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Description  |
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Powder-form polymer mixtures of partially crosslinked, particulate silicone
rubber and at least one thermoplastic organic polymer are protected in
European patent application No. 87 116 839.9. These powder-form polymer
mixtures are prepared by mixing dispersions of polymers, including graft
polymers, with emulsions or dispersions of partially crosslinked,
particulate silicone rubbers and then coagulating and drying the resulting
mixtures.
According to the above-cited European patent application No. 87 116 839.9,
the powder-form polymer mixtures are used as additives for thermoplastic
molding compounds to improve their property spectrum, including in
particular their fire behavior.
Further development of this invention has now surprisingly shown that the
use of special silicone resins instead of silicone rubbers in accordance
with the above-cited European patent application No. 87 116 839.9 produces
a further improvement in fire behavior, which is noticeable above all
after storage for 7 days at 70.degree. C.
Accordingly, the present invention relates to powder-form polymer mixtures
of silicone resins (B) having the following empirical formula
##EQU1##
in which R is a monofunctional hydrocarbon radical which may even be
substituted, but more especially a methyl and/or phenyl group, R' is an
alkyl group or a hydrogen atom, x has a value of 0.75 to 1.75 and y has a
value of 0.0001 to 0.5 and in which the silicone resin is made up of units
corresponding to the formula SiO.sub.4/2, RSiO.sub.3/2, R.sub.2
SiO.sub.2/2 and/or R.sub.3 SiO.sub.1/2 and of thermoplastic polymers (A),
the ratio by weight of silicone resin (B) to polymer (A) being between
0.1% by weight to 99.9% by weight and 50% by weight to 50% by weight,
preferably between 5% by weight to 95% by weight and 40% by weight to 60%
by weight and more preferably between 8% by weight to 92% by weight and
20% by weight to 80% by weight.
The proportion of silicone resin (B) in the powder-form mixture is thus
between 0.1% by weight and 50% by weight, preferably between 5% by weight
and 40% by weight and more preferably between 8% by weight and 20% by
weight, based on the total weight of silicone resin (B) and thermoplastic
polymer (A).
Preferred silicone resins (B) corresponding to formula (I) are those in
which at least 80% by weight of all the substituents R are methyl or
phenyl groups.
The powder-form polymer mixtures are prepared by
I. mixing a dispersion of an organic, thermoplastic polymer (A) having an
average particle diameter (d.sub.50) of from 0.05 to 30 .mu.m and
preferably from 0.05 to 5 .mu.m and a solids content of 20% by weight to
60% by weight, based on the weight of the dispersion of component (A),
with an emulsion of a silicone resin (B) corresponding to formula (I) and
having an average particle diameter (d.sub.50) of from 0.05 .mu.m to 3
.mu.m and preferably from 0.1 .mu.m to 1 .mu.m and a solids content of up
to 60% by weight, preferably from 30% by weight to 50% by weight, based on
the weight of the emulsion of component (B), so thoroughly and in such a
quantitative ratio that the particles undergo hardly any agglomeration and
mixtures of 0.1% by weight to 50% by weight, preferably 5% by weight to
40% by weight and more preferably 8% by weight to 20% by weight silicone
resin (B) with 99.9% by weight to 50% by weight, preferaby 95% by weight
to 60% by weight and more preferably 92% by weight to 80% by weight
thermoplastic polymer (A), based on the total weight of silicone resin (B)
and thermoplastic polymer (A) are present,
II. the mixture thus obtained is coagulated in known manner at 20.degree.
C. to 120.degree. C. and at pH values of 7 to 2 and preferably at pH
values of 5 to 3 with formation of a finely divided mixture of components
(A) and (B) and
III. after isolation, the coagulate is dried in known manner at
temperatures of 50.degree. C. to 150.degree. C. and more especially at
temperatures of 80.degree. C. to 120.degree. C.
Accordingly, the present invention also relates to a process for the
production of the powder-form polymer mixtures according to the invention
which is characterized in that the mixtures are prepared by steps I, II
and III as described above.
In one preferred embodiment of the process according to the invention,
aqueous dispersions of component (A) are used.
