CA2037182A1 - Impact resistant polycarbonate moulding compositions - Google Patents
Impact resistant polycarbonate moulding compositionsInfo
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- CA2037182A1 CA2037182A1 CA 2037182 CA2037182A CA2037182A1 CA 2037182 A1 CA2037182 A1 CA 2037182A1 CA 2037182 CA2037182 CA 2037182 CA 2037182 A CA2037182 A CA 2037182A CA 2037182 A1 CA2037182 A1 CA 2037182A1
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- 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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
IMPACT RESISTANT POLYCARBONATE MOLDING COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
A thermoplastic molding composition comprising (i) a polycarbonate based on a substituted dihydroxydiphenyl cycloalkane, (ii) a graft polymer, and (iii) a hydrogenated nitrile rubber or a copolymer of ethylene/vinyl acetate, is disclosed. The composition which is characterized by its toughness at low temperatures, high dimensional stability under heat and high resistance to organic solvents is suitable for the manufacture of molded articles, in particular, external parts of motor vehicles.
LeA 27,476
ABSTRACT OF THE DISCLOSURE
A thermoplastic molding composition comprising (i) a polycarbonate based on a substituted dihydroxydiphenyl cycloalkane, (ii) a graft polymer, and (iii) a hydrogenated nitrile rubber or a copolymer of ethylene/vinyl acetate, is disclosed. The composition which is characterized by its toughness at low temperatures, high dimensional stability under heat and high resistance to organic solvents is suitable for the manufacture of molded articles, in particular, external parts of motor vehicles.
LeA 27,476
Description
2~3~2 Impact Resistant Polycarbonate Mouldiny C~positions This invention relates to thermoplastic moulding compositions composed of polycarbonates with high heat distortion temperatures, graft polymers and hydrogenated, randomly structured nitrile rubbers or ethylene/vinyl acetate co-polymers and to the use of the thermoplastic moulding compounds for the manufacture of moulded products of various kinds.
Thermoplastic moulding compositions obtained from polycarbonates with high heat distortion temperatures and modifiers for improving the toughness of the polycarbonates are known and are described in German Patent application P 3 833 953.6 A
Moulded articles produced from these moulding compounds, however, generally have insufficient toughness at low temperatures and resistance to organic solvents so that they are only of limited use for example for the external parts of motor vehicles.
It is therefore an object of the present invention to avoid the above described disadvantages of these moulding ` 20 compounds and to provide improved thermoplastic moulding compounds based on polycarbonates having high heat LeA 27 476 . .
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- 2 ~ 2 distortion temperatures.
The present invention therefore relates to thermoplastic mould-ng ~ompositions containing A) from 20 to 97 parts by weight, preferably from 40 to 95 parts by weight, of a polycarbonate based on substituted dihydroxydiphenyl cycloalkanes corres-ponding to formula (I) R~ Rl H ~ H (I) , R~ ~4 wherein Rl and R2 denote, independently of one another, hydrogen, halogen, preferably chlorine or bromine, Cl to Cg alkyl, Cs to C6 cycloalkyl, C6 to C10 aryl, preferably phenyl, and C7 to Cl2 aralkyl, preferably phenyl-Cl to C4 alkyl, in particular benzyl, m denotes an integer with a value from 4 to 7, preferably 4 or 5, R3 and R4 are selected individually for each X and denote , independently of one another, hydrogen or Cl to C6 alkyl, and X denotes carbon, under the condition that on at least one carbon atom denoted by X, both R3 and R4 are alkyl groups, LeA 27 476 ~ .
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B) from 3 to 80 parts by weight, preferably from 5 to 60 parts by weight, of a graft polymer of resin-forming monomers (graft monomers) on a rubber (graft basis) and C) from 1 to 50 parts by weight, preferably from 3 to 40 parts by weight, of a hydrogenated, randomly structured nitrile rubber, A ~ s ~ C adding up in each case to 100 parts by weight.
Ethylene/vinyl acetate copolymers may be used instead of the nitrile rubber of component C). The quantity of the ethylene/vinyl acetate copolymers is from 1 to 50 parts by weight, preferably from 3 to 40 parts by weight, the sum of A ~ B + C adding up to 100 parts by weight.
In formula (I), R3 and R4 are preferably both alkyl on one or two of the carbon atoms denoted by X, more preferably on only ~ne carbon atom X. The preferred alkyl group is methyl; the X atoms in the a position to ~he diphenyl-substituted carbon atom (C-l) are preferably not dialkyl substituted but alkyl disubstitution is preferred in the ~ position to C-l.
Dihydroxydiphenyl cycloalkanes having 5 or 6 ring carbon atoms in the cycloaliphatic group (m = 4 or 5 in formula (I)) are preferred, e.g. the diphenols corresponding to the formulae (IIa) to (IIc):
Rl Rl H ~ ~ ~ ~IIa~
R2 ~ ~3 R2 H3CCH~
Thermoplastic moulding compositions obtained from polycarbonates with high heat distortion temperatures and modifiers for improving the toughness of the polycarbonates are known and are described in German Patent application P 3 833 953.6 A
Moulded articles produced from these moulding compounds, however, generally have insufficient toughness at low temperatures and resistance to organic solvents so that they are only of limited use for example for the external parts of motor vehicles.
It is therefore an object of the present invention to avoid the above described disadvantages of these moulding ` 20 compounds and to provide improved thermoplastic moulding compounds based on polycarbonates having high heat LeA 27 476 . .
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- 2 ~ 2 distortion temperatures.
