Note: Descriptions are shown in the official language in which they were submitted.
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23443-321D
This is a divisional application of Serial NoO 509,477
filed May 20, 1986.
The present invention relates to a polyphenylene ether
based thermoplastic molding resin.
Polyphenylene ethers (PPE) are technical high perfor-
mance thermoplastic materials which have high melt viscosities and
softening points. They are therefore suitable in numerous
engineering applications in which stability at high temperatures
is important (see US Patents 3,306,874, 3,306,875, 3,257,357 and
3,257~358). ~owever, certain properties of polyphenylene ethers
make the same undesirable in many engineering applications. For
example, molded parts of polyphenylene ethers are brittle, because
of their poor impact resistance.
The high melt viscosities and softening points of PPEs,
difficulties in processing. Further, consideration must be given
to the fact that polyphenylene ethers tend to be unstable and
discolor at high temperatures.
Another characteristic of polyphenylene ethers is that
they are soluble in many organic solvents or swell to a large
extent. This means that PPEs are unsuitable in applications where
they would as a matter of course come into contact with organic
solvents~
Another characteristic of polyphenylene ether resins is
that their properties can be improved by mixing with other
polymers. Thus, for example, blends of PPE with impact-resistant
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polys-tyrenes have attained substantial technical importance ~see
German Patents 2,119,301 and 2,211,005). These resln ~ompounds
can be readily processed into molded parts which have sufficient
impact-resistance. However, the compounded material has the dis-
advan-tage that with increasing polystyrene content, the heat
distortion temperature of the blends decreases when tested. These
resin blends also, however, have unsatisfactory solvent resis-
tance.
Compound blends of polyphenylene ethers and polyamides
exhibit good flowability and also ~ood solvent resistance (see
examined German Patent Application Nos. 1,694,290 and Published
Unexamined Japanese Patent Application No. 78-847,390). However,
such resin blends are usual.ly brittle, because the two components
are incompatible and are poorly dispersable in each other.
Aromatic polyamides, such as the types which have been used and
which are described, for example, in Published Unexamined European
Patent Application No. 0,131,445, have poor processibility with
polyphenylene ethers. However, bet-ter compatibility of both
phases can be achieved by functionalizing the polyphenylene ether
component, e.g., with maleic anhydride, in the presence of a
radical initiator (J.5/906,452). However, the use of a radical
initiator leads to an undesirable and uncontrolled partial gelling
of the PPE-phase.
In view of the above stated compatability problems oE
PPE-polyamide, it has been suggested that the compatibility of
both polymers can be increased by adding a sufficient quantity of
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a lubricant such as an organic phosphate (see Unexa~ined
European Applicati.on ~o. 0,129,825) or a diamide (see Unexamined
European Patent Application No. 0,115,218) to the .resin blends.
However, thi.s attempted solution to the problem is not
satisfactory, because, although improved compatability is
achieved, the resin blend exhibits considerably reduced heat
distortion temperature.
The same disadvan-tages are characteristic of molding
compounds to which copolymers of styrene and unsaturated acid
derivatives have been added (see Unexamined European Patent
Application 0,046,040).
Another reference, which is European Patent No.
0,024,120, discloses resinous compound blends which are composed
of a polyphenylene ether, a polyamide, a third component and,
appropriately, a high-molecular caoutchouc polymer. Suitable
third components include liquid diene-polymers, epoxy resins or a
compound having a double or triple bond and a functional group
such as an acid, anhydride, ester, amino or alcohol group.
~owever,the impact resistance of the resinous compound which is
obtained is insufficient for many applications. A need therefore
continues to exist for a molding composition based on polypheny-
lene ether which is readily processible and which exhibits
improved properties.
Accordingly, it is attempted in the present invention
to provide a thermoplastic resin composition which gives molded
products having high solvent resistance, high impact resistance
and a high heat distortion temperature under hea-t, and good phase
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bonding which is recognizable by high elongation values at the
point of tearing.
Accordingly, an aspect of the present invention provides
a thermoplastic resin composition which comprises:
a) from 5 to 85 parts by weight preferably 20 to 50
parts by weight, of a melted or remelted preliminary molding
compound consisting of:
60 to 98 parts by weight of a polyphenylene ether,
40 to 2 parts by weight of a polyoctylene,
0.1 to 5 parts by weight of maleic anhydride, and
from 0.1 to 5 parts by weight of a further acid deriva-
"~ tive which has a melting point below 100C and which is selected
from the group consisting of an unsatura-ted mono- or dicaxboxylic
acid having up to 14 carbon atoms, an anhydride thereof, which
excludes maleic anhydride, and an ester of said mono- or
dicarboxylic acid with an alcohol of up to 6 carbon atoms;
(b) from 95 to 15 parts by weiyht preferably 80 to 50
parts by weight, of an aliphatic homopolyamide or a copolyamide
containing a preponderant amount of aliphatic monomer units.
