[0001] The present invention concerns heterogeneous blend comprising polycarbonate and rubber
modified copolymers.
[0002] French patent 2.187.841 relates to a composition containing a polycarbonate which
may be prepared from dihydroxylated aromatic compounds, such as bis(hydroxyphenyl)
phenylmethane and a nitrile rubber which is an elastomeric copolymer containing 50%
in weight of a copolymerized diene such as butadiene with at least 2% of an acrylic
monomer such as acrylonitrile. These blends present good impact resistance.
[0003] French patent 1.604.656 discloses a blend of a grafted polymer obtained by polymerising
a conjugated diene and then by polymerizing an acrylonitrile or acrylic ester monomer
and a monovinyl aromatic monomer in the presence of prepolymerized latex polymer,
a copolymer such as acrylonitrile copolymerized with a monovinylic aromatic hydrocarbon,
and a polycarbonate prepared from bisphenol A and phosgene.
[0004] US patent 3.873.641 teaches molding compositions containing polycarbonates of bisphenol-A
and rubber-modified copolymers. The blends of this reference, while showing improved
heat distortion, suffer from reduced impact resistance. The blends of the present
invention provide economical polycarbonate compositions which exhibit improved processibiity
while retaining or exceeding the desirable properties characteristic of polycarbonates
such as impact strength, heat resistance and resistance to stress cracking.
[0005] The heterogeneous blend according to the invention comprises 10 a 90% by weight of
a polycarbonate and 90 to 10% by weight of a rubber-modified copolymer of a monovinylidene
aromatic monomer and an alpha, beta-ethylenically unsaturated comonomer having a pendant
polar group, saidl rubber-modified copolymer containing (a) a rubber (b) a random
copolymer of the monovinylidene aromatic monomer and the polar comonomer and (c) a
graft copolymer containing the rubber grafted or blocked with a copolymerized mixture
of the monovinylidene aromatic monomer and the polar comonomer, said random copolymer
having a solubility parameter within the range from 9.2 to 11.2, and are characterized
in that the polycarbonate comprises a trityl diol.
[0006] The polycarbonate blends of this invention are suitably employed in most of the applications
in which polycarbonates and rubber modified polymers have previously been utilized.
Applications of particular interest for these polycarbonate blends are housings for
electrical appliances, radio and television cabinets, automotive equipment including
ornaments and lawn equipment including lawn furniture and the like.
[0007] The polycarbonate compositions of the present invention are heterogeneous blends
wherein the essential components, i.e., the polycarbonate and rubber-modified copolymer,
exist as at least two separate and distinct phases. The proportions of the blend components
are not particularly critical and each component can vary from 10 to 90 weight percent
based on the total blend weight. So long as there is sufficient of each component
to provide the impact resistance described hereinafter, proportions of the blend components
within the aforementioned range of proportions are suitable. Preferably, however,
the blend comprises from 40 to 90 weight percent of the trityl diol polycarbonate,
most preferably from 50 to 80 weight percent, and from 60 to 10 weight percent of
the rubber-modified monovinylidene aromatic copolymer, most preferably from 50 to
20 weight percent.
[0008] The blends of the present invention are normally solid thermoplastic materials, preferably
having melt flow viscosities as determined by ASTM D-1 238-65T (Condition I) in the
range from 0.1 to 5 decigrams per minute (dg/min), more preferably from 0.3 to 2 dg/min,
most preferably from 0.5 to 2 dg/min.
[0009] While the blends of this invention exhibit improved flow properties as might be expected,
they exhibit heat and impact resistance which are unusually high in view of the heat
and impact resistances of the blend components. Most surprisingly, in some preferred
embodiments, the impact resistance of the blend actually exceeds the impact resistance
of the polycarbonate component. In other embodiments, the notched Izod impact resistance
of injection molded samples of the blend exceeds 4 foot-pounds/inch of notch (214
Newton-meters/meter of notch), and often exceeds 5 foot-pounds/ inch of notch (267
Newton-meters/meter of notch) as determined by ASTM D-256.
