EP3280759A1 - Cocondensats à blocs, composés de polysiloxanes et de (co)polycarbonates à base de dihydroxydiphénylcycloalcane - Google Patents

Cocondensats à blocs, composés de polysiloxanes et de (co)polycarbonates à base de dihydroxydiphénylcycloalcane

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Publication number
EP3280759A1
EP3280759A1 EP16713480.8A EP16713480A EP3280759A1 EP 3280759 A1 EP3280759 A1 EP 3280759A1 EP 16713480 A EP16713480 A EP 16713480A EP 3280759 A1 EP3280759 A1 EP 3280759A1
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EP
European Patent Office
Prior art keywords
alkyl
homopolycarbonate
block cocondensate
formula
block
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP16713480.8A
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German (de)
English (en)
Inventor
Alexander Meyer
Klaus Horn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
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Covestro Deutschland AG
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Publication date
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Publication of EP3280759A1 publication Critical patent/EP3280759A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the present invention relates to block cocondensates of polysiloxanes and Dihydroxydiaryl- cycloalkane-based (co) polycarbonates and a method for producing such block cocondensates.
  • the invention further relates to the use of these block cocondensates for the production of moldings and extrudates.
  • polysiloxane-polycarbonate block cocondensates have good low-temperature impact resistance, chemical resistance and outdoor weatherability properties as well as aging properties and flame resistance. They are in these properties z.T. superior to the conventional polycarbonates (homopolycarbonate based on bisphenol-A).
  • cocondensates are industrially produced starting from the monomers mostly via the phase boundary process with phosgene. Further, the preparation of these siloxane cocondensates via the melt transesterification process using diphenyl carbonate is known. These processes have the disadvantage that the industrial plants used for the production of standard polycarbonate are used and therefore have a large plant size. The production of special block cocondensates is often not economically viable on these plants because of the smaller volume of these products. Further, the feedstocks needed to make the cocondensates, such as e.g. the polydimethylsiloxanes that affect equipment, as they can lead to contamination of the system or the solvent cycles. In addition, toxic starting materials such as phosgene are required for production or, as in the melt transesterification process, they require a high energy requirement.
  • a disadvantage of all these processes is the use of organic solvents in at least one step of the synthesis of the silicone-polycarbonate block copolymers, the use of phosgene as a starting material or the insufficient quality of the cocondensate.
  • the synthesis of the cocondensates starting from the monomers is very complicated both in the phase boundary process and in particular in the melt transesterification process.
  • melt processes a low vacuum and low temperatures are used to prevent evaporation and thus removal of the monomers. Only at later stages of the reaction, where higher molecular weight oligomers have formed, can lower pressures and higher temperatures be used. This means that the reaction must be conducted over several stages and the reaction times are therefore correspondingly long.
  • Block cocondensates of polysiloxane and copolycarbonate based on dihydroxydiphenyl cycloalkanes are known in principle.
  • the production of such block cocondensates in the phase interface method is described in EP 0374635 and DE 38 42 931.
  • the preparation of such block cocondensates in the melt transesterification or reactive extrusion process, however, is not described.
  • the materials described in EP 0374635 are characterized by a high heat resistance and a high notched impact strength. The rheological properties are not described.
  • the object was therefore to provide molding compositions based on siloxane-containing block cocondensates, which are distinguished by high heat resistance and high notched impact strength and can be produced with an improved or simplified process. Furthermore, the block cocondensates should have good rheological properties.
  • block cocondensates of polysiloxanes and dihydroxy-diarylcycloalkane-based (co) polycarbonates can be prepared starting from commercially available polycarbonates.
  • both the use of phosgene and the monomers bisphenol A and diphenyl carbonate can be avoided.
  • a process has surprisingly been found with which a block cocondensate comprising siloxane blocks and dihydroxydiphenylcycloalkane-based structural units can be prepared in the melt transesterification process from the corresponding polysiloxanes and polycarbonate (s).
  • the cocondensates have a combination of high notched impact strength and high heat resistance. These block cocondensates also have good rheological properties.
  • the invention thus comprises block cocondensates
  • R 1 and R 2 independently of one another represent hydrogen, halogen, C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, phenyl or C 7 -C 12 -aralkyl,
  • R 3 and R 4 are individually selectable for each X and are independently hydrogen or C 1 -C 6 alkyl
  • n is an integer from 4 to 7
  • R 5 is H, Cl, Br, C 1 to C 4 alkyl or C 1 to C 4 alkoxy,
  • R 6 and R 7 are independently selected from aryl, C 1 to C 10 alkyl and C 1 to C 10 alkylaryl,
  • V is O, S, C1 to C6-alkyl or C1 to C6-alkoxy
  • W is a single bond, S, C1 to C6-alkyl or C1 to C6-alkoxy,
  • Y is a single bond, -CO-, -O-, C 1 - to C 6 -alkylene, C 2 to C 5 -alkylidene, a C 5 to C 6 -cycloalkylidene radical which is mono- or polysubstituted by C 1 to C 4 alkyl may be substituted, or for C6 to C12 arylene which may be condensed with another aromatic ring containing heteroatoms, m is an average number of repeating units of 1 to 10, o represents an average number of repeating units of 1 to 500 stands, and
  • p and q are each 0 or 1;
  • C 1 -C 4 -alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, C 1 -C 6 -alkyl
  • n-pentyl 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neo-pentyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl , 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3 , 3-dimethylbutyl, 1-
  • alkyl radical for example in alkoxy radicals, alkylene radicals and alkylidene radicals.
