J ~ A
A Coo(cH2cH2o)7cH3
A A CH3
A ~ ~COOCH2~CH2)10cH3 ~ ~ COOCH2CH--OH
A ~ COO(CH2CHphCH3 A ~ COO(CH2CHp)7CH2CH3
. ~, A
A CHl 16 1 3 3 7 3 1 0
A~COOCH2CH--OH A~coocH2cH--OH
COO(CH2CHp)~C~I) A~CoO(cH2cH~o~5ocH3
A ~ [COOCH2CH--OH ~ ~COOCH2CH--OH
A COO(CH2CHp)4--C A
A CH~ o ~
A~ COOCH2--CH--OH R--OC ~ A
A COO(CH2CHp),~, C f A
A~COO(CHzCHpbH A~coo2cH2cHp)~2H
COOH
COOH
A X ~ COO(CHzCHp~H A ~ COO(CH2CHp)~H
COO(CHzCHphCH~ COO(CH2CHp)~CH3
A~COOH A~A
COOH
C80H
A~COOH - --I HH--OH
C80(CH2CHpk~H COO(CH2CHPh--CH
~, COOH --CH2--CH2~
N--~CH2~2 17CH3
A ~ COO(CH2--CH2--0~50 --CH2--CH2~
1337310
A ~ CoocH2-cHp~-cH2-cH-N(cHl~ A ~ COO(CH2CHp ~-CH2-lCH~-CHO
A o
COOH (CHOH~ ~ COOIH~
A~coo(cH2cHpb --C ~f COO(CH--CHp)3(CH2CHp)l~H
_ 2
COO~CH2CHP)9cH2cH2N~cH)k
A~A
COOH
A fH3 CH3 1 ~
A ~ COOCH2-CH-OH HOCH-CHpC ~ A
A ~ COO(CH2CHp)l 1~ C~A
COOH
A~$A A~COO[CH2CH20b--CCH3
COO(CH2CHp)15H
A~NH(cH - cHpb-33cH2 - cH - NHlc~A
COOH --CH2--CH2~
~ ~ N(cH2h-l7cH3
A ~f Ct~O(CH2--CHpb 50 --CH2--CH2
_ 2
COOH ~ ~ COOH
,~ CONH(CH2--CHPb ~o --CH2 COO(CH2CHP)~--CH2--CH2N~CH3)2
1 3373 1 0
18
Coo(cH2cHpj7cH~ A
A~-4~ A~COO~CH2CH20)o 25CHzCH2N(CH2)l7CH3
COOCH2--CH--OH A
A ~ Co~CH ~ HphCH3 A ~ COOCH~CH~Ob-lCI-~CHz)l~~CH~
A ~ CH3
A~COOH COOH ~COOCH2--CH--OH
COO~CH2CH20)9--~C~COOCH2~H--CIH2 ~CONH(CH2CH20)7CHl
9r ~ COOCH~CH-OH 9r ~ COOCH~CH-OH
C ~ CH2CHp~7~CH3 B~CO-NH(CH2CH20)7~H~
8r C~O(CH2CHp)7,"CH3
CH~CH20~7~CH3 ~ Br
COOCH2CHOH
CH3
Br ~ C ~ CH~CH--OH O~C ~ Br Br ~ COOCH~H-OH ~O~C ~ ~r
8r Co~ cH20)l~--C 11~ llr COO(CH2CHp), C Br F3r
O ~r
~ ~ OOOC~H~ C~H~C ~ ~
llr COO(CH~CH20h~ C 11-
e L~
~ ;s , ~
19 1 3373 1 0
CH3 CH3
The R in the above formula is --CH2--CH--OH or--CH--CH2--OH
The brominated and/or chlorinated compounds that may be used in combination
with the tetrahalophth~l~tes are any of those that are well known in the art. Preferred
halogenated flame retardant examples are
1 3373 1 0
8r Br Br Br Br
HO~C~OH Br~O~O~Br
Br Br Br Br " Br
HOCH CHzO~ C~ OCH~CH~OH br~ OCH~CHzO~ br
Br Br ~C~ Br ~}Br5
BrBr Br
CH2=CHCHp~CH~OCH2CH=CH2 ~Br~
(~ = 4~o6)
1 3373 1 0
21
Br Br Br
CHl=CcOcH2cH20~cH~ocH2cHtoccH=cH2 Br~OH
Br Br Br
O O
Il 11
Brs~ _~ Br~,~X NCH2CH2N ~ Br~
Il 11
O O
O O
Il 11
~0~ ~ NCH2CH2N
Br,~ Br~, O O
(~ + y = 5-8)
22 1 3373 1 0
COCH2CH20CH2CH20H C2H5
Bt4 ~ COCH2CHCH3
Br5
Br Br
1~')~Br''~COR"OH ~Ç~ CH2Br
Br~BrICoOR'''OH Br
where R" nd R"' ~re
rlkyl~n~ or ~ Ikyl~
23 1 33731 0
In practicing this invention, (II) the tetrahalophth~l~te by itself or additionally
with (III) other bromin~ted and/or chlorinated flame retardants is added to (I) the resin
in any convenient manner, such as blending or extruding in order to get a uniform
composition. Flame retardant synergists such as antimony oxide (Sb203) may also be
added if desired. In addition, other additives such as thermal stabiliærs, ultraviolet
stabilizers, reinforcing agents, organic polymers, mold release agents, blowing agents,
colorants, and the like may also be optionally included. A further advantage of the
tetrahalophth~lates alone or in combination with other brominated and/or chlorinated
compounds as used in this invention is their improved compatibility with the resins.
Detailed Resin Descriptions
(A) The ABS resins that may be used in this invention are, in general, derived from
acrylonitrile, styrene, and butadiene and have the following general structure:
H H ~ H H
_f_f _C-C=C-f c f
c~y'~ butadienc
styrenc
wherein x, y and z may independently vary from about 10 to about 1,~00. It is
understood that analogs of each
. ~
1''`'''``~'
1 33731 0
24
of the components above that comprise the ABS resins
may be substituted in whole or in part.