It is particularly preferred to use a mixture of dispersions of component
(A) which contains from 20% to 80% by weight of finely divided polymer
(average particle diameter d.sub.50 =0.05 to 0.15 .mu.m) and 80 to 20% by
weight of coarsely divided polymer (average particle diameter d.sub.50
=0.20 to 0.8 .mu.m and more especially 0.25 to 0.5 .mu.m).
The dispersions of component (A) contain polymer particles in
uncrosslinked, partially crosslinked or highly crosslinked form. The
dispersion medium used may be water or an organic solvent, such as an
ester, a hydrocarbon, a halogenated hydrocarbon, an alcohol or mixtures
thereof. The preferred medium is water. Dispersions such as these are
known, for example from EP-A 28 344 and DE-AS 20 47 427. They are standard
polymer dispersions of the type which can be obtained by emulsion
polymerization or by dispersion of a polymer.
The dispersions of component (A) suitable for use in accordance with the
invention preferably contain thermoplastic homopolymers or copolymers of
olefinically unsaturated monomers, such as styrene, .alpha.-methyl
styrene, p-methyl styrene, halogen styrene, acrylonitrile,
methacrylonitrile, alkyl acrylate, alkyl methacrylate, maleic anhydride,
N-substituted maleic imide, vinyl acetate, vinyl chloride, vinylidene
chloride, vinylidene fluoride, and/or thermoplastic graft polymers of
these monomers on rubbers having glass transition temperatures below
0.degree. C., preferably below -10.degree. C., the graft polymers
containing from 8 to 80% by weight rubber.
Particularly suitable polymers for dispersions of component (A) are
homopolymers of styrene, methyl methacrylate and vinyl chloride,
copolymers thereof with at least one of the monomers acrylonitrile,
methacrylonitrile, N-substituted maleic imide (more especially N-phenyl
maleic imide or N-cyclohexyl maleic imide), alkyl methacrylate or alkyl
acrylate, and also graft polymers, for example of polybutadiene,
polychloroprene or styrene/butadiene or acrylonitrile/butadiene copolymer
rubbers having gel contents (as measured at 20.degree. C.) of greater than
30% by weight, of alkyl acrylate rubbers, EPDM rubbers
(ethylene/propylene/diene/monomer rubbers) or of silicone rubbers grafted
with styrene, .alpha.-methyl styrene, acrylonitrile, methyl methacrylate,
vinyl chloride, vinyl acetate or mixtures thereof.
The emulsions of the silicone resins (B) suitable for use in accordance
with the invention preferably contain water as the dispersion medium.
The production of the silicone resins corresponding to formula (I) is
known. For their subsequent processing to emulsions, these silicone resins
may be used as such or in the form of solutions in suitable organic
solvents. Silicone resin solutions should best contain no more than 60%
solvent, because the solvent has to be subsequently evaporated off again.
The production of silicone resin emulsions is also known and is described,
for example, in DE-OS 3 200 709. The silicone resin emulsions are
particulate and, as already mentioned, have average particle diameters
(d.sub.50 values) of from 0.05 to 3 .mu.m and more especially from 0.1 to
1 .mu.m.
The thorough mixing of the dispersion of component (A) with the emulsion of
component (B) with no agglomeration is carried out, for example, by
intensively stirring both the dispersion of component (A) and the emulsion
of component (B) together in the desired quantitative ratio according to
the invention, optionally followed by thorough mixing in an emulsifying
machine. After thorough dispersion, 1.8% by weight, based on the polymer
solids, of phenolic antioxidants are added in the form of an aqueous
dispersion and incorporated in the mixture.
The coagulation of the mixture of the dispersion of component (A) and the
emulsion of component (B) is carried out, for example, by introducing the
mixture of the dispersion of component (A) and the emulsion of component
(B) in a thin stream with stirring into a 1% aqueous solution of magnesium
sulfate and acetic acid in each case. The temperature of the precipitation
solution is in the range from 80.degree. to 90.degree. C.
The coagulated mixture is isolated, for example, by filtration or
centrifugation and repeated washing with distilled water until the washing
water is free from electrolyte.
The coagulated mixture is dried to constant weight, for example at
100.degree. C. in a vacuum drying cabinet until a white powder is
obtained.