The present invention therefore relates to thermoplastic mould-ng ~ompositions containing A) from 20 to 97 parts by weight, preferably from 40 to 95 parts by weight, of a polycarbonate based on substituted dihydroxydiphenyl cycloalkanes corres-ponding to formula (I) R~ Rl H ~ H (I) , R~ ~4 wherein Rl and R2 denote, independently of one another, hydrogen, halogen, preferably chlorine or bromine, Cl to Cg alkyl, Cs to C6 cycloalkyl, C6 to C10 aryl, preferably phenyl, and C7 to Cl2 aralkyl, preferably phenyl-Cl to C4 alkyl, in particular benzyl, m denotes an integer with a value from 4 to 7, preferably 4 or 5, R3 and R4 are selected individually for each X and denote , independently of one another, hydrogen or Cl to C6 alkyl, and X denotes carbon, under the condition that on at least one carbon atom denoted by X, both R3 and R4 are alkyl groups, LeA 27 476 ~ .
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B) from 3 to 80 parts by weight, preferably from 5 to 60 parts by weight, of a graft polymer of resin-forming monomers (graft monomers) on a rubber (graft basis) and C) from 1 to 50 parts by weight, preferably from 3 to 40 parts by weight, of a hydrogenated, randomly structured nitrile rubber, A ~ s ~ C adding up in each case to 100 parts by weight.
Ethylene/vinyl acetate copolymers may be used instead of the nitrile rubber of component C). The quantity of the ethylene/vinyl acetate copolymers is from 1 to 50 parts by weight, preferably from 3 to 40 parts by weight, the sum of A ~ B + C adding up to 100 parts by weight.
In formula (I), R3 and R4 are preferably both alkyl on one or two of the carbon atoms denoted by X, more preferably on only ~ne carbon atom X. The preferred alkyl group is methyl; the X atoms in the a position to ~he diphenyl-substituted carbon atom (C-l) are preferably not dialkyl substituted but alkyl disubstitution is preferred in the ~ position to C-l.
Dihydroxydiphenyl cycloalkanes having 5 or 6 ring carbon atoms in the cycloaliphatic group (m = 4 or 5 in formula (I)) are preferred, e.g. the diphenols corresponding to the formulae (IIa) to (IIc):
Rl Rl H ~ ~ ~ ~IIa~
R2 ~ ~3 R2 H3CCH~
LeA 27 476 .
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~37~ ~2 Rl Rl }~o~ ~ c - ~OH (IIb) R2 H3C~<CH3 R2 H3C C~3 Rl R
Hu 5 z~ ;r H ( I Ic ) C~3;
among which, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (formula IIa with Rl and R2 both denoting H) is particularly preferred.
The substituted dihydroxydiphenyl cyc].oalkanes corres-ponding to formula (I) and the correspondirlg polvcarbonates (component A) may be prepared according to German Patent lS application DE-A 38 32 396. The polycarbonates used are high molecular weight, tfiermoplastic, aromatic poly-carbonates with weight average molecular weights Mw of at least 10,000, preferably from-20,000 to 300fO00.
.
According to the invention there may be used either one diphenol corresponding to formula (I) to form homopoly-carbonates or several diphenols corresponding to formula (I) ~.
to form copolycarbonates.
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Further, the diphenols corresponding to formula (I) may also be used as mixtures with other known diphenols (such 25 as those described, for example, in D~-A 38 32 396) for the preparation of high molecular weight, thermoplastic aromatic polycarbonates used as component A.
Known branching agents may be used for the preparation of ~:
_4_ .
LeA 27 476 .
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2~3r3~ ~2 t.~e polycarbonates put into the process, as well as chain terminators for regulating the molecular weight; see in this connection again DE-A 38 32 396. The said DE-A 38 32 396 also mentions the quantities of other diphenols which may be used as well as the quantities of chain terminators and branching agents.
The graft polymers used as component B may be polymers of resin-forming monomers prepared in the presence of rubbers.
They include, for example, graft copolymers with rubbery elastic properties which have been prepared from at least two of the following monomers: chloroprene, butadiene~l,3), isoprene, styrenes, acrylonitri~es, ethylene, propylene, vinyl acetate and (meth)acrylic acid esters having 1 to 8 carbon atoms in the alcohol component; in other words, polymers such as those described, for example, in "Methoden der Organischen Chemie" (Houben-Weyl), Volume 14/1, Georg Thienle--Ver~ag, Stuttgart 1961, pacles 393 to 406, and in C.B. Bucknall, "Toughened Plastics", Applied Science Publishers, London 1977. The preferred polymers B are partially cross-linked and have gel contents above 20% by weight, preferably above 40% by weight, most preferably above 60% by weight.
Preferred graft polymers B are obtained by the polymer-isation of:
25 B.l from 5 to ~() partC by weight, preferably from 30 to 80 parts by weight, of a mixture of B.l.l from '0 to ~l5 parts by weight of styrene, ~--methyl styrene, styrenes halogenated or methyl substituted in the nucleus, methyl methacrylate or mixtures of these compounds and B.1.2 from 5 to 50 parts by weight of acrylonitrile, LeA 27 476 .
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met:hacrylonitrile, methyl methacrylate, maleic acid anhydride, Cl to C4 alkyl-substituted or phenyl-N-substituted maleimidesor mixtures of these compounds in the presence of 5 B.2 from 10 to 95 parts by weight, preferably from 20 to 70 parts by weight, of rubber, i.e. polymers having a glass transition temperature below -10C.
Examples of preferred graft polymers B include polybutadiene which have been grafted with styrene and/or acrylonitrile and/or tmeth)acrylic acid alkyl esters, butadiene/styrene copolymers and acrylate rubbers;. i.e. copolymers of the type described in DE-OS 1 694 173; polybutadienes grafted with acry].ic or methacrylic acid alkyl esters, vinyl acetate, acrylonitrile, styrene and/or alkyl styrenes, 15 butadiene/styrene copolymers or butadiene/acrylonitrile copolymers, polyisobutenes and polyisoprenes as described e.g. in DE-OS 2 348 377 (corresponding to US-P 3,919,353).
