Silicone-containing block copolycarbonates with small domain sizes
阅读说明：本技术 具有小的畴尺寸的含硅氧烷的嵌段共聚碳酸酯 (Silicone-containing block copolycarbonates with small domain sizes ) 是由 A·迈耶 U·利森费尔德 J·哈金斯 于 2020-03-30 设计创作，主要内容包括：本发明涉及制备聚硅氧烷-聚碳酸酯嵌段共缩合物的方法,其中使用包含脂族基团和芳族基团的硅氧烷组分作为介体。本发明同样涉及聚碳酸酯组合物以及特殊的硅氧烷组分用于降低聚硅氧烷-聚碳酸酯嵌段共缩合物中硅氧烷畴的粒度分布的用途。(The invention relates to a method for producing polysiloxane-polycarbonate block cocondensates, wherein a siloxane component comprising aliphatic and aromatic groups is used as a mediator. The invention likewise relates to polycarbonate compositions and to the use of specific siloxane components for reducing the particle size distribution of the siloxane domains in polysiloxane-polycarbonate block cocondensates.)
1. A polycarbonate composition comprising
(i) At least one polysiloxane-polycarbonate block cocondensate,
(ii) at least one siloxane of the general chemical formula (I), (Ia) or any mixture thereof,
wherein Z1、Z2And Z3Each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-di-caprolactone, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, phenylethyl optionally substituted with alkyl or alkoxy groups, benzeneIsopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN,
R8and R9Each independently of the other being an aliphatic or aromatic radical, with the proviso that, in formula (I) or (Ia), at least one R8Is an aliphatic radical and at least one R9Is an aromatic radical, and
s、s1、s2、s3and s4 Each independently of the others is a natural number from 1 to 250,
(iii) optionally at least one further polymer different from component (i), and
(iv) optionally at least one additional additive.
2. The polycarbonate composition of claim 1,
r in the general chemical formula (I) or (Ia)8Each, independently of the others, being methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, C5 to C18-alkyl or phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl optionally substituted by alkyl or alkoxy,
r in the general chemical formula (I) or (Ia)9Each, independently of the others, being methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, C5 to C18-alkyl or phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl optionally substituted by alkyl or alkoxy,
with the proviso that at least one R8Is methyl, ethyl, propyl, butyl, isopropyl, vinyl, isobutyl or C5 to C18-alkyl and at least one R9Is phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl optionally substituted by alkyl or alkoxy, and
z in the general formula (I) or (Ia)1、Z2And Z3Each independently of the others having the meaning mentioned in claim 1.
3. The polycarbonate composition of claim 2,
in the general formula (I) or (Ia)R8Each independently of the others being methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3) -phenyl, -CH2-CH2-CH2- (2-methoxy) phenyl or phenyl, and
r in the general chemical formula (I) or (Ia)9Each independently of the others being methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3) -phenyl, -CH2-CH2-CH2- (2-methoxy) phenyl or phenyl,
with the proviso that at least one R8Is methyl or ethyl and at least one R9Is trimethylphenyl or phenyl, and
z in the general formula (I) or (Ia)1、Z2And Z3Each independently of the others having the meaning mentioned in claim 1.
4. The polycarbonate composition according to any of claims 1 to 3, wherein the at least one siloxane of component (II) is represented by general chemical formula (II), general chemical formula (IIa), general chemical formula (III) and/or general chemical formula (IV),
wherein Z1、Z2And Z3Each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-di-caprolactone, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, optionally substituted with alkyl or alkoxy groupsSubstituted phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN, preferably methyl, methoxy, ethoxy, hydrogen or hydroxy,
R10each, independently of the others, hydrogen, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, isononyl or isodecyl,
R11each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-di-caprolactone, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, phenylethyl optionally substituted with alkyl or alkoxy, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chloro, fluoro or CN,
r is a natural number from 0 to 3,
s and t are each, independently of one another, a natural number from 1 to 250, preferably from 1 to 100, particularly preferably from 5 to 75, and
w and v are each, independently of one another, a natural number from 1 to 250, preferably from 1 to 100, particularly preferably from 5 to 75, and
the groups having the indices s, w, v, t and u can be present distributed randomly in the siloxane of component (ii).
