FLAME-RETARDANT POLYPHENYLENE ETHER RESIN COMPOSITION

SUSBTANCE RETARDATRICE DE FLAMMES, DE TYPE RESINE D'ETHER DE POLYPHENYLENE

English Abstract

ABSTRACT OF THE DISCLOSURE
Flame-retardant composition comprising (1) a novel
organic phosphorous compound having a substituent of
<IMG>
where R3, R4 and R5 each is a monofunctional residue selected
from a hydrogen atom, a halogen atom, an alkyl or aralkyl group
having 1 to 8 carbon atoms, a cyclohexyl group and a phenyl group,
on an amino group of an aromatic amino compound and (2) a mixture
resin of polystyrene and polyphenylene ether grafted or not with a
styrenic compound, said (1) being 2-20% by weight and (2) 80-98%
by weight, on the basis of the composition. The resins of the
present invention are useful as raw materials for shaping articles
which require flame retardancy.
- 1 -

Claims

What we claim is:
1. A flame-retardant polyphenylene ether resin
composition, substantially comprising 80 to 98% by weight
of a mixed resin consisting of 20 to 80% by weight of a
polyphenylene ether represented by the generic formula:
<IMG> (A)
(wherein, R1 and R2 each denote an alkyl group having 1 to
4 carbon atoms and n denotes the degree of polymerization)
and 20 to 80% by weight of a styrenic polymer and 2 to 20%
by weight of at least one member selected from the group
consisting of organic phosphorus compounds represented by
the generic formula:
<IMG> (B)
(wherein, Ar denotes a trifunctional aromatic residue, Z
and Z' each denote a monofunctional residue selected from
the class consisting of a hydrogen atom, an alkyl group
having 1 to 4 carbon atoms, an aryl group having 6 to 10
carbon atoms and a -NH2-yXy group, X denotes a residue of
the formula
<IMG> (C)
- 29 -

wherein, R3, R4 and R5 each denote a monofunctional residue
selected from the class consisting of a hydrogen atom,
a halogen atom, an alkyl having 1 to 8 carbon atoms, an
aralkyl group, a cyclohexyl group and a phenyl group,
x denotes an integer having the value of 1 or 2 and y
denotes an integer having the value of 0, 1 or 2).
2. The resin composition according to Claim 1,
wherein the residue (C) is such that all R3, R4 and R5
each are a hydrogen atom.
3. The resin composition according to Claim 1,
wherein the residue (C) is such that R4 and R5 each are
a chlorine atom and R3 is a hydrogen atom.
4. The resin composition according to Claim 1,
wherein the residue (C) is such that all R3, R4 and R5
each are a t-butyl group.
5. The resin composition according to Claim 1,
wherein the residue (C) is such that R5 is a phenyl group
and R3 and R4 each are a hydrogen atom.
6. The resin composition according to Claim 1,
wherein the residue (C) is such that R3 and R5 each are
a methyl group and R4 is a t-butyl group.
7. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that
Ar is a group of the formula <IMG> and Z and Z' each
are a -NH2-yXy group.
8. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that Ar
is a group of the formula <IMG>, Z is a phenyl group and
Z' is -NH2-yXy group.
- 30 -

9. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a hydrogen atom and Z' is a
-NH2-yXy group.
10. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a hydrogen atom and
Z' is a-NH2-yXy group.
11. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group and Z and Z' each are a-NH2-yXy
group.
12. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a phenyl group and Z' is a
-NH2-yXy group.
13. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a methyl group and Z' is a
-NH2-yXy group.
14. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z a hydrogen atom and Z' is a
-NH2-yXy group.
15. The resin composition according to Claim 1,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a hydrogen atom and Z' is a
-NH2-yXy group.
- 31 -

16. The resin composition according to claim 1,
wherein the organic phosphorus compound (B) is such that Ar is
a <IMG> group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
17. The resin composition according to claim 1,
wherein the organic phosphorus compound (B) is such that Ar is a
<IMG> group or <IMG> group and Z and Z' each are a phenyl group.
18. The resin composition according to claim 1,
wherein the organic phosphorus compound (B) is such that Ar is a
<IMG> group and Z' is a -NH2-yXy group.
19. The resin composition according to claim 1,
wherein the organic phosphorus compound to be used is a mixture
consisting of organic phosphorus compounds of the formula (B)
wherein x is 1 or 2 and y is 0, 1 or 2.
20. The resin composition according to claim 1,
wherein the polyphenylene ether (A) is such that R1 and R2
each are a methyl group.
21. A flame-retardant polyphenylene ether resin com-
position, substantially comprising 80 to 98% by weight of a resin
component and 2 to 20% by weight of at least one member selected
from the group of organic phosphorus compounds represented by
the generic formula:
<IMG>
(B)
(wherein, Ar denotes a trifunctional aromatic residue, Z and Z'
each denote a monofunctional residue selected from the class con-
sisting of a hydrogen atom, an alkyl group having 1 to 4 carbon
atoms, an aryl group having
- 32 -