The ratio of tetrahalophthalate or a mixture of
tetrahalophthalate and one or more brominated and/or
5 chlorinated compounds to ABS resins that will impart
flame retardancy to the latter may vary from 1:100 to
about 1:2 depending on the application. In addition,
the ratio of tetrahalophthalate to other brominated
and/or chlorinated compounds may vary from 100:0 to
10 about 1:99.
(B) The styrenic resins that may be used in the present
invention are the following: polystyrene homopolymer,
both crystalline and non-crystalline forms; expandable
polystyrene beads, and rubber-modified polystyrene which
15 include medium impact polystyrene, high impact polysty-
rene (HIPS), and super high impact polystyrene.
The homopolymers of styrene, both crystalline and
non-crystalline, have the following repeatable unit
wherein n is greater than 1 to about 2000-3000. The
20 non-crystalline forms are generally prepared by poly-
merizing styrene with peroxide catalyst such as those
described in U.S. Patent 4,281,067 while the crystal-
line stereoregular isotactic form uses Ziegler-Natta
catalysts [See I. Pasquon in Encyclopedia of Polymer
25 Science and Technology, Vol. 13, pp. 14, 19-20, and
31 (1970)].
l 3373 1 0
Expandable polystyrene beads are those that are
prepared by incorporating a volatile expanding or blowing
agent during the polymerization of styrene. The blowing
or expanding agents that may be used to cause polystyrene
5 to foam are well known in the art. They may be liquid or
gaseous, do not dissolve the styrene polymer, and have
boiling points below the softening point of the polymer
(See Column 6 in U.S. Patent 4,618,468). Suitable blowing
agents are aliphatic hydrocarbons such as propane, butane,
10 pentane, hexane, heptane, cyclohexane or halogen hydro-
carbons such as methyl chloride, dichlorodifluoromethane,
1,1,2 trifluoroethane, 1,1,2 trichloroethane and the like.
Mixtures of the above may also be used. Typically,
expanding agents are used in amounts of about 2 to 20%
15 by weight.
Rubber-modified polystyrenes that are suitable include
medium, high, and super high impact polystyrenes. In these
compositions, the rubber is dispersed in the polystyrene
matrix as discrete particles (See U.S. Patent 4,341,890).
20 Many rubber-modified styrenes are prepared by polymerizing
styrene in the presence of a rubber such as polybutadiene
or a styrene-butadiene copolymer (SBR). Some grafting of
the styrene to the rubber takes place during polymerization.
The weight ratio of the rubber to polystyrene may vary from
25 about 2:98 to about 25:75. In general the moderate impact
polystyrene will contain about 2 to about 4% rubber, the
""- 1 3373 1 0
26
high impact polystyrene greater than about 10% to about
25%. [See H. Keskkula in "Encyclopedia of Polymer Sci-
ence and Technolo~y" Vol. 13, pp. 396 and 400-404 (1970)].
(C) The polycarbonate resins that may be employed in the
5 present invention use typical dihydric phenols such as
are disclosed in U.S. Patent 3,334,154, which is incor-
porated herein by reference. They are as follows:
2,2 bis-(4-hydroxyphenyl)-propane; hydroquinone;
resorcinol; 2,2 bis-(4-hydroxyphenyl)-pentane;
2,4' dihydroxydiphenyl methane;
bis-(2-hydroxyphenyl)-methane;
bis-(4-hydroxyphenyl)-methane;
bis-(4-hydroxy-5-nitrophenyl)-methane;
1,1 bis(4-hydroxyphenyl)-ethane;
3,3 bis-(4-hydroxyphenyl)-pentane;
2,2' dihydroxydiphenyl sulfone;
4,4' dihydroxydiphenyl ether; and
4,4' dihydroxy-2,5-diethoxydiphenyl ether.
-
27 1 3373 1 0
Example 1
To 1,392 g (3.0 moles) of tetrabromophthalic anhydride were added 1,050 g
(3.0 moles) of Methoxy Carbowax 350TM in the presence of 22.0 g of sodium acetate.
The ~ Lule was heated at 90C for 8 hours in a nitrogen atmosphere. The reactioniX~UlC was filtered hot to remove the sodium acetate. The analytical data were
consistent with the assigned structure.
Elr~COO(CHzCHzO)7a~CH3
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 llli~ule was heated at 60-100C. The solvent and
residual propylene oxide were removed to give the product in almost quantitative yield.
The analytical data were consistent with the assigned structure:
Br~COO(CHzCH20)7~,~CH3
~r f COO--CHz--fH--OH
~r CH3
28 l 3373 1 0
Example 3
To 92.8 g (0.2 moles) of tetrabromophthalic anhydride is added all at once 80 g
(0.2 mole) of Carbowax 400TM and the mixture heated to 120 - 130C for 2.5 hours.
The desired product is isolated in essentially ~lualllilaLive 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.
Br~COOH
Br l~r COO(CH2CH2CH20)gH.
Example 4
To 240 g (0.24 mole) of the compound of Example 3 is added 45.3 g (0.24
mole) of trimellitic anhydride and heated at 155C under nitrogen for about 7 hours.
The infrared spectrum indicated the completion of the reaction by the substantial
disappearance of the anhydride absorption band at 5.65. The product was isolated in
essentially quantitative yield. Analy. Calcd.; % Br, 30.3%; Mol. Wt. 1056;
neutralization equivalent, 352; Found: % Br, 29.4; Mol. Wt., 1014; neutralization
equivalent, 351. The spectral data was consistent with the structure:
Br~COOH COOH
8rJ~ COO~CH2CH2CH20 )~ COOH
Br O
29 1337310
Example 5
To 156.3 g (0.18 mole) of the compound of Example 3 is added 70.9 g (0.18
mole) 2,3-dibromopropyl trimellitate. The ~ e is heated at 130-140C for 6 hours
with stirring to give the product as a brown opaque oil. Isolation afforded the product
in essentially 4u~~ live yield and the analysis is consistent with the structure being:
Br~COOH COOH
BrJ~COO(CH2CH2CHp)g--C~ Br Br
(~d isomen)
1 33731 0
Exarnples 6 to 11
The following p~ ions were carried out as in Exarnple 1 using the reactant
set forth below.