5. The polycarbonate composition of claim 4, wherein in formula (II), (IIa), (III) and (IV)
Z1、Z2And Z3Each, independently of the others, being methyl, vinyl, methoxy, ethoxy, hydrogen or hydroxy, preferably methyl, hydroxy or a mixture of methoxy and ethoxy,
R10is hydrogen or a methyl group, or a mixture thereof,
R11each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-di-caprolactone, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, optionally alkyl or alkoxy substitutedPhenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN, preferably methyl or phenyl,
r is a natural number from 0 to 3,
s is a natural number from 5 to 75,
t is a natural number from 1 to 75,
w is a natural number from 5 to 75,
v is a natural number from 1 to 75, and
u is a natural number from 1 to 10.
6. Process for preparing polysiloxane-polycarbonate block cocondensates, in which
Reacting A) at least one polycarbonate with
B) At least one hydroxyaryl-terminated (poly) siloxane, use of
C) At least one siloxane of the general chemical formula (I), (Ia) or any mixture thereof,
wherein Z1、Z2And Z3Each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-di-caprolactone, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, phenylethyl optionally substituted with alkyl or alkoxy, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chloro, fluoro or CN,
R8and R9Each independently of the other being an aliphatic or aromatic radical, with the proviso that, in formula (I) or (Ia), at least one R8Is an aliphatic radical and at least one R9Is an aromatic radical, and
s、s1、s2、s3and s4Each independently of the others is a natural number from 1 to 250,
in the melt, characterized in that the method comprises the step of adding component C) to component A), component B) and/or a mixture of components A) and B).
7. The method of preparing a polysiloxane-polycarbonate block cocondensate according to claim 6, characterized in that,
wherein component B) is a hydroxyaryl-terminated (poly) siloxane of formula (1),
wherein
R5Is hydrogen or C1 to C4 alkyl, preferably hydrogen or methyl,
R6and R7Independently of one another, is a C1 to C4 alkyl group, preferably methyl,
y is a single bond, -CO-, -O-, C1-to C5Alkylene radical, C2-to C5Alkylidene or C5-to C6Cycloalkylidene radical, which may be substituted by C1-to C4Alkyl is mono-or polysubstituted, preferably a single bond, -O-, isopropylidene or is C5-to C6Cycloalkylidene radical, which may be substituted by C1-to C4-alkyl is mono-or polysubstituted,
v is oxygen, C2-C6 alkylene or C3-to C6-alkylidene, preferably oxygen or C3-alkylene,
when q = 0, W is a single bond,
when q = 1, W is oxygen, C2-C6-alkylene or C3-C6-alkylidene, preferably oxygen or C3-alkylene,
p and q are each independently 0 or 1,
o is the average number of repeating units of from 10 to 400, preferably from 10 to 100, and
m is the average number of repeating units from 1 to 10, preferably from 1.5 to 5.
8. The method for preparing a polysiloxane-polycarbonate block cocondensate according to any one of claims 6 or 7, characterized in that,
component B) is a hydroxyaryl-terminated (poly) siloxane of formula (2), (3), (VII), (VIII) or (IX):
wherein R1 is hydrogen, C1-C4-alkyl, preferably hydrogen or methyl,
r2 is independently aryl or alkyl, preferably methyl,
x is a single bond, C1 to C5-alkylene, C2 to C5-alkylidene, C5 to C12-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, preferably a single bond, isopropylidene, C5 to C12 cycloalkylidene or oxygen, very particularly preferably isopropylidene,
n is a number from 10 to 150,
m is a number from 1 to 10,
wherein a in formulae (VII), (VIII) and (IX) is an average number from 10 to 400, preferably from 10 to 100, particularly preferably from 15 to 50.