  • Aryl represents a carbocyclic aromatic radical having 6 to 34 skeleton carbon atoms. The same applies to an arylene radical and to the aromatic part of an arylalkyl radical, also called aralkyl radical, and also to aryl constituents of more complex groups, such as, for example, arylcarbonyl radicals.
  • Examples of "C6-C34-aryl” are phenyl, o-, p-, m-tolyl, naphthyl, phenanthrenyl, anthracenyl or fluorenyl.
  • Arylalkyl or “aralkyl” in each case independently a straight-chain, cyclic, branched or unbranched alkyl radical as defined above, which may be monosubstituted, polysubstituted or completely substituted by aryl radicals as defined above.
  • Alkylaryl means an alkyl radical as defined above defined by an aryl radical as defined above.
  • C 1 -C 6 -alkylene represents a straight-chain or branched alkylene radical having 1 to 6 carbon atoms.
  • C 2 -C 5 -alkylidene denotes a C 2 -C 5 -alkyl radical bonded via a double bond as defined above.
  • C 6 to C 12 -arylene denotes an arylene radical having 6 to 12 aromatic carbon atoms.
  • C 5 -Cycloalkyl stands for a cyclopentanyl radical and "C 6 -cycloalkyl” stands for a cyclohexanyl radical.
  • C 5 -C 6 cycloalkylidene means a doubly bonded via a carbon atom C 5 -C 6 - cycloalkyl radical as defined above.
  • ppb and ppm are parts by weight.
  • the block cocondensate according to the invention contains, as component (A), 1-80% by weight of structural units of the general formula (1), the amount given being based on the total weight of the block cocondensate.
  • the content of structural units of the formula (1) is preferably from 5.0 to 75% by weight, particularly preferably from 10 to 70% by weight and very particularly preferably from 20 to 70% by weight, based in each case on the total weight of the block cocondensate.
  • R 1 and R 2 independently of one another, are methyl, phenyl or H and n is an integer from 4 to 5.
  • Very particularly preferred structural units of the general formula (1) are those which are derived from 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).
  • the structural units of the general formula (1) are preferably contained in the cocondensate in the form of copolycarbonate blocks containing the structural units of the general formula (1).
  • the copolycarbonate blocks further comprise structural units derived from a diphenol of general formula (3)
  • R 8 and R 9 independently of one another are H, C 1 -C 18 -alkyl, C 1 -C 18 -alkoxy, halogen or optionally substituted aryl or aralkyl, preferably H or C 1 -C 12 -alkyl, particularly preferably H or C 1 -C 8 -alkyl and very particularly preferably H or methyl, and
  • Z is a single bond, -CO-, -O-, C 1 - to C 6 -alkylene, C 2 to C 5 -alkylidene or C 6 to C 12 -arylene, which may be condensed with another aromatic ring containing heteroatoms , particularly preferably represents isopropylidene.
  • Suitable diphenols of the formula (3) are, for example, hydroquinone, resorcinol, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, ⁇ , ⁇ '- bis (hydroxyphenyl) diiso- propylbenzenes, and their alkylated, nuclear alkylated and nuclear halogenated compounds.
  • diphenols of the formula (3) are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl, 4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1.3 -bis- [2- (4- hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2 Bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane and 1,3-bis- [2- (3 , 5-dimethyl-4-hydroxyphenyl) -2-propan
  • diphenols of the formula (3) are 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and 2,2-bis (3-methyl, 4-hydroxyphenyl) propane. Very particular preference is given to bisphenol A.
  • the block cocondensate according to the invention contains as component (B) siloxane blocks of the general formula (2).
  • R 5 is preferably H or methyl, more preferably H.
  • R 6 and R 7 are preferably methyl.
  • Y preferably represents a single bond, -CO-, -O-, C 1 - to C 5 -alkylene, C 2 to C 5 -alkylidene or a C 5 to C 6 -cycloalkylidene radical which is mono- or polysubstituted with C 1 to C 4 -alkyl may be substituted, particularly preferably a single bond, -O-, isopropylidene or a C 5 to C 6 - Cycloalkylidenrest which may be mono- or polysubstituted with C 1 to C 4 -alkyl, and in particular for isopropylidene.
  • o stands for an average number of repeat units from 10 to 400, particularly preferably 10 to 100, very particularly preferably 20 to 60.
  • m is preferably one for an average number of repeating units of 1 to 6, more preferably 2 to 5.