6 to 10 carbon atoms and a -NH2-yXy group, X denotes a
residue of the formula
<IMG>
(C)
wherein R3, R4 and R5 each denote a monofunctional residue
selected from the class consisting of a hydrogen atom,
a halogen atom, an alkyl having 1 to 8 carbon atoms, an
aralkyl group, a cyclohexyl group and a phenyl group, x
denotes an integer having the value of 1 or 2 and y
denotes an integer having the value of 0, 1 or 2), said
resin component comprising a graft copolymer and a styrenic
polymer, said graft copolymer having polyphenylene ether
in an amount of 20 to 80% by weight of the resin component
and having 20 to 200 parts by weight of a styrenic compound
or a combination of a styrenic compound and a vinyl compound
copolymerizable therewith grafted onto 100 parts by weight
of a polyphenylene ether represented by the generic formula:
<IMG> (A)
(wherein, R1 and R2 each denote an alkyl group having 1 to
4 carbon atoms and n denotes the degree of polymerization).
22. The resin composition according to Claim 21,
wherein the residue (C) is such that all R3, R4 and R5 each
are a hydrogen atom.
- 33 -

23. The resin composition according to Claim 21,
wherein the residue (C) is such that R4 and R5 each are
a chlorine atom and R3 is a hydrogen atom.
24. The resin composition according to Claim 21,
wherein the residue (C) is such that R3, R4 and R5 each
are a t-butyl group.
25. The resin composition according to Claim 21,
wherein the residue (C) is such that R5 is a phenyl group
and R3 and R4 each are a hydrogen atom.
26. The resin composition according to Claim 21,
wherein the residue (C) is such that R3 and R5 each are
a methyl group and R4 is a t-butyl group.
27. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a group of the formula <IMG> and Z and Z' each are
a -NH2-yXy group.
28. The resin composition according to Claim 21,
wherein the organic phophorus compound (B) is such that
Ar is a group of the formula <IMG> , Z is a phenyl group
and Z' is a -NH2-yXy group.
29. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a hydrogen atom and Z' is a
-NH2-yXy group.
- 34 -

30. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a hydrogen atom and
Z' is a -NH2-yXy group.
31. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group and Z and Z' each are a -NH2-yXy
group.
32. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a phenyl group and Z' is a
-NH2-yXy group.
33. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a methyl group and Z' is a
-NH2-yXy group.
34. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a hydrogen atom and Z' is a
-NH2-yXy group.
35. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a hydrogen atom and Z' is a
-NH2-yXy group.
36. The resin composition according to Claim 21,
wherein the organic phosphorus compound (B) is such that
Ar is a <IMG> group, Z is a hydrogen atom and Z' is a
-NH2-yXy group.
- 35 -

37. The resin composition according to claim 21,
wherein the organic phosphorus compound (B) is such that Ar is
a <IMG> group or <IMG> group and Z and Z' each are a phenyl group.
38. The resin composition according to claim 21,
wherein the organic phosphorus compound (B) is such that Ar is
a <IMG> group, Z is a phenyl group and Z' is a -NH2-yXy group.
39. The resin composition according to claim 21,
wherein the organic phosphorus compound to be used is a mixture
consisting of organic phosphorus compounds of the formula (B)
wherein x is 1 or 2 and y is 0, 1 or 2.
40. The resin composition according to claim
wherein the polyphenylene ether (A) is such that R1 and R2 each
are a methyl group.
- 36 -

Description

1088;~38
Thi~ invcntion rela~es to a flame-retardant poly-
phenylene ether r~sin composition. More particularLy, the present
invention relates to a flame-retardant resin composition having
a novel organic phosphorus compound incorpoxated into a resin
composition which has a styrenic polymer added to either a poly-
phenylene ether or a polyphenylene ether having ~raft copolymerized
thereto a styrenic compound.
Polyphenylene ethers are excellent in mechanical
properties, electrical properties, res~stance to chemicals and
thermal resistance and en~oy advantageous attributes such as low
hydroscopicity and high dimensional stability. For the out-
standing quality, they have been arresting keen attention.
Further, olyphenylene ethers exhibit an excellent flame-retarding
property such that they are rated as self-extinguishing a~d non-
dripping by the Testing Method D-635 of ASTM and the Specification
No. 94 of the Underwriter' Laboratories (hereinafter referred to
UL-94). However, it has been long since deficient fabricability ~ -
of polyphenylene ethers was pointed out. The poor fabricability
has so far remained as the most serious defect for polyphenvlene
ethers. As measures for overcoming this defect, there have been
suggested a number of methods resorting to incorporation of
styrenic polymers. For example, Japanese Patent Publication No.
17812/lg68 (July 29/68, A. Fujiwara et al.), U.S. Patent No.
3,383,435 (May 1~/68, E.P. Cijek) and others have disclosed blended
compositions of polyphenylene ethers with styrenic polymers. ~
Resin compositions which contain graft copolymers having styrenic -
compounds grafted onto polyphenylene ethers have been disclosed in
Japanese Patent PublicatiGn Nos. 1210/1972 (Jan. 13/72, S. Nakashio
et al.) and 27809/1971 (Aug. 12/71, A. Nakanishi et al.), Japanese
30 Patent Laid-open Publication Nos. 98446/1974 (Sept. 18/74, H.
Suzaki et al.) and 51150/1975 (~ay 7/75, S. Izawa et al.), U.S.
.~