9. The method for preparing a polysiloxane-polycarbonate block cocondensate according to any one of claims 6 to 8, characterized in that,
r in the general chemical formula (I) or (Ia)8Each, independently of the others, being methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, C5 to C18-alkyl or phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl optionally substituted by alkyl or alkoxy, and
r in the general chemical formula (I) or (Ia)9Each independently of the others being methyl, ethyl, propyl, butyl, isoPropyl, isobutyl, vinyl, C5 to C18-alkyl or phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl optionally substituted by alkyl or alkoxy,
with the proviso that at least one R8Is methyl, ethyl, propyl, butyl, isopropyl, vinyl, isobutyl or C5 to C18-alkyl and at least one R9Is phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl optionally substituted with alkyl or alkoxy.
10. The method for preparing a polysiloxane-polycarbonate block cocondensate according to any one of claims 6 to 9, characterized in that,
r in the general chemical formula (I) or (Ia)8Each independently of the others being methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3) -phenyl, -CH2-CH2-CH2- (2-methoxy) phenyl or phenyl, and
r in the general chemical formula (I) or (Ia)9Each independently of the others being methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3) -phenyl, -CH2-CH2-CH2- (2-methoxy) phenyl or phenyl,
with the proviso that at least one R8Is methyl or ethyl and at least one R9Is trimethylphenyl or phenyl.
11. The process for preparing polysiloxane-polycarbonate block cocondensates according to any of claims 6 to 10, characterized in that the siloxane of the at least one component C) is represented by the general chemical formula (II), the general chemical formula (IIa), the general chemical formula (III) and/or the general chemical formula (IV),
wherein Z1、Z2And Z3Each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-dihexanolide, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN, preferably methyl, methoxy, hydrogen or hydroxy, optionally substituted by alkyl or alkoxy,
R10each, independently of the others, hydrogen, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, isononyl or isodecyl,
R11each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-di-caprolactone, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, phenylethyl optionally substituted with alkyl or alkoxy, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chloro, fluoro or CN,
r is a natural number from 0 to 3,
s and t are each independently a natural number from 1 to 250, preferably from 1 to 100, particularly preferably from 5 to 75,
w and v are each independently a natural number from 1 to 250, preferably from 1 to 100, particularly preferably from 5 to 75, and
the radicals having the indices s, w, v, t and u can be present distributed randomly in the siloxane of component C).
12. The process for preparing polysiloxane-polycarbonate block cocondensates according to claim 11, characterized in that in the general chemical formulae (II), (IIa), (III) and (IV)
Z1、Z2And Z3Each, independently of the others, being methyl, vinyl, methoxy, ethoxy, hydrogen or hydroxy, preferably methyl, hydroxy or a mixture of methoxy and ethoxy,
R10is hydrogen or a methyl group, or a mixture thereof,
R11each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-di-caprolactone, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, phenylethyl optionally substituted with alkyl or alkoxy, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chloro, fluoro or CN,
r is a natural number from 0 to 3,
s is a natural number from 5 to 75,
t is a natural number from 1 to 75,
w is a natural number from 5 to 75, and
v is a natural number from 1 to 75.
13. The process for preparing polysiloxane-polycarbonate block cocondensates according to any of claims 6 to 12, characterized in that 0.01 to 20% by weight of component C) is added to component a), component B) and/or the mixture of components a) and B), wherein the% by weight is based on the sum of components a), B) and C).
14. Use of siloxanes of the general formula (I), (Ia) or any mixtures thereof for reducing the particle size distribution of the siloxane domains in a polysiloxane-polycarbonate block cocondensate in a process for preparing polysiloxane-polycarbonate block cocondensates,
wherein Z1、Z2And Z3Each independently of the others, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, ethenyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; mono-di-caprolactone, methoxy, ethoxy, propoxy, butoxy, glycidoxypropyl, phenylethyl optionally substituted with alkyl or alkoxy groups,Phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN,
R8and R9Each independently of the other being an aliphatic or aromatic radical, with the proviso that, in formula (I) or (Ia), at least one R8Is an aliphatic radical and at least one R9Is an aromatic radical, and
s、s1、s2、s3and s4 Each independently of the others, is a natural number from 1 to 250.