  • the product of o times m is preferably a number between 12 and 400, more preferably 15 and 200.
  • siloxane blocks have the general formula (2a):
  • R 5 is H or methyl, particularly preferably H,
  • R 6 and R 7 are methyl
  • Y is a single bond, -O-, isopropylidene or a C5 to C6 cycloalkylidene radical which may be mono- or polysubstituted by C1 to C4-alkyl, in particular isopropylidene.
  • m stands for an average number of repeating units of 1 to 6, preferably 2 to 5, o stands for an average number of repeating units of 1 to 100, and p is 0 or 1, and the product of m times o is a number between 15 and 200
  • the proportion of the siloxane blocks of the formula (2), preferably (2a), in the block cocondensate is preferably from 0.5 to 20.0% by weight, particularly preferably from 1.0 to 10% by weight, based on the total weight of the block cocondensate.
  • the block cocondensate according to the invention contains, as component (C), homopolycarbonate blocks which contain no structural units of the formula (1) and have a number average molecular weight M n of at least 2,000 g / mol.
  • the number-average molecular weight M n of the homopolycarbonate blocks is preferably at least 4,000 g / mol, more preferably 5,000 to 20,000 g / mol.
  • the homopolycarbonate blocks have structural units of the general formula (3)
  • Z, R 8 and R 9 have the meaning already defined in connection with component (A).
  • Particular preference is given to homopolycarbonates based on a diphenol selected from the group consisting of 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl, 4-hydroxyphenyl) -propane, 2,4-bis (4-hydroxyphenyl) -2- methylbutane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, bis (3, 5-dimethyl-4- hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulf
  • the homopolycarbonate blocks used in the preparation have an average molecular weight Mn of at least 2000 g / mol as measured by polycarbonate standard gel permeation chromatography and can be derived from a homopolycarbonate obtained by the melt transesterification method or the interfacial method.
  • the homopolycarbonate may be linear or branched.
  • the homopolycarbonate blocks are derived from a homopolycarbonate obtained by the melt transesterification process, hereinafter referred to as "melt polycarbonate".
  • melt polycarbonate a homopolycarbonate obtained by the melt transesterification process
  • LPC solution-prepared polycarbonate
  • One difference is increased levels of phenolic OH end groups in the SPC.
  • Another difference is the branching structures contained in the SPC, which result from the so-called Fries rearrangement in the melt.
  • the block cocondensates according to the invention therefore have one or more branching structures of the formulas (I) to (IV)
  • the phenyl rings are unsubstituted or independently of one another may be monosubstituted or disubstituted by C1 to C8 alkyl and / or halogen, preferably C1 to C4 alkyl, more preferably methyl, but are preferably present unsubstituted,
  • X is a single bond, C 1 to C 6 alkylene, C 2 to C 5 alkylidene or C 5 to C 6 cycloalkylidene which may be monosubstituted or polysubstituted by C 1 to C 4 alkyl, preferably a single bond or C 1 to C 4 alkylene, and particularly preferably for isopropylidene, stands, and
  • the total amount of the structural units (I) to (IV) is 50 to 2000 ppm, particularly preferably 50 to 1000 ppm, particularly preferably 80 to 850 ppm (determined after hydrolysis, based on the Homopolycarbonatblöcke).
  • branching structures (I) to (IV) are incorporated in the polymer chain of the block cocondensate, preferably in the homopolycarbonate blocks.
  • the respective block cocondensate is subjected to total saponification and thus the corresponding degradation products of the formulas (Ia) to (IVa) formed, the amount of which is determined by HPLC.
  • HPLC HPLC
  • the amount of the compound of the formula (Ia) released in this case is preferably from 20 to 800 ppm, more preferably from 25 to 700 ppm, and especially preferably from 30 to 500 ppm, based on the homopolycarbonate blocks.
  • the amount of the compound of the formula (IIa) released in this case is preferably 0 (ie below the detection limit of 10 ppm) to 100 ppm, more preferably 0 to 80 ppm and particularly preferably 0 to 50 ppm, based on the homopolycarbonate blocks.
  • the amount of the compound of the formula (IIIa) released in this case is preferably 0 (ie below the detection limit of 10 ppm) to 800 ppm, more preferably 10 to 700 ppm and particularly preferably 20 to 600 ppm and very particularly preferably 30 to 350 ppm, based on the homopolycarbonate blocks.
  • the amount of compound of formula (IVa) released thereby is 0 (i.e., below the detection limit of 10 ppm) to 300 ppm, preferably 5 to 250 ppm, and most preferably 10 to 200 ppm, based on the homopolycarbonate blocks.
  • the amount of the structures of formulas (I) to (IV) is set equal to the amount of the released compounds of formulas (Ia) to (IVa).
  • the proportion of the structural units of the formula (3) in the block cocondensate is preferably at least 10.0% by weight, particularly preferably at least 20.0% by weight, based on the total weight of the block cocondensate.