1088Z3~
Pat~nt No~. 3,S86,73~ (June 22/71, T. Takemura et al.) and
3,929,931 (Dec. 30/75, S. Izawa et al.) and others.
These resin compositions formulated to impart
improved fabricability to polyphenylene ethers, however, have
a disadvantage that they do not prove suitable for a wide range
of industrial applications in terms of inflammability because
styrenic polymers incorporated therein are resins of a type such
that they are destitute of self-extinguishing property and n~n-
dripping property and, once ignited, cannot but be left to burn
out completely.
An object of the present invention is to provide
polyphenylene ether resin compositions improved both in fabric- -
ability and flame-retardancy.
To be more specific, the present invention aims to
-provide a flame-retardant composition which is characterized by -
substantially comprising 80 to 98~ by weight (based on the total
composition) of a resin component obtained by mixing a styrenic
polymer with either a polyphenylene ether or a polyphenylene ether
having a styrenic compound with or without a vinyl compound co-
polymerizable therewith graft-copolymerized thereon, in such a
proportion that the polyphenylene ether component represented by
the generic formula: ~
~ R
- t `R2 1 (A ;
(wherein, Rl and R2 each denote an alkyl group having 1 to 4 carbon
atoms and n denotes the degree of polymerization) will
B
.

1088Z3~
account for 20 to 80% by weight (based on the total weight
of resin component~ and 2 to 20% by weight of at least one
member selected from the group consisting of novel organic
phosphorus compounds represe~ted by the generic formulas:
[ 2-x ~
(wherein, Ar denotes a trifunctional aromatic residue, Z
and Z' each denote a monofunctional residue selected from
the class consisting of a hydrogen atom, an alkyl group
having 1 to 4 carbon atoms, an aryl group having 6 to 10
carbon atoms and a -NH2 yXy group, X denotes a residue of
the formula
~3 ~ (C)
0= P o 5
CH2
wherein R3, R4 and R5 each denote a monofunctional residue
selected from the class consisting of a hydrogen atom, a .
halogen atom, an alkyl having 1 to 8 carbon atoms, an aralkyl
group, a cyclohexyl group and a phenyl group, x denotes an
integer having the value of 1 or 2 and y denotes an integer
having the value of 0, 1 or 2).
Examples of the aforementioned polyphenylene ethers
used for the present invention include poly(2,6-dimethyl-
phenylene-1,4-ether), poly(2,6-diethylphenylene-1,4-ether),

1~88238
pol~y(2-methyl-6-ethylphenylene-1,4-ether), polyt2-methyl-6-
propylphen~lene-1,4-ether), poly(2,6-dipropylphenylene-1,4-
ether), poly(2-ethyl-6-propylphenylene-1,4-ether), poly(2-
methyl-6-butylphenylene-1,4-ether) and poly(2--ethyl-6-
butylphenylene-1,4-ether). The most advantageous poly-
phenylene ether for the purpose of the present lnvention is
poly(2,6-dimethylphenylene-1,4-ether). This particular
polymer excels in compatibility with styrenic polymers,
permits resin compositions of varying proportions to be
readily prepared and manifests an outstanding effect in
imparting flame-retardancy due to its synergism with
organic phosphorus compounds.
For the present invention to be effectively worked,
the number-average molecular weight of a poIyphenylene ether -
is selected from the range of 6,000 to 30,000, preferably
7gO00 to 25,000. Use of a polyphenylene ether having a
mlmber-average molecular weight of less than 6,ooo proves
undesirable because the polymer notably degrades the
resultant resin composition in physical properties,
particularly creep properties. Use of a polyphenylene ether
having a higher molecular weight exceeding 30,000 is likewise
undesirable because the polymer seriously degrades the resin
composition in ~abricability, causes degradation of the
styrenic polymer andinhibits maintenance of balanced physical
properties.
In the polyphenylene ether having a ~tyrenic com-
pound graft-copolymerized thereon for use in the present
invention, the term "styrenic compound" is meant to embrace
styrene and various derivatives of styrene such as alkylation
products and halogenation products of styrene. Concrete
;
-- 5 --

1088238
eYamples are styrene, ~-methyl styrene, 2,4-dimethyl styrene,
monochloro-styrene, dichloro-styrene, p-methyl styrene, ethyl
styrene and the like.
At the time of polymerization, these styrenic
compounds may be used in combination with 30% by weight or
less of copolymerizable vinyl compounds such as, for example,
methyl methacrylate, acrylonitrile, methacrylonitrile and
butyl acrylate. Alternatively, the graft copolymerization
may be effected by using two or more kinds of styrenic
compounds at the same time.
The graft copolymer to be used in the resin com-
position of the present invention is desired to have 20 to -
200 parts by weight of a styrenic compound with or without
a vinyl compound copolymerizable therewith graft polymerized
onto 100 parts by weight of a polyphenylene ether. If the -
amount of the styrenic compound with or without the vinyl
comonomer is less than the lower limit 20 parts by weight,
then the resultant graft copolymerized polyphenylene ether ;
is substantially the same in quality as the polyphenylene
ether in the form of a homopolymer. If the amount of the
styrenic compound with or without the vinyl comonomer used
in the graft polymerization exceeds the upper limit 200 parts
by weight, then the styrenic compound with or without the
vinyl comonomer degrades the physical properties, particularly,
impact strength, of the resultant resin composition.
The term "styrenic polymer" as used in the present
invention is meant to refer to a polymer formed preponderantly
of a styrenic compound and possessed of a num~er-average
molecular weight desirably in the range of from 50,000 t~
2009000, preferably from 60,000 to 150,000. If the number-
6 --
: . ,. ~ , .
- ` ' - :
`

