JPH06157890A - Compatible transparent thermoplastic polymer mixture and molding and coated and fiber-reinforced laminate produced therefrom - Google Patents

Abstract

PURPOSE: To obtain a compatible thermoplastic polymer mixture having high transparency, by mixing a specific copolycarbonate and a specific methacrylate copolymer.

CONSTITUTION: The thermoplastic polymer mixture comprises a copolycarbonate mentioned below (A) and a methacrylate copolymer mentioned below (B). The copolycarbonate (A) is constituted of 95 to 5 wt.% bisphenol A unit and from 5 to 95 wt.% bisphenol unit of formula I. Also, the methacrylate copolymer (B) is constituted of 99 to 1 wt.% methyl methacrylate unit and occasionally from 1 to 99 wt.% (meth)acrylic ester unit of formula II having from 0 to 40 wt.% α,β-unsaturated monomer unit and a carbon cyclic group in an ester group. Furthermore, the copolymer (B) has a molecular weight of at least 3×10⁴, etc. In the formulae, R₁ is H or the like; R₂ is a cycloalkyl group or the like; R₃ is H or the like; Y is Q-Y; Y is an aryl group or the like; and Q is an alkylene group or the like.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to compatible polymer mixtures consisting of copolycarbonates A) and methacrylate copolymers B) which are distinguished by a high transparency and their use.

[0002]

Polymer mixtures containing aromatic polycarbonates are known.

Published German patent application No. 2329
No. 585, a mixture of thermoplastics, polystyrene and aromatic polycarbonate having 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane units. This gives a compatible and transparent molding material. Unlike this, 2,
The mixture of 2-bis- (4-hydroxyphenyl) -propane-polycarbonate (bisphenol-A-polycarbonate) and polystyrene is incompatible.

JP-A-45-16063 discloses a mixture of polymethylmethacrylate, a colorless and clear transparent plastic and bisphenol-A-polycarbonate, also a transparent plastic, as a mixture having a pearly luster. There is clear evidence of the absence of a homogeneous, transparent polymer mixture as described.

Improved polycarbonate molding materials are
According to the description of DE-A-2264268 (= FR-A-2167650), polycarbonate is added with 90-75% by weight of methyl methacrylate and the formula:

[0006]

[Chemical 3]

Alkyl (meth) acrylates 10 to 2 represented by the formula: wherein X represents a hydrogen atom or a methyl group, and R represents an organic group having 4 to 12 carbon atoms.
Obtained when 5% by weight of a methacrylate copolymer is added. With the addition of 0.01 to 50% by weight of copolymer, the melt viscosity of the polycarbonate continues to decrease as the amount of copolymer added increases, without compromising clarity. Therefore, the above-mentioned copolymer is a polymerization plasticizer, and its average molecular weight M _w can be measured using, for example, gel permeation chromatography or a light scattering method (in this regard, for example, H.F. Mark, et al., En
cyclopedia of Polymer Sci
ence and Technology, Volume 10,
Pp. 1-19, J. Wiley, 1987), in order to achieve the described compatibility, M _w ≤15000, based on specific tests with the corresponding copolymers.
Must be Dalton. Further, in order to produce a polymer alloy having industrially important properties in the high polymethacrylate content region, the above copolymer has a molecular weight region M _w <5 × based on the known decrease in mechanical properties. 1
0 ⁴ Daltons, in particular M _w <3 × 10 ⁴ Daltons,
However, it is completely unsuitable (in this regard,
For example, Kunststoff-Handbuch, I.
Volume X, page 112 et seq., See Vieweg / Esser). A thermoplastic molding material as a polymer mixture consisting of polycarbonate, methyl methacrylate, a copolymer of styrene and N-phenylmaleinimide and a rubber grafted with methyl methacrylate is disclosed in EP-A-173146. According to the description, they are not compatible.

Similarly, from the description of EP-A-144231, which consists of EPDM rubber grafted with polycarbonate and methyl methacrylate and N-phenylmaleinimide and / or methylmethacrylate and N-phenylmaleinimide. The known polymer mixtures are not completely compatible and are therefore not transparent.