ABS polymers such as those described in DE-OS 2 035 390 or in DE-OS 2 248 242(corresponding to US-P 3,644,574 and ~ -4, O 13, 613 ) are particularly preferred polymers B.
The most:preerred gr.aft polymers B are those which may be prepared by a grafti.ng reaction of a~ from 10 to 70% by weight, preEerably from 15 to 50%
by weight, especially from 20 to 40% by weight, based on graft product B, of at least one acrylic or meth-acrylic acid ester, or from 10 to 70% by weight, preferably from 15 to 50% by weight, especially from 20 to 40% by weight, of a mixture of from 10 to 50%
by weight, preferably from 20 to 35% by weight, based on the mixture, of acrylonitrile or acrylic acid ester or methacrylic acid ester and ~rom 50 to 90~ by weight, preferably from 65 to 80% by weight, based on the .
LeA 27 476 ____--.~ .
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`~37:~2 mixt`ure, of styrene (graft basis B.l) on . from 30 to 90% by weight, preferably from 50 to 85%
by weight, in particular from 60 to 80% by weight, based on graft product B, of a hutadiene polymer containing at least 50~ by weight, based on ~ , of butadiene groups (graft basis B.2), the gel content of the butadiene polymer ~ preferably amounting to at least 70% by weight (determined in toluene), the degree of grafting G of the graft polymer preferably being from 0-15 to 0-55 and the average particle diameter d50 of the graft polymer B preferably being from 0-05 to 2 ~m, more preferably from 0-1 to 0-6 ~m.
Acrylic acid esters and methacrylic acid esters (~) are esters of acrylic acid or methacrylic acid and monohydric alcohols having 1 to 8 carbon atoms.
Methyl, ethyl and propyl methacrylates, n butyl acrylate and t-butyl (meth)acrylate are preferred.
In addition to its butadiene groups, the butadiene polymer (~) may contain up to 50% by weight, based on (~), of residues of other ethylenically unsaturated monomers such styrene, acrylonitrile, esters of acrylic or methacrylic acid having 1 to 4 carbon atoms in the alcohol component (such as methyl acrylate, ethyl acrylate, methyl meth-acrylate or ethyl methacrylate), vinyl esters and/or vinyl ethers. Pure polybutadiene is preferred.
Since, as is known, the graft monomers are not completely grafted on the grat basis in the grafting reaction, the term "graft: polymers B" usecl in the present invention are understood to be products obtained by the polymerisation of graft monomers B.l in the presence of the graft basis B.2.
LeA 27 476 ,: ' ~ : ,' . : , The degree of qrafting G denotes the ratio by weight of grafted graft monomers to the graft basis and has no dimension.
The average particle diameter d50 is the diameter which is greater than that of 50% by weight of the particles and smaller than that of the remaining 50~ by weight of particles. It may be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z.
Polymere 250 (1972), 782-796).
Another group of very highly preferred polymers B are the graft polymers obtained . from 20 to 90% by weight of acrylate rubber having a glass transition temperature below -20C as graft basis B.2 and ~. from 10 to 80% by weight of polymerisable, ethylen-ically unsaturated monomers whose homopolymers or co-polymers have a glass transition temperature above 25C, used as graft monomers B.l.
The acrylate rubbers (~) in this graft polymer B are preferably obtained from acrylic acid alkyl esters, optionally with up to 40% by weight, based O~ ), of other polymerisable, ethylenically unsaturated monomers.
The preferred polymerisable acrylic acid esters include Cl to Cg alkyl esters, for example, methyl, ethyl, butyl, n-octyl and 2-ethyl-hexyl esters; halogenated alkyl esters, preferably halogeno-Cl-C8-alkyl esters such as chloroethyl acrylate, and mixtures of these monomers.
For cross-linking, monomers having more than one polymer-isable double bond may be copolymerised. Examples of cross-linking monoiners :inc`.u~e esters of unsaturated mono-LeA 27 476 ::
~ ` , ` ' carboxylic acids having 3 to 8 car~on atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, e.g. ethylene glycol dimethacrylate or allyl meth-S acrylate; multiunsaturated heterocyclic compounds such astrivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinyl benzenes; and triallyl phosphate and diallyl phthalate.
Allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least 3 ethylenically unsaturated groups are preferred cross-linking monomers.
The cvclic monomers, triallyl cyanurate, triallyl iso-cyanurate, trivinyl cyanurate, triacryloyl hexahydro-s-triazine and triallyl benzenes are particularly preferredcross-linking monomers.
The quantity of cross-linking monomers is preferably from 0-02 to 5% by weight, in particular from 0-05 to 2% by weight, based on graft basis (I).
When cyclic cross-linking monomers having at least 3 ethylenic~lly unsaturated groups are used, the quantity is advantageously limited to below 1~ by weight of the graft basis (~).
Preferred ''other~l polymerisable, ethylenically unsaturated monomers which may be used for the preparation of the graft basis (I) in addition to the acrylic acid esters include, for example, acrylonitrilel styrene, a-methyl styrene, acrylamides, vinyl-Cl-C6-alkyl ethers, methyl methacrylate and butadiene. Emulsion polymers having a gel content of at least 60% by weight are preferred acrylate rubbers used as graft basis (~
LeA 27 476 ,~ .
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~37~32 Silicone rubbers having graft active points as described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS
3 631 539 are also suit~ble as graft basis as defined under B.2.