1088238
average molecular weight of the styrenic polymer is below
50,000, there is a disadvantage that the physical properties
of the resultant resin, particularly impact strength and
creep properties, are deficient. If it exceeds 200,000,
however, there ensues and adverse effect upon the moldability
and fabricability, which results in various undesirable
phenomena such as thermal deterioration of the composition
at the time of fabrication and inferior impact resistance of
the shaped article due to residual strain.
The term "styrenic compound" as used herein
refers to the same compound as is used for the graft
copolymerization described above. The styrenic polymers
usable for this invention further include those commonly
known rubber-reinforced styrenic resins. For example~ rubber-
reinforced polystyrene resins and acrylonitrile-butadiene-
styrene copolymer resins are embraced in the scope of this
invention. The proportion of the styrenic polymer to the
total resin component of the composition (inclusive of the
styrenic polymer which is chemically bonded to the poly-
phenylene ether in consequence of the graft copalymerization)is selected from the range of 20 to 80% by weight, preferably
from 25 to 75% by weight. If the content of the styrenlc
polymer is less than the lower limit 20% by weight, the
styrenic polymer fails to impart ample fabricability to the
resultant resin composition. If the content exceeds the
upper limit 80% by weight, it is difficult to confer desired
flame-retardancy upon the resultant resin composition, even
after by mixing with the organic phosphorus compound of the
present invention.
-- 7 --
.
.

1088238
Concrete examples of the trifunctional aromatic
residue in the generlc formula (B) are as follows:
N N ~ ~ ~ CH2 ~ ,
, ~o~ ~ lrS~
Concrete examples of the X component contalned in
the organic phosphorus compound represented by the generic
formula (B) will be shown below in structural formula.
t-Bu . :
O=P O O=P- O CH3
CH2- CH2~
, ~C~
CH2- ~ =P CQ
~ / 3
O = P--O O = P--O
CH2- CH2 ::
.:
.-
.. -- 8 --
,

- 10882~
.: ' ,
t-Bu 8 17 .
O= P- O t-Bu = P_
CH2 CH2
t-Bu CH
~\~) C6H13
O ~ O= P- CH~
CH2 \=:/ ' CH2
t-Bu
~: t-Bu ~
O= P- O :t-Bu i O ~ p_ O
: : CH2- CH2- ~ ~:-
The compounds of the generic formula (B~ are used ~.
either singly or 1n the form of a mixture consi~king of two
- or more members.
he organic phosphorus compounds represented by : :
: 5 the generic formula (B) (hereinafter called novel organic
~ phosphorus compounds) which are usable for the present
::: invention are novel ones that are obkained by a method in
, ~ : : .
which organic phosphorus compounds represented by the generic
formula:
.
_ g _
. .

-` ~088238
~ 4
3 ~ ~
0= P- 0 R
~l2OH
(wherein, R3, R4 and R5 each clenote a hydrogen atom, a halogen
atom, an alkyl having 1 to ~ carbon atoms, an aralkyl group, a
cyclohexyl group or a phenyl group) (refer to Japanese Patent
Publication No. 17979/1975 (June 5/75, T. Saito) in the Offici.al
Gazette) to dehydrogenation condensation in conjunction with .~
an aromatic amino compound having amino groups directly bonded . .
with aforementioned trifunctional aromatic residue. Alternatively,
organic phosphorus compounds represented by the generic formula:
3 ~ /
0= ~- 0 R5
(wherein, R3, R4 and R5 are as defined in the immediately pre-
ceding generic formula) (refer to Japanese Patent Publication
No. 45397/1974 (Dec. 4/74, T. Saito) in the Official Gazette)
may be subjected to dehydrogenation (or de-alcohol) condensation
in conjunction with an aromatic compound having methylolated s
amino groups directly bonded with the above trifunctional
aromatic residue or said aromatic compound whose methylol groups ~ :
are esterified.)
~ - 10 - .
! ~

108823~
The novel organic phosphorus,compound content
required for manifestation of the effect of this invention is
selected in the range of from 2 to 20%, preferably from 3 to
15%,'by weight based on the total weight of the composition. If --
the content of the novel organic phosphorus compound is less than
the lower limit 2~, there is an undesirable result that the resin
composition will not easily acquire a qualitv capable of satisfying
UL-94 tests for self-extinguishing property and non-dripping
property. If the novel organic phosphorus compound is added in
an amount greater than the upper limit 20%, then the resin com-
position has a disadvantage that its physical properties, ~,
particularly heat deflection temperature and impact strength,
cannot be maintained in the ranges warranting practical utility. '~
The method to be used for the production of the
composition of the present invention is not particularly limited, ~; ~
i.e, the components may be mixed by any method effective at all ;~ `
for the purpose, One typical example of the methods advantage-
ously available comprises the steps of thoroughly mixing the
resin destined to form the backbone of the final composition
with the novel organic phosphorus compound in a dry blender,
melting and kneading the mixture in an extruder and molding the
molten mixture into pellets.
Needless to mention, it is permissible to incor- ~;
~orate in the composition of the present invention other additives
such as, for example, a plasticizer, a pigment,
.`'
, . . .