15. Use according to claim 14, characterized in that the process for preparing polysiloxane-polycarbonate block cocondensates comprises at least one reactive extrusion or at least one melt transesterification.
Examples
The invention is described in more detail below with the aid of examples, in which, unless stated otherwise, the determination methods described here are used for all corresponding amounts in the context of the invention.
MVR
Unless otherwise stated, the Melt Volume Rate (MVR) was determined according to ISO 1133 (2011) (at 300 ℃; 1.2 kg), provided that no other conditions were described.
Viscosity of solution
Measurement of solution viscosity: the relative solution viscosity (. eta.rel; also known as eta rel) was determined in methylene chloride at a concentration of 5g/l at 25 ℃ using a Ubbelohde viscometer.
Evaluation of siloxane domain size by means of Atomic Force Microscopy (AFM)
The siloxane domain size and distribution was determined by means of atomic force microscopy. For this purpose, the corresponding samples (frit form of laboratory batches or pellets of extruded batches) were cut at low temperature (nitrogen cooling) with the aid of an ultra-thin microtome. A Bruker D3100 AFM microscope was used. AFM images were taken at room temperature (25 ℃, 30% relative humidity). A "soft intermittent contact mode" or "tapping mode" is utilized for the measurement. A "tapping mode cantilever" (NanoWord pointprobe) with a spring constant of about 2.8 Nm-1 and a resonance frequency of about 75 kHz was used for scanning of the probe. The tapping force is controlled by the ratio of the nominal value amplitude and the free oscillation amplitude (the amplitude of the probe tip free oscillation in air). The sampling rate was set to 1 Hz. To capture surface morphology, phase contrast and topography images were captured over a 2.5 μm x 2.5.5 μm area. The particles or siloxane domains were automatically evaluated by light-to-dark contrast (from phase contrast images) by Olympus SIS image evaluation software (Olympus Soft Imaging Solutions GmbH, 48149, munster, germany). The diameter of the particle is determined by the diameter of the corresponding circle of equal area of the longest extension of the particle.
Multiple phase contrast images (particle count greater than 200) were evaluated as described above. The individual diameters are classified and the distribution of the diameters is done by image evaluation software. Thereby being assigned to the respective D values. The value of D gives the proportion of particles which are smaller than the given value. At a D90 value of x, 90% of the particles are smaller than x. Furthermore, the proportion of particles smaller than 100nm is also determined from the distribution.
Influence of the addition of component C)
Starting materials:
component A polycarbonate
PC 1: as starting material for reactive extrusion, linear bisphenol a polycarbonate with phenol-based end groups and a solution viscosity of 1.17 was used (see description above). The polycarbonate is free of additives such as UV stabilizers, mold release agents or heat stabilizers. The polycarbonate is prepared by the melt transesterification process as described in DE 102008019503. The polycarbonate had a phenolic end group content of 0.16%.
Component B siloxane
A bisphenol A end-capped polydimethylsiloxane of formula 3, wherein n is about 30 and m is 3 to 4 (R)1 = H, R2= methyl, X = isopropylidene), a hydroxyl content of 18 mg KOH/g, a viscosity of 400 mpa.s (23 ℃); the siloxane was mixed with sodium caprylate, sodium content 2.5 ppm.
Component C or (ii):
linear oligosiloxanes of the formula (I), in which Z1And Z2＝OH，R8Methyl, R9Phenyl, where s averages about 4 (oligomeric mixtures with chains where s is 2 to about 10).
The method comprises the following steps:
the protocol of the experimental setup can be seen from fig. 1.