Tct-~b.~ lpi~
E~mplc No.A-~lyd.;dc Hydro~y ~ ' Product Structurc
6 1.0 mole HOCH2CHpCH2CH2OH Br
1 0 mole
Pr~,~COOH
8r f COO(CH2CH20)2H
Elr
7 1.0 mole HO(CH2CH2O)~H Br
(Carbow~ 200)TM 13r~COOH
Br ~~ COO(CH2CH2O)~H
av.
Elr
8 1.0 mole HO(CH2CH2O)13H Br
(Carbowa~ 6'00)TM
10 mole Br~T~COOH
Br ~ COO~CH2CH20)13H
Br av.
9 1.0 mole HO(CH2CH2O)23H ~r
(Carbowa~ l000)TM E3r~g~COOH
Br ~ COO~CH2CH2O33H
av.
Br
t,
-
31 l 3373 1 0
Examples 6 to 11 - continued
The following ~ ald~ions were carried out as in Example 1 using the reactant
set forth below.
T.L~
E~mple No. Anhydride Hydro~y CC , ~u ' Product Structure
1.0 mole HO(CH2CH20)~H. Br
(rOI~ ~l E-2000)X
t O mole Br~COOH
Br ~ COO(CH2CH20)4sH
Br av.
I l 2.0 mole HO(CH2CH20hH Br Br
(C~rl:lowu~ 400)*
1.0 mole Br~COOH HOOC ~ ~ Br
Br ~ COO(CH2CH20hC I Br
Br O Br
Example 12
To 96.4 g (0.2 mole) of tetrabromoterephthalic acid is added all at once 160 g
(0.2 mole) of Carbowax 400* and 300 g toluene co~ g 1.0 g P-toluene sulfonic
acid. The ~ c; is heated to reflux until 3.6 g (0.2 mole) water was collected. The
toluene is removed under reduced P1eS~Ue to give a clear viscous liquid in essentially
quantitative yield.
COOH
r~ r
COO(CH2CH20ha~
* Trade-mark
,.~
32 1 3373 ~ 0
Example 13
To 86.4 g (0.1 mole) of the compound of Example 3 is added all at once 21.8 g
(0.1 mole) pyromellitic dianhydride and the lni~ e heated to 120-130C for 2.5 hours
to give the desired product. Water, 1.8 g (0.1 mole), is added to open the rcm~ining
anhydride group and the analytical data are consistent with the assigned structure:
Br~COOH HOOC
Br~COO(CH2CHp)g~C~COOH.
Br O ~
COOH
Example 14
To 86.4 g (0.1 mole) of the compound of Example 3 is added all at once 10.9 g
(00.05 mole) of pyromellitic dianhydride and the mixture heated to 120-130C for 2.5
hours to give the desired product. The analytical data are con~i~tenl with the assigned
structure: 1l
8r~COOH ~COOH
Br COO(CH2Ch20)9 HOOC
Br av. 2 a
(u~d omers)
Example 15
To 86.4 g (0.1 mole) of the compound of Example 3 is added all at once 21.8 g
(0.01 mole) of phthalic anhydride and the ~ e heated to 120-130~C for 2.5 hours
to give the desired product. The analytical data are consistent with the assigned
structure:
8r COOH HOOC
Br~ COO(CH2CHPh--C~)
Br Br
1 33731 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 120-130C for 2.5 hours to give the desired product. The
analytical data are con~i~tent with the ~igne(l structure:
Br
B-~COOH --CH2~
11 --CH2--C--C2H5
8r ~ COO(CH2CHp~--CH2
Example 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 ~lliXlUle heated to 120-130C for 2.5 hours to give the desired product. The
anal,vtical data are consistent with the assigned structure:
Br
Br~COOH --CH2~
1~)1 7H3 --CH2~C--C2Hs
Br --1' COO(CH2CH20)90~ CH2
Br _ 3
, .
34 1 33731 0
Example 18
To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 350.0 g (1.0
mole) of Methoxy Carbowax 350* in presence of 7.0 g of sodium acetate. The ~ Lule
is heated at 90C for 8 hours in a nitrogen atmosphere. The reaction lllixlule is filtered
hot to remove sodium acetate to give the expected product in nearly qu~llilalive yield.
The analytical data are consistent with the assigned structure:
Cl~ ~ ~COO(CH2CHp)7a~CH3
Example 19
To 634.0 g (1.0 mole) of the composition of Example 18 is added 116 g (2.0
moles) of propylene oxide in 200 ml of toluene. The reaction mixture is heated from
60-100C for 3-5 hours, and then concentrated to give the product in nearly
quantitative yield. The analytical data are consistent with the assigned structure:
Cl_ ~ l ,COO(CH2CHp)~aVCH3
Cl ~ COOCH2f H--OH
a CH3
$ Trade-mark
,...