1~8238
a reinforcing agent a riller, an extender and a stabilizer
as occasion demands.
Now, the present inventlon will be described more
specifically with reference to examples thereof. Whenever
there are mentioned parts and percents, they invariably mean
parts by weight and percents by weight.
Example l:
In a four-necked flask fitted with a stirrer and
a thermometer, 77 parts of a phosphorus compound represented
by the following formula and 29 parts of benzoguanamine were
heated in an oil bath until the temperature within the flask
rose to 170C.
~ ,.~,
O = P--O
CH2-OH
With the contents kept under agitation, the temperature was
elevated to 230C over a period of one hour. Under a
reduced pressure (30 mmHg of inner pressure~, the water
formed by the reaction was removed. When the reaction was
continued for two hours at 230C under the reduced pressure,
distillation of water ceased to proceed. At this point,
the product of reaction was taken out of the flask, cooled
and pulverized. The product was found to have a melting
point of 128C. The infrared absorption spectrum indicated
decreases of OH group and NH2 groupO It was ascertained by
the results of the elementary analysis that the reaction
produced a novel organic phosphorus compound of the following
,
, ' "'

1088238
formula. , ,
G ~1~ J 2 (e~)2
In a blender, 35 parts of poly(2,6-dimethyl-
phenylene-1,4~ether) having a number-average molecular weight
of 12,500, 65 parts of a rubber-reinforced styrene-acrylo- . -
nitrile copolymer having an average acrylonitrile content of ' '
4% and a styrene-butadiene copolymer rubber content of 9.0%
and 8 parts of thè novel organic phosphorus compound
mentioned above were thoroughly mixed. ~hereafter, the result- ~ -
ant mixture was melted and kneaded and molded into pellets
by use of an extruder maintained at temperatures in the
range of from 220 to 270C. The mixed resin thus produced
could be injection molded under conditions of 250C and 600
kg/cm . The molded product was found by tests to have a
tensile strength of 440 kg/cm2 (by the method of ASTM D638,
: which applie,s hereinafter), an Izod impact strength of 12.0
kg.cm/cm (by the method of ASTM D256, which applies hereln-
after) and a heat deflection temperature of 88,2C (by the '
method of ASTM D648, which applies hereinafter). The mixed
~:: resin of this example was tested for inflammability by the
method of UL-94. The ignition time was found to be 7.5
seconds at the most and 2.8 seconds on the average. In the
creep test under tension which was performed at 23C under
a load of 210 kg, the amount of creep after 1,000 hours of
test was 0.99%. "
-- 13 --

1~88238
i`xample 2:
In a blender, 60 parts of poly(2,6-dlmethylphenylene-
].,4-ether) having a number-average molecular weight of 21,000,
40 parts of a rubber-reinforced polystyrene containing 8% Or
polybutadiene rubber and 6 parts of the same r.ovel organic
phosphorus compound as used in Example 1 were mixed. The
resultant mixture was melted and kneaded in an extruder kept
at temperatures in the range of from 230 to 280C, to produce
pellets. Tne mixed resin thus produced could be in~ection
molded under conditions of 260C and 700 kg/cm2. It was
found to have a tensile strength of 620 kg/cm2, an Izod
impact strength of 10.5 kg.cm/cm and a heat deflection
temperature of 109.0C. In the test for inflammability by
the method of UL-94, the i~nition time was found to be 5.5
seconds at most and 1.8 seconds on the average. Thus, the
product was in the V-0 grade. In the creep tests under
tension which were performed at 60C under a load of 105 kg
and at 23C under a load of 210 kg, the amounts of creep ~ .
after 1,000 hours were o . 58% and 1.01%, respectively.
Example 3:
In an extruder maintained at temperatures in the
range of from 220 to 280C, a resin component consisting of
65 parts of poly(2,6-dimethylphenylene-1,4-ether) having a
number-average molecular weight of 99500, 20 parts of a
polystyrene-grafted polybutadiene having a polybutadiene
content of 40% and 15 parts of a polystyrene having a
number-average molecular weight of 105,000 was melted and
kneaded and molded to produce a mixed resin in the form
of pellets. In a blender, 100 parts of the pellets and
4.5 parts of the same novel organic phosphorus compound
- 14 -
-

108823~
as used in Example 1 were mixed. The resultant mlxture was
melted and kneaded in an extruder kept at temperatures in
the range of from 200 to 260C. The resln composition thus
produced could be in~ection molded under conditions of 240C ;~
and 450 kg/cm2. It was found to have a tensile strength of
660 kg/cm2, an Izod impact strength of 18.5 kg.cm/cm and a
heat deflection temperature of 120C. In the test for
inflammability by the method of ~JL-94, the ignition time
was 4.2 second at most and 2.6 seconds on the average. Thus,
the product was in the V-O grade. In the creep tests under
tension performed at 60C. under a load of 105 kg and at 23C
under a load of 210 kg, the amounts of creep were 0.51% and
o.83% respectively, after 1,000 hours.
Example 4: `
The procedure of Example 1 for the prepar~tion of
the organic phosphorus compound was repeated, except 99
parts of a phosphorus compound of the formula
: ~ ~ ' ' ,
~;~ 1- CR
was used in place o~
.
: O=P--O
~: CH2-OH
'
- 15 -