  • the block cocondensates according to the invention can be obtained by reacting the corresponding hydroxyaryloxy-terminated siloxanes with (co) polycarbonates containing structural units of the formula (1) and homopolycarbonates.
  • Another object of the invention is therefore a process for the preparation of a block cocondensate according to the invention comprising the reaction
  • R 5 , R 6 , R 7 , V, W, Y, o, p, q and m have the same meaning as in formula (2); and (c) and a homopolycarbonate
  • the reaction is preferably carried out at temperatures of 280 ° C to 400 ° C, more preferably 300 ° C to 390 ° C, more preferably from 320 ° C to 380 ° C and most preferably from 330 ° C to 370 ° C, and pressures from 0.001 mbar to 50 mbar, preferably 0.005 mbar to 40 mbar, more preferably 0.02 to 30 mbar and most preferably 0.03 to 5 mbar, preferably in the presence of a catalyst.
  • block cocondensates are as component (a) (co) polycarbonates (ie homo- or copolycarbonates) based on bisphenols of the formula (1 ') and optionally one or more further diphenols of the formula (3) - as in connection with Component A of the block cocondensate according to the invention described - needed.
  • copolycarbonates of structure (3c) are used:
  • R 10 is C 1 to C 6 -alkyl, preferably C 1 to C 4 -alkyl
  • R 11 is H, n-butyl or tert-butyl, preferably H or tert-butyl
  • copolycarbonates to be used according to the invention preferably have molecular weights Mw (weight average Mw, determined by gel permeation chromatography GPC measurement) of 12,000 to 120,000 g / mol, preferably 15,000 to 80,000 g / mol, in particular 18,000 to 60,000 g / mol, most preferably 18,000 up to 40,000 g / mol.
  • Mw weight average Mw, determined by gel permeation chromatography GPC measurement
  • Molecular weights can also be indicated by the number average Mn, which are likewise determined after prior calibration on polycarbonate by means of GPC.
  • the hydroxyaryloxy-terminated siloxanes of the formula (2b) to be used as component (b) can be obtained according to the process described in US 2013/0267665 A1.
  • siloxanes of the formula (2b) having a weight-average molecular weight M w of from 3000 to 20,000 g / mol, more preferably from 3,500 to 15,000 g / mol, determined by gel permeation chromatography and bisphenol A standard.
  • homopolycarbonates having a number-average molecular weight of 2,000 g / mol, preferably 6,500 to 14,000 g / mol (measured by gel permeation chromatography with polycarbonate standard (bisphenol A-PC) are used.) These homopolycarbonates preferably have a content of phenolic OH groups from 250 ppm to 1000 ppm, preferably 300 to 900, and more preferably from 350 to 800 ppm.
  • homopolycarbonates based on bisphenol A are used.
  • these homopolycarbonates contain phenol as an end group.
  • homopolycarbonates are suitable for the preparation of the block cocondensates according to the invention which were prepared by the melt transesterification process. Very particular preference is given to polycarbonates whose preparation is described in DE 102008019503.
  • components (a) to (c) are reacted together in the following amounts:
  • the reaction preferably takes place in the presence of a phosphonium catalyst of the formula (4)
  • R a , R b , R c and R d are independently C 1 -C 10 alkyl, C 6 -C 14 aryl, C 7 -C 15 arylalkyl or C 5 -C 6 cycloalkyl, and
  • A- is an anion selected from the group consisting of hydroxide, sulfate, hydrogensulfate, bicarbonate, carbonate, halogen and alkoxides, or aroxides of the formula -OR e , where R e is C 6 -C 14 -aryl, C 7 -C 15 -Arylalkyl or C 5 -C 6 cycloalkyl.
  • the homopolycarbonate used preferably has one or more branching structures of the formulas (I) to (IV), as they have already been defined in connection with component (C) of the block cocondensate according to the invention.
  • the total amount of the structural units (I) to (IV) is 50 to 2000 ppm, particularly preferably 50 to 1000 ppm, particularly preferably 80 to 850 ppm (determined after hydrolysis, based on the homopolycarbonate).
  • branching structures (I) to (IV) are incorporated into the polymer chain of the homopolycarbonate.
  • the homopolycarbonate undergoes a total saponification to form the corresponding degradation products of formulas (Ia) to (IVa), as already described in connection with component (C) of the block cocondensate according to the invention.
  • the amounts of degradation products are determined by HPLC.
  • the amount of the compound of the formula (Ia) released in this case is preferably from 20 to 800 ppm, more preferably from 25 to 700 ppm, and especially preferably from 30 to 500 ppm, based on the homopolycarbonate.
  • the amount of the compound of the formula (IIa) released in this case is preferably 0 (ie below the detection limit of 10 ppm) to 100 ppm, more preferably 0 to 80 ppm and particularly preferably 0 to 50 ppm, based on the homopolycarbonate.
  • the amount of the compound of the formula (IIIa) released in this case is preferably 0 (ie below the detection limit of 10 ppm) to 800 ppm, more preferably 10 to 700 ppm and particularly preferably 20 to 600 ppm and very particularly preferably 30 to 350 ppm, based on the homopolycarbonate.