[0010] The trityl diol polycarbonates employed in the practice of this invention are polymers
of trityl diols including copolymers thereof with other aromatic diols wherein the
diols are linked together through carbonate linkages. In this polycarbonate, the proportion
of trityl diol is such preferably that the polycarbonate has a Vicat softening temperature
of at least 160°C, preferably at least 175°C. Generally the Vicat softening point
of the polycarbonate is no greater than 270°C, preferably less than 210°C. Preferably
such proportions of the trityl diol ranges from 10 to 100 mole percent, more preferably
from 10 to 60 mole percent and most preferably from 20 to 40 mole percent based on
the total diol content of the polycarbonate. While the molecular weight of the polycarbonate
is not particularly critical, it is advantageously sufficient to provide the polycarbonate
with the desired Vicat softening point. Preferably the weight average molecular weight
of the polycarbonate is from 15,000 to 75,000, more preferably from 20,000 to 40,000
and most preferably from 25,000 to 35,000.
[0011] The trityl diols as used herein are those compounds having an ar,ar'-dihydroxytrityl
nucleus represented by the formula:
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0001)
wherein the aromatic rings may bear, in addition to the hydroxy substituents such
substituents as, for example, H, F, Cl, Br, I, -N0
2, alkyl, acyl, carboxylate ester, sulfonate ester, an oxycarbonyl group, secondary
amide group or oxysulfonyl group bridging the methan carbon atom and the ortho carbon
atom of the non hydroxylated ring, a carbonyl group bridging the ortho carbon of the
non hydroxylated ring and the ortho carbon of one of the hydroxylated rings, or by
an -0- group bridging the hydroxylated aromatic rings meta to the hydroxyls.
[0012] Representative trityl diols include phenolphthalein type compounds as described in
U.S. Patent No. 3,036,036 corresponding to formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0002)
in which R, substituents are independently selected from the group consisting of H,
lower alkyl radicals having 1-4 carbon atoms, Cl, Br, I and NO
2; phenolsulfonephthalein compounds as described in US patent 3.036.037 corresponding
to formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0003)
in which R
1 has the meaning as above defined; phthalidein compounds as described in US patent
3,036,038 corresponding to formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0004)
fluorescein compounds as described in US patent No 3,036,039 corresponding to formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0005)
in which has the meanings are as above defined, and phenolphthalimidene compounds
corresponding to the phenolphthalein compounds described in US patent No 3,036,036.
The hexagons represent in the above mentioned formulae benzene rings.
[0013] Of the foregoing trityl diol compounds, phenolphthalein and substituted phenolphthalein
wherein the substituents are chlorine and bromine are preferred, with phenolphthalein
being the most preferred. All of the foregoing trityl diols may be prepared by known
methods as exemplified in the aforementioned patents.
[0014] In addition to the aforementioned trityl diol, the polycarbonate may contain residues
of other diols, preferably aromatic diols such as the dihydric phenols represented
by the formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0006)
wherein A is an aromatic group such as, for example, phenylene, biphenylene, naphththylene,
and anthrylene, E is alkylene or alkylidene such as, for example, methylene, ethylene,
ethylidene, propylene, propylidene, isopropylidene, butylene, butylidene, isobutylidene,
and amylidene or E may be cycloalkylene such as, for example, cyclopentylene or cyclohexylene,
a sulfur containing linkage such as sulfide, sulfoxide or sulfone, an ether linkage,
a carbonyl group, or a tertiary nitrogen group; R is hydrogen or a monovalent hydrocarbon
group such as, for
'example, alkyl, aryl, arylalkyl, or cycloaliphatic; Y is chlorine, bromine, fluorine
or R wherein R is defined as above; m is any whole number from and including 0 to
the number of positions on A available for substitution; p is any whole number and
including 0 to the number of positions available on E; S is 0 or 1; and U is 0 or
1.
[0015] Examples of such dihydric phenols include the bis(hydroxyphenyl) alkanes such as
2,2-bis-(4-hydroxyphenyl)propane [bisphenol-A], 2,4'-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl)-methane,
1,1-bis(4-hydroxyphenyl)ethane and other bisphenol-A type diols as described in U.S.
Patent No. 3,028,365 as well as the corresponding aromatically substituted or aliphatically
substituted dihydric phenols wherein the substituents are halogens such as, for example,
Cl, F, Br, I, and other substituents such as, for example, -N0
2, alkyl, acyl, carboxylate ester, and sulfonate ester. Of the foregoing dihydric phenols,
bisphenol-A and substituted bisphenol-A are preferred, with bisphenol-A being most
preferred.