-` 1088238
:[t was confirmed by the infrared absorption spectrum and
the re~ults of elementary analysis that the reaction produced
c~n novel organic phosphorus compound of the following formula:
2 ,~= p- 0 c~)2
~N~ ~ CH2-
In a blender, 5 parts of this novel organlc phos-
phorus compound and 100 parts of the mixed resin pellets --~
obtained in Example 3 were thoroughly mixed. The resultant
mixture was melted and kneaded in an extruder. The resin
composition thus produced could be in~ection molded under
conditions of 240C and 500 kg/cm2. It was found to have
a tensile strength of 590 kg/cm2, an Izod impact strength
of 16.8 kg.cm/cm and a heat deflection temperature of 116.5C. `
In the inflammability test by the method of U~-94, the ignition
- time was 3.5 seconds at most and 1.6 seconds on the average.
Thus, the product was in the V-O grade.
Reference Example 1:
This example involved use of an organic phosphorus
compound which had not undergone-the reaction with an amino
group-containing compound to illustrate, through comparison
of the results with those of Example 4, how much the omission
of said reaction affected the heat deflection temperature.
In a blender~ 100 parts~of the mixed resin pellets
obtained in Example 3 and 5 parts of an organic phosphorus
compound represented by the following formula were thoroughly
mixed and then melted and kneaded in an extruder. The resin
- 16 -
. . .
. . ~ ...~:.
`:

` 108823~
compos~tion thus produced could be in~ection molded under
cond1tions Or 280C and 550 kg/cm2.
~\~ ' .
O = P--O
It was found to have a tenslle strength of 590 kg/cm2, an
Izod impact strength of 11.8 kg.cm/cm and a heat deflection
temperature of 109.5C. In the inflammability test by the
method of UL-94, the ignition time was 7.4 seconds at most
and 3.1 seconds on the average. Thus, the product was in
the V-0 grade.
Example 5:
10Under continued agitation, 50 parts of poly(2,6-
dimethylphenylene-1~4-ether) having a number-average
molecular weight of 9,700,20 parts of styrene and 1.0 part
of di-t-butyl peroxide were heated to 150C over a period
of 10 minutes and then to 240C over the following period
of 10 minutes. The reaction product was molded into pellets
by use of an extruder. The graft copolymer thus produced was
found to have a polystyrene content of 26%. In 40 mQ of
methylene chloride, 2.0 g of the polymer was dissolved and
was left to stand at 30C. Even after 6 hours of this
standing, absolutely no precipitation was recognized. This
proves that no homopolymer of polyphenylene ether remained
in the graft copolymer.
In a blenderg a mixture consisting of 50 parts of
this graft copolymer~ 20 parts of a polystyrene-grafted

11~88Z38
polybutadiene having a polybutadiene content Or 40% and
30 parts of a polystyrene havin~ a number-average molecular
weight of 88,ooo was thorou~lly mixed with 5.0 parts of the
same novel organic phosphorus compound as used in ~xample 1.
The resultant mixture was melted and kneaded in an extruder
kept at temperatures in the range of from 200 to 260C.
The resin composition thus produced could be in~ection
molded under conditions of 220C and 450 kg/cm2. It was
found to have a tensile strength of 430 kg/cm2, an Izod
impact strength of 22.5 kg.cm/cm and a heat deflection
temperature of 106.5C. In the test for inflammability
performed by the method of UL-94, the ignition time was
found to be 8.8 seconds at most and 4.2 seconds on the
average. Thus the product was in the V-0 grade.
Example 6:
In a blender, 60 parts of the graft copolymer
obtained in Example 5, 30 parts of a rubbRr-reinforced
polystyrene having a polybutadiene rubber content of 8%,
10 parts of a polystyrene-grafted polybutadiene having
a polybutadiene content of 40% and 3.5 parts of the same
novel organic phosphorus compound as used in Example 4
were thoroughly mixed. In an extruder kept at temperatures
in the range of from 200 to 260C, the resultant mixture
was melted and kneaded. The resin composition thus produced
could be in~ection molded under conditions of 230C and 450
kg/cm2. It was found to have a tensile strength of 460
kg/cm2, an Izod impact strength of 23.0 kg.cm/cm and a heat
deflection temperature of 112'`C. In the test for inflam-
mability performed by the method of UL-94, the ignition time
was found to be 11.8 seconds at most and 6.8 seconds on
- 18 -
., .
-
.. ~ '

-- 1088238
t;he average. Thus, the product was in the V-l ~rade.
Examples 7 ~10:
By followin~ the procedure of Example 1, novel
organic phosphorus compounds were prepared by using not the
phosphorus compound
~9
o = P o
CH2H
itself but its derivatives. By following the procedure of
Example 4, the compounds were converted into resin compo-
sitions. These compositions were tested for inflammability
by the method of UL-94. The results are shown collectively
in Table 1.
-- 19 --
.
; ' ` ' , .