  • the amount of the compound of formula (IVa) released thereby is 0 (i.e., below the detection limit of 10 ppm) to 300 ppm, preferably 5 to 250 ppm, and most preferably 10 to 200 ppm, based on the homopolycarbonate.
  • the amount of the structures of formulas (I) to (IV) is set equal to the amount of the released compounds of formulas (Ia) to (IVa).
  • Another object of the invention is obtained by the novel process block cocondensate.
  • the block cocondensates according to the invention are suitable for the preparation of molding compositions and moldings and extrudates produced therefrom.
  • Another object of the invention is therefore the use of the block cocondensates for the production of molding compositions and moldings or extrudates produced therefrom.
  • the molding compositions may further contain UV absorbers, mold release agents, heat stabilizers and / or processing stabilizers and optionally further additives.
  • Suitable UV absorbers are described, for example, in EP 1 308 084 A1, in DE 102007011069 A1 and in DE 10311063 A1.
  • Particularly useful ultraviolet absorbers are hydroxy-benzotriazoles, such as 2- (3 ', 5'-bis (1,1-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole (Tinuvin ® 234, BASF AG, Ludwigshafen), 2- (2'-hydroxy-5 '- (tert-octyl) phenyl) benzotriazole (Tinuvin ® 329, BASF AG, Ludwigshafen), 2- (2'-hydroxy-3' - (2-butyl) - 5 '- (tert-butyl) phenyl) benzotriazole (Tinuvin ® 350, BASF AG, Ludwigshafen), bis (3- (2H-benzotriazolyl) -2-hydroxy-5-tert-octyl) methane, (Tinuvin ® 360, BASF AG, Ludwigshafen), (2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy)
  • Particularly preferred ultraviolet absorbers are 2- (2'-hydroxy-5 '- (tert-octyl) phenyl) benzotriazole (Tinuvin ® 329, BASF AG, Ludwigshafen), bis (3- (2H-benzotriazolyl) - 2-hydroxy-5-tert-octyl) methane, (Tinuvin ® 360, BASF AG, Ludwigshafen) and 2- (3 ', 5'-bis (1,1-dimethylbenzyl) -2'-hydroxy-phenyl) - Benzotriazole (Tinuvin ® 234, BASF AG, Ludwigshafen), with bis (1,1-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole is very particularly preferred.
  • the UV absorbers are preferably present in an amount of 0.05% to 10.00% by weight, more preferably 0.10% to 1.00% by weight, most preferably 0.10 Wt .-% to 0.50 wt .-% and particularly preferably 0.10 wt .-% to 0.30 wt .-%, used in the molding compositions according to the invention.
  • Suitable mold release agents are esters of aliphatic long-chain carboxylic acids with monohydric or polyhydric aliphatic and / or aromatic hydroxy compounds.
  • Preferred aliphatic carboxylic acid esters are compounds of the general formula (6):
  • R 12 is an aliphatic, saturated or unsaturated, linear, cyclic or branched alkyl radical, preferably C 12 -C 30 -alkyl radical
  • R 13 an alkylene radical, preferably C 2 -C 20 -alkylene radical, of a monohydric to trihydric aliphatic alcohol R 13 - (OH) u + v.
  • suitable aliphatic carboxylic acid esters according to the invention are: glycerol monostearate, palmityl palmitate and stearyl stearate.
  • carboxylic acid esters of the formula (6) are esters of pentaerythritol, glycerol, trimethylolpropane, propanediol, stearyl alcohol, cetyl alcohol or myristyl alcohol with myristic, palmitic, stearic or montanic acid and mixtures thereof.
  • Particularly preferred are pentaerythritol tetrastearate, stearyl stearate and propanediol distearate, or mixtures thereof, and most preferably pentaerythritol tetrastearate.
  • suitable aliphatic carboxylic esters are glycerol monostearate, palmityl palmitate and stearyl stearate. It is also possible to use mixtures of different carboxylic acid esters.
  • Preferred carboxylic acid esters are esters of pentaerythritol, glycerol, trimethylolpropane, propanediol, stearyl alcohol, cetyl alcohol or myristyl alcohol with myristic, palmitic, stearic or montanic acid and mixtures thereof.
  • pentaerythritol tetrastearate particularly preferred are pentaerythritol tetrastearate, stearyl stearate and propanediol distearate, and mixtures thereof.
  • pentaerythritol tetrastearate particularly preferred are pentaerythritol tetrastearate, stearyl stearate and propanediol distearate, and mixtures thereof.
  • pentaerythritol tetrastearate particularly preferred are pentaerythritol tetrastearate.
  • the mold release agents are preferably used in concentrations of 0.00% by weight to 1.00% by weight, preferably 0.10% by weight to 0.75% by weight, particularly preferably 0.15% by weight to 0.60 wt .-%, and most preferably 0.20 wt .-% to 0.50 wt .-%, based on the weight of the molding composition used.