[0016] In the polycarbonate, these diols, other than the trityl diol, constitute the remaining
diol proportion of the polycarbonate. Preferably, they constitute from 0 to 90 mole
percent, more preferably from 40 to 90 mole percent, and most preferably from 20 to
40 mole percent based on the total diol content of the polycarbonate. For the purposes
of this invention, it should be understood that the aforementioned mole percentages
of the trityl diol as well as the other diol are based on the total diol residue of
the polycarbonate and do not include the linking carbonyl groups.
[0017] The trityl diol polycarbonate is readily prepared by phosgenating the trityl diol
or a mixture of the trityl diol with the other diol under the conditions described
for preparing the trityl diol polycarbonates of U.S. Patent No. 3,036,036. Alternatively,
the trityl diol can be reacted with the bischloroformate derivatives of one or more
of the other diols.
[0018] The rubber-modified monovinyldiene aromatic copolymer utilized in the practice of
this invention is a normally solid polymeric material having a rubber polymer portion
containing polymerized monomeric rubber precursor such as conjugated diene, a random
copolymer portion containing copolymerized monovinylidene aromatic monomer and copolymerized
a,p-ethylenically unsaturated polar comonomer such as ethylenically unsaturated nitrile,
and a graft copolymer portion containing a rubber portion grafted or blocked with
a copolymerized mixture of the monovinylidene aromatic monomer and the polar monomer.
The relative proportions of the aforementioned rubber, random and graft copolymer
portions are not particularly critical.
[0019] Preferably, however, the weight ratio of total rubber including the rubber portion
of the graft copolymer to total copolymerized monovinylidene aromatic/polar monomer
including that present in the graft copolymer is from 50:1 to 0.01:1, more preferably
from 10:1 to 0.05:1, and most preferably from 1:1 to 0.1 to 1. The weight ratio of
the graft copolymer to the total rubber-modified copolymer is preferably from 0.98:1
to 0.01:1, more preferably from 0.5:1 to 0.01:1, and most preferably from 0.15:1 to
0.03:1. In the graft copolymer, the weight ratio of the rubber to the copolymerized
mixture is preferably from 9:1 to 0.2:1 more preferably from 4:1 to 0.5:1 and most
preferably from 2.5:1 to 0.8:1. Also in the graft copolymer the ratio of the monovinylidene
aromatic monomer to the polar comonomer is generally within the range specified for
the random copolymer hereinafter. The molecular weight of the rubber-modified copolymer
is not particularly critical so long as its melt flow viscosity is such that it can
be melt blended with the aforementioned polycarbonate. Preferably; however, the melt
flow viscosity of the rubber-modified copolymer as determined by ASTM D 1238 65T(I)
is from 0.01 to 10, more preferably from 0.1 to 5, and most preferably from 2 to 3,
deciliters per minute.
[0020] The chemical composition of the rubber portion is not particularly critical so long
as it can impart the desired elastomeric character to the rubber-modified copolymer
and can form a graft or block copolymer containing the random monovinylidene aromatic
copolymer. Preferably the rubber portion is a rubber polymer of a conjugated diene
represented by the formula:
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0007)
wherein X is individually hydrogen, alkyl having from 1 to 5 carbon atoms, chloro
or bromo. Examples of suitable dienes include butadiene, isoprene, 1,2-hexadiene,
methyl-1 ,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-3-ethyl-1,3-butadiene,
2-ethyl-1,3-pentadiene, 1,3- and 2,4-hexadienes, chloro- and bromo-substituted butadienes
such as dichlorobutadiene bromobutadiene, chloroprene, dibromobutadiene, and mixtures
thereof. Of the foregoing dienes, butadiene and isoprene are preferred, with butadiene
being especially preferred. Examples of diene rubbers suitably employed in the practice
of this invention are homopolymers of butadiene and isoprene, copolymers of butadiene
or isoprene and styrene, copolymers of butadiene and acrylonitrile, and copolymers
of styrene, butadiene and acrylonitrile.
[0021] In the preferred diene rubbers, the amount of diene is sufficient to provide the
desired elastomeric character. An especially preferred group of diene rubbers are
those containing from 50 to 100 weight percent of butadiene and/or isoprene polymerized
or copolymerized form and up to 50 weight percent of monovinylidene aromatic hydrocarbon
polymerized or copolymerized form, such as styrene and/or an unsaturated nitrile such
as acrylonitrile. Particularly advantageous are the homopolymers of butadiene and
copolymers of butadiene with up to 50 weight percent of styrene. These preferred diene
rubbers exhibit glass transition temperatures (Tg) generally less than 0°C; more preferably
less than -30°C and most preferably from -110°C to -50°C as determined by ASTM D-746-56T.