The powder-form polymer mixtures according to the invention are suitable as
flameproofing agents for thermoplastics. To this end, they are used in
such quantities that the content of silicone resin (B) in the
flame-resistant thermoplastic molding compound is at most 5% by weight,
preferably from 4% by weight to 0.25% by weight and more preferably from
2.5% by weight to 0.5% by weight, based on the total weight of
flame-resistant thermoplastic molding compound.
Accordingly, the present invention also relates to the use of the
powder-form polymer mixtures according to the invention as flameproofing
agents for thermoplastics in quantities of at most 5% by weight,
preferably in quantities of from 4% by weight to 0.25% by weight and more
preferably in quantities of from 2.5% by weight to 0.5% by weight, based
on the total weight of flame-resistant thermoplastic molding compound, of
silicone resin (B).
Suitable thermoplastics which may be flameproofed with the powder-form
polymer mixtures according to the invention are, on the one hand, the
above-mentioned thermoplastic polymers suitable for the production of the
powder-form polymer mixtures according to the invention, more especially
ABS, polystyrene, high-impact polystyrene and PVC.
On the other hand, thermoplastic polycarbonates, thermoplastic polyamides,
thermoplastic aliphatic polyesters, such as for example polyalkylene
terephthalates, thermoplastic aromatic polyesters, such as
bisphenol-A-terephthalates, aromatic thermoplastic polyarylene sulfones,
thermoplastic polyphenylene ethers and thermoplastic polyphenylene
sulfides, are suitable thermoplastics for flameproofing.
The thermoplastics may be flameproofed with the powder-form polymer
mixtures according to the invention either individually or in the form of
mixtures of different thermoplastics, i.e. in the form of alloys.
Particularly suitable thermoplastics suitable for flameproofing in
accordance with the present invention are ABS, thermoplastic
bisphenol-A-polycarbonate thermoplastic polycaproic amide,
polyhexamethylenediaminoadipic acid amide, polyethylene terephthalate and
polybutylene terephthalate and also mixtures of these particularly
suitable thermoplastics.
The powder-form polymer mixtures according to the invention are
incorporated in the thermoplastics by melt compounding of the
thermoplastics in the form of granulates or powders with the powder-form
polymer mixtures according to the invention at a temperature in the range
from 200.degree. C. to 300.degree. C. in standard mixers, such as
kneaders, extruders, rolls and screws.
Accordingly, the present invention also relates to a process for the
incorporation of the powder-form polymer mixtures according to the
invention in thermoplastics which is characterized in that the
thermoplastics are melt-compounded with the powder-form polymer mixtures
according to the invention in standard mixers at temperatures in the range
from 200.degree. C. to 300.degree. C.
The present invention also relates to mixtures of thermoplastics with the
powder-form polymer mixtures according to the invention.
The use of the powder-form polymer mixtures according to the invention as
additives for thermoplastics improves not only the flame resistance of the
thermoplastics, but also various other properties of the thermoplastics,
including their impact strength, their heat resistance and their mold
release behavior.
On the other hand, the addition of the powder-form polymer mixtures
according to the invention to the thermoplastics does not adversely affect
the surface properties of the thermoplastics; the affinity of moldings of
the thermoplastics for lacquering is not affected by the incorporated
powder-form polymer mixtures according to the invention.
Although it was already known that polysiloxanes could be used to reduce
the tendency towards dripping of flame-resistant polycarbonates (DE-OS 25
35 261) and flame-resistant polycarbonate alloys (DE-OS 29 18 882 and
EP-OS 00 19 127), the subject of the present invention, namely the
powder-form polymer mixtures and their use as flameproofing agents, could
not be derived therefrom.
Standard additives for the particular thermoplastics, such as stabilizers,
pigments, flow aids, antistatic agents, mold release agents and/or other
flameproofing agents, may additionally be incorporated in the
thermoplastics before, during or after the incorporation in accordance
with the invention of the powder-form polymer mixtures according to the
invention.
Other flameproofing agents than the powder-form polymer mixtures suitable
for use in accordance with the invention are those of the type normally
used for the particular thermoplastics, i.e. for example metal salts,
halogen compounds or phosphorus compounds. Other flameproofing agents such
as these may not only be added to the thermoplastics as additives, they
may also be included--as in the case of halogen for example--in the
synthesis of the particular thermoplastics through the use of suitable
halogen-containing reactants.