  • Suitable thermal and / or processing stabilizers are preferably selected from the group of phosphates, phosphines, phosphites and phenolic antioxidants and mixtures thereof. These are preferably used in an amount of from 0.01% by weight to 0.10% by weight, based on the weight of the molding compositions.
  • Suitable thermal stabilizers are triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butyl) butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol
  • TPP triphenylphosphine
  • Irgafos® 168 tris (2,4-di-tert-butylphenyl) phosphite
  • tris nonylphenyl
  • thermostabilizers are phenolic antioxidants, such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones. Particularly preferred are Irganox® 1010 (pentaerythritol-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate; CAS: 6683-19-8) and Irganox 1076® (2,6-di-tert-butyl -4- (octadecanoxycarbonylethyl) phenol) used.
  • Irganox® 1010 penentaerythritol-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate
  • CAS 6683-19-8
  • Irganox 1076® 2,6-di-tert-butyl -4- (octadecanoxycarbonylethyl) phenol
  • phosphate-based processing stabilizers can be used.
  • the phosphate preferably has the following structure (7)
  • R 14 , R 15 and R 16 independently of one another may denote H, identical or different linear, branched or cyclic alkyl radicals, preferably C 1 -C 18 alkyl radicals.
  • Suitable phosphates are, for. B. mono-, di- and trihexyl phosphate, triisoctyl phosphate and trinonyl phosphate.
  • the phosphate used is triisooctyl phosphate (tris-2-ethyl-hexyl-phosphate). It is also possible to use mixtures of different mono-, di- and trialkyl phosphates.
  • the phosphates can be present in amounts of less than 0.05% by weight, preferably from 0.00005% by weight to 0.05% by weight, particularly preferably 0.0002 to 0.05% by weight, very particularly preferably from 0.0005 wt .-% to 0.03 wt .-% and in particular from 0.001 to 0.0120 wt .-%, based on the total weight of the molding composition, are used.
  • the molding compositions may contain further additives, preferably in amounts of 0.10 to 8.00 wt .-%, particularly preferably 0.20 to 3.00 wt .-%.
  • the other additives are customary polymer additives, such as those described in EP-A 0 839 623, WO-A 96/15102, EP-A 0500496 or "Plastics Additives Handbook", Hans Zweifel, 5th Edition 2000, Hanser Verlag, Kunststoff described flame retardants, optical brighteners, Flow improvers, inorganic pigments, colorants, mold release agents or processing aids.
  • Colorants in the context of the invention are both dyes and pigments.
  • Suitable colorants are, for example, sulfur-containing pigments such as cadmium red and cadmium yellow, iron cyanide-based pigments such as Berlin blue, oxide pigments such as titanium dioxide, zinc oxide, red iron oxide, black iron oxide, chromium oxide, titanium yellow, zinc-iron-based brown, titanium-cobalt-based Green, cobalt blue, copper-chromium based black and copper-iron based black or chromium-based pigments such as chrome yellow, phthalocyanine-derived dyes such as copper phthalocyanine blue and copper phthalocyanine green, condensed polycyclic dyes and pigments such as azo-based (eg.
  • Azogelb sulfur indigo dyes, Perynon-based, perylene-based, quinacridone-derived, dioxazine-based, isoindolinone-based and quinophthalone-derived derivatives, anthraquinone-based, heterocyclic systems.
  • MACROLEX® ® Blue RR MACROLEX® ® Violet 3R
  • MACROLEX® ® Violet B Lixess AG, Germany
  • Sumiplast ® Violet RR Sumiplast ® Violet B
  • Sumiplast ® Blue OR (Sumitomo Chemical Co., Ltd. )
  • Diaresin ® violet D Diaresin ® Blue G, Diaresin ® Blue N (Mitsubishi Chemical Corporation), Heliogen ® blue or green Heliogen ® (BASF AG, Germany).
  • cyanine derivatives quinoline derivatives, anthraquinone derivatives, phthalocyanine derivatives and perinone derivatives are preferred.
  • the molding compositions may further contain (co) polycarbonates.
  • Both homopolycarbonates and copolycarbonates are suitable for this purpose. These can be linear or branched in a known manner.
  • the preparation of the polycarbonates can be carried out in a known manner by the melt transesterification process or the interfacial process.
  • homo- and copolycarbonates having structural units which are derived from those derived from one or more diphenols of the general formula (3), in particular bisphenol A.
  • homopolycarbonates based on bisphenol A are particularly preferred.
  • the preparation of the molding compositions containing the block cocondensate according to the invention is carried out by conventional incorporation methods by combining, mixing and homogenizing the individual components, wherein in particular the homogenization preferably takes place in the melt under the action of shear forces.
  • the merging and mixing takes place before the melt homogenization using powder premixes. It is also possible to use premixes which have been prepared from solutions of the mixture components in suitable solvents, optionally homogenizing in solution and subsequently removing the solvent.
  • the components of the molding compositions of the invention can be introduced by known methods or as a masterbatch.