In the rubber-modified copolymer, the diene rubber advantageously has an average particle
size of 10 micrometers or less, preferably in the range from 0.2 to 5 micrometers.
Such preferred diene rubbers also exhibit intrinsic viscosities as determined at 25°C
in toluene of from 0.1 to 5.
[0022] In addition to the aforementioned monomeric components, it should be understood that
the rubber portion may also contain relatively small amounts, usually less than 2
weight percent based on the rubber, of a crosslinking agent such as, for example,
divinylbenzene, diallylmaleate, and ethylene glycol dimethacrylate provided that such
crosslinking does not eliminate the desired elastomeric: character of the rubber.
[0023] The random copolymer portion of the rubber-modified copolymer including the graft
copolymer is suitably any normally solid random copolymer of at least one monovinylidene
aromatic monomer and at least one copolymerizable alpha, beta-ethylenically unsaturated
monomer having a pendant polar group (a so-called polar comonomer). The type and amount
of the polar comonomer in the random copolymer are such that the solubility parameter
of the random copolymer is from 9.2 to 11.2 preferably from 9.3 to 10.8. The solubility
parameter is defined as the square root of the energy of vaporisation per cubic centimeter
of the polymer, and is defined in "SOLUBILITY OF NON-ELECTROLYTES" Third ed (1950)
Reinhold Publishing Company p. 123 to p. 133. Preferably the random copolymer contains
polymerized therein from 50 to 95, most preferably from 65 to 85 weight percent of
the monovinylidene aromatic monomer, which is preferably styrene, and from 5 to 50,
most preferably from 15 to 35 weight percent of the polar comonomer, which is preferably
an a,[3-ethylenically unsaturated nitrile, particularly acrylonitrile.
[0024] The monovinylidene aromatic monomer is suitably one represented by the formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0008)
wherein X is as defined hereinbefore and Z is hydrogen or methyl. Examples of monovinylidene
aromatic compounds include styrene, a-methylstyrene, ar-chlorostyrene, ar-methylstyrene,
ar- ; bromostyrene, ar-(t-butyl)styrene with styrene being preferred.
[0025] Suitable polar comonomers include the a,p-ethylenically unsaturated nitriles such
as acrylonitrile, methacrylonitrile, fumaronitrile as well as mixtures thereof with-
other polar comonomers that are copolymerisable with the unsaturated nitrile or the
aromatic monomer. Examples of such other polar comonomers include α,β-ethylenically
unsaturated carboxylic acids and their anhydrides and alkyl, aminoalkyl and hydroxyalkyl
esters such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, ethyl
acrylate, butyl acrylate, methyl methacrylate, hydroxyethyl and hydroxypropyl acrylates,
or aminoethyl acrylate. When the polar comonomer is a mixture of unsaturated nitrile
and another polar comonomer, the concentration of the nitrile comonomer in the mixture
is such that the random copolymer contains at least 5 weight percent of the nitrile
comonomer. Of the foregoing polar comonomers, the ethylenically unsaturated nitriles
are preferably employed alone, with acrylonitrile being the most preferred nitrile.
[0026] Of the aforementioned rubber-modified graft copolymers, the so-called ABS resins,
particularly those that are mixtures of styrene/acrylonitrile copolymer with a graft
of the same copolymer on a diene rubber, are especially preferred.
[0027] In general, the method employed in preparing the rubber-modified copolymer is not
particularly critical since the impact strength of the resultant polycarbonate composition
is suitable when any aforementioned rubber-modified copolymer (regardless of method
of preparation) is employed therein. However, it is found that the most improvement
in impact resistance is obtained when preformed diene rubber is dissolved or dispersed
in the monovinylidene aromatic monomer and the polar comonomer and thereafter heated
to polymerize the monomers. Polymerization can be effected by heating the solution
of rubber and monomer in mass, in emulsion, or while dispersed as droplets in an inert
aqueous medium and at temperatures between 50° and 180°C and pressures ranging from
subatmospheric to superatmospheric. Although not required, it is sometimes desirable
to employ a polymerization initiator such as benzoyl peroxide, di-t-butyl peroxide,
dicumyl peroxide, t-butyl hydroperoxide, cumyl hydroperoxide, t-butyl peracetate or
other similar free-radical generating peroxygen catalysts. The preferred rubber-modified
copolymers are prepared by conventional ABS polymerization methods, e.g., those described
in U.S. Patent Nos. 2,769,804; 3,168,593; 3,243,481; 3,426,103; 3,442,981; 3,499,059;
and 3,660,535.