The gel content of the graft basis B. 2 is determined in dimethyl formamide at 25C (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
The hydrogenated nitrile rubbers used as component C are products obtained by the hydrogenation of randomly structured copolymers of from 90 to 45% by weight, preferably from 85 to 50% bv weight, especially from 82 to 52~ by weight, of at lei~st one conjugated diene, from 10 to 55~ by weight, prefera:bly from 15 to 50% by weight, i5 especially from 18 to 48% by weight, of at least one unsaturated nitrile and from 0-to 10% by weight, preferably from 0 to 8% by weight, of at least one other monomer which is copolymerisable with conjugated dienes and unsaturated nitriles.
Examples of suitable conjugated dienes include butadiene-(1,3), 2-methylbutadiene-(1,3), 2,3-dimethylbutadiene-(1,3) and pentadie.ne-(1.3); acrylonitrile and methacrylonitrile are suitable unsaturated nitriles.
Aromatic vinyl compounds,(meth)acrylic acid esters having from 1 to 12 carbon atoms in the alcohol component and a, ~-unsaturated mono- or di-carboxylic acids may be used as further monomers.
The following are specific examples: aromatic vinyl compounds such as styrene, substituted styrenes, e.g. o-, m- and p-methvl styrene, ethyl styrene, vi.nyl naphthalene and vinyl pyridine; (m~ h)acry:l.ic acid esters such as methyl :
LeA 27 476 , .
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(meth)acrylate, ethyl (meth)acrylate, n-~utyl (meth)-acrylate, 2-ethylhexyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; among the unsaturated carboxylic acids, ~,~ -unsaturated monocarboxylic acids having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid and crotonic aeid and a,~-unsaturated dicarboxylie aeids having 4 to 5 earbon atoms, sueh as maleie, fumarie, eitraeonie and itaeonie aeid; further, semiesters of ~,~-unsaturated diearboxylic acids, such as maleic acid-n-dodeeyl semi-esters and fumarie aeid-n-butyl semiesters.
Examples of further monomers inelude vinyl ehloride, vinylidene ehloride, N-methylol aerylamide, vinyl alkyl ethers having 1 to 4 earbon atoms in the alkyl group and vinyl esters of earboxylie aei~s having 1 to 18 earbon atoms, sueh as vinyl aeetate or vinyl stearate.
Speeifie examples of eopolymers to be hydrogenated inelude aerylonitrile/isoprene eopolymers, aerylonitirle/isoprene/
butadiene terpolymers, aerylonitrile/butadiene/n-butyl aerylate terpolymers, aerylonitrile/butadiene/2-hydroxy-propyl methaerylate terpolymers and aerylonitrile/butadiene/methaerylie aeid terpolymers. Aerylonitrile/butadiene eopolymers are partieularly preferred.
The proaration of hvdrogenated nitrile rubbers with preservation of the nitrile groups is known, e.g. from 25 ~-OS 3 32S 974.
The degree of hydrogenation (pereentage of hydrogenated C-C double bonds, based on the total number of C-C double bonds orgiinally present in the polymer) of the polymer used as eomponent C is determined by IR or NMR speetroscopy and amQunts to at least 80%, preferably at least 90%, espeeially 95%.
LeA 27 ~76 . . ;
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The hydrogenated polymers used as component C are gel free and soluble in ketones such as acetone or butanone, in ethers such as tetrahydrofuran or dioxane and in chlorinated hydrocarbons such as dichloromethane or chlorobenzene. The molecular weights of the hydrogenated nitrile rubbers are from 500 to 800,000 (g/mol) preferably from 10,000 to 600,000 ~g/mol), especially from 30,000 to 400,000 (g/mol) (Mn, number average, determined by gel permeation chroma-tography).
The ethylene/vinyl acetate copolymers to be used instead of hydrogenated nitrile rubbers contain from 10 to 90% by weight, preferably from 20 to 85~ by weight, of vinyl acetate, based on the total quantity of copolymers. The preparation of co?o]ymers is known and is described in, for example, "Encyclopedia of Polymer Science and Technology", Volume 15, 577 to 677 (1971), EP 0 078 122, DE 1 815 337, DE 1 914 756 and DE 3 000 009.
The moulding compounds according to the invention may contain the usual quantities of additives conventionally used ~or polycarbonates and graft polymers, such as stabilizers, pi~ments, mould release agents, flame retardant; and antistatic agents.
The moulding compounds according to the invention may be prepared by mixing the components in known manner and melt compounding or melt extruding them at elevated temperatures, preferably at 200 to 350C, in the usual apparatus such as internal kneaders, extruders or double shaft screws.
The cc~mponents may be mixed together in succession or simuItaneously.
The moulding compounds according to the invention may be used for the production of mouided articles of all kinds, LeA 2~ 476 - -, ~ ~ 3 ~ 2 e.g. by injection moulding. The following are examples of moulded articles: housing parts (e.g. for domestic appliances such as juice presses, coffee machines, mixers), cover plates for the building industry and motor vehicle parts. They are also used for electrical apparatus, e.g.
for multipoint connectors, on account of their excellent electrical properties.
Moulded articles may also be produced by deep drawing previously produced boards or films.
The invention further relates to the use of the moulding compounds described for the production of moulded articles.
The thermoplastic moulding compounds according to the invention are distinguished by their very good notched impact strength even at low temperatures, improved solvent resistance (ESC characteristics) and high dimensional sta-bility under heat.
LeA 27 476 . ' ' -:: , .. . .