Another aspect of the present invention provides a
process for producing the thermoplastic resin composi-tion as
defined above, comprising:
;~ (a) treating a solid mixture of the polyphenylene
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ethers and the polyoctenylenes, with maleic anhydride and said
acid component;
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(b) melting the mixture obtained; and then
(c) adding said polyamide to said melt.
Still another aspect of the invent:ion provides a process
for production shaped articles, which process comprises molding
-the thermoplastic resin composition defined above into the desired
shaped article.
Ye~ further aspect of the invention provlcles a shaped
article produced by molding the thermoplastic resin composition
defined above.
Thermoplastic resin compositions within the scope of
the present invention are those thermoplastic resin formulations
which can be processed into molded articles or into semiproducts
by thermoplastic processing. The thermoplastic resin compositions
may be processed in gran~1lates form, Eor example. It is of
importance that the molding compound is melted or remelted prior
-to its use in the thermoplastic compositions.
Suitable polyphenylene ether starting materials include
polyethers which are based on 2,6- dimethylphenol, with the ether
oxygen of one unit being bonded to the benzene nucleus of the
adjacent unit. At least 50 units should be ~oined togetherO
In principle, other o,o'-dialkylphenols can also be used,
whose alkyl residue preferaby has a maximum of 6 carbon atoms,
with the proviso that such molecules do not contain a tertiary
carbon atom in the alkyl groups. Hcwever, phenol compounds which
are substituted in the alpha position by a tertiary alkyl residue
particularly a tertiary butyl resldue, only in one ortho position
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can also be employed. Each of the monomer phenols mentioned may
be substituted by a methyl group in the 3-position, and also in
the 5-position. Mixtures of the above men-tioned monomer phenols
can be used as well.
The polyphenylene ethers can be produced from the
phenols, e.g~, in the presence of complex-forming agents such as
copper bromide and morpholine (see German Unexamined Patent
Applications 3,224,692 and 3,224,691). The viscosity numbers,
determined by the procedure of DIN 53 728 in chloroform at 25C,
are in the range from 35 to 80 cm3/g. A preferred polyphenylene
ether is the polymer of 2,6-dimethylphenol, which is poly-(2,6-
dimethyl-1,4-phenylene ether) which has a viscosity number of 40
to 70 cm3/g.
The polyphenylene ethers are usually employed :in the
form of a powder or as granulates.
The polyoctenylene ingredient of the melted or remelted
preliminary molding compound is produced by the ring-opening or
ring-extending polymerization of cyclo-octene (see, e.g., A.
Draxler, Kautschuk, Gummi, Kunststoffe 1981, pages 185 to 190).
Polyoctenylenes having different amounts of cis- and trans double
bonds, as well as different J-values and correspondingly different
molecular weights, are obtainable according to methods known from
the literature. Preferred polyoctenylenes are those with a
viscosity number of 50 to 350 cm3/g, preferably-80 to 160 cm3/g,
as determined in 0.1% solutions in toluene. These polyoctenylenes
have usually from 55 to 95%, preferably 75 to 85% of the double
bonds in the trans-form.
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Various procedures may be used to produce a mixture of the
polyphenylene ether and the polyoctenylene. One procedure is to
dissolve both polymers in a suitable solvent, and then the mix-ture is
isolated by evaporation of the solvent or by precipitation of the
mixture with a nonsolvent. Another possible procedure is to unite
both polymers in a melt. Further details of this procedure can be
found in German Patent Application P 3 436 780.2 entitled
"Thermoplastic Compounds On The Basis Of Polyphenylene Ethers And
Polyoctenylenes, As Well As A Process For Their Production."
The polymer mixture which is obtained by an appropriate
procedure is then treated with a mixture of maleic anhydride and
the further acid derivative. This is accomplished by diefusing a
liquid mixture of both acid materials into the solid melted or
remelted preliminary molding compound at temperatures under 100C,
preferably under 50C, under such conditions that no sticking of
the granules takes place. This is achieved, for example, by large
area application. ~inally the mixture is remelted at a tempera-
ture of 270 to 350C.
It is very lmportant that the further acid derivative
has a melting point under 100C. Suitable acid derivatives
include unsaturated mono- and dicarboxylic acids having up to 14
carbon atoms, their anhydrides, except for maleic anhydride, and
esters of the acids with saturated or unsaturated alcohols which
have up to 6 carbon atoms. The esters of acrylic acid and of
fumaric acid with saturated alcohols are preferred, especially
those with n-butanol. A mixture of 0.1 to 5 parts by weight each
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of maleic anhydride and the further acid derivative is used per
100 parts by weight of the total of the polyphenylene ether and
the polyoc-tenylene.
