Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 39~ 8CH-2373
This in~ention is ~irected to a novel thermoplastic
molding composition comprisin~ an aromatic carbonate polymer
and a thermoplastic polyester resin derived from cyclohexane-
dimethanol. This composition may additionally contain a
reinforcing amount of a reinforcing filler.
Polycarbonates are well known and have been widely
employed for the production o~ thermoplastic molded articles.
Polycarbonate is a high performance plastic with good
impac~ strength. In addition to ductility timpact strength),
general purpose polycarbonate has high transparency, wide
temperature limits (high impact resistance below -60C and a ~
UL thermal endurance rating of 115C with impact), good ~ ~ `
dimensional stability high creep resistance and electrical
properties which qualify it as sole support for current carrying
parts (up to 125C without loss of impact strength).
-, Polycarbonate has low water absorption, good stain
' resistance and a wide range of colorability. A weak area for~!
;' polycarbonate is its relatively limited range of chemical
¦ resistance, which necessitates careful appraisal of
- ~0 applications involving contact with certain organic solvents, ;~
some detergents, strong alkali, certain fats, oils, and
........................................................................ .
greases. Also, another weak area of polycarbonates is that
they have high melt viscosities which makes them to some
extent difficult to mold. `
Attempts have been made to blend polycarbonates with
various polymeric systems. Generally, the polycarbonate is not
: . .
miscible with uniformity with the other polymer system.
However, U.S. Patent 3,218,372 dated November 16, 1975, for
example, describes compositions of polyalkylene terephthalate
`~l 30 and polycarbonate resins. These unreinforced compositions
- are described as having a reduced melt viscosity and as
..
- having a higher ductility than the polyalkylene terephthalate
, r
'' ~ - . . . :
8CH-2373
3~
resins. Even in the occasional instances where the polyc~rbonate
is miscible with the other polymer system, the properties
which make polycarbonate a high performance plastic are
generally reduced without additional advantages.
It has been discovered that when an aromatic carbonate
polymer is added to a polyester polymer derived from cyclohexane-
dimethanol, the polycarbonate is compatable with this polyester
over a wide range. An article molded from this composition
retains the transparent characteristics of an article molded
from the polycarbonate. Also, this is achieved without any
appreciable decrease in the mechanical and physical properties,
. .
such as Gardner impact strength, tensile strength or flexural
~ strength, of a typical polycarbonate molding composition.
- Also, the composition of the instant invention has a reduced
, melt viscosity which results in easier molding. Further, an
1 article molded from this composition has better hydrolysis
``' resistance and reduced water vapor transmission rate (this is
1 important in bottles and packaging).
, :- .
-I The instant thermoplastic molding composition comprises:
(a) an aromatic carbonate polymer; and
(b) a polyester polymer derived from cyclohexane-
dimethanol. In a preferred embodiment, the instant thermoplastic
composition comprises:
(a) an aromati~ carbonate polymer;
~ (b) a polyester polymer derived from cyclohexane-
'i dimethanol; and
(c) a reinforcing amount of a reinforcing filler.
The aromatic carbonate polymer of the instant
, invention has recurring units of the formula:
- 30 A
-1 - R - C - R - O - C - O I.
- 2
: . ~
, ,, . : - . :
~ 23~
wherein each -R- is selected from the group consisting of ~:
~ phenylene, halo-substituted phenylene and alkyl substituted :-;
t` phenylene; and A and B are each selected from the group ;~
consisting of hydrogen, hydrocarbon radicals free from aliphatic
unsaturation and of radicals which together with the adjoining ~:
`; .
, ' --C-- ;
atom form a cycloal]cane radical, the total numbe~- of carbon
i ~ atoms in A and B being up to 12.
The aromatic carbonate polymer of this invention may
be prepared by methods well known in the art and as described
~`. in U.S. Patent 3,989,672 dated November 2, 1976. : ;~
. Also, included herein are branched polycarbonates
` wherein a polyfunctional aromatic compound is reacted with
the dihydric phenol and carbonate precursor to provide a
thermoplastic randomly branched polycarbonate wherein the
. recurring units of formula I. contain branching groups.