Although the addition of the powder-form polymer mixtures according to the
invention improves the mold-release behavior of the thermoplastics, mold
release may be further enhanced by the addition of typical mold release
agents for the particular thermoplastics.
Mold release agents such as these are, for example, fatty acid esters of
long-chain monoalcohols, such as stearyl alcohol trihydric alcohols, such
as glycerol or trimethylol propane tetrahydric alcohols, such as
pentaerythritol, or hexahydric alcohols, such as sorbitol for example.
Accordingly, the present invention also relates to a process for the
additional incorporation of stabilizers, pigments, flow aids, antistatic
agents, mold release agents and/or other flameproofing agents in the
thermoplastics which is characterized in that stabilizers, pigments, flow
aids, antistatic agents, mold release agents and/or other flameproofing
agents are added to and mixed with the thermoplastics before, during or
after the incorporation of the powder-form polymer mixtures according to
the invention.
The present invention also relates to mixtures of thermoplastics with the
powder-form polymer mixtures according to the invention and, in addition,
with stabilizers, pigments, flow aids, antistatic agents, mold release
agents and/or other flameproofing agents.
The thermoplastics in which the powder-form polymer mixtures according to
the invention and, optionally, the stabilizers, pigments, flow aids,
antistatic agents, mold release agents and/or other flameproofing agents
mentioned above are incorporated, may be processed to moldings by any of
the methods normally used for processing thermoplastics, such as
granulation, injection molding, extrusion, calendering, pressing and blow
molding.
The moldings in question may be used, for example, as plastics components
in the automotive industry, in the building industry and in the electrical
industry and also for domestic appliances.
EXAMPLES
A) Preparation of a polymer dispersion of component (A)
Dispersion of an ABS graft polymer of 50% by weight of a
styrene/acrylonitrile mixture (ratio 72:28) on 50% by weight particulate
polybutadiene having an average particle diameter (d.sub.50) of 0.4 .mu.m
obtained by emulsion polymerization. The dispersion has a solids content
of 30% by weight.
B) Preparation of a silicone resin emulsion of component (B) corresponding
to empirical formula (I), in which x is 1.25.
A silicone resin emulsion, in which the silicone resin consists of 70 mol-%
MeSiO.sub.3/2, 15 mol-% Me.sub.2 SiO.sub.2/2, 10 mol-% PhSiO.sub.3/2 and 5
mol-% Me.sub.3 SiO.sub.1/2 units, contains 1% hydroxyl groups and is
diluted with equal parts toluene, is prepared.
To this end, 38.8 kg deionized water is introduced into a stirred vessel
and heated to 60.degree. C. 1.2 kg of an emulsifier mixture having an HLB
value of approximately 15 (oleyl alcohol containing 2 ethylene oxide units
and polyoxyethylene triglyceride) are then added with stirring. After
stirring for 10 minutes, 60 kg of the above resin solution are added over
a period of 2 hours, followed by stirring for 30 minutes. The emulsion is
then homogenized 3 times in a high-pressure emulsifying machine. The
emulsion obtained has an average particle size of 0.8 .mu.m, remains
stable in storage for longer than 3 months and has a solids content of
30.5% by weight.
C) Preparation of an emulsion of the silicone rubber according to European
patent application No. 87 116 839.9 (LE A 24 884-EP) =Example 1 of this
European patent application which is being included here for comparison
purposes.
38.4 Parts by weight octamethyl cyclotetrasiloxane, 1.2 parts by weight
tetramethyl tetravinyl cyclotetrasiloxane and 1 part by weight
.gamma.-mercaptopropyl methyl dimethoxysilane are stirred with one
another. 0.5 Part by weight dodecyl benzenesulfonic acid in 58.4 parts by
weight water is then added over a period of 1 hour with intensive
stirring. The pre-emulsion is homogenized twice at 200 bar in a
high-pressure emulsifying machine. Another 0.5 part dodecyl
benzenesulfonic acid is added.