FIG. 1 shows a scheme for preparing a siloxane-containing block cocondensate. The polycarbonate (component A) was metered into the twin-screw extruder (1) by means of gravity feed (2). The extruder (model ZSE 27 MAXX, Leistritz extrusion Stechnik GmbH, Nelumberg) is a co-rotating twin-screw extruder with a vacuum zone for the separation of the vapors. The extruder consists of 11 shell parts (a to k) -see fig. 1. In housing part a, polycarbonate is added by means of a differential metering balance (2), and polycarbonate is melted in housings b and c. In the case part d, a liquid silicone component (component B) was added. The shells d and e are furthermore used for incorporation of the liquid silicone component (component B). Shell sections e, g, i and j are equipped with degassing ports to remove condensed products. The housing part e is assigned to the first vacuum phase and the housing parts g, i and j are assigned to the second vacuum phase. The vacuum in the first vacuum stage is from 45 to 65 mbar absolute. The vacuum in the second vacuum stage is less than 1 mbar. The silicone (component B) is preloaded into the tank (3) and fed into the extruder by means of the metering pump (4). The vacuum is generated by vacuum pumps (5) and (6). The steam was taken from the extruder and collected in 2 condensers (9). The molten strand is guided into a water bath (10) and comminuted by means of a pelletizer (11).
Example 1:
for preparation, polycarbonate (component A) was mixed with 0.5% of component C in a solids mixer.
1.9kg/h of polycarbonate (component A) were metered into the twin-screw extruder (1) by means of gravity feed (2). The number of revolutions of the extruder was set to 120 l/min. 0.09kg/h of component B was fed by means of a pump (4) into the housing (d) of the extruder. A vacuum of 55 mbar was applied to housing (e) and a vacuum of 0.5 mbar was applied to each of housings (g), (i) and (j). The shells (g) to (k) are brought to a temperature of 350 ℃.
The resulting polycondensate had a light color and had an MVR of 2.1. 880 objects which can be assigned to the soft phase and thus to the siloxane phase were identified in an AFM photograph of 10 x 10 μm size. The size distribution of the object had a D90 diameter of 115 nm. The largest object identified corresponds to an equivalent circular diameter of 156 nm.
Comparative example 2:
1.9kg/h of polycarbonate (component A) were metered into the twin-screw extruder (1) by means of gravity feed (2). The number of revolutions of the extruder was set to 120 l/min. 0.09kg/h of component B was fed by means of a pump (4) into the housing (d) of the extruder. A vacuum of 63 mbar was applied to housing (e) and a vacuum of 0.5 mbar was applied to each of housings (g), (i) and (j). The shells (g) to (k) are brought to a temperature of 325 ℃.
The resulting polycondensate had a light color and had an MVR of 4.4. In an AFM photograph of 10 x 10 μm, 624 objects which could be assigned to the soft phase and thus to the siloxane phase were identified. The size distribution of the object had a D90 diameter of 185 nm. The largest object identified corresponds to an equivalent circular diameter of 516 nm.
The following examples were carried out in the same manner as in example 1 or comparative example 2, with the parameters given being varied:
table 1:
component C)
[ weight% ]]
Number of revolutions of extruder
[rpm]
Production volume
[kg/h]
Barrel temperature [ ° c
C]
MVR
Comparative example 3
-
120
2.0
320
6.8
Example 4
0.5
180
2.0
310
8.5
Comparative example 5
-
120
2.0
325
4.4
Example 6
0.5
120
2.0
350
2.1
Comparative example 7
-
120
1.42
320
9.5
Example 8
1.0
120
1.05
320
5.6
Example 9
0.5
120
1.42
320
8.1
As can be seen from the table, comparative example 3 and example 4 are substantially comparable to each other. Despite the use of slightly different extruder revolutions and barrel temperatures, polymers with comparable MVR were obtained. The examples therefore differ in that component C) is added in example 4 and in that component C) is absent in comparative example 3).
A similar conclusion can be drawn on the comparability of comparative example 5 with example 6 and of comparative example 7 with examples 8 and 9. This comparison is useful for evaluating the effect of adding component C) (and the amount added thereof).