~,~ The preferred polycarbonate resins may be derived
;' from the reaction of bisphenol-A and phosgene. These ~ .
polycarbonates have from 10-400 recurring units of the ~ ;
formula~
:` CH O
~ 1 3 ~ ll II. : `
O ~ c ~ r O c . ~
: C~I3
~ The polycarbonate should have an intrinsic viscosity
;` between 0.3 and 1.0, preferably from 0.40 to 0.65 as
:
measured at 25C in methylene chloride.
.:
; The instant polyesters are prepared by condensi.ng
~ either the cis- or trans- isomer (or a mixture thereof) 1,4-cyclo-
.~ hexanedimethanol with a hexacarbocyclic dicarboxylic acid so
:
:~ 30 as to produce a polyester having recurring units having the
; ~ following formula:
. ~
-- 3
'~'
~239~ 8CH-2373
CH - CH C! O
2 2 \ tl 11 III .
O CH2 C ~ CH - CH2 - 0-~ - R - C -
CH2 CH2
wherein the substituted cyclohexane ring i5 selected from the
group consisting of the cis- and trans-isomers thereof and R
represents an organic radical containing from 6 to 20 carbon
ato~s which is the decarboxylated residue derived from a
hexacarbocyclic dicarboxylic acid.
The preferred polyester resins may be derived from the
reaction of either the cis- or trans- isomer (or a mixture
thereof) of 1l4-cyclohexanedimethanol with a mixture of iso- and
terephthalic acids. These polyesters have recurring units of
the formula:
/ CH2 ~ CH2 ~ ~ IV.
CH - CH
These polyesters can be produced by well known methods
-~ in the art such as those set forth in U.S. Patent 2,901,466,
::
dated August 25, 1959.
Of course, it is understood that the polyester resins
. ~ ,
of this invention can be prepared by condensing 1~4-cyclohexane-
dimethanol and minor amounts of other bifunctional ~
glycols with the hexacarbocyclic dicarboxylic acid. These other -;
bifunctional glycols include the polymethylene glycols containing
` from 2 to 10 or more carbon atoms such as ethylene glycol,
butylene glycol, etc. ~
Examples of hexacarbocyclic dicarboxylic acids wherein ~ ;;
the carboxy radicals are attached in para relationship to a
hexacarbocyclic residue indicated by R in formula III include
terephthalic acid, trans-hexhydroterephthalic acid, p,p'-sulfonyl-
dibenzoic acid, 4,4'-diphenic acid, 4,4'-benzophenonedicarboxylic
acid, 1,2-di(p-carboxyphenyl) ethane, 1,2-di~p-carboxyphenoxy)
8~H-2373
~V~Z39~ ~:
ethane, 4,4'-dicarboxydiphenyl ether, etc. and mixtures of these.
All of these acids contain at least one hexacarbocyclic nucleus.
Fused rings can also be present such as in 1,4- or 1,5-naphtha-
lenedicarboxylic acid. The hexacarbocyclic dicarboxylic acids
are preferably those containing a trans-cyclohexane nucleus or
an aromatic nucleus containing from one to two benzene rings of
which at least one has the usual benzenoid unsaturation. Of
course, either fused or attached rings can be present. All of
the compounds named in this paragraph come within the scope of
this preferred group. The preferred dicarboxylic acid is
terephthalic acid, or mixtures of terephthalic and isophthalic
acids.
... .
These polyesters should have an intrinsic viscosity
between 0.40 and 2.0 dl./g. measured in a mixture of 40%
tetrachloroethane/60~ phenol solution or a similar solvent at
25C-30C. Especially preferred polyester will have an
intrinsic viscosity in the range of 0.6 and 1.2 dl./g.
The reinforcing agents may be selected from finely
divided aluminum, iron or nickel and the like, metal oxides and
non-metals, such as carbon filaments, silicates, such as mica,
aluminum silicate (clay), talc, asbestos, titanium dioxide,
Wollastonite, novaculite, potassium titanate and titanate
whiskers, glass flakes, glass beads and fibers, and polymeric
fibers and combinations thereof.