  • the individual components of the molding compositions in conventional devices such as screw extruders (for example twin-screw extruder, ZSK), kneaders, Brabender or Banbury mills can be brought together and mixed, homogenized and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • screw extruders for example twin-screw extruder, ZSK
  • kneaders for example twin-screw extruders
  • Brabender or Banbury mills can be brought together and mixed, homogenized and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the molding compositions can be processed into articles or moldings, in which, for example, the molding compositions are initially extruded into granules as described and processed by means of suitable processes into various products or shaped articles in a known manner.
  • the molding compositions may in this context, for example, by hot pressing, spinning, blow molding, deep drawing, extrusion or injection molding in products or moldings, shaped objects such as toy parts, fibers, films, tapes, plates such as solid sheets, multi-wall sheets or corrugated sheets, vessels, pipes or other Profiles are transferred. Also of interest is the use of multilayer systems.
  • the application may be simultaneous or immediately after the formation of the body, e.g. by coextrusion or multi-component injection molding.
  • the application can also be done on the finished shaped body, e.g. by lamination with a film or by coating with a solution.
  • Sheets of base and optional topcoat / optional topcoats can be made by (co) extrusion, direct skinning, direct coating, insert molding, film backmolding, or other suitable methods known to those skilled in the art.
  • the molding compound which is optionally pretreated by means of drying, for example, is fed to the extruder and melted in the plasticizing system of the extruder.
  • the plastic melt is then pressed through a slot die or a web plate nozzle and thereby deformed, brought in the nip of a smoothing calender in the desired final shape and fixed in shape by mutual cooling on smoothing rolls and the ambient air.
  • the temperatures required to extrude the composition are adjusted, usually following the manufacturer's instructions.
  • Contain the molding materials for example, polycarbonates high melt viscosity, these are usually processed at melt temperatures of 260 ° C to 350 ° C, according to the cylinder temperatures of the plasticizing cylinder and the nozzle temperatures are set.
  • thermoplastic melts of different composition can be superimposed and thus produce multilayer sheets or films (for coextrusion see for example EP-A 0110 221, EP-A 0110 238 and EP-A 0 716 919, for details of the adapter and nozzle method, see Johannaber / Ast: “Kunststoff-medianconom", Hanser Verlag, 2000 and in Kunststoff Kunststoff: “Coextruded Films and Sheets: Future Perspectives, Requirements, Equipment and Production, Quality assurance ", VDI publishing house, 1990).
  • thermoplastic substrates With the thermoplastic substrates described above, moldings can also be produced by injection molding.
  • the methods for this are known and in the "Injection Molding Manual", Friedrich Johannnaber / Walter Michaeli, Kunststoff; Vienna: Hanser, 2001, ISBN 3-446-15632-1 or "instructions for the construction of injection molds," Menges / Michaeli / Mohren, Kunststoff; Vienna: Hanser, 1999, ISBN 3-446-21258-2 described.
  • Injection molding is a forming process used in plastics processing.
  • the respective material, or the molding compound is plasticized in an injection unit with an injection molding machine and injected into an injection mold.
  • the cavity, the cavity, of the tool determines the shape and the surface structure of the finished component.
  • Injection molding here includes all injection molding processes including multi-component injection molding and injection compression molding.
  • plastic moldings For the production of plastic moldings known in plastics processing injection molding and injection compression molding variants are used. Conventional injection molding methods without injection-compression molding are used in particular for the production of smaller injection molded parts, in which short flow paths occur and can be operated with moderate injection pressures. In the conventional injection molding process, the plastic mass is injected into a cavity formed between two closed position-fixed mold plates and solidifies there.
  • Injection-molding processes differ from conventional injection-molding processes in that the injection and / or solidification process is performed by performing a mold plate movement.
  • the mold plates are already in front of the injection process slightly open to compensate for the shrinkage that occurs during later solidification and to reduce the required injection pressure.
  • a vorvergrösserte cavity is present. Dipping edges of the tool guarantee even with slightly open mold plates still sufficient tightness of vorvergrösserten cavity.
  • the plastic mass is injected into this vorvergrösserte cavity and then pressed or subsequently while performing a tool movement in the closing direction.
  • Products, moldings or molded articles which are preferred according to the invention are plates, foils, pipes, glazings, for example car windows, windows of rail and aircraft vehicles, car sunroofs, safety windows, roofs or building glazings, lamp covers for the interior area of vehicles and buildings, exterior lamp covers, e.g. Covers of street lamps, visors, spectacles, extrusion and solution films for displays or electric motors, also ski films, traffic light housing, traffic light covers, traffic lights, containing the molding compositions of the invention.
  • double-wall sheets or multi-sheet sheets can be used.
  • further material parts may be contained in the products according to the invention.
  • glazings can have sealing materials on the edge of the glazings.
  • roofing may, for example, metal components such as screws, metal pins or the like, which can serve for attachment or guidance (in folding or sliding roofs) of the roofing elements.