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Examples Component A 1 Polycarbonate based on bisphenol A/l,l-bis-(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane (molar ratio 55:45):
1,436-4 g (6~3 mol) of bisphenol A (2,2-bis-(4-hydroxy-phenyl)propane, 2,387-0 g (7-7 mol) of 1,1-bis-(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane, 7,476-0 g (84 mol) of 45% NaOH and 33O7 litres of water were dissolved in an inert gas atmosphere with stirring. A solution of 36-9 g ~0-392 mol) of phenol in 11 litres of methylene chloride and 13 litres of chlorobenzene were then added. 2,772 g (28 mol) of phosgene were introduced into the thoroughly stirred solution at pH 13 to 14 and at 21 to 25C. 14 ml of ethyl piperidine were then added and the reaction mixture was stirred for a further 45 minutes. The aqueous phase, which was free from bisphenolate,was separated off and the organic phase was washed free from electrolyte with water after acidification with phosphoric acid and freed from solvent. The polycarbonate had a relative solution viscosity of 1-30. The glass temperature of the polymer was found to be 206C (DSC).
_omponent A 2 P~lycarbonate based on bisphenol A/l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (molar ratio 65:35). Preparation as under A 1.
Component B 1 Graft polymer of 50 parts by weight of a copolymer of styrene and acrylonitrile in the ratio of 72:28 on 50 parts by weight of particulate cross-linked polybutadlene rubber (average particle diameter d50 = 0O4 ~m) prepared by LeA 27 476 :
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emulsion polymerisation.
Component B 2 Graft polymer of 50 parts by wei.ght of a copolymer of styrene and acrylonitrile in the ratio of 90:10 on 50 parts by weight of particulate, cross-linked polybutadiene rubber (average particle diameter d50 = 0-4 ~m) prepared by emulsion polymerisation.
Component C 1 Hydrogenated nitrile rubber on a randomly structured acrylonitrile/butadiene copolymer having an acrylonitrile content of 34-1% by weight, a degree of hydrogenation above 99-2% (determined by infrared spectroscopy) and a Mooney vi.scosity ML 1 + 4 ~l00C) of 70 (determined according to DIN 53 523).
Component C ~
Copolymer of ethylene/vinyl acetate in a ratio by weight of ethylene to vinyl acetate of 30:70.
Preparation and testing of the moulding compounds according to the invention _ _ Components A, B and C were melted at temperatures of from 250 to 300^ in a 1-3 litre internal kneader and homogenised.
Rods measuring 80 x 10 x 4 mm (processing temperature 280C) were produced ~rom the moulding compounds in an injection moulcling machi.ne ar.d used for testing the notched impact strengt:h (b~ met:hod ISO 180 lA) at the temperature indicated in Ta.ble 2.
The ESC characteri.stic was t~ted on rods measuring 80 x 10 -lS-LeA 27 476 -- - - ` .. ~ . .; ~. , :
-: - ' . ' - ~ ; , x 4 mm (mass temperature 280C). A mixture of 50 volumes~
of toluene/50 volumes~O of isooctane and 42-5 voluMes% of toluene/42~5 volumes% of isooctane/1~ volumes~ of methanol was used as fuel simulator. The samples were prestretched by means of a template in the form of a circular arc and kept in the fuel simulator for 5 minutes at room temperature.
The amount of prestretching ~x was 0-4 to 2~4~. The tension crack response was assessed over the breakage in dependence upon the amount af prestretching.
The vicat softening temperature (method A/120) was determined ` according to DIN 53 460 on rods measuring 80 x 10 x 4 mm.
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h ..
o . ~ Q
o h ,_1 --1Q N
~ ` ~::
Q~ ~I o\O ~
Il) O h -- ~ Q~ C o l ~ Z~) h ~:: O h ~: Q
N a~ ~~ rl U ~ S: -1 U
~ U~ a~ O ~ h fl~ O Xu~ o ~o) QJ O
C/~ WH m u~ H Ei m ~ Q ~
~.
,:
--19- .~: .
.
LeA 2 7 4 7 6 ~.
2 ~ 3 '~
As Table 2 shows, the addition of graft polymer/hydrogenated nitrile rubber or of graft polymer/ethylene-vinyl acetate copolymer to polycarbonates based on substit~ted cyclo-alkanes results in a marked improvement in notched impact strength at room temperature and at lower temperatures. In addition, the solvent resistance of injection moulded parts is increased.
LeA 27 476 - .. :
.
, :
... . .
.. ~
'~
.
' ~ ' ' '
.
- ,: ~ . ~
, ~ : . . ..
:' :
.
., - . ~
~37~ ~2 Rl Rl }~o~ ~ c - ~OH (IIb) R2 H3C~<CH3 R2 H3C C~3 Rl R
Hu 5 z~ ;r H ( I Ic ) C~3;
among which, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (formula IIa with Rl and R2 both denoting H) is particularly preferred.
The substituted dihydroxydiphenyl cyc].oalkanes corres-ponding to formula (I) and the correspondirlg polvcarbonates (component A) may be prepared according to German Patent lS application DE-A 38 32 396. The polycarbonates used are high molecular weight, tfiermoplastic, aromatic poly-carbonates with weight average molecular weights Mw of at least 10,000, preferably from-20,000 to 300fO00.
.
According to the invention there may be used either one diphenol corresponding to formula (I) to form homopoly-carbonates or several diphenols corresponding to formula (I) ~.
to form copolycarbonates.
;~ :
Further, the diphenols corresponding to formula (I) may also be used as mixtures with other known diphenols (such 25 as those described, for example, in D~-A 38 32 396) for the preparation of high molecular weight, thermoplastic aromatic polycarbonates used as component A.
Known branching agents may be used for the preparation of ~:
_4_ .
LeA 27 476 .
, : . .. . . . .
.
2~3r3~ ~2 t.~e polycarbonates put into the process, as well as chain terminators for regulating the molecular weight; see in this connection again DE-A 38 32 396. The said DE-A 38 32 396 also mentions the quantities of other diphenols which may be used as well as the quantities of chain terminators and branching agents.
The graft polymers used as component B may be polymers of resin-forming monomers prepared in the presence of rubbers.