,~
-
1337310
Example 20
To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 200.0 g (1.0
mole) of Carbowax 200* in the presence of 7.0 g of sodium acetate. The mixture is
heated at 90nC for 8 hours in a nitrogen atmosphere. The reaction mixture is filtered
hot to remove sodium acetate to generate the expected product in nearly quanlil~live
yield. The analytical data are conci~tent with the assigned structure:
Cl~ ~ ~COO(CH2CHlO)~arH
Cl--~COOH
Example 21
To 484.0 g (1.0 mole) of the product of Example 21 is added 116.0 g (2.0
moles) of propylene oxide in 200 ml of toluene. The reaction mixture is warmed at
60-100C for 3-5 hours, and then concentrated to give the product in nearly
quantitative yield. The analytical data are con~i~tent with the assigned structure:
Cl~cootcH2cH2o)4arH
Cl f COOCH~--fH--OH
Cl CH3
Example 22
To 284.0 g(1.0 mole) of tetrachlorophthalic anhydride is added 400.0 g(1.0
mole) of Carbowax 400* in the presence of 7.0 g of sodium acetate. The mixture is
heated at 90C for 8 hours in a nitrogen atmosphere. The reaction mixture is filtered
hot to remove sodium acetate to generate the expected product in nearly quantitative
* Trade-mark
- 1337310
36
yield. The analytical data are consistent with the assigned structure:
cl cl
Cl~ COO(CH2CH20)g"~H
Cl COOH
Example 23
To 46.4 g (0.1 mole) of tetrabromophthalic anhydride is added all at once 44.1 g
(0.1 mole) of polyoxyethylated dimethylamine (CH3)2N(CH2CH2O)gH) dissolved in 100
ml of toluene. The mixture was heated at 100-110C for 4-5 hours and then
concentrated to give the desired product in essentially quantitative yield. The analytical
data are consistent with the assigned structure:
O 8r
(CH3hN(--CH2CH20--)9arlCI~xBr
Example 24
To 92.8 g (0.2 mole) of tetrabromophthalic anhydride is added 80 g (0.2 mole)
7 CH3
H2N--CH--CH2UocH2--CH--]5.60rNH2
(Jeffamine D-400) and the mixture heated to about 120C. The final product is
obtained in almost quantitative yield. The analytical data are consistent with the
assigned structure:
Br
8r~COOH ICH3 CH3
8r Elr CONHCH--CH2(ocH2--CH--)5.6~NH2
~"
-
37 1337310
Example 25
Poly(ethylene glycol 300), 204.5 g (0.67 mole) was refluxed (T = 117C) with
600 ml of toluene for 1.5 hours in order to remove a small amount of water present in
the glycol. The ~ e was cooled to about 100C and tetrabromophthalic 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 50C,
propylene oxide, (156.4 g, 2.69 moles, 100% excess) was added and the mixture heated
to and held at 100C for 2.5 hours. When the solution cooled to about 50C it was
filtered through a bed of diatomaceous earth and decolorizing charcoal. The filtrate
was distilled to remove the solvent to give 904.1 g of product as a viscous liquid.
Calcd. % Br, 47.4. Found % Br, 46.5. Analytical data is consistent with the assigned
structure.
Br~OOCH2CI CH3 CH3C112COl~
Br Br C0 (CH~CH20)~7--ICI Br Br
Example 26
This compound was prepared by the procedure described in Example 25 except
that poly(ethylene glycol 200) was used in place of poly(ethylene 300). Product is
viscous liquid.
.,
1337310
38
Calcd. % Br, SlØ Found % Br, 49.3. Analytical data was consistent with the
assigned structure.
Br O H H O Br
Br ~ COCH2CCH3 CH3CH2COC ~ 8r
Br ~ CO (CH2CH20)4_s--C Br
Br O O Br
Example 27
This compound was prepared by the procedure described in Example 25 except
that poly(ethylene glycol 600) was used in place of poly(ethylene glycol 300). Product
is a viscous liquid. Calcd. % Br, 39.5. Found % Br, 39.3. Analytical data is
consistent with the assigned structure.
Br 1l H H O Br
Br~COCH2CCHj CH3CI H2COC`~T'Br
Br~CO--(CH2CH20)~2 ~ICI~Br
Example 28
This compound was prepared by the procedure described in Example 25 except
that poly(ethylene glycol 400) was used in place of poly(ethylene glycol 300). Product
is a viscous liquid. Calcd. % Br, 44.2. Found % Br, 44Ø Analytical data is
consistent with the assigned structure.
Br~COCH2CCH3 CH3ÇH~COC~8r
Br Br ICI O ~CH2CH20)8_~ 0 Br Br
~_ t337310
39
Example 29
Methanol (54. 1 g, 1.5 mole), tetrabromophthalic anhydride (695.6 g, 1.6
moles), and potassium acetate, 2.73 g were refluxed for 4 hours with 500 ml of toluene.
After cooling the reaction mixture to room temperature, propylene oxide (87.12 g, 1.5
moles) were added and the lllixlule reacted at 80C for 2.5 hours. Product was
obtained as a viscous liquid after distilling out the toluene. Calcd. % Br, 57.7. Found
% Br, 57.2. Analytical data is consistent with assigned structure.
Br
r~~ OCH~CHCH~
Br O OH
Example 30
This compound was prepared by the procedure similar to that described in
Example 29 except that methoxycarbowax 350 was used in place of methanol and
ethylene oxide in place of propylene oxide. Calcd. % Br, 37.8. Found % Br, 37.2.
Analytical data is consistent with assigned structure.
Br 8
Br~ ~ ~COtCH2CH20)7CH3
EIr ~--COCH2CH20H
Br O
-
1 33731 0
Example 3 1
This compound was prepared by the procedure in Example 29 except that 2-
methoxyethanol is used in place of methanol. Product is viscous liquid. Calcd. % Br,
53.6. Found % Br, 52Ø Analytical data is consistent with assigned structure.
8r O H
Elr~COCH~CCH3
8r Br IC~OCH2CHpCH3
Example 32
This compound was prepared by the procedure outlined in Example 29 except
that methoxycarbowax 350 was used in place of methanol and epoxybutane in place of
propylene oxide. Product is a viscous liquid. Calcd. % Br, 36.5. Found % Br, 37.2.
Analytical data is consistent with assigned structure.
Br O H
ll l
8r~ OH
Br~f CO(CH2CH20hCH3
Hr O
Example 33
This compound was prepared by the procedure outlined in Example 29 except
that 2-ethylhexanol-1 was used in place of methanol. Product is a viscous liquid.
~,
41 1 33731 0
Calcd. % Br, 50Ø Found % 52.7. Analytical data is consistent with the assigned
structure.
Br 1O H
8r ~,COCH2CCH3
Br~f COCH2fHC4Hg
Bt O C2H~
Example 34
This compound was prepared by the procedure described in Example 29 except
that stearyl alcohol was used in place of methanol. Product is a viscous liquid. Calcd.
% Br, 41Ø Found % Br, 43Ø Analytical data is consistent with the assigned
structure.
Br O H
Br ~ COCH2CCH3
Br~~~ CO(CH2)17CH3
Br o
Example 35
This compound was prepared by the procedure described in Example 29 except
that 2,3-dibromo-propanol-1 was used in place of methanol. Product is a viscous
liquid. Calcd. % Br, 64.8. Found % Br, 61.9 Analytical data is consistent with the
42 1 3373 1 0
assigned structure.