[0028] In addition to the aforementioned polycarbonate and rubber-modified copolymer, it
is sometimes desirable to include a random, block or graft copolymer of a monovinylidene
aromatic monomer and a polar comonomer, other than the polar comonomer of the aforementioned
random copolymer, as a third component in the blend. This third component copolymer
may also be modified with a rubber as defined hereinbefore. This other or third component
copolymer is normally employed in concentrations from 1 to 25, preferably from 5 to
20, weight percent based on the total blend. This third component copolymer preferably
has a solubility parameter from 9.8 to 10.8.
[0029] Exemplary third component copolymers include copolymers of monovinylidene aromatic
monomers as defined hereinbefore, preferably styrene, and polar monomers other than
the aforementioned nitriles, preferably the a,p-ethylenically unsaturated carboxylic
acids or anhydrides, most preferably maleic anhydride. In the third component copolymer,
the monovinylidene aromatic monomer constitutes from 50 to 95, preferably from 67
to 90, weight percent and the molar comonomer constitutes from 50 to 5, preferably
from 33 to 10, weight percent. In addition, this third component advantageously contains
up to 40, preferably from 5 to 40, weight percent of a rubber, preferably a diene
rubber as defined hereinbefore.
[0030] In the preparation of the polycarbonate blend of the present invention, the polymeric
components are combined by conventional mixing techniques such as admixing of granular
or particulate polymeric components and subsequent malaxation of components at temperatures
sufficient to cause heat plastification thereof. Alternatively, the blends may be
prepared by heat plastifying the higher melting polymeric components and adding the
other components thereto either in granular or heat plastified form. When a third
component monovinylidene aromatic copolymer such as a styrene/maleic anhydric copolymer
is to be employed, it is generally desirable to combine the rubber-modified copolymer
and the third component copolymer into a uniform mixture prior to combining with the
polycarbonate.
[0031] One particularly convenient method for preparing the polycarbonate blend in accordance
with the present invention is to dry blend a particulate of the polycarbonate with
a particulate of the rubber-modified copolymer or a mixture thereof with the third
component copolymer and directly feed this dry blend into a heat fabricating apparatus
such as a screw extruder or a reciprocating screw injection molding machine. The particular
manner of mixing these components in heat plastified form is not critical but sufficient
working should be employed to insure a uniform distribution of each of the components
throughout the resulting polycarbonate composition. In addition to the foregoing mixing
procedures, other conventional mixing procedures may be employed including hot roll
milling or kneading.
[0032] The following examples are given to illustrate the invention but should not be construed
as limiting its scope. Unless otherwise indicated, all parts and percentages are by
weight.
Example 1
[0033] A 500-gm portion of granular bisphenol-A/phenolphthalein copolycarbonate having a
weight average molecular weight of 26,000 and containing the monomeric species in
a 3:1 weight ratio wherein the granules have a major dimension of about 1/8 inch (about
3 mm) is dry blended with a 500-gm portion of ABS resin granules (major dimensions
of about 1/8 inch (about 3 mm)) by tumbling for one-half hour. The ABS resin contains
a graft copolymer having a butadiene rubber backbone and graft portion of random styrene/acrylonitrile
copolymer, an ungrafted butadiene rubber and a random styrene/acrylonitrile copolymer.
The rubber particles in the ABS resin have diameters in the range of 0.5 to 2 micrometers.
The random copolymer in the ABS resin contains 73 weight percent copolymerized styrene
and 27 weight percent copolymerized acrylonitrile and has a solubility parameter of
9.8. The ABS resin is prepared by mass polymerizing 64 weight parts of styrene and
25 weight parts of acrylontrile in the presence of about 11 weight parts of butadiene
rubber.
[0034] The resulting dry blended granules of polycarbonate and ABS resin are charged to
an 0.8 inch (20 mm) twin-screw mixing extruder (Welding Engineers) having a barrel
temperature (feed to die) profile of 475°F (246°C), 500°F (260°C), 550°F (288°C),
550°F (288°C), 525°F (274°C) and 500°F (260°C). The dry blend is thereby heat plastified,
extruded, granulated and molded into bars for testing for impact resistance and heat
resistance as reported in Table I. Residence time of the blended material in the extruder
is about 90 seconds and the extruder is operated at 190 to 250 rpm.