They include, for example, graft copolymers with rubbery elastic properties which have been prepared from at least two of the following monomers: chloroprene, butadiene~l,3), isoprene, styrenes, acrylonitri~es, ethylene, propylene, vinyl acetate and (meth)acrylic acid esters having 1 to 8 carbon atoms in the alcohol component; in other words, polymers such as those described, for example, in "Methoden der Organischen Chemie" (Houben-Weyl), Volume 14/1, Georg Thienle--Ver~ag, Stuttgart 1961, pacles 393 to 406, and in C.B. Bucknall, "Toughened Plastics", Applied Science Publishers, London 1977. The preferred polymers B are partially cross-linked and have gel contents above 20% by weight, preferably above 40% by weight, most preferably above 60% by weight.
Preferred graft polymers B are obtained by the polymer-isation of:
25 B.l from 5 to ~() partC by weight, preferably from 30 to 80 parts by weight, of a mixture of B.l.l from '0 to ~l5 parts by weight of styrene, ~--methyl styrene, styrenes halogenated or methyl substituted in the nucleus, methyl methacrylate or mixtures of these compounds and B.1.2 from 5 to 50 parts by weight of acrylonitrile, LeA 27 476 .
2~3'~ ~ 8~
met:hacrylonitrile, methyl methacrylate, maleic acid anhydride, Cl to C4 alkyl-substituted or phenyl-N-substituted maleimidesor mixtures of these compounds in the presence of 5 B.2 from 10 to 95 parts by weight, preferably from 20 to 70 parts by weight, of rubber, i.e. polymers having a glass transition temperature below -10C.
Examples of preferred graft polymers B include polybutadiene which have been grafted with styrene and/or acrylonitrile and/or tmeth)acrylic acid alkyl esters, butadiene/styrene copolymers and acrylate rubbers;. i.e. copolymers of the type described in DE-OS 1 694 173; polybutadienes grafted with acry].ic or methacrylic acid alkyl esters, vinyl acetate, acrylonitrile, styrene and/or alkyl styrenes, 15 butadiene/styrene copolymers or butadiene/acrylonitrile copolymers, polyisobutenes and polyisoprenes as described e.g. in DE-OS 2 348 377 (corresponding to US-P 3,919,353).
ABS polymers such as those described in DE-OS 2 035 390 or in DE-OS 2 248 242(corresponding to US-P 3,644,574 and ~ -4, O 13, 613 ) are particularly preferred polymers B.
The most:preerred gr.aft polymers B are those which may be prepared by a grafti.ng reaction of a~ from 10 to 70% by weight, preEerably from 15 to 50%
by weight, especially from 20 to 40% by weight, based on graft product B, of at least one acrylic or meth-acrylic acid ester, or from 10 to 70% by weight, preferably from 15 to 50% by weight, especially from 20 to 40% by weight, of a mixture of from 10 to 50%
by weight, preferably from 20 to 35% by weight, based on the mixture, of acrylonitrile or acrylic acid ester or methacrylic acid ester and ~rom 50 to 90~ by weight, preferably from 65 to 80% by weight, based on the .
LeA 27 476 ____--.~ .
- . . .
- .
~. , , ' :~
:, . :
`~37:~2 mixt`ure, of styrene (graft basis B.l) on . from 30 to 90% by weight, preferably from 50 to 85%
by weight, in particular from 60 to 80% by weight, based on graft product B, of a hutadiene polymer containing at least 50~ by weight, based on ~ , of butadiene groups (graft basis B.2), the gel content of the butadiene polymer ~ preferably amounting to at least 70% by weight (determined in toluene), the degree of grafting G of the graft polymer preferably being from 0-15 to 0-55 and the average particle diameter d50 of the graft polymer B preferably being from 0-05 to 2 ~m, more preferably from 0-1 to 0-6 ~m.
Acrylic acid esters and methacrylic acid esters (~) are esters of acrylic acid or methacrylic acid and monohydric alcohols having 1 to 8 carbon atoms.
Methyl, ethyl and propyl methacrylates, n butyl acrylate and t-butyl (meth)acrylate are preferred.
In addition to its butadiene groups, the butadiene polymer (~) may contain up to 50% by weight, based on (~), of residues of other ethylenically unsaturated monomers such styrene, acrylonitrile, esters of acrylic or methacrylic acid having 1 to 4 carbon atoms in the alcohol component (such as methyl acrylate, ethyl acrylate, methyl meth-acrylate or ethyl methacrylate), vinyl esters and/or vinyl ethers. Pure polybutadiene is preferred.
Since, as is known, the graft monomers are not completely grafted on the grat basis in the grafting reaction, the term "graft: polymers B" usecl in the present invention are understood to be products obtained by the polymerisation of graft monomers B.l in the presence of the graft basis B.2.
LeA 27 476 ,: ' ~ : ,' . : , The degree of qrafting G denotes the ratio by weight of grafted graft monomers to the graft basis and has no dimension.
The average particle diameter d50 is the diameter which is greater than that of 50% by weight of the particles and smaller than that of the remaining 50~ by weight of particles. It may be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z.
Polymere 250 (1972), 782-796).
Another group of very highly preferred polymers B are the graft polymers obtained . from 20 to 90% by weight of acrylate rubber having a glass transition temperature below -20C as graft basis B.2 and ~. from 10 to 80% by weight of polymerisable, ethylen-ically unsaturated monomers whose homopolymers or co-polymers have a glass transition temperature above 25C, used as graft monomers B.l.
The acrylate rubbers (~) in this graft polymer B are preferably obtained from acrylic acid alkyl esters, optionally with up to 40% by weight, based O~ ), of other polymerisable, ethylenically unsaturated monomers.