The emulsion is stirred for 2 h at 85.degree. C. and then for 36 h at room
temperature and subsequently neutralized with 5N NaOH. A stable emulsion
having a solids content of approximately 36% is obtained. The polymer has
a gel content of 82% by weight, as measured in toluene, and an average
particle size (d.sub.50) of 0.3 .mu.m.
The silicone rubber of this emulsion has an x value of 2 in empirical
formula (I).
EXAMPLE 1
Preparation of a powder-form polymer mixture according to the invention of
the silicone resin emulsion of Example B) and the thermoplastic polymer
dispersion of Example A).
The polymer dispersion of Example A) is mixed with the silicone resin
emulsion of Example B) in such a way that the mixture contains 90% by
weight (A) and 10% by weight (B), based on solids. The mixture is
stabilized with 1.8% by weight, based on polymer solids, of phenolic
antioxidants and thoroughly stirred. The mixture is coagulated with an
aqueous solution of MgSO.sub.4 (Epsom salt) and acetic acid at 85.degree.
to 95.degree. C. and at pH values of 4, filtered and washed until free
from electrolyte, followed by drying at 100.degree. C. to form a powder.
This powder may be compounded with other thermoplastics.
COMPARISON EXAMPLE (corresponds to Example 2 of European patent application
No. 87 116 839.9 (Le A 24 884-EP)).
The powder-form polymer mixture is prepared as described in Example 1
above, except that the silicone rubber emulsion of Example C) is used
instead of the silicone resin emulsion of Example B) and the silicone
content amounts to 10% by weight.
The powder obtained may be compounded with other thermoplastics.
EXAMPLE 2 and COMPARISON TESTS 1 and 2
Components, production and testing of the molding compounds.
Materials used:
I. Aromatic polycarbonate of 10% by weight tetrabromobisphenol A and 90% by
weight bisphenol A having a relative viscosity, as measured in CH.sub.2
Cl.sub.2 at 25.degree. C. of 1.284 (0.5% by weight solution).
II. Thermoplastic polymer of styrene and acrylonitrile having an
acrylonitrile content of 23% by weight and an average molecular weight of
60,000.
III. ABS graft polymer of 50% by weight of a styrene/acrylonitrile mixture
(ratio by weight 72:28) on 50% by weight particulate polybutadiene having
an average particle diameter (d.sub.50) of 0.4 .mu.m obtained by emulsion
polymerization.
IV. Silicone-resin-containing polymer of Example 1.
IVa. Silicone-rubber-containing polymer of the Comparison Example.
V. Triphenyl phosphate (TPP).
VI. Pentaerythritol tetrastearate (PETS).
Production and testing of the molding compounds:
The molding compounds were produced by direct compounding of the components
listed in Table 1 in a Banbury internal kneader (Pomini-Farell) of the Br
type (1.2 l) or the OOC type (3 l) at a temperature of 230.degree. to
240.degree. C., followed by granulation.
TABLE 1
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Component I II III IV IVa V VI
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Quantities in % by weight
Comparison Test 1
58.0 17.5 13.7 -- -- 9.9 0.9
Example 2 58.0 17.5 3.7 10 -- 9.9 0.9
Comparison test 2
58.0 17.5 3.7 -- 10 9.9 0.9
(= Example 4 of
European patent
application
no. 87 116 839.9)
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The molding compounds obtained are injection-molded at 260.degree. C.
(unit: Werner und Pfleiderer DKS 275 screw, locking force 275 MP, screw
diameter 56 mm, length L/D-23/1) and subjected to the following tests:
impact strength according to DIN 53 543 (a.sub.n)
notched impact strength according to DIN 53 453 (a.sub.k)
fire test UL 94 of Underwriters' Laboratories, page 94.
The results obtained are shown in Table 2.
TABLE 2
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UL 94/1.6 mm-bar
storage of test
specimens
a.sub.n
a.sub.k standard 70.degree. C./
(kJ/m.sup.2)
(kJ/m.sup.2)
climate 7 days
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Comparison test 1
u.b. 14 V-2 V-2
Example 2 u.b. 14 V-0 V-0
Comparison test 2
u.b. 13 V-0 V-1
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*u.b. = Test specimens unbroken
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