Br 1l `1
Bt_T~,COCH2CCH3
Brf ~COCH2CHCH28r
Br 0 8r
Example 36
This compound was prepa~ed by the procedure outlined in Example 29 except
that epichlorohydrin was used in place of propylene oxide. Calcd. % Br, 35.7. Found
% Br, 35.4. Analytical data is consistent with the assigned structure.
Br 01 H
Br~COCH2CCHzCI
Br~ Iclo(cH2cH2o)7cH3
Example 37
To a solution of methoxycarbowax 350 (300.0 g, 0.89 mole) in dry toluene (184
ml) was added sodium methoxide (48.0 g, 0.90 mole) in methanol. The methanol was
then distilled off atmospherically. Tetrabromophthalic anhydride was then added (442.2
g, 0.89 mole) along with an additional 50 ml of toluene. The reaction mixture was
refluxed for 2 hours and after cooling to room temperature, epichlorohydrin (106.94 g,
1.16 moles) was added. The mixture was refluxed for 20 hours. After the solvent and
`_ 133731Q
43
excess epichlorohydrin were distilled, a viscous dark product was obtained. Calcd. %
Br, 37.2. Found % Br, 40.4. Analytical data is con~i~t~nt with assigned structure.
8r 0
Br~COCH2CH\ ~CH2
Br~ CO~CH2CH20)~CH3
Br O
Example 38
Methoxycarbowax 350 and toluene were refluxed for 1 hour in order to distill
out a small amount of water. Tetrabromophthalic anhydride (1:1 mole ratio with
methoxycarbowax 350) and sodium acetate were added and the mixture refluxed for 17
hours. After cooling to room l~ dlule, an excess of diazomethane (prepared from
the decomposition of M-methyl-N-nitroso-p-toluene sulfonamide by sodium hydroxide)
in ethyl ether was added and the llli~ e allowed to stand 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 % Br, 37.4.
Analytical data is consistent with the assigned structure.
Br O
Br~ COtCH2CH20)~CH3
Br O
"r
-
44 13373iO
Example 39
Di(2-ethylhexyl) tetrabromophth~l~te was prepared by the procedure described
by Spatz et. al (I & EC Product Research and Development, Vol. 8. No. 4, 395 (1969).
Br~OCH2CHG,Hg
E3r Br o C2H5
Example 40
Poly(ethylene glycol 600) 885.4 g (1.40 moles), tetrabromophthalic anhydride,
1298.4 g (2.80 moles), potassium acetate, 1.35 g, and toluene (1000 g) were charged
into a one-gallon glass-lined reactor and heated to 120~C. After 4 hours at this
temperature, ethylene oxide, 246.68 g (5.60 moles) was pumped into the reactor in 3/4
hour while m~ g the temperature at 120C. After one hour longer of heating, the
mixture was cooled to room temperature, the excess ethylene oxide was then vented,
and the product collected. After stripping off the toluene, 2250 g of the product was
isolated in 99% yield as a viscous liquid. Calcd. % Br, 39.2. Found % Br, 38.8.
133731 ~
Analytical data is consistent with the assigned structure.
o 1o
Br~,~COCH2CH20H HOCH2CH20 C~}, Br~
COtCH2CH20)12-lJ C
O O
Example 41
To the product of Example 3, 453.8 g (0.27 mole), acetic anhydride, 83.4 g
(0.82 mole), pol~SSiulll acetate, 1.0 g, and toluene, 400 ml, were refluxed for 8 hours.
After cooling to room temperature, the reaction mixture was transferred to a separatory
funnel and extracted first with 100 ml of a 16% potassium bicarbonate solution and
then with 100 ml of water. After ~ tilling off the solvent, 335.0 g (64% yield) of
product was obtained as a viscous liquid. Calcd. % Br, 36.8. Found % Br, 32.9.
Analytical data is consistent with the assigned structure.
O H O O H O
COCH2COCCH3 CH3COCCH20 C
8r~ CH3 CH3 ~ Br~
CO(CH2CH20)12-l- C
O O
Example 42
Tetrabromophthalic anhydride, 231.9 g (0.50 mole), 2-ethylhexanol, 130.2 g (1.0
mole), and potassium acetate, 0.24 g were heated to and kept at 120C for 4 hours.
46 133731 ~
The mixture was cooled to 60C and potassium carbonate, 35.9 g (0.26 mole), was
added. Relle~tecl mixture to 80C and kept it at this t~ ?elalule for 2 hours. Cooled
i~lule to 60C and added triethylamine, 14.2 g (0.14 mole). Reh~tecl lllixlule to
70C and added methyl iodide, 113.6 g (0.8 mole) in 20 mim-tes Heated mixture to
70-75C and kept it at this temperature for 2 1/2 hours. Cooled llli~lule to room
temperature and filtered it in order to remove by-product potassium iodide. The filtrate
was distilled to remove toluene and 290 g of crude product was collected as a pale
yellow liquid. Extracted this product with 3 times 100 ml of a 6.5% potassium
carbonate solution followed by 2 times 100 ml of water and once with 30% sodium
chloride solution. Dried the organic phase over anhydrous m~gnesium sulfate
overnight. Filtered off magnesium sulfate and after removing the solvent from filtrate
by rli~till~tion, 204 g of product was obtained in 67% yield as a pale yellow liquid.
Calcd. % Br, 52.6. Found % Br, 52.2. Analytical data is consistent with the assigned
structure.
~ COCH3
BrJ,~ H
COCH2C--C~,Hg
O C~H5
47 ~ 3373 1 0
Example 43
Tetrabromophthalic anhydride, 231.9 g (0.5 mole), 2-[2-methoxyethoxy]-ethanol,
360.5 g (3.0 moles), stannous oxalate, 2.32 g, and xylene, 200 ml, were refluxed (temp.
160C) for 18 hours during which time, theory water was collected. The xylene and
excess 2-[2-methoxyethoxy]-ethanol were distilled under reduced ples~u~e to give 332 g
of crude product as a wet white solid. Redissolved 256 g of this material in toluene
(1000 ml) and extracted it with 3 times 200 ml of a 7.5% potassium bicarbonate
solution followed by one extraction with 200 ml of water. Dried the organic phase
with anhydrous m~gnesium sulfate overnight. After removing the m~gnesium sulfate
by filtration, toluene was removed by (li~till~tion to give 45 g of a yellow liquid
product. Overall yield is 17%. Calcd. % Br, 46.6. Found % Br, 45.7. Analytical
data is con~ tent with the assigned structure.