EP 262502 (= US Pat. No. 4,749,745) discloses methacryl as a comonomer which is substituted on the amide nitrogen with a cyclic group and which does not have outstanding UV absorption. Thermoplastically processable methyl methacrylate copolymers with amides are described. This copolymer is a polycarbonate,
Especially with bisphenol-A-polycarbonate,
A clear, thermoplastically processable polymer mixture is formed.

EP-A-283975 (= US Pat. No. 4,950,716) discloses bisphenol-A-polycarbonate and a methacrylate copolymer composed of methyl methacrylate and N-cyclohexylmaleimide units. A transparent, thermoplastically processable polymer mixture consisting of is described.
In order to form the methyl methacrylate copolymer, depending on the selection, another monomer is added to the monomer in an amount of 0 to 0.
It can be shared in an amount of 40% by weight. Advantageously, the polymer mixtures described above can be used in optical components as a result of their low optical birefringence and low water absorption.

European Patent Application Publication No. 297285 (= US Pat. No. 4,906,696) describes that bisphenol-A-polycarbonate and methyl methacrylate 95 to 5% by weight and acrylic and / or methacrylic acid ester 5 are used. ˜95% by weight with carbocyclic groups in the ester groups and further containing another α, β-unsaturated monomer as polymer component in an amount of 0-40% by weight. It relates to transparent, thermoplastically processable polymer mixtures which consist of good methacrylate copolymers.

European Patent Publication No. 321878 (= US Pat. No. 4,906,699) and European Patent Publication No. 326938 (= US Pat. No. 49).
No. 97883) describes impact modifiers for bisphenol-A-polycarbonates, which are mixed polymers consisting of an elastomer content and a methyl methacrylate copolymer content covalently bonded to each other. , In this case the methyl methacrylate copolymer is itself such that it is compatible with bisphenol-A-polycarbonate.

Usually, the mixture of polymers is incompatible. Despite the increasing number of falsifications found in recent years, the experience of those skilled in the art is still today stipulated by the following term: "Miscility is the"
exception, immiscibility
is the rule "(for this, Kirk
-Othmer, Encyclopedia of C
chemical Technology, 3rd edition, 1st
Volume 8, page 460, J. Am. See Wiley, 1982).

Recently, the importance of compatible polymer blends, which usually combine the advantages of thermoplastic post-processability with the advantages of reusability and clarity, has grown. The generally satisfactory mechanical properties, which are usually regenerable and usable, are associated with the above advantages.

By partial substitution of the bisphenol-A group from bisphenol-A-polycarbonate, for example, cyclohexylidene- or cyclododecyldiene, which has a significantly higher thermoforming stability than bisphenol-A-polycarbonate. It can be derived from lidene-bisphenol, a so-called copolycarbonate A). In contrast to this, indeed, a relatively high instability to the effects of weather (as in the case of bisphenol-A-polycarbonate), a marked decrease in toughness for bisphenol-A-polycarbonate and high post-processing temperatures. And thus has a high melt viscosity which limits the thermal oxidation load of component A).

Compatible polymer alloy PM consisting of copolycarbonate A) and methacrylate copolymer B)
[And not only for mixtures from A) and B)], the person skilled in the art is generally familiar with bisphenol-A-polycarbonates (or in general:
It is not possible to find an analog of another mixed component). For example, the slightest change in the copolymer composition is 2
Incompatibility can occur in the case of compatible mixtures of two copolymers [in this regard, see, for example, J. Pfenn
ig, H.I. Keskkula, J .; Barlow and D.M. Paul, Makromolecules 18th
Vol., Pp. 1937 et seq. (1985); W. Kam
Mer et al., Acta Polymeric No. 40
(2), pp. 75 et seq. (1989)].

[0017]

The present invention has the above-mentioned problems.