Homo- and copolymers, preferably oE exclusively
aliphatic s-tructure, are suitable polyamides. In particular, the
6-, 4,6-, 6,6-, 6,12-, 11- and 12-polyamides are preferred. Also
suitable, however, are mixed aliphatic-aromatic copolyamides,
provided the amount of fundamental aliphatic units in the
polyamide is preponderant (see US Patents 2,071,250; 2,071,251,
2,130,523, 2,130,948; 2,241,322; 2,312,966; 2,512,606; 3,393,210,
Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.18, John
Wiley & Sons (1982), pages 328 through 435). The number average
molecular weight of the polyamides used Eor this purpose is
usually higher than 5,000, preferably higher than 10,000.
The mixing of the polyamide ingredient with the melted
or remelted preliminary molding compound treated with acid is
effected by mixing the two melts into a well-kneading aggregate a-t
a temperature 250 to 350C, preferably at 270 to 310C.
It is advantageous to premix the two components while
dry and then to extrude them or to add the polyamide into the melt
of the melted or remelted preliminary moldîng compound treated
with acid.
In mixing the polyamide ingredient with the melted or
remelted preliminary molding compound treated with acid, from 95
to 15 parts by weight of the molding compound treated with acid.
Preferred quantities of ingredients are 80 to 50 parts by weight
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o-f the polyamide with 20 to 50 parts by weight of the molding
compound.
The thermoplastic molding resin composition may additio-
nally contain unmodified or impact-resistant modified polystyrene
resins. In order to obtain the desired high heat distortion
temperature, the thermoplastic molding resin formulations should
contain relatively small amoun-ts of the polystyrene ingredient.
The thermoplastic molding resin composition oE the
invention may also additionally contain a flame retardant, as
we]l as such additional ingredients as pigments, oligomers and
polymers, anti-static agents, stabilizers and auxiliary processing
products, as well as reinforcing agents. The amount oE the
reinforcing agent shoul.d be ~lp to 50~, that of the flame retardant
up to 15~ and that of all the other added substances together up
to 5%. In each case the stated quantities are based on the total
quantity of thermoplastic molding resin composition.
Suitable flame retardants include aromatic phosphorus
compounds such as triphenylphosphine oxide and triphenylphosphate.
Conventional halogen containing flame retarding agents may also be
used and these compounds include the halogen containing organic
compound~ disclosed in the monograph of H. Vogel,
"Flammenfestmachen von Kunststoff", Huethig-Verlag, 1966, pages 94
to 102.
However, halogenated polymers such as halogenated
polyphenylene ethers (see German unexamined patent application
3,334,068) or brominated oligo- or polystyrenes can also be
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considered. The compounds should contain more than 30% by weight
halogen D
In the event that a halogen-containing flame retarding
agent is employed, it is recommended that a synergist be used.
Suitable such synergists include compounds of antimony, boron and
tin. In general, they are used in quantities of 0.5 to 10 ~ by
weight, based on the amount of thermoplastic molding resin compo-
sitions.
Glass and carbon fibers are especially suitable as
reinforcing agents.
Suitable stabilizers include organic phosphites such as
didecylphenylphosphite and trilaurylphosphite, sterically blocked
phenols, as well as tetramethy:Lpiperidine, benzophenone an~
triazole derivatives.
Suitable auxiliary processing agents include waxes such
as oxidized carbohydrates, as well as their alkali metal salts
and alkaline earth metal salts.
The thermoplastic molding resin composition obtained
can be processed by the processes normally used for the processing
of thermoplastics, e.g., injection molding and extrusion, into
various molded articles.
Molded objects, which are used in various technical
fields of application such as pipes, plates, casings and other
technical products for the automotive, electrical and precision
mechanics industries can be prepared from the present thermoplas-
tic resin composition.
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In contrast to state-of-the-art resins, products
prepared from the molding resin of the present invention are
distinguished hy good high heat distortion temperature and good
resistance to solvents. When the present thermoplastic resin
composition is molded, it is distinguished by having a high impact
resistance.
Having generally described -~his invention, a further
understanding can be obtained by reference to certain specific
examples which are provided herein for purposes of illustration
only and are not intended to be limiting unless otherwise
specified.
The viscosi~ number (J) of polyphenylene ether is
measured in cm3/~ by -the procedure of DIN 53 728 at 25C in
chloroform (concentration 0.5~ by weigh-t).
The notched-bar impact strength (a ) of molded objects
was measured by the procedure o~ DIN 53 433 wi-th a rectangular
notch at room temperature on standard small bars injection-molded
at 290C.