8r~COCH2CHpCH2CH20CH3
COCH2CH20CH2CHpCH3
48 1 3373 1 0
Exarnple 44
This compound was prepared by the procedure outlined in Example 43 except
using 2-[2-methoxyethoxy]-ethanol.
Bt~COCH2CllpCH2CH20C2H5
COCH2CHpCH2CH20C2H5
Example 45
This compound was prepared by the procedure outlined in Example 1 except
that docosyl alcohol (behenyl alcohol) was used in place of poly(ethylene glycol 600)
and propylene oxide in place of ethylene oxide. Product is a viscous liquid. Calcd. %
Br, 37.7. Found % Br, 36.5. Analytical data is consistent with the assigned structure.
O H
~ COCH2¢0H
E3r4~ CH3
CO(CH2321CH3
49 1 33731 0
Example 46
This compound was prepared by the procedure outlined in Example 1 except
that tricontyl alcohol was used in place of poly(ethylene glycol 600) and propylene
oxide in place of ethylene oxide. Product is a viscous liquid.
O H
ll l
~ COCH2COH
l~r~,--~ CH3
CO(CH2)29CH3
Example 47
This compound was prepared by the procedure outlined in Example 4 except
that methoxycarbowax 550 was used in place of 2-[2-methoxyethoxy]-ethanol.
8r4 ~ CO(CHzCH20)iICH3
CO(CH2CHp)lICH3
-
1 33731 0
Examples 48-58 --- Compositions With ABS Resins
In the following examples, the flame retardancy of
the compounds of this invention are demonstrated with
respect to ABS resins. The compositions were prepared
5 by mixing together the flame retardants, antimony oxide,
and ABS on a roller until the compounds were blended
thoroughly. The compounds were pelletized at 230-245C
and then injection molded into test specimens at 230C.
The UL-94 vertical burn test was run and compared to a
10 control consisting of ABS itself.
ABS = Acrylonitrile-styrene-butadiene terpolymer
DTBPE = 1,2-bis(2,4,6-tribromophenoxy)-ethane
(70% Bromine)
DOTBP = Dioctyl tetrabromophthalate (45% Bromine)
AO = Antimony Oxide
51 1 3373 1 0
Table I (A)
Example No 48(b) 49(c) 50 5l
ABS(a) 100 100 100100
DTBPE - 22 11 5.5
5 DOTBP - - 1725.7
AO 4 4 4
UL-94 @ 0.125"Failed V-0 V-0 V-0
@ 0.062" Failed V-l V-l V-l
10 (a) Cyclolac~ T, a product of Borg-Warner Co., U.S.A.
(b) control (100% ABS)
(c) comparison (no tetrahalophthalate ester)
The above clearly demonstrates the flame retardancy
of the ABS compositions of this invention relative to
15 the control. These compositions have at least equivalent
flame retardancy to the conventional flame retardant used
in ABS (DTBPE).
-
52 1 33731 0
Examples 52-55
Impact strength of the various materials were deter-
mined according to ASTM D256.
Table II(A)
5 Example No _(b) 53(C) 54 55_
ABS(a) 100 100 100 100
DTBPE - 22 11 5.5
DOTBP - - 17 25.7
AO - 4 4 4
10 NOTCHED IZOD IMPACT
(ft-lb/in notch) 3.34 1.26 1.98 1.66
(a) Cycolac~T, a product of Borg-Warner Co., U.S.A.
(b) control (100% ABS)
15 (c) comparison (no tetrahalophthalate ester)
As can be seen from the data above, the conventional
flame retardant, DTBPE, greatly reduces the impact strength
of ABS compared to those examples where a portion of the
DTBPE is replaced by the ABS-containing flame retardant
20 compositions of this invention.
53 1 3373 1 0
Examples 56-58
Heat Reflection Temperature (HDT) of the various
materials were determined according to ASTM D648.
Table III(A)
5 Example No. 56(b)57(c) 58
ABS(a) 100 100 100
DTBPE - 22 11
DOTBP - - 17
AO ~ 4 4
10 HEAT DEFLECTION TEMP. (HDT)
@ 264 psi (F) 182 167 166
(a) Cycolac~ T, a product of Borg-Warner Co., U.S.A.
(b) control (100% ABS)
15 (c) comparison (no tetrahalophthalate ester)
The data above shows that there is negligible charge
in HDT when a portion of the conventional flame retardant,
DTBPE, is replaced by the esters disclosed in this inven-
tion.
1337310
54
Examples 59-64 --- Compositions With Polystyrene Resin~
In the following examples, the flame retardancy of
the compositions of this invention are demonstrated.
The compositions were prepared by mixing together the
5 flame retardants, antimony oxide, and high impact poly-
styrene on a roller until the compounds were blended
thoroughly. The compounds were pelletized at 200-260C
and then injection molded into test specimens at 230C.
The UL-94 vertical burn test was run and compared to a
10 control consisting of the impact polystyrene itself.
HIPS = High Impact Polystyrene
DBDPO = Decabromodiphenyl Oxide (83% Bromine)
DOTBP = Dioctyl Tetrabromophthalate (45% Bromine)
AO = Antimony Oxide
-
1 3373 1 0
Table I(B)
Example No 59(b) 60(C) 61 62 63 64
Percenta~e Composition
HIPS(a) 100 84 81.5 73.9 83 80.8
5 DBDPO - 12 9 - 9
DOTBP - - 5.5 22.1 4.316.4
AO - 4 4 4 3.7 2.8
UL-94 @ 0.125" Failed V-0 V-0 V-0 V-0 V-0
@ 0.062 Failed V-2 V-0 V-0 V-0 V-2
(a) Polysar~ 525, a product of Polysar, Inc., U.S.A.
(b) control (100% polystyrene)
(c) comparison (no tetrahalophthalate ester)
The above results clearly demonstrate the superior
15 flame retardancy of the styrene-containing flame retardant
composition of this invention over the conventional flame
retardant used in polystyrene (DBDPO).