[0018]

Surprisingly, however, it is surprising that certain mixtures of copolycarbonates A) and methacrylate copolymers B) form compatible transparent polymer alloys PM. Was found. This polymer alloy has the following: a1) bisphenol-A units 95 to 5% by weight and a2) formula I:

[0019]

[Chemical 4]

[Wherein R ₁ represents a hydrogen atom or an optionally branched alkyl group having 1 to 6 carbon atoms, and R ₂ represents 1 to 6 carbon atoms. A substituted or unsubstituted cycloalkyl group having 5 to 16 carbon atoms, a phenyl group, a benzyl group and / or 2-
A phenylethyl group, and R ₁ and R ₂ together represent a substituted or unsubstituted cycloalkylidene group having 4 to 16 carbon atoms]. Carbonates A) and the following: b1) b-1) methylmethacrylate units in an amount of 99-1% by weight and, optionally, an additional 0-40% by weight.
Formula II with an α, β-unsaturated monomer unit different from and b2) a carbocyclic group in the ester group:

[0021]

[Chemical 5]

[In the formula, R ₃ represents a hydrogen atom or a methyl group, X represents Y or Q-Y, and in this case, Y
Represents a substituted or unsubstituted cycloalkyl group having 5 to 12 carbon atoms, or represents an alkyl- or oxyalkyl-substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and Q represents a branched chain. Represents an alkylene group having 1 to 6 carbon atoms which may be chain-like or represents an oxyalkylene group having 2 to 6 carbon atoms] and / or a methacrylic ester unit 1 to 99 % Of methacrylate copolymer B), and the methacrylate copolymer B) has a molecular weight M _w of at least 3 × 10 ⁴ Daltons.

The contents of the monomer groups a1) and a2) on the one hand and b1) and b2) on the other hand are replenished up to 100% by weight, respectively.

Another preferred embodiment of the present invention is copolycarbonate A) and a glass transition temperature T _g <10.
From a biphasic impact modifier C) consisting of an elastomer phase having a temperature of 0 ° C. and an elastomer phase having a hard layer at least partially grafted from a copolymer B) having a surprisingly high impact resistance Is a mixture PL.

Copolycarbonates A) Copolycarbonates A) are bisphenol-A units and bisphenol units according to claim 1, for example 1,1.
-Bis- (4-hydroxyphenyl) cyclopentane,
1,1-bis- (4-hydroxyphenyl) cyclohexane, 1,1-bis- (4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 1,1-bis- (4-hydroxyphenyl) cyclooctane, 1,1
-Bis- (4-hydroxyphenyl) cyclododecane,
2,2-bis- (4-hydroxyphenyl) -1-phenyl-ethane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl-methane, 3,3-bis- (4-hydroxyphenyl) -2,4-Dimethylpentane or 4,4-bis- (4-hydroxyphenyl) -heptane, 1,1-bis (4-hydroxyphenyl) -cyclododecane and 1,1-bis (3,5-dimethyl- 4-
Hydroxyphenyl) cyclododecane (in this regard, Kirk-Othmer, Encyclopedi
a of Chemical Technology,
Third Edition, Volume 18, Pages 479-494, Volume 6, First
06-116, J. Wiley, 1982). The above bisphenols, as a homopolycarbonate, ie after reaction with phosgene, have in part a clearly higher glass transition temperature T _g than the bisphenol-A-polycarbonate and thus a higher thermoforming stability. It also has sex. Correspondingly, the glass transition temperature T _g of copolycarbonates A) containing bisphenol-A units and the above bisphenols increases with increasing content of the above bisphenols.
For example, bisphenol-A- with T _g = 148 ° C.
For polycarbonates, homopolycarbonates with 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane units have a T _g = 23.
Having 9 ° C. Commercially available copolycarbonates (eg APEC-HT®-type, Bayer) consisting of the abovementioned units have a glass transition temperature of up to about 190 ° C.

Average molecular weight of copolycarbonate M _w (M _w
For the measurement of the above, refer to the above) is 2 × 10 ⁴ ~
Within the range of 6 × 10 ⁴ Daltons, DIN 53460
The Vicat softening temperature measured by ∑ corresponds to approximately the glass transition temperature.

Polymethacrylate Copolymer B) The preparation of copolymer B) is carried out by known methods for the polymerization of α, β-unsaturated compounds, in particular by radical polymerization.
For example, it is carried out in bulk, in solution or as a suspension polymerization: As initiators, for this purpose azo compounds such as azodiisobutyronitrile, peroxides such as dibenzoyl peroxide or dilauroyl peroxide or redox are used. The system is used or the starting groups can be prepared radiochemically (in this regard,
For example, H. Rauch-Puntigam, Th. Vo
elker "Acryl- und Methacry"
Leverbindungen ”, Springer-V
erlag, Heidelberg, 1967; Ki
rk-Othmer, Encyclopedia of
Chemical Technology, Volume 1,
Pp. 386 et seq. Wiley & Sons, 19
See 1978).