1088Z38
Table 1
Test of resin composltion
Example Organic for inflammability by the
~o. phosphorus method of UL-94
compound used Maximum Averaee Ratin
(seconds) (seconds) g
7 ~, 9 . 2 Ll ~ 5 V_O
t-Bu
CH3--.
8 =I~ CH3 10.3 4.3 V-l
CH2H
".,: .
CH3 ~
9 o=P~o ?.4 4.4 V-0 ` ~:
2H
6 13 ~CLI3 11.2 4,9 ~ V_1
CH2OH
:~ ~
Examples 11-13:
The procedure of Example 5 was repeated with the ~ :
amount of styrene for graft polymerization varied~ to produce
resin compositions. The compositions were tested for inflam- ~ .
mability. The results are collectively shown ln Table 2. -:
"
' 20 - ~ :
.,
,, . - ~ , .~ .. . . .

~C~88Z3B .,
Table 2
Test of resin composition for
Example Amount of inflammability by the method
~!o. polystyrene in of UL-94
graft copolymer
(%) Maximum Average Rating
(seconds) (seconds)
11 34 13.5 8.4 V-l
12 45 20.2 12.6 V-1
13 58 24.4 20.8 V-l
Examples 14 -18: `~
The procedure of Example 6 was repeated with the
added amount of the nove' organic phosphorus compound varied.
The resin compositions obtained consequently were tested for
inf'lammability. The results are collectively shown in
Table 3.
Table 3
Test of resin composition
Example Amount of organic for inflammability by the
No.phosphorus method of UL-94
compound added
(parts) (seconds) (seconds) Rating
142.5 20.5 14.6 V-l
154.5 10.1 4.8 V-l
16 9 4.0 2.5 V-0
17 13 3.5 1.4 V-0
18 18 1.9 0.9 V-0
Example 19:
A novel organic phosphorus compound was synthe-
sized by repeating the procedure of Example 1, except 9.7
parts of melamine was used in place of the benzoguanamine.

1088Z38
The product showed a melting point of 137C. The infrared
absorption spectrum indicated decreases of OH group and NH2
group. It was confirmed b~y the results of the elernentary
~nalysis that the reactlon produced a novel organic phos-
~horus compound of the followin~ formula.
N~ N ~ ( ~ )4
N- C~ ~C- N 2 CH2
In a blender, 4.0 parts of this novel organic
phosphorus compound was thoroughly mixed with 100 parts of
pellets of the mixed resin obtained in Example 3. The
resultant mixture was melted and kneaded in an extruder
kept at temperatures in the range of from 200 to 260C.
The resin composition thus produced could be injection
molded under conditions of 240C and 450 kg/cm . It was
found to have a tensile strength of 620 kg/cm2, an Izod
impact strength of 19.2 kg.cm/cm and a heat deflection
temperature of 121C. In the test for inflammability
conducted by the method of UL-94 a the ignition time was
10.6 seconds at most and 4.1 seconds on the av~ra~e.
Thus, the product was in the V-l grade.
Example 20: : ;
In a four-necked flask fitted with a stirrer and
a thermometer, 85 parts of a phosphorus compound represented
by the following formula
- - 22 -
- , . , . :

- 1088Z38
o= P-o
CH2OH ~
and 15 parts of methaphenylene diamine were heated in an
oil bath until the temperature within the flask rose to
180C. Under continued agi~ation, the temperature was
further raised to 230C over a period of one hour, during
which period the formed water was removed under reduced
pressure (interior pressure 40 mmHg). When the reaction
- was continued at 230C under said reduced pressure for
two hours~ distillation of water ceased to occur. At this
time, the product was taken out of the flask, cooled and
pulverized. It showed a melting point of 119C. It was
confirmed by the results of the infrared absorption spectrum
and the elementary analysis that the reaction produced a
novel organic phosphorus compound of the following formula:
N ~ N ~] H2 ~ )2
~ thorough mixture of 65 parts of polyt2,6-
dimethylphenylene-1,4-ether) having a number-average
molecular weight of 18,000, 15 parts of styrene and l.0
part of di-t-butyl peroxide was passed through an extruder
kept at temperatures in the range of from l90 to 230C to
undergo polymerization and pelletization at the same time.
The graft copolymer thus obtained was found to have a
polystyrene content of 17.7%. When a 2.0-g portion of - -
- 23 -

-` 108823~
the polymer was dissolved in 40 mQ of methylene chloride
and the solution was left to stand at 30C overnight,
absolutely no precipitate was found. This proves that no
homopolymer of polyphenylene ether remained in the graft
copolymer.
In a blender, a resln component consisting of 50
parts of this graft copolymer, 20 parts of a styrene-grafted
polybutadiene having a polybutadie~;? content of 40% and 30
parts of a polystyrene having a number-average molecular
weight of 85,ooo was thoroughly mixed with 6 parts of the
novel organic phosphorus compound of which the method of
preparation has been indicated in this example. The
resultant; mixture was melted and kneaded in an extruder
kept at temperatures in the range of from 200 to 240C.
The resin composition thus produced could be inJection
molded under conditions of 220C and 450 kg/cm2. It was
found to have a tensile strength of 440 kg/cm2, an Izod
impact strength of 18.5 kg.cm/cm and a heat deflection
temperature of 107C. In the test for inflammability
performed by the method of UL-94 3 the ignition tiMe was -`
found to be 7.5 second at most and 3.9 seconds on the
average. Thus~ the product was in the V-O grade.
Example 21:
In a four-necked flask fitted with a stirrer and
a thermometer, 72 parts of a phosphorus compound represented
by the following formula:
. .
O = I - O
- 24 -
' ' ' .