TABLE 2 Domain distribution results
Particle size distribution;
of average particle diameter
D90 value [ nm ]]
<Content of 100nm particles
[%]
<Bulk of 200nm particles
Volume fraction [% ]]
Comparative example 3
124.9
75.3
84.9
Example 4
105.9
87.6
88.3
Comparative example 5
184.7
54.2
49.9
Example 6
115.0
80.0
100.0
Comparative example 7
101.2
88.7
25.0
Example 8
91.0
94.5
100.0
Example 9
98.8
90.3
61.0
The positive effect of the low molecular weight siloxanes according to the invention is shown in example 4 according to the invention in the case of a throughput of 2.0kg/h and materials with an MVR in the range from about 7 to 9 (comparative example 3 and example 4). Example 4 according to the invention has a significantly lower value of D90 compared to comparative example 3 and therefore provides a polymer morphology with smaller siloxane domain sizes. Lower viscosities can be achieved by increasing the reaction temperature (comparative example 5 and example 6). Example 6 according to the invention, which contains the low molecular weight siloxane additive according to the invention as component C), shows a D90 value which is distinctly lower than in comparative example 5.
At lower throughputs (1.4 kg and less than 2.0 kg/h), the positive effect of adding a special siloxane component is likewise shown. Example 9 according to the invention, although having a similar value of D90 as comparative example 7, the proportion of particles with a volume of <200nm is significantly greater than in example 9 according to the invention. Particles having a large volume are particularly critical with regard to processing defects, for example in injection molding. Further advantages are obtained if the proportion of the siloxane component according to the invention is increased (example 8), as can be seen from the lower D90 value of the particles and the better volume distribution (particles with a volume of >200nm no longer being present).
Influence of the chemical Structure of component C)
Starting materials:
component A polycarbonate
PC A As starting material for reactive extrusion a linear bisphenol A polycarbonate with phenol-based end groups from Covestro Deutschland AG was used, which has a melt volume index, measured at 300 ℃ and under a load of 1.2kg, of from 59 to 62 cm310min (according to ISO 1033). The polycarbonate is free of additives such as UV stabilizers, mold release agents or heat stabilizers. The polycarbonate is prepared by the melt transesterification process as described in DE 102008019503. The polycarbonate had a phenolic end group content of about 600 ppm.
PC B As starting material for reactive extrusion a linear bisphenol A polycarbonate with phenol-based end groups having a solution viscosity of about 1.17 was used. The polycarbonate is free of additives such as UV stabilizers, mold release agents or heat stabilizers. The polycarbonate is prepared by the melt transesterification process as described in DE 102008019503. The polycarbonate had a phenolic end group content of about 1600 ppm.
And (B) component:
siloxane-1
A bisphenol A end-capped polydimethylsiloxane of formula 3, wherein n is about 15 and m is 3 to 4 (R)1 = H, R2= methyl, X = isopropylidene), wherein the hydroxyl content is 27.8 mg KOH/g, the viscosity is 165 mpa.s (23 ℃); the sodium content was about 4 ppm.
Siloxane-2:
a hydroquinone blocked polydimethylsiloxane of formula 2 wherein n is about 20 and m is 3 to 4 (R)1 = H, R2= methyl), wherein the hydroxyl group content was 22.2 mg KOH/g, the viscosity was 177 mpa.s (23 ℃); the sodium content was about 3 ppm.
Siloxane-3:
a bisphenol A end-capped polydimethylsiloxane of formula 3, wherein n is about 30 and m is 3 to 4 (R)1 = H, R2= methyl, X = isopropylidene), wherein the hydroxyl content is 17.9 mg KOH/g, the viscosity is 402 mpa.s (23 ℃); the sodium content was about 3 ppm.
Component C or (ii):
linear oligosiloxanes of the formula (I), in which Z1And Z2＝OH，R8Methyl and R9Phenyl where s is an average of about 4 (oligomer mixture with a chain where s is 2 to about 10).
Comparison components:
octaphenylcyclotetrasiloxane (CAS: 546-56-5), 95% from ABCR GmbH & Co.KG (Karlsruhe Germany).