The copolymers B) according to the invention preferably have 5 to 95% by weight of methyl methacrylate units, particularly preferably 20 to 90% by weight, very particularly preferably 50 to 80% by weight and correspondingly. Very particularly preferably with 20 to 50% by weight of acrylate and / or methacrylate units copolymerized with the methyl methacrylate of formula I above. The copolymer B) is present in an amount of 0 to 40% by weight, in particular 1 to
25% by weight of α, β-unsaturated monomer units such as styrene, α-methylstyrene, acrylic acid, methacrylic acid and / or C ₂ -C ₁₀ alkyl esters of acrylic or methacrylic acid. It is possible, in this case, the alkyl radicals may optionally be branched. The compatibility of a polymer depends on its molecular weight, and in particular the compatibility of a polymer usually decreases with increasing molecular weight. The copolymers B) according to the invention can be measured using, for example, light scattering methods or gel permeation chromatography treatments (see above) from 3 × 10 ⁴ to about 3
× 10 ⁵ Dalton, preferably 5 × 10 ^{4 to} 1.5 × 10
^{It has} an average molecular weight M _w of ⁵ Daltons. This is DI
About 18~110cm ³ g ~ ¹ were measured in chloroform as solvent by N51562, preferably 30-7
This corresponds to a reduced viscosity η spez / C of 5 cm ³ g- ¹ . The regulation of the molecular weight is carried out by polymerization in the presence of molecular weight regulators, in particular the mercaptans known for regulating the molecular weight (in this regard, for example Houben-Weyl, M.
et der der organischen C
hemi, Volume XIV / 1, p. 66, 1961;
Kirk-Othmer, Encyclopedia
of Chemical Technology, No. 1
Volume, p. 296, John Wiley & Son
s, 1978).

The monomers of the formula I can be used, for example: cyclopentyl (meth) 2 acrylate,
Cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, 2-cyclohexylethyl (meth) acrylate, 3-cyclohexylpropyl (meth) acrylate, 4-tert-butylcyclohexyl (Meth) acrylate, phenyl (meth) acrylate and their alkyl-substituted, alkoxy- and alkylamine-substituted derivatives having 1 to 6 carbon atoms in the alkyl, such as especially p-methoxyphenyl. (Meth) acrylate, N, N
-Dialkylamino-substituted phenyl (meth) acrylate or alkyl (oxy) phenyl (meth) acrylate, such as 2-phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenyl Ethyl (meth) acrylate, 3-phenylpropyl (meth) acrylate, 2-naphthyl (meth) acrylate.

The copolymers B) according to the invention can be thermoplastically processed into colorless, clear, colorless moldings having a Vicat softening temperature of about 100 to 130 ° C. according to DIN 53460.

Impact modifier C) The impact modifier C) according to the invention for the copolycarbonate A) comprises a hard phase c2) covalently bonded to the tough phase c1) and at least partly to c1). It is a polymer having at least two phases.

By definition, the tough phase c1) is a polymer having a glass transition temperature T _g <10 ° C., preferably <-10 ° C. (for the measurement of T _g , for example A. Turi,
"Thermal Characterization
of Polymeric Materials ”, pp. 169 et seq., Academic Press, New
York, 1981). Preferably,
The polymer c1) is selected from the group consisting of polyolefins, polydienes, polysiloxanes and polyacrylates. The polyolefin is preferably ethylene,
Homopolymers or copolymers of propylene and isobutylene (in this regard Ullmanns Ency
klopadie der technischen
Chemie, 4th Edition, Volume 19, 167-226.
Page, Verlag Chemie, 1980). Generally, the average molecular weight M _w of a polyolefin is
It is in the range of 10 ⁴ to 10 ⁶ daltons. Of particular importance are ethylene-propylene-diene polymers (EPDM:
Ullmann, Volume 12, 619-, in the above cited document.
621; Kirk-Othmer, Encyclop.
edia of Chemical Technology
y, 3rd edition, volume 8, pages 492-500, J. Wil
ey, 1979). As the diene component, dicyclopentadiene, ethylidene norbornene or trans-hexadiene-1,4 is preferably used. The molecular weight M _w of EPDM polymers produced on a large industrial scale is generally in the range of 5 × 10 ^{4 to} 5 × 10 ⁵ Daltons. The kinetic freezing temperature is described as -45 to -30 ° C (sequential), where the terpolymer is completely amorphous due to the ethylene content up to 60% by weight. . EPTM polymers (ethylene-propylene-triene) can also be used with EPDM polymers.