1~8238
and 28 ~arts of bis(methoxymethyl)-paraphenylenediamine
:~ere heated in an oil bath until the temperature within
the flask rose to 160C. Under continued agitation, the
temperature was further raised to 220C over a period of
one hour, during which period the reaction was continued
removlng the formed methanol under a reduced pressure
(interior pressure 30 mmHg). The interior temperature was
raised up to 250C. After the distillation of methanol
ceased to proceed, the product was taken out of the flask,
cooled and finely pulverized. This product showed a melting
point of 152C. It was confirmed from the results of the
infrared absorption spectrum and the elementary analysis
that the reaction produced a novel organic phosphorus
compound of the following formula:
L N~ N 1~ ( O = ~=O ))2
CH2
In a blender, 3.5 parts of this novel organic
phosphorus compound, 70 parts of the styrene-grafted
polyphenylene ether obtained in Example 20, 20 parts of a
styrene-grafted polybutadiene having a polybutadiene content
of 40% and 10 parts of a polystyrene having a number-average
molecular weight of 92,000 were thoroughly mixed. The
resultant mixture was melted and kneaded in an extruder
kept at temperatures in the range of from 210 to 260C.
The resin composition thus produced could be injection
molded under conditions of 240C and 550 kg/cm2. It was
found to have a tensile strength of 520 kg/cm2, an Izod
- 25 -
~.

1088238
~mpact strength of 23.5 kg.cm/cm and a heat deflection
temperature of 224C. In the test for lnflamma~illty
performed by the method of UL-94, the ignition time was
found to be 6.5 seconds at most and 3 . 8 seconds on the
average. Thus, the product was in the V-O grade.
Example 22- 24:
The procedure of Example 21 was repeated, except
the aromatlc amino compound derivatives shown in Table 4
were used in place of bis(methoxymethyl)-paraphenylenediamine.
The results of the inflammability test conducted on
the resultant resin compositions by the method of UL-94 are
shown in the following table.
Table
Test of resin composition
Ex- Aromatic amino for inflammability by the
ample compound derivatlve method of UL-94
No. used Maximum Average Ratin
(seconds) (seconds) g
'"
22 (CH3OCH2NH - ~CH2 7.2 4.5 V-O ~
CH 3
23 CH3OCH2NHl~NHCH2OcH3 5.0 2.9 V-0 ;
NHCH20CH3
NHC~120C4H9 .
24 ~ 9.2 5.1 V-l
~; NHcH2oc4H9
~ .
Examples 25 - 27:
The procedure of Example 20 was repeated~ except
the diamines shown in Table 5 were used in place of
.
-- 26 --
:; : . .. .
' ' . ' . ~
; ~

1088238
rnethaphenylene dlamine. The re~ults of the test performed
on the resultant resin compositions for inflammability by
l;he method of UL-94 are shown in the ollowing table.
Table 5
Test of resin composition for
inflammabllity by the method
Example Diamine used of UL-94
No. Maximum Average Ratlng
(seconds) (seconds)
CH3 ~ 8.6 4.6 V-O
NH2
:
26 H2N - ~ NH2 5.2 4.1 V-O
27 ~2N ~ N~2 9.1 2 V-l
Example 28-31:
The procedure of Example 21 was repeated~ except
varying combinations of phosphorus compounds and aromatic
amino compound derivatives were used. The resultant resin
compositions were tested for strengths and l'or inflammability
by UL-94. The results are collectively shown in Table 6.
~, - 27 --
:~

1088Z38
W ~ ~ ~ tq
- o ~ co o 1- 3 x
~ W
~o~ o~ ~ ~o~ ' ~'
o~ o~ o,~, o~ C~ ~. '
C~
~ ~ ~ ~ ~ D
W W ~ W ~D ~
g g g o ~ ~ :.
~ ~ X ~ ~ P~ :' ~
~ C~ . :~
~ ~CD~-
~ I X ~o ~ ~Z :C o
O ~ O r3
¢ ~ roO w
,,- .- .
w ' - ~
. ~ u~ ~3
. ~ ~D
Ul Ul ~ \~109 ~ 3 ~.
IJ W ~ 1--~ tD ~q .:
.o o ~n o~ 3 ~
I`~ ~ .-
. ~ ~
Ul 1'~ H
C~ ~ N
l-- ~ ~ ~ ~ O O
o
~n o o~ ~n ~o
~_ ~ .'
1-- ~ 3 cs H ~ :.
. . . . o 1' ~ ~ ~
co ~ ~ ~ C~n
~q ~ ~ P~
_~ I ~ ~
~n ~ ~ p~ O
~D C ~ 3
(D
. . . . O
~o w 1\) ~ 3 P' IJ- o
~q ~
~ ¢ ¢ ¢ ' ~ ' ~
~ I I I ~ P~
o 1- 1- o ~ ~ .'
;
-- 28 --
.
: . :- . .
.:~ ,. .