Catalyst masterbatch (without silicone-based additive component):
the tetraphenylphosphonium phenolate from Rhein Chemie Rheinau GmbH (Mannheim, Germany) was used as catalyst in the form of a masterbatch. Tetraphenylphosphonium phenolate was used as mixed crystals with phenol and contained about 70% tetraphenylphosphonium phenolate. The following amounts are based on the material obtained from Rhein Chemie (as mixed crystals with phenol).
The masterbatch was prepared as a 0.25% blend. To this end 4982g of polycarbonate PC A were mixed with 18g of tetraphenylphosphonium phenolate in a drum mixer for 30 minutes with rotation. The masterbatch was metered in a ratio of 1:10, so that the catalyst was present in a proportion of 0.025% by weight in the total amount of polycarbonate.
Comparative example 10:
42.5 g of polycarbonate pellets (PC A; 85% by weight), 2.5g of siloxane-1 (5% by weight) and also 5g (10% by weight) of the catalyst masterbatch and 0.1g (0.2% by weight) of octaphenylcyclotetrasiloxane are weighed into a 250 ml glass flask with stirrer and short-path separator. The apparatus was evacuated and purged with nitrogen (3X each). The mixture was melted in 10 minutes under vacuum by means of a metal bath preheated to 350 ℃. The pressure in the apparatus is about 1.5 mbar. The reaction mixture was stirred under this vacuum for 30 minutes. Subsequently, nitrogen was introduced and the polymer melt was removed. An opaque white polymer was obtained. The solution viscosity of the product was eta rel = 1.345.
Comparative example 11:
42.5 g of polycarbonate pellets (PC A; 85% by weight), 2.5g of siloxane-2 (5% by weight) and 5g (10% by weight) of the catalyst masterbatch (in contrast to the data above which also contains 1.66% by weight of octaphenylcyclotetrasiloxane) are weighed into a 250 ml glass flask with stirrer and short-path separator. The apparatus was evacuated and purged with nitrogen (3X each). The mixture was melted in 10 minutes under vacuum by means of a metal bath preheated to 350 ℃. The pressure in the apparatus is about 1.5 mbar. The reaction mixture was stirred under this vacuum for 30 minutes. Subsequently, nitrogen was introduced and the polymer melt was removed. An opaque white polymer was obtained. The solution viscosity of the product was eta rel = 1.46.
Example 12:
47.4g of polycarbonate pellets (PC B; 94.8% by weight) are weighed into a 250 ml glass flask with stirrer and short-path separator. The apparatus was evacuated and purged with nitrogen (3X each). The mixture was melted by a metal bath preheated to 350 ℃ at normal pressure over 10 minutes. A siloxane mixture consisting of 2.5g of siloxane-3 (5% by weight) and 0.13g (0.2% by weight) of component C (dissolved in siloxane-3) was added at 10 mbar. The pressure in the apparatus is then reduced to about 1.5 mbar. The reaction mixture was stirred under this vacuum for about 5 minutes. Subsequently, nitrogen was introduced and the polymer melt was removed. An opaque white polymer was obtained. The solution viscosity of the product was eta rel = 1.38.
TABLE 3 Domain distribution results
Particle size distribution, D90 value of average particle diameter [ nm ]]
<Content of 100nm particles [% ]]
Example 12
110.4
85.3
Comparative examples 10 and 11 show a significantly coarse particle distribution in AFM; therefore, no accurate evaluation is performed, and only an estimation is performed.
TABLE 4 Domain distribution results
Diameter of large particle (40 mu m photo)
[nm]
Diameter of small particles (2.5 mu m photo)
[nm]
Comparative example 10
1700 (very long)
20-270 (round)
Comparative example 11
1000 (slight long)
26-240 (round)
Comparison of example 12 with comparative examples 10 and 11 shows that the addition of compounds having aliphatic and aromatic groups in the preparation of polysiloxane-polycarbonate block cocondensates leads to a reduced siloxane domain distribution compared to compounds having only aromatic groups.
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