The polydienes used are, in particular, the known rubber types in question, for example polybutadiene, poly-2-chlorobutadiene or polyisoprene (Ullm).
ann, cited document, 4th edition, 12th volume, 595-595
See page 635). The molecular weight M _w is usually 10 ⁴ ~
It is 10 ⁶ Daltons.

Further, as the toughness phase c1), polysiloxane (ISO 1629, 1st edition, M according to 1976) is used.
Q, MPQ, MPVQ) are described. Conventionally, conventional silicone rubbers have polydimethylsiloxane chains modified by special substituents (see Ullmann, cited above, volume 13, pages 628-663). The room temperature cross-linked type is a polysiloxane having a molecular weight _Mw 10 ⁴ to 10 ⁶ Dalton with a terminal functional group. The heat-vulcanized type is based mostly on polydimethylsiloxane (MQ) and can be crosslinked with rapidly decomposing diacrylic peroxide at elevated temperatures, for example 150 ° C.

Preferably a polyacrylate is used for c1), the monomer component of which guarantees a glass transition temperature T _g of the resulting homo- or copolymer of <10 ° C., preferably <-10 ° C. To do. The glass transition temperature of a homopolymer or a copolymer is known or can be measured in advance by a known method (in this regard, for example, J. Br.
andrup, E .; H. Immergut, Polym
er Handbook, Volume III, 144-14
P. 8, J. See Wiley, 1975). Preferably, the polyacrylate is produced by polymerization in an aqueous emulsion, partly in suspension. Toughness phase c
In the case of polyacrylates as 1), the production by emulsion polymerization is particularly advantageous. This is because a substance having a defined grain structure can be produced particularly easily by the above method. Particular preference is given here to latex particles which consist of the copolymer B) according to claim 1 and which have on the inside an outer coating c2) containing a rubber of a crosslinked polyacrylate c1). Latex particles having at least a three-stage structure, i.e. particles having further hard polymer nuclei in the polyacrylate c1), are quite particularly advantageous. As a whole, the polyacrylate particles forming the impact modifier C) are 0.1 to 3 μm, preferably 0.1 to 3 μm.
It should have a diameter of 5-1 μm (along with the deposited hard nuclei). In principle, the structure of latex particles of this kind and the isolation of polymer-solids is described in DE-A-3300256 (= US Pat. No. 4,513,118).

In the case of emulsion polymerization, preference is given to working in the neutral or weakly acidic pH range, the use of long-chain alkylsulfates or alkylsulfonates being advantageous. As initiators, the known azo compounds in question and organic or inorganic peroxides such as persulfates / bisulfites are preferably used. Generally, the content of the initiator is in the range of 10 to ³ to 1% by weight based on the monomer. As acrylic monomers, mention is made in particular of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and alkoxy acrylates (see US Pat. No. 3,488,321). Normal,
The acrylate elastomer c1) further contains a crosslinking monomer, for example allyl methacrylate or ethylene glycol dimethacrylate, in a content of 0.1 to 5% by weight. In particular, ethyl acrylate and butyl acrylate are mentioned as the main constituents.