Although it is only necessary to use a reinforcing
amount of the reinforcing agent, from 1-60 parts by weight of
the total weight of the composition may comprise the reinforcing
agent. A preferred range is from 5-40 parts by weight.
The preferred reinforcing agents are of glass, and
it is preferred to use fibrous glass filaments, mixtures of
glass and talc, glass and mica and glass and aluminum silicate,
for example. The preferred filaments for plastics reinforcement
.
-- 5 --
~8~3~ 8CH-2373
are made by mechanical pulling. Preferably, the glass filament
diameters ran~e from about 0.00012 to about 0.00075 inch, bu~
this is not critical to the present invention. ;
The aromatic carbonate polymer may comprise from
1 to 99 parts by weight of the composition and the polyester resin
. ~ ,
derived from cyclohexanedimethanol resin may comprise from 99
to 1 parts by weight of the composition. Preferably, the
aromatic carbonate polymer comprises from 25 to 98 by weight of
the composition and the polyester derived from cyclohexane-
dimethanol comprises from 2 to 75 by weight of the composition~
The instant composition may be prepared by anystandard procedure and the particular method employed is not
critical. For example, pellets made from the polycarbonate
resin can be blended with pellets made from the instant
polyester resin in an extruder under standard conditions. ;~
Obviously, other materials can also be employed with
- the composition of this invention and include such materials as
antistatic agents, pigments, mold release agents, thermal ~;
stabilizers, impact modifiers, extenders, UV stabilizers,
:~- 20 nucleating agents, flame retardants and the like.
Illustrative flame retardants are disclosed in ~-~
U.S. Patents No. 3,917,559 dated November 4, 1975; ;~
: :
No. 3,919,167, dated November 11, 1975; No. 3,926,908, dated
December 16, 1975; No. 3,931,100 dated January 6, 1976;
No. 3,933,734 dated ~anuary 20, 1976; No. 3,948,851, dated
April 6, 1976; No. 3,951,910 dated April 20, 1976; No. 3,953,396
dated April 20, 1976, and No. 3,940,366, dated February 24, 1976.
Preferred flame retardant additives are metal salts
~` of sulfonic acids. These are the alkali metal or alkaline earth
metal salts of: monomeric or polymeric aromatic sulfonic acids;
monomeric or polymeric aromatic sulfone sulfonic acids; aromatic
. , .
ketone sulfonic acids; heterocyclic sulfonic acids; halogenated ~
.,' ~ .
~ - 6 -
',, '
,~ .
- , , - . .
: : . .- : : , - :~ .. : : :
8CH- 2 3 7 3
methane sulfonic acids; halogenated non-aromatic carboxylic
acids; aromatic sulfide sulfonic acids; monomeric or polymeric
aromatic ether sulfonic acids; aliphatic and olefinic
sulfonic acids; monomeric or polymeric phenol ester sulfonic
acids; unsubstituted or halogenated oxocarbon acids; monomeric
and polymeric aromatic carboxylic acids and esters and monomeric
and polymeric aromatic amide sulfonic acids.
These flame retardant additives are used in minor
amounts~ preferably from 0.01 to about 10 weight percent, based
on the weight of the combination of the aromatic carbonate
polymer and polyester.
; In order to more fully and clearly illustrate the
present invention, the ~ollowing specific examples are
presented. It is intended that the examples be considered as
illustrative rather than limiting the invention disclosed
and claimed herein. In the examples, all parts and percentages
are on a weight basis unless otherwise specified.
.
:. EXAMPLE
. ,
The following compositions were prepared by meIt
blending the components in an extruder (all parts are by weight):
:
A B C D E F
-- -- -- _ _ _ ,
polycarbonate resin* - 100 75 70 60 40 35
poly(l,4-cyclohexanedimethanol - 25 - 40 60 35
terephthalate-co-isophthalate)**
:, ,
glass - - 30 - - 30
,.1 * LEXAN~ 101 (General Electric Company)
'~ ** KODAR~ A150 (Eastman Kodak Company)
The compositions of Example I were tested and
found to have the following physical properties as set forth
in Table I.