Examples 58 through 64 are all run at equal bromine
levels. Partial or total replacement of the conventional
20 flame retardant (DBDPO) with the esters disclosed in this
invention improves the flame retardancy of the polystyrene
as can be seen by the UL-94 results for the 0.062" speci-
mens. Examples 63 and 64 clearly demonstrate that
the total bromine levels can be reduced when the compo-
25 sitions of this invention are used and still yieldcomparable or better flame retardancy.
, ~
.....
56 1337310
Examples 65-70
Impact strength of the various materials were
determined according to ASTM D2463.
Table II(B)
5 Example No 65(b)66(C) 67 68 69 70
HIPS(a) 100 84 81.5 76.4 73.9 80.8
DBDPO - 12 9 3
DOTBP - - 5.5 16.6 22.1 16.4
AO - 4 4 4 4 2.8
10 Gardner Impact
(in-lb/mil) 0.096 0.067 0.0700.084 0.115 0.095
(a) Polysar~ 525 from Polysar, Inc.
(b) control (100% polystyrene)
15 (c) comparison (no tetrahalophthalate ester)
As can be seen from the data above, the conventional
flame retardant, DBDPO, greatly reduces the impact strength
of the polystyrene (see Example 66). The compositions
containing the material of the invention clearly improve
20 the impact strength to a point where it is better than
the comparison example.
57 l 3373 1 0
Example 71-74
The extrusion rates were measured during pelletiza-
tion to determine the processing characteristics of the
compounds.
Table III(B)
Example No 71(C) 72 73 74
HIPS(a) 84 81.5 79 76.4
DBDPO 12 9 6 3
DOTBP - 5.5 ll 16.6
10 AO 4 4 4 4
Extruder Flow Rate
(lbs/hr) 3.4 3.7 4.2 7.9
(a) Polysar~ 525, a product of Polysar, Inc., U.S.A.
15 (c) comparison (no tetrahalophthalate ester)
The data above clearly demonstrates the improved
processability of the styrene-containing flame retardant
of this invention.
58 1337310
Examples 75-79---Compositions With Polycarbonate Resins
In the following examples, the flame retardancy of
the compositions of this invention are demonstrated with
respect to polycarbonate resins. The compositions were
5 prepared by mixing together the flame retardants, antimony
oxide, and polycarbonate resin on a roller until the com-
pounds were blended thoroughly. The compounds were pel-
letized at 160-305C and then injection molded into test
specimens at 271C. The UL-94 vertical burn test was run
10 and compared~to a control consisting of the polycarbonate
resin itself. The following tests were performed on
the various materials according to the appropriate ASTM
method.
1. Limited Oxygen Index (LOI) - ASTM D-2863
2. Melt Flow - ASTM D-1238
3. Tensile Strength - ASTM D-638
PC = Polycarbonate polymer
BPC = Brominated Polycarbonate Oligomer (58% Bromine)
DOTBP = Dioctyl Tetrabromophthalate (45% Bromine)
59 1 3373 1 0
TABLE I (C)
Example No 75(b) 76(c) 77 78 79
PC(a) 100.0 87.5 86.6 84.9 84.0
BPC - 12.5 9.4 3.1
5 DOTBP - - 4.0 12.0 16.0
LOI 28 39 37 37 37
Melt Flow 26.8 19.1 37.5 >100 >100
(g/10 min)
Tensile Strength
10 at Yield (PSI)(d)9210 10220 10010 10100 10300
% Elongation
at Yield 17.9 18.8 17.4 14.3 15.9
(a) "Lexan" 141, a product of General Electric, U.S.A.
15 (b) control (100% polycarbonate)
(c) comparison (no tetrahalophthalate ester)
(d) PSI = pounds per square inch. 1 PSI = .0145 g/cm2
1 337 3 1 0
The above clearly demonstrates the significant im-
provement in flame retardancy of the polycarbonate resin
containing compositions of this invention relative to the
control. These polycarbonate resin containing compositions
5 have at least comparable flame retardancy to the conven-
tional flame retardant, BPC, used in polycarbonate.
Examples 76-79 are all run at equal bromine levels.
Partial or total replacement of the conventional flame
retardant, BPC, with the esters disclosed in this inven-
10 tion results in greatly enhanced flow characteristics asshown by the improved melt flow properties measured ac-
cording to ASTM D-1238.
The polycarbonate resin containing compositions of
this invention show improved tensile properties when
15 compared to the control, and comparable to that of the
conventional flame retardant, BPC. Furthermore, the
polycarbonate resin containing compositions of this
invention maintain percent elongation.
The data above clearly demonstrates the improved
20 processability of the polycarbonate resin containing
compositions of this invention.
61 1 3373 1 0
Examples 80-86 --- Compositions With PBT Resins
In the following examples, the flame retardancy of
the compounds of this invention are demonstrated. The
compositions were prepared by mixing together the flame
5 retardants, antimony oxide, and polybutylene terephthalate
(PBT) on a roller until the compounds were blended thor-
oughly. The compounds were pelletized at 150-216C and
then injection molded into test specimens at 235C. The
UL-94 vertical burn test was run and compared to a con-
10 trol consisting of PBT itself. Melt flow of the variousmaterials were determined according to ASTM D-1238.
PBT = Polybutylene Terephthalate
BPC = Brominated Polycarbonate Oligomer
(58% Bromine)
DOTBP = Dioctyl Tetrabromophthalate (45% Bromine)
AO = Antimony Oxide
- 62 1337310
TABLE I (D)
Example No 8o(b) 81(C) 82 83
PBT(a~ 100.0 85.0 82.8 80.7
BPC - 15.0 7.5
5 DOTBP - - 9.7 19.3
Antimony Oxide - 5.0 5.0 5.0
UL-94 Rating
@ 0.125" V-2 V-0 V-0 V-0
@ 0.063" V-2 V-0 V-0 V-0
10 Melt Flow 27.6 36.2 55.1 72.6
(g/10 min)
(a) "Celanex" 2000, a product of Hoechst-Celanese Corp.,
U.S.A.