[0035] For the purpose of comparison, several other phenolphthalein copolycarbonates and
ABS resins are combined at different portions to form blends and are tested for impact
and heat resistance. The results of these tests are also reported in Table IA.
1. A heterogeneous blend comprising 10 to 90 percent by weight or a polycarbonate
and 90 to 10 percent by weight of a rubber-modified copolymer of a monovinylidene
aromatic monomer and an alpha, beta-ethylenically unsaturated comonomer having a pendent
polar group, said rubber-modified copolymer containing (a) a rubber (b) a random copolymer
of the monovinylidene aromatic monomer and the polar comonomer and (c) a graft or
block copolymer containing the rubber grafted or blocked with a copolymerized mixture
of the monovinylidene aromatic monomer and the polar comonomer, said random copolymer
having a solubility parameter within the range from 9.2 to 11.2 characterized in that
the polycarbonate comprises a trityl diol having an ar, ar'-dihydroxy trityl nucleus
represented by the formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0012)
wherein the aromatic rings optionally are substituted by substituents selected from
F, Cl, Br, I, NO
2, alkyl, acyl, carboxylate ester, sulfonate ester, by an oxycarbonyl group, secondary
amide group or oxysulfonyl group bridging the methan carbon atom and the ortho carbon
atom of the non hydroxylated ring, by a carbonyl group bridging the ortho carbon of
the non-hydroxylated ring and the ortho carbon of one of the hydroxylated rings, or
by an -0- group bridging the hydroxylated aromatic rings meta to the hydroxyls.
2. The blend of claim 1 characterized in that the polycarbonate has a Viscat softening
point of at least 160°C.
3. The blend as defined in claim 1, characterized in that said trityldiol is a phenolphthalein
compound corresponding to formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0013)
in which the R, substituents are independently selected from H, lower alkyl radicals
having 1-4 carbon atoms, CI, Br, I and N0
2; the corresponding phenolphthalimidine compounds, a phenolsulfonephthalein compound
corresponding to formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0014)
in which R
1 has the meaning as above defined; a phthalidein compounds corresponding to formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0015)
a fluorescein compound corresponding to formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0016)
in which R
1 has the meaning as above defined, the hexagons corresponding to benzene rings.
4. The blend as defined in claim 3 characterized in that said trityl diol is phenolphthalein
optionally substituted by chlorine or bromine.
5. The blend as defined in any one of claims 1 to 4, characterized in that the molar
proportion of trityl diol ranges from 10 to 100 moles percent based on the total diol
content of the polycarbonate.
6. The blend as defined in any one of claims 1 to 5, characterized in that the polycarbonate
is a copolycarbonate of from 10 to 60 moles percent of phenolphthalein and from 90
to 40 moles percent of another dihydric phenol, said moles percentages being based
upon the total diol content of the copolycarbonate.
7. The blend of claim 6, characterized in that it contains residues of dihydric phenols
represented by the formula
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0017)
wherein A is an aromatic group: E is alkylene, alkylidene, cycloalkylene, a sulfur
containing linkage, an ether linkage, a carbonyl group, a tertiary nitrogen group;
R is hydrogen or a monovalent hydrocarbon group: Y is chlorine, bromine, fluorine
or R wherein R is defined as above; m is any whole number from and including 0 to
the number of positions on A available for substitution; p is any whole number and
including 0 to the number of positions available on E; s is 0 or 1 and u is 0 or 1.
8. The blend of claim 7 characterized in that the dihydric phenol is a bis (hydroxyphenyl)
alkane.