The elongation a-t tear (epsilonR) was determined by
the procedure of DI~ 53 455 on shoulder bars injection molded at
290C
The Vicat softening temperature was determined by the
; procedure of DI~ 53 699 on 4 mm thick molded articles
injection-molded at 29aoc.
Exam~les
Manu~acture and origin o~ the components:
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1. Polyphenylene ether
Polyphenylene ether is obtained by the oxidative
coupling of 2,6-dimethylphenol. The reaction is stopped when the
desired J-value for the product is obtained, and the product is
extracted as described in German Unexamined Patent Applications
3,313,864 and 3,332,377.
Example 1.1
A polyphenylene ether having a J-value of 55 cm3/g is
produced by the procedure described above. The solvent is removed
by evaporation and the melt is extruded by way of a degassing
extruder. The product obtained is granulated and dried.
Example 1.2
A polyphenylene ether having a J-value of 55 cm3/g is
produced in the form of a 10~ toluene solu-tion.
2. Polyoctenylenes
A polyoctenylene having a J-value of 120 cm3/g and a
trans-content of 80~ is used. Such a product is available commer-
cially under the trademarX of VESTENAMER~ 8012 (manufacturerO
HULS AKTIENGESELLSCHAFT, D-4370 Marl 1). Additional characteris-
tic data on this product can be found in the periodical"Kautschuk, Gummi, Kunststoffe",1981, pages 185 to 190, as well as
in the Huls-Data Sheet No. 2247 "VESTENAMER 8012." The
polyoctenylene can also be produced by the procedure described in
K.J. Ivin "Olefin Metathesis," Academic Press, pages 236 ff.,
1983 and in the literature references cited there.
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3. Mixture of polyphenylene ethers and polyoctenylene
In the solution described in Example 1.2, -the
polyoctenylene is dissolved by the procedure of Example 2, with 10
parts by weigh-t of polyoctenylene for every 90 parts by weight of
polyphenylene ether. The remaining solvent is removed by means of
a degassing extruder, and the product is granulated and dried.
4. Production of the melted or remelted preliminary molding
compound.
To 2 kg of the mixture according to example 3 aliquid
mixture (temperature 50C) of the acid derivatives, shown in Table
1 are added in small amounts in a laboratory mixer at room temper-
ature, without sti.cking of the granules.
In a twin-screw kneading machine, the -thusl.y treated
granules are remelted at 290C melting temperature, granulated and
dried.
Table 1
Test 4.1 Test 4.2
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Quantity of the mixture
of PPE and polyoctenylenes 2000 g 2000 g
Quantity of maleic anhydride 20 g 20 g
Further acid derivative n-butyl fumaric
acrylate acid-di-n-
butylester
Quantity o the further acid
derivative 20 g 20 q
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Comparative Test A
To 2 kg of the mixture according to example 3 is added
portionally a liquid mixture of 20 g maleic anhydride and 20 g
n-butyl acrylate (temperature 50C). The reaction mixture is
mixed immediately with the polyamide i.e. without remelting prior
to its use.
Comparative Test B
A 20 g amount of maleic anhydride is admixed in a twin-
screw kneading machine to 2 kg PPE by the procedure of Example 1.1
at a melting temperature of 290C. The product is subsequently
granulated and dried.
Comparative Test C
Similar to the procedure of Example B, 20 g maleic
anhydride and 10 9 dicumyl peroxide are admixed with 2 kg PPE.
5. Molding compositions
The mixtures produced by the procedures described in
Examples 4.1,4.2, A' B and C are mixed with polyamides as describ-
ed in Table 2, and the resulting mixture is remelted at 290C in a
twin-screw extruder, the dispersion action of which is reinforced
by kneading blocks. The material is then granulated and dried.
The product is injection molded into normal bodies and tested.
ULTRAMID~ B 4, a product of BASF AG, D-6700
Ludwigshafen, is used as a polyamide 6 compound. ULTRAMID~ A 4,
a product of BASF AG, D-6700 Ludwigshafen, is used as a polyamide
66 compound. VESTAMID~ L 1900, a product of Huls AG D-4370
Marl, is used as a polyamide 12 compound.
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Table 2 shows that the values of the elongation at tear
as well as the values of the notched~bar impact strength are
reduced substAntially,
- if the preform is not remelted ~see comparative test A).
- if maleic anhydride is employed instead of a mixture of maleic
anhydride and a further acid derivative and if PPE is used instead
of a mixture of PPE and polyoctenylene.
- if an organic peroxide is employed instead of a mixture of
maleic anhydride and a further acid derivative.
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Having now fully described the invention, lt will be
apparent to one of ordinary skill in the art that many changes and
modifications can be made thereto without departing from the
spirit or scope of the present invention as set forth herein.