(b) control (100% polybutylene terephthalate)
15 (c) comparison (no tetrahalophthalate ester)
1 3373 1 0
63
The above clearly demonstrates the flame retardancy
of the compositions of this invention relative to the
control. These compositions have at least equivalent
flame retardancy to the BPC conventional flame retardant
5 used in PBT (Example 81).
Examples 81-83 are all run at equal bromine levels.
Partial or total replacement of the conventional flame
retardant (BPC) with the compositions of this invention
results in enhanced flow characteristics as shown by the
10 improved melt flow properties measured according to ASTM
D-1238.
Examples 84-86
The following tests were performed on the various
materials according to the appropriate ASTM method.
1. Impact Strength - ASTM D-256
2. Tensile Strength - ASTM D-638
3. Heat Deflection Temperature (HDT) - ASTM D-648
4. Melt Flow - ASTM D-1238
64 l 33731 0
TABLE II (D)
Example No 84(b~ 85(c) 86
PBT(a) 100 85.0 83.8
BPC - 15.0 11.3
5 DOTBP - - 4.9
Antimony Oxide - 5.0 5.0
LOI 25 32 32
UL-94 Rating
@ 0.125 V-2 V-0 V-0
@ 0.063 V-2 V-0 V-0
Notched Izod 0.45 0.33 0.60
(lbs/inch)
Tensile ~ength 7320 8040 7750
(PSI)
% Elongation 10.9 10.3 11.8
HDT (F)/(C) 127/53 149/65 135/57
Melt Flow 27.6 36.2 61.9
(g/10 min)
20 (a) "Celanex" 2000, a product of Hoechst-Celanese Corp.,
U.S.A.
(b) control (100% polybutylene terephthalate)
(c) comparison (no tetrahalophthalate ester)
(d) PSI = pounds per inch. 1 PSI = .0145 g/cm2
-
1 3373 1 0
As can be seen from the data above, polybutylene
terephthalate resin compositions containing the flame
retardants of this invention greatly improve the impact
strength relative to the control (Example 84) and the
5 BPC conventional flame retardant, (Example 85) used in
PBT while maintaining both tensile strength and percent
elongation properties.
In addition, the flame retardants of this invention
significantly improve the heat distortion temperature
10 (HDT) and flow properties relative to the control.
The data above clearly demonstrates the improved
processability of the polybutylene terephthalate con-
taining compositions according to this invention.
Examples 87-91 ---Compositions With SMA resins
In the following examples, the flame retardancy of
the compounds of this invention are demonstrated. The
compositions were prepared by mixing together the flame
retardants, antimony oxide, and SMA on a roller until
the compounds were blended thoroughly. The compounds
20 were pelletized at 95-245C and then injection molded
into test specimens at 190-204C. The UL-94 vertical
burn test was run and compared to a control consisting
of SMA itself. Melt flow of the various materials were
determined according to ASTM D-1238.
66 1 3373 1 0
SMA = Styrene-Maleic Anhydride Polymer
DBDPO = Decabromodiphenyl Oxide (83% Bromine)
DOTBP = Dioctyl Tetrabromophthalate (45% Bromine)
AO = Antimony Oxide
-
67 1 3373 1 0
TABLE I (E)
Example No 87(b) gg(c) 89 90 91
SMA(a) 100.0 82.7 81.5 80.4 76.8
DBDPO - 13.8 12.4 11.0 6.9
5 DOTBP - - 2.6 S.1 12.8
Antimony Oxide - 3.5 3.5 3.5 3.5
UL-94 Rating
@ 0.125" Failed V-0 V-0 V-0 V-0
@ 0.063" Failed V-0 V-0 V-0 V-0
10 Melt Flow 1.16 1.84 2.08 3.32 6.76
(g/10 min)
(a) "Dylark" 250, a product of Arco Chemicals, U.S.A.
(b) control (100% styrene-maleic anhydride copolymer)
(c) comparison (no tetrahalophthalate ester)
The above clearly demonstrates the flame retardancy of
the compositions of this invention relative to the control.
These compositions have at least equal flame retardancy to
the DBDPO commercial conventional flame retardant used in
SMA (Example 87).
Examples 88-91 are all run at equal bromine levels.
Partial replacement of the conventional flame retardant
68 1 33731 0
(DBDPO) with the compositions of this invention results
in enhanced flow characteristics as shown by the improved
melt flow properties measured according to ASTM D-1238.
Examples 92-95
The following tests were performed on the various
materials according to the appropriate ASTM method.
1. Impact Strength - ASTM D-256
2. Tensile Strength - ASTM D-638
3. Heat Deflection Temperature (HDT) - ASTM D-648
4. Melt Flow - ASTM D-1238
~ 69 l 3373 1 0
TABLE II (E)
Example No 92(b) 93(c) 94 95
SMA(a) 100.0 82.7 81.5 80.4
DBDPO - 13.8 12.4 11.0
5 DOTBP - - 2.6 5.1
Antimony Oxide - 3.5 3.5 3.5
LOI 18.7 27.6 28.6 23.1
UL-94 Rating
@ 0.0125" Failed V-0 V-0 V-0
@ 0.063" Failed V-0 V-0 V-0
Notched Izod 2.34 1.02 1.56 1.96
(lbs/inch)
Tensile Strength (Yield) 3950 3880 3830 3700
(PSI)( )
15 % Elongation 8.7 7.4 7.7 8.1
HDT (F) 197 197 191 192
Melt Flow 1.16 1.84 2.08 3.32
(~/10 min)
~,t
(a) "Dylark" 250, a product of Arco Chemicals, U.S.A.
20 (b) control (100% styrene-maleic anhydride copolymer)
(c) comparison (no tetrahalophthalate ester)
(d) PSI = pounds per inch. 1 PSI = .0145g/cm2
1 337 3 1 0
As can be seen from the data above, SMA resin composi-
tions containing the flame retardants of this invention
greatly improve the impact strength relative to the control
(Example 92) and the DBDPO commercial flame rètardant with
5 PBT (Example 93), while maintaining both tensile strength
and percent elongation properties.
In addition, the 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 pro-
cessability of the styrene-maleic anhydride copolymer resin
containing compositions of this invention.