  • other materials may be combined with the molding compositions of the invention, e.g. in 2-component injection molding.
  • the corresponding component with IR-absorbing properties can be provided with an edge which is e.g. serves for bonding.
  • the polycarbonate has a relative solution viscosity of 1.205. This polycarbonate contains no additives such as UV stabilizers, mold release agents or thermal stabilizers.
  • the polycarbonate was prepared by a melt transesterification process as described in DE 102008019503
  • MVR melt volume rate
  • M n number average molecular weight
  • the product contains triphenylphosphine and pentaerythritol tetrastearate.
  • Such copolycarbonates are available under the trade name Apec® from Bayer MaterialScience.
  • Linear copolycarbonate based on bisphenol A (57% by weight) and bisphenol TMC (43% by weight), with phenol-based end groups and with a melt volume rate (MVR) of 9.5 cc / 10 min, measured at 330 ° C and 2.16 kg load according to ISO 1133).
  • MVR melt volume rate
  • Such copolycarbonates are available under the trade name Apec® from Bayer MaterialScience. Siloxane component:
  • the preparation of the siloxane is described for example in DE 19710081.
  • the catalyst used is tetraphenylphosphonium phenolate from Rhein Chemie Rheinau GmbH (Mannheim Germany).
  • the substance is used as a mixed crystal with phenol and contains about 70 wt .-% Tetraphenylphosphoniumphenolat. The following amounts refer to the substance obtained from Rhein Chemie (as mixed crystal with phenol).
  • the relative solution viscosity ( ⁇ rel , also referred to as eta rel) was determined in dichloromethane at a concentration of 5 g / l at 25 ° C with a Ubbelohdeviskosimeter.
  • the flow behavior is determined by determining the melt viscosity using a cone-plate viscometer. In this case, the value of the viscosity is used with low shear and high shear:
  • the notch impact test is performed on the basis of the Charpy impact test.
  • the test procedure is carried out according to DIN EN ISO 179 with a drop weight apparatus on 80 ⁇ 10 ⁇ 3 mm test bars with 2 mm V notch.
  • the impact occurs on the narrow side opposite the notch (notch in tension zone); the drop height is 0.5 m; the drop weight is 1.86 kg.
  • the distance between the supports is 40 mm.
  • Example 1 Preparation of a block copolycarbonate according to the invention
  • Example 2 Preparation of a block copolycarbonate according to the invention
  • Example 5 Preparation of a blend of BPA-based homopolycarbonate PC 2 and copolycarbonate CoPC 2 (comparison, without siloxane blocks)
  • the molding compositions according to the invention have a tough behavior in impact test (Examples 1 and 2).
  • TMC-containing copolycarbonates have a brittle behavior in impact test (Example 4).
  • blends of homopolycarbonate and TMC-containing copolycarbonate behave brittle over wide mixing ranges.
  • a siloxane-containing block copolymer which was obtained by another method without using the homopolycarbonate PC1, also behaves brittle (Example 3).
  • the molding compositions of the invention also show advantages over the prior art in the flowability.
  • inventive block copolycarbonate of Example 1 has a higher molecular weight compared to the copolycarbonate of Example 4 or the blend of Example 5 (this is indicated by the higher solution viscosity and the higher zero viscosity), the flowability under shear is surprisingly better.
  • the molding compositions of the invention show significant advantages in the mechanical and in the rheological properties.

Abstract

La présente invention concerne des cocondensats à blocs, composés de polysiloxanes et de (co)polycarbonates à base de dihydroxydiarylcycloalcane ainsi qu'un procédé de production de tels cocondensats à blocs. L'invention concerne en outre l'utilisation de ces cocondensats à blocs pour produire des pièces moulées et des extrudats.
EP16713480.8A 2015-04-07 2016-04-04 Cocondensats à blocs, composés de polysiloxanes et de (co)polycarbonates à base de dihydroxydiphénylcycloalcane Withdrawn EP3280759A1 (fr)

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EP15162554 2015-04-07
PCT/EP2016/057326 WO2016162301A1 (fr) 2015-04-07 2016-04-04 Cocondensats à blocs, composés de polysiloxanes et de (co)polycarbonates à base de dihydroxydiphénylcycloalcane

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KR (1) KR20170134408A (fr)
CN (1) CN107428926B (fr)
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EP3910001A1 (fr) * 2020-05-13 2021-11-17 SHPP Global Technologies B.V. Copolymère de polycarbonate et composition d'extrusion de film associée, film extrudé, et condensateur
EP4089132B1 (fr) 2020-05-13 2024-03-27 SHPP Global Technologies B.V. Copolymère de polycarbonate et composition d'extrusion de film associée, film extrudé, et condensateur
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US20180079862A1 (en) 2018-03-22
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WO2016162301A1 (fr) 2016-10-13
CN107428926B (zh) 2021-02-09
KR20170134408A (ko) 2017-12-06
CN107428926A (zh) 2017-12-01
US10407541B2 (en) 2019-09-10

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