The preferred polymerisable acrylic acid esters include Cl to Cg alkyl esters, for example, methyl, ethyl, butyl, n-octyl and 2-ethyl-hexyl esters; halogenated alkyl esters, preferably halogeno-Cl-C8-alkyl esters such as chloroethyl acrylate, and mixtures of these monomers.
For cross-linking, monomers having more than one polymer-isable double bond may be copolymerised. Examples of cross-linking monoiners :inc`.u~e esters of unsaturated mono-LeA 27 476 ::
~ ` , ` ' carboxylic acids having 3 to 8 car~on atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, e.g. ethylene glycol dimethacrylate or allyl meth-S acrylate; multiunsaturated heterocyclic compounds such astrivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinyl benzenes; and triallyl phosphate and diallyl phthalate.
Allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least 3 ethylenically unsaturated groups are preferred cross-linking monomers.
The cvclic monomers, triallyl cyanurate, triallyl iso-cyanurate, trivinyl cyanurate, triacryloyl hexahydro-s-triazine and triallyl benzenes are particularly preferredcross-linking monomers.
The quantity of cross-linking monomers is preferably from 0-02 to 5% by weight, in particular from 0-05 to 2% by weight, based on graft basis (I).
When cyclic cross-linking monomers having at least 3 ethylenic~lly unsaturated groups are used, the quantity is advantageously limited to below 1~ by weight of the graft basis (~).
Preferred ''other~l polymerisable, ethylenically unsaturated monomers which may be used for the preparation of the graft basis (I) in addition to the acrylic acid esters include, for example, acrylonitrilel styrene, a-methyl styrene, acrylamides, vinyl-Cl-C6-alkyl ethers, methyl methacrylate and butadiene. Emulsion polymers having a gel content of at least 60% by weight are preferred acrylate rubbers used as graft basis (~
LeA 27 476 ,~ .
:
"
.
, . : :. , .. ;~ . :
~37~32 Silicone rubbers having graft active points as described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS
3 631 539 are also suit~ble as graft basis as defined under B.2.
The gel content of the graft basis B. 2 is determined in dimethyl formamide at 25C (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
The hydrogenated nitrile rubbers used as component C are products obtained by the hydrogenation of randomly structured copolymers of from 90 to 45% by weight, preferably from 85 to 50% bv weight, especially from 82 to 52~ by weight, of at lei~st one conjugated diene, from 10 to 55~ by weight, prefera:bly from 15 to 50% by weight, i5 especially from 18 to 48% by weight, of at least one unsaturated nitrile and from 0-to 10% by weight, preferably from 0 to 8% by weight, of at least one other monomer which is copolymerisable with conjugated dienes and unsaturated nitriles.
Examples of suitable conjugated dienes include butadiene-(1,3), 2-methylbutadiene-(1,3), 2,3-dimethylbutadiene-(1,3) and pentadie.ne-(1.3); acrylonitrile and methacrylonitrile are suitable unsaturated nitriles.
Aromatic vinyl compounds,(meth)acrylic acid esters having from 1 to 12 carbon atoms in the alcohol component and a, ~-unsaturated mono- or di-carboxylic acids may be used as further monomers.
The following are specific examples: aromatic vinyl compounds such as styrene, substituted styrenes, e.g. o-, m- and p-methvl styrene, ethyl styrene, vi.nyl naphthalene and vinyl pyridine; (m~ h)acry:l.ic acid esters such as methyl :
LeA 27 476 , .
:. , : .
:: , , , . ~.
. .
.
(meth)acrylate, ethyl (meth)acrylate, n-~utyl (meth)-acrylate, 2-ethylhexyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; among the unsaturated carboxylic acids, ~,~ -unsaturated monocarboxylic acids having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid and crotonic aeid and a,~-unsaturated dicarboxylie aeids having 4 to 5 earbon atoms, sueh as maleie, fumarie, eitraeonie and itaeonie aeid; further, semiesters of ~,~-unsaturated diearboxylic acids, such as maleic acid-n-dodeeyl semi-esters and fumarie aeid-n-butyl semiesters.
Examples of further monomers inelude vinyl ehloride, vinylidene ehloride, N-methylol aerylamide, vinyl alkyl ethers having 1 to 4 earbon atoms in the alkyl group and vinyl esters of earboxylie aei~s having 1 to 18 earbon atoms, sueh as vinyl aeetate or vinyl stearate.
Speeifie examples of eopolymers to be hydrogenated inelude aerylonitrile/isoprene eopolymers, aerylonitirle/isoprene/
butadiene terpolymers, aerylonitrile/butadiene/n-butyl aerylate terpolymers, aerylonitrile/butadiene/2-hydroxy-propyl methaerylate terpolymers and aerylonitrile/butadiene/methaerylie aeid terpolymers. Aerylonitrile/butadiene eopolymers are partieularly preferred.
The proaration of hvdrogenated nitrile rubbers with preservation of the nitrile groups is known, e.g. from 25 ~-OS 3 32S 974.
The degree of hydrogenation (pereentage of hydrogenated C-C double bonds, based on the total number of C-C double bonds orgiinally present in the polymer) of the polymer used as eomponent C is determined by IR or NMR speetroscopy and amQunts to at least 80%, preferably at least 90%, espeeially 95%.
LeA 27 ~76 . . ;
., . , ~ . , ~3~
The hydrogenated polymers used as component C are gel free and soluble in ketones such as acetone or butanone, in ethers such as tetrahydrofuran or dioxane and in chlorinated hydrocarbons such as dichloromethane or chlorobenzene. The molecular weights of the hydrogenated nitrile rubbers are from 500 to 800,000 (g/mol) preferably from 10,000 to 600,000 ~g/mol), especially from 30,000 to 400,000 (g/mol) (Mn, number average, determined by gel permeation chroma-tography).