,
- 7 -
8CH-2373
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u~ ~ a~ co
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u~ ~ o o
u~ ~ ~ o
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r~ OD CO O
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: ~ ~ N o
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m l U~
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8CH-2373
The following compositions were prepared by melt
blending the components in an extruder (all parts by weight):
G H I J K L M
polycarbonate resin* 100 75 70 60 50 40 35
poly(l,4-cyclohexanedimethanol - 2 5 - 4 0 5 0 6 0 3 5
terephthalate-co-isophthalate)**
glass - - 30 - - - 30
~ * LEXAN 101
: * * KODAR A15 0 - ~
The compositions of Example II were tested and ~ `
~; found to have the following physical property as set forth
in TABLE I I . - `
TABLE II
G H I J K L M
Gardner Impact Strength (in.-lbs.)560 560 8 560 560 560 8
EXAMPLE III
.,-~
, The followi~g compositions were prepared by melt
blending the components in an extruder (all parts by weight): ;
~ _ P O R S T U
polycarbonate resin* 100 90 75 60 50 40
poly(l,4-cyclohexanedimethanol _ 10 25 40 50 60 90 100
terephthalate-co-isophthalate)**
* LEXAN 101
** KODAR A150
The melt vlscosity of the compositions of Example III
were measured and the results are set forth in TABLE III.
:
- TABLE III
:~
N O P Q R S T U
Melt Viscosity 9872 8710 6452 4970 4264 3551 2440 2303
(poise) -
; 30 Time (sec.) 43.3 38.2 28.3 21.8 18.7 15.6 10.7 10.1
.,
- ' ~
:~ _ g _
. ~
, ,
,, .
8CH-2373
~)8:2 394
EXAMPLE IV
The following compositions were prepared by melt
blending the components in an extruder (parts by weiyht):
V W
polycarbonate resin* 100 95
poly(l,4-cyclohexanedimethanol
terephthalate-co-isophthalate)** - 5
* LEXAN 101
** KODAR A150
The compositions of Example IV were tested and
found to have the following physical properties as set forth
in TABLE IV. ;~
TABLE IV
~ V W ~
Melt Viscosity (poise) 3250 2485
Notched izod impact strength (ft.lbs./in.) 14.7 15.5 ;~;
Double gated izod impact strength (ft-lbs) 40 40
EXAMPLE V
The following compositions were prepared by melt
blending the components in an extruder (parts by weight)~
X Y . :~
..
polycarbonate resin* 91 87.6
` glass 0 4
poly(l,4-cyclohexanedimethanol
terephthalate-co-isophthalate)** 9 8.4
* LEXAN 101
** KODAR A150
The compositions of Example V were tested and
found to have the following physical properties as set forth `
in TABLE V.
TABLE V
:~ _ Y ~ '
Notched izod impact strength (ft-lbs/in) 1.9 3.3
Flexural modulus (psi) 500,000 496,000
Flexural streng~h (psi) 15,000 15,400
, - 10 -
. . - .,-- - -, . .. : j
Z3~3~
8cH~2373
EXAMPLE VI
The following compositions were prepared by melt
blending the components in an extruder ~parts by weight):
A' B'
polycarbonate resin* 75 75
poly(l,4-cyclohexanedimethanol
terephthalate-co-isophthalate)** 25
poly(ethylene terephthalate)*** - 25
* LEXAN 101
** KODAR A150
*** VITEL VFR 3801
The compositions of Example VI were tested and
found to have the following physical properties as set forth in
TABLE VI.
TABLE VI ,
` A' B'
Light Transmission (~) 87 35
Tensile elongation (%) 148 108
From the preceding Tables, it can be seen that the
.;~ . - ..
~ 20 composition of the instant invention retains the useful
-~ properties of aromatic polycarbonate resins while additionally
- demonstrating improved melt flow properties without loss of
impact strength.
~; Although the above examples have shown various
modifications of the present invention, other variations are
possible in the light of the above teachings. It is therefore
to be understood that changes may be made in the particular
embodiments of the invention described which are within the
full intended scope of the invention as defined by the
appended claims.
"'..'
. :
- 11 -