The hard phase c2) consisting of the copolymer B) according to claim 1 is covalently bonded to the tough phase c1) at least partially, that is, at least 5% by weight based on c2).
In order to carry out the bonding effectively, known bridging monomers which have in their molecule a C═C double bond which is preferably activable for at least two radicals in the tough phase c1), such as di- or Tri (meth) acrylate is incorporated. So-called graft crosslinkers, such as allyl (meth) acrylate or triallyl cyanurate, are particularly advantageous. The graft crosslinking agent is preferably 0.1 to c1).
Used in an amount of ~ 5% by weight. The impact modifier C) can be produced according to a known method as follows. In general, preferably selected from the group of, for example, polyolefins, polydienes or polysiloxanes, preferably in the form of a solution in a solvent suitable for further working up, for example in a solvent suitable for radical polymerization of the monomers c2) or B). Defined polymer c1) (H. Rauch-Puntiga
m, Th. Voelker, Acryl-und Me
thacrylverbindungen, Sprin
ger, 1967; Brandrup, E .; H.
Imergut, Polymer Handboo
k, see references cited above). In this case, in particular, the solvent transfer reaction (Uebertraggungstreakt)
The tendency toward (ion) is impaired. For example, esters such as butyl acetate or ethyl acetate, hydrocarbons such as toluene or ketones such as acetone are mentioned. In general, starting from a solution having a content of 10 to 60% by weight of polymer c1), the monomers as described under c2) and the polymerization auxiliaries are added to this solution, for example by dropwise addition. The polymerization is usually carried out at elevated temperature, for example in the range 80 to 140 ° C. As initiators, it is possible to use, for example, peroxides or azo compounds which are customary per se (in this regard, H. Rauch-Puntiga).
m, Th. Voelker, Acryl-und Me
thacrylverbindungen, supra). In the case of low-boiling solvents, it is possible to use, for example, dibenzoyl peroxide, whereas in the case of high-boiling solvents, for example, tertiary butyl compounds, such as tertiary butyl peroctoate, can preferably be used. However, the monomer itself constituting the polymer c2) can also be used as the solvent.

The impact modifier C) is preferably obtained, for example, by precipitation from a solution with methanol as precipitating agent or by degassing in an extruder. In particular,
In the case of latex dispersion, the product obtained in C) is a precipitate,
It can be obtained by spray drying, freeze coagulation or by pressing in an extruder.

Polymer Mixtures PM and PL According to the Invention
Characterization and manufacture of polymer mixtures PM according to the invention as compatible mixtures
Is characterized according to known criteria (in this regard, Kirk-Othmer, cited above, 18th).
Vol. Pp. 457-460; Brandrup, Imme.
rgut, Polymer Handbook, No. 2
Edition, Volume III, page 211, Wiley Inters.
Science, 1975).

Compatible Polymer Mixtures (Polymer Alloys)
In the case of PM, one observes some refractive index and a glass transition temperature between the glass transition temperatures of both polymer components A) and B). Further, regarding the compatibility of the polymer mixture,
Its presence is based on the method that upon heating, the mixture, which was previously clear and transparent, is separated into various phases and becomes optically turbid. LCST (Lower Critic)
The occurrence of al Solution Temperature) is adopted. The method is unequivocal evidence that the original polymer mixture consists of only one homogeneous phase, which exists in thermodynamic equilibrium.
R. Paul, Polymer Blend & Mi
xtures, pages 1-3, Martinius Nij
hoffPublishers, Dordrecht,
See Boston 1985). In this regard, experimentally, the turbidity point T _Tr (turbidity temperature) can be determined, for example, from a Kofler-Heizbank hot bar.
(Chem. Ing.-Techni
k, p. 289, 1950).

The mixtures PM and PL can be produced by various mixing methods, for example by intensive mechanical mixing of the components in the melt or in the extruder. The polymer mixture PM is a so-called "solutio" from a common solvent.
n cast polyblends "(in this regard, Kirk-Othme.
r, Encyclopedia of Chemica
l Technology, 3rd edition, 18th volume, 44th
Pp. 3 to 478, J. Wiley, 1982): In another method, for the preparation of the polymer mixture, the individual polycarbonates A) are added to the monomer mixture of another copolymer B). It can be dissolved, in which case B) is prepared by polymerization in the presence of A).
The mixing method is not limited.