1. Mélange hétérogène comprenant 10 à 90% en poids d'un polycarbonate et 90 à 10%
en poids d'un copolymère modifié par du caoutchouc d'un monomère monovinylidène-aromatique
et d'un comonomére alpha,beta-éthyléniquement insaturé ayant un groupe polaire latéral,
ledit copolymère modifié par du caoutchouc contenant (a) un caoutchouc, (b) un copolymère
irrégulier du monomère monovinylidène-aromatique et le comonomère polaire, et (c)
un copolymère greffé ou séquencé contenant le caoutchouc greffé ou bloqué avec un
mélange copolymèrisé du monomère monovinylidène-aromatique et du comonomère polaire,
ledit copolymère irrégulier ayant un paramètre de solubilité allant de 9,2 à 11,2,
caractérisé par le fait que le polycarbonate comprend un trityldiol ayant un noyau
ar,ar'-dihydroxytrityle représenté par la formule
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0018)
dans laquelle les noyaux aromatiques sont éventuellement substitués par des substituants
choisis parmi F, CI, Br, 1, N0
2, alkyle, acyle, ester carboxylique, ester sulfonique, par un groupe oxycarbonyle,
un groupe amide secondaire ou un groupe oxysulfonyle pontant l'atome de carbone méthanique
et l'atome de carbone ortho du cycle non hydroxylé, par un groupe carbonyle pontant
le carbone ortho du noyau non hydroxylé et le carbone ortho de l'un des noyaux hydroxylés,
ou par un groupe -0- pontant les noyaux aromatiques hydroxylés en méta par rapport
aux hydroxyles.
2. Mélange selon la revendication 1, caractérisé par le fait que le polycarbonate
a un point de ramollissement Vicat d'au moins 160°C.
3. Mélange selon la revendication 1, caractérisé par le fait que ledit trityldiol
est; un composé phénolphtaléine correspondant à la formule:
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0019)
dans laquelle les substituants R
1 sont choisis indépendamment parmi H, des radicaux alkyle inférieurs ayant 1 à 4 atomes
de carbone, CI, Br, I et NO
2; les composés phénolphtalimidine correspondants, un composé phénolsulfonephtaléine
correspondant à la formule:
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0020)
dans laquelle R
1 a la signification définie ci-dessus; un composé phtalidine correspondant à la formule:
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0021)
un composé fluorescéine correspondant à la formule:
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0022)
dans laquelle R
1 a la signification définie ci-dessus, les hexagones correspondant aux noyaux benzéniques.
4. Mélange selon la revendication 3, caractérisé par le fait que ledit trityldiol
est la phénolphtaléine éventuellement substituée par du chlore ou du brome.
5. Mélange selon l'une quelconque des revendications 1 à 4, caractérisé par le fait
que la proportion molaire de trityldiol va de 10 à 100% en mole, basés sur la teneur
totale en diol du polycarbonate.
6. Mélange selon l'une quelconque des revendications 1 à 5, caractérisé par le fait
que le polycarbonate est un copolycarbonate ayant 10 à 60% en mole de phénolphtaléine
et de 90 à 40% en mole d'un autre phénol dihydrique, lesdits pourcentages en mole
étant basés sur la teneur totale en diol du copolycarbonate.
7. Mélange selon la revendication 6, caracérisé par le fait qu'il contient des résidus
de phénols dihydriques représentés par la formule:
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0023)
dans laquelle A est un groupe aromatique: E est un groupe alkylène, alkylidène, cycloalkylène,
une liaison contenant du soufre, une liaison éther, un groupe carbonyle, un groupe
azote tertiaire; R est de l'hydrogène ou un groupe hydrocarboné monovalent; Y est
du chlore, du brome, du fluor ou bien R dans lequel * R est défini comme ci-dessus;
m est un nombre entier quelconque allant de et comprenant 0 jusqu'au nombre de positions
disponibles sur A pour la substitution; p est un nombre entier quelconque et comprend
0 jusqu'au nombre de positions disponibles sur E; s est 0 ou 1 et u est 0 ou 1.
8. Mélange selon la revendication 7, caractérisé par le fait que le phénol dihydrique
est un bis(hydroxyphényl) alcane.