First, a mechanical mixture of mixed components is produced,
In this case, it is advantageous to use slow-acting devices from solids such as granules or pearl polymers, for example drum mixers, lane hoop mixers, double-chamber mixers or plow mixers. Started at. A slow-acting mixing device causes mechanical mixing without eliminating phase boundaries (Ullmanns Encyclopaedie).
der Technischen Chemie, 4th
Edition, Volume 2, Pages 282-311, Verlag Ch
(See emie). Subsequently, by homogenous mixing in the melt, using a heatable mixer, at a temperature suitable for the mixer, for example 150-300 ° C. in a kneader.
Alternatively, advantageously in an extruder such as for example a single or multi-screw type extruder or optionally in an extruder with an oscillating screw and a shear pin (eg in a Bussco-Kneter). ), Thermoplastically processed.

Advantageous Effects of the Invention The polymer alloy PM according to the invention as claimed in claim 1 can be of industrial importance owing to its compatibility already. This polymer mixture PM is usually clear and colorless and transparent. The slight flowability of the copolycarbonates A) is markedly increased by alloying with the already small contents of the copolymer B), while the slight thermoforming stability of the copolymer B) is It is increased by alloying.

Another important use is the notch of copolycarbonates A), preferably by the incorporation of an impact modifier C) consisting of an elastomer phase c1) and a hard phase c2) which is compatible with A). The increase in impact strength [c2) corresponds in composition to copolymer B)].

The following examples are useful for illustrating the present invention.

The following properties were measured: LCST by measuring the cloud point T _Tr on a Coffrel hot bar (see above) 1. Vicat softening point VET according to DIN 53460 at ° C 3. Reduced viscosity η _spec / C in chloroform according to DIN 51562 4. 4. Average molecular weight _Mw by gel permeation chromatography (see above) 5. Glass transition temperature T _g by differential thermal analysis (DSC, see above) 6. Impact resistance (SZ) and notch impact strength (KSZ) according to DIN53453 or ISO / R179

[0047]

【Example】

Example 1 Illustrative Preparation of Copolymer B To a monomer mixture consisting of methyl methacrylate, a monomer according to formula I of claim 1 and optionally another monomer, based on the total of the monomers. 0.2% by weight of dilauroyl peroxide as polymer initiator and 0.55% by weight of dodecyl mercaptan as molecular weight regulator are added. This solution was placed in a pipe (Foliensc)
hlauch) at 50 ° C. for 18 hours and 60 ° C. for 2 hours
Polymerize for 2 hours and heat treat at 110 ° C. for 3 hours in a drying cabinet for final polymerization. The polymer thus obtained has an average molecular weight M _w of 6 × 10 ^{4 to} 1.5 × 10 ⁵ and an intrinsic boundary viscosity η _spec / C of 40 to 75 cm ³ g to ¹ .

Example 2 Preparation and characterization of a polymer mixture PM consisting of copolycarbonate A) and copolymer B) The copolymer B) obtained according to the description of Example 1 was used as copolycarbonate APEC®. HT9351 (Baye
r company), bisphenol-A unit 65 mol% and 3,
Copolycarbonate consisting of 35 mol% 3,5-trimethylcyclohexylidene-bisphenol units is mixed in a drum mixer at the stated mixing ratio and extruded as strips using a single screw extruder. For band samples, visual test, measurement of glass transition temperature T _g ,
Measure the Vicat softening point and measure the turbidity temperature T _Tr using a Coffrel hot bar:

[0049]

[Table 1]

Example 3 Preparation of impact modifier C) for copolycarbonate A) with core-shell structure In a Witt's vessel (Witt's chen Topf) with a heating device, stirrer and volume of 6 l. In addition, 1170 g of water (distilled), 0.1 g of acetic acid (concentrated), 0.005 g of ferric sulfide and 1775 g of distilled water, 4 g of C15-paraffin sulfonate, 1656 g of butyl acrylate.
25 g of a monomer emulsion ME1 consisting of and 33.8 g of allyl methacrylate are charged and the polymerization is initiated at 50 ° C. with 18 g of tert-butyl hydrogen peroxide and 2.5 g of sodium hydroxymethylsulfinate. . 2.5 hours after the temperature maximum is reached, another 3450 g of monomer emulsion ME1 are added and polymerized (core polymer).

After the reaction has subsided, the dispersion obtained is treated with 50
Hold at ° C. Distilled water 960 for 2 hours at the above temperature
g, C15-paraffin sulfonate 2 g, methyl methacrylate 455 g, phenyl methacrylate 455 g
And a monomer emulsion ME2 consisting of 4.6 g of dodecyl mercaptan and 0.9 g of tert-butyl peroxide.
Polymerize in the presence of. After feeding, post-heat at 50 ° C. for 30 minutes.

The impact modifier C) is isolated as a pulverulent substance by freeze agglomeration of the resulting polymer.

Example 4 Preparation and characterization of a polymer mixture PL consisting of copolycarbonate A) and impact modifier C) 20% by weight of the modifier C) described in Example 3 (to a butyl acrylate content of 13% by weight). (Correspondingly) to the copolycarbonate A) APEC® HT9351 described in Example 2.
(Bayer) mixed with 80% by weight, then ground and poured into molds. This gives a glittering opalescent polymer mixture with distinctly improved notch impact strength and very good thermoforming stability. : Mixing property conditions described in Example 4 Polymer mixture PL APEC (registered trademark) HT9351 SZ (KJm ~ ² ) at 23 ° C No break No break KSZ (KJm ~ ² ) At 23 ° C 24.0 7.6- At 20 ° C 21.9 8.5 VET (° C) 166 185

Claims (4)

[Claims] 1. In a compatible transparent thermoplastic polymer mixture PM consisting of copolycarbonate A) and a methacrylate copolymer B), the copolycarbonate A) is: a1) a bisphenol-A unit 95. ˜5% by weight and a2) Formula I: [In the formula, R ₁ represents a hydrogen atom or a carbon atom 1 to
6 optionally represents a branched alkyl group, R ₂ represents an optionally branched alkyl group having 1 to 6 carbon atoms or 5 to 16 carbon atoms.
A substituted or unsubstituted cycloalkyl group, phenyl group, benzyl group and / or 2-phenylethyl group having ₁ to 4 carbon atoms, and R ₁ and R ₂ together represent 4 carbon atoms.
Represents a substituted or unsubstituted cycloalkylidene group having 16 to 16 units) and a methacrylate copolymer B).
Are the following: b1) methylmethacrylate units in an amount of 99-1% by weight and, optionally, in an amount of 0-40% by weight, b2).
Formula II having an α, β-unsaturated monomer unit different from and b2) a carbocyclic group in the ester group: [In the formula, R ₃ represents a hydrogen atom or a methyl group, and X
Represents Y or Q-Y, in which Y represents a substituted or unsubstituted cycloalkyl group having 5 to 12 carbon atoms or an alkyl or oxyalkyl substituted having 6 to 12 carbon atoms. Or represents an unsubstituted aryl group, Q is a carbon atom which may be branched 1
Represents an alkylene group having from 6 or 2 carbon atoms
Represents an oxyalkylene group having 6 to 6 units) and is composed of 1 to 99% by weight of an acrylic ester unit and / or a methacrylic ester unit, and is a copolymer B).
Has a molecular weight M _w of at least 3 × 10 ⁴ Daltons, and on the one hand the monomer groups a1) and a2) and on the other hand b
Compatible and transparent thermoplastic polymer mixtures, characterized in that the contents of 1) and b2) are each replenished up to 100% by weight. 2. A polymer mixture PL, wherein said polymer mixture is copolycarbonate A) 5-9 according to claim 1.
5% by weight and the following: c1) 20-90 parts by weight of at least one optionally crosslinked tough phase with a glass transition temperature T _g <10 ° C. c2) In the composition, the methacrylate according to claim 1. 80 to 10 parts by weight of at least one copolycarbonate A) -compatible copolymer at least partially covalently bound to c) corresponding to copolymer B) and c3) the methacrylate of claim 1. Copolymer B), optionally further comprising 0 to 50 parts by weight of at least 1
Polymeric blends, characterized in that they consist of 95 to 5% by weight of two biphasic impact modifiers C). 3. Moldings, coatings and processes for producing fiber-reinforced laminates, characterized in that the polymer mixtures PM and PL according to claims 1 and 2 are used. And a method for producing a fiber reinforced laminate. 4. A method for producing shaped bodies usable for optical purposes, characterized in that the polymer mixture according to claim 1 is used for producing shaped bodies usable for optical purposes. Law.