1. Ein heterogenes Gemisch, bestehend aus 10 bis 90 Gewichtsprozent eines Polycarbonats
und aus 90 bis 10 Gewichtsprozent eines gummi-modifizierten Copolymers eines monovinyliden-aromatischen
Monomers und aus einem Alpha,Beta-ethylenisch ungesättigten Co-Monomer mit einer hängenden
polaren Gruppe, wobei dieses gummi-modifizierte Copolymere enthält: (a) einen Gummi,
(b) ein zufälliges Copolymer des monovinyliden-aromatischen Monomeren und das polare
Co-Monomer und (c) ein Pfropf- oder Block-Copolymer, das den Gummi aufgepfropft oder
aufgeblockt mit einem copolymerisierten Gemisch des monovinyliden-aromatischen Monomeren
und das polare Comonomer enthält, wobei das Zufallscopolymer einen Lösungsparameter
im Bereich von 9,2 bis 11,2 hat, dadurch gekennzeichnet, dass das Polycarbonat ein
Trityldiol enthält, das einen ar,ar'-Dihydroxy-titryl-Kern nach der folgenden Formel
hat:
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0024)
worin die aromatischen Ringe wahlweise substituiert werden können durch Substituierten
nach Wahl aus der Gruppe F, Cl, Br, J, N0
2, Alkyl, Acyl, Carbonsäureester, Sulfonsäureester, durch eine Oxycarbonyl-Gruppe,
eine sekundäre Amidgruppe oder Oxysulfonylgruppe als Brücke zwischen dem Methan-Kohlenstoffatom
und dem Ortho-Kohlenstoffatom des nicht-hydroxylierten Rings, durch eine Carbonylgruppe
als Brücke zwischen dem Ortho-Kohlenstoff des nicht-hydroxylierten Rings und dem Ortho-Kohlenstoff
eines der hydroxylierten Ringe, oder durch eine -0- Gruppe als Brücke zwischen den
hydroxylierten aromatischen Ringen in Metastellung zu den Hydroxylen.
2. Das Gemisch gem. Anspruch 1, gekennzeichnet dadurch, dass das Polycarbonat eine
Vicat-Erweichungstemperatur von mindestens 160°C hat.
3. Das Gemisch gem. Definition in Anspruch 1, dadurch gekennzeichnet, dass es sich
bei dem genannten Trityldiol handelt um; eine Phenolphthaleinverbindung der Formel
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0025)
worin die R
i-Substituenten unabhängig gewält werden aus der Gruppe H, niedere Alkylradikale mit
1-4 Kohlenstoffatomen, Cl, Br, J oder NO
2; die entsprechenden Phenolphthalimidin-Verbindungen, eine Phenosulfonphthalein-Verbindung
der Formel
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0026)
in der R
1 die oben definierte Bedeutung hat; eine Phthalidin-Verbindung der Formel
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0027)
eine Fluoreszeinverbindung der Formel
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0028)
in der R
I die oben definierte Bedeutung hat, wobei es sich bei den Sechsecken um Benzolringe
handelt.
4. Das Gemsich gem. Definition in Anspruch 3, dadurch gekennzeichnet, dass es sich
bei dem Trityldiol um Phenolphthalein handelt, das wahlweise durch Chlor und Brom
substituiert wird.
5. Das Gemisch gem. Definition in einem beliebigen der Ansprüche 1-4, dadurch gekennzeichnet,
dass das Molverhältnis des Trityldiol zwischen 10 und 100 Molprozent bezogen auf den
Gesamtdiolgehalt des Polycarbonats liegt.
6. Das Gemsich gem. Definition in einem beliebigen der Ansprüche 1 bis 5, dadurch
ge- kennzeichnet, dass es sich bei dem Polycarbonat um ein Copolycarbonat von 10 bis
60 Molprozent des Phenolphthaleins und von 90 bis 40 Molprozent eines anderen zweiwertigen
Phenols handelt, wobei diese Molprozente auf den gesamten Diolgehalt des Copolycarbonats
bezogen werden.
7. Gemisch gem. Anspruch 6, dadurch gekennzeichnet, dass es Rest von zweiwertigen
Phenolen enthält gem, der Formel
![](https://data.epo.org/publication-server/image?imagePath=1982/17/DOC/EPNWB1/EP78100158NWB1/imgb0029)
in dieser ist A eine aromatische Gruppe: E = Alkylen, Alyliden, Cycloalkylen, eine
Schwefel-enthaltende Bindung, eine Ätherbindung, eine Carbonylgruppe, eine tertiäre
Stickstoffgruppe; R = Wasserstoff oder eine einwertige Kohlenwasserstoffgruppe: Y
= Chlor, Brom, Fluor oder R worin R wie oben definiert ist; m = eine beliebige ganze
Zahl von einschliesslich 0 bis zu einer Zahl, die die in A zur Substitution möglichen
Stellungen angibt; p = eine beliebige ganze Zahl von einschliesslich 0 bis zu einer
Zahl, die die in E möglichen Stellungen angibt; s = 0 oder 1 und u = 0 oder 1.
8. Das Gemisch gem. Anspruch 7, dadurch gekennzeichnet, dass es sich bei dem zweiwertigen
Phenol um ein bis-(Hydroxyphenyl)-Alkan handelt.