The ethylene/vinyl acetate copolymers to be used instead of hydrogenated nitrile rubbers contain from 10 to 90% by weight, preferably from 20 to 85~ by weight, of vinyl acetate, based on the total quantity of copolymers. The preparation of co?o]ymers is known and is described in, for example, "Encyclopedia of Polymer Science and Technology", Volume 15, 577 to 677 (1971), EP 0 078 122, DE 1 815 337, DE 1 914 756 and DE 3 000 009.
The moulding compounds according to the invention may contain the usual quantities of additives conventionally used ~or polycarbonates and graft polymers, such as stabilizers, pi~ments, mould release agents, flame retardant; and antistatic agents.
The moulding compounds according to the invention may be prepared by mixing the components in known manner and melt compounding or melt extruding them at elevated temperatures, preferably at 200 to 350C, in the usual apparatus such as internal kneaders, extruders or double shaft screws.
The cc~mponents may be mixed together in succession or simuItaneously.
The moulding compounds according to the invention may be used for the production of mouided articles of all kinds, LeA 2~ 476 - -, ~ ~ 3 ~ 2 e.g. by injection moulding. The following are examples of moulded articles: housing parts (e.g. for domestic appliances such as juice presses, coffee machines, mixers), cover plates for the building industry and motor vehicle parts. They are also used for electrical apparatus, e.g.
for multipoint connectors, on account of their excellent electrical properties.
Moulded articles may also be produced by deep drawing previously produced boards or films.
The invention further relates to the use of the moulding compounds described for the production of moulded articles.
The thermoplastic moulding compounds according to the invention are distinguished by their very good notched impact strength even at low temperatures, improved solvent resistance (ESC characteristics) and high dimensional sta-bility under heat.
LeA 27 476 . ' ' -:: , .. . .
:
, ~ ~ 3 7 ~
Examples Component A 1 Polycarbonate based on bisphenol A/l,l-bis-(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane (molar ratio 55:45):
1,436-4 g (6~3 mol) of bisphenol A (2,2-bis-(4-hydroxy-phenyl)propane, 2,387-0 g (7-7 mol) of 1,1-bis-(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane, 7,476-0 g (84 mol) of 45% NaOH and 33O7 litres of water were dissolved in an inert gas atmosphere with stirring. A solution of 36-9 g ~0-392 mol) of phenol in 11 litres of methylene chloride and 13 litres of chlorobenzene were then added. 2,772 g (28 mol) of phosgene were introduced into the thoroughly stirred solution at pH 13 to 14 and at 21 to 25C. 14 ml of ethyl piperidine were then added and the reaction mixture was stirred for a further 45 minutes. The aqueous phase, which was free from bisphenolate,was separated off and the organic phase was washed free from electrolyte with water after acidification with phosphoric acid and freed from solvent. The polycarbonate had a relative solution viscosity of 1-30. The glass temperature of the polymer was found to be 206C (DSC).
_omponent A 2 P~lycarbonate based on bisphenol A/l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (molar ratio 65:35). Preparation as under A 1.
Component B 1 Graft polymer of 50 parts by weight of a copolymer of styrene and acrylonitrile in the ratio of 72:28 on 50 parts by weight of particulate cross-linked polybutadlene rubber (average particle diameter d50 = 0O4 ~m) prepared by LeA 27 476 :
.
' ~ . ,, ~ .
- 2 ~3 3 P~
emulsion polymerisation.
Component B 2 Graft polymer of 50 parts by wei.ght of a copolymer of styrene and acrylonitrile in the ratio of 90:10 on 50 parts by weight of particulate, cross-linked polybutadiene rubber (average particle diameter d50 = 0-4 ~m) prepared by emulsion polymerisation.
Component C 1 Hydrogenated nitrile rubber on a randomly structured acrylonitrile/butadiene copolymer having an acrylonitrile content of 34-1% by weight, a degree of hydrogenation above 99-2% (determined by infrared spectroscopy) and a Mooney vi.scosity ML 1 + 4 ~l00C) of 70 (determined according to DIN 53 523).
Component C ~
Copolymer of ethylene/vinyl acetate in a ratio by weight of ethylene to vinyl acetate of 30:70.
Preparation and testing of the moulding compounds according to the invention _ _ Components A, B and C were melted at temperatures of from 250 to 300^ in a 1-3 litre internal kneader and homogenised.
Rods measuring 80 x 10 x 4 mm (processing temperature 280C) were produced ~rom the moulding compounds in an injection moulcling machi.ne ar.d used for testing the notched impact strengt:h (b~ met:hod ISO 180 lA) at the temperature indicated in Ta.ble 2.
The ESC characteri.stic was t~ted on rods measuring 80 x 10 -lS-LeA 27 476 -- - - ` .. ~ . .; ~. , :
-: - ' . ' - ~ ; , x 4 mm (mass temperature 280C). A mixture of 50 volumes~
of toluene/50 volumes~O of isooctane and 42-5 voluMes% of toluene/42~5 volumes% of isooctane/1~ volumes~ of methanol was used as fuel simulator. The samples were prestretched by means of a template in the form of a circular arc and kept in the fuel simulator for 5 minutes at room temperature.
The amount of prestretching ~x was 0-4 to 2~4~. The tension crack response was assessed over the breakage in dependence upon the amount af prestretching.
The vicat softening temperature (method A/120) was determined ` according to DIN 53 460 on rods measuring 80 x 10 x 4 mm.
LeA 27 476 - ~
- : ., .. , . :
": ~ , :,, " , :: ~"" , .; . . :
:
~" .:
;~ 0 3 ~18 2 o o CO , ~, ~
_ U~
a) ,_ o o ~n o o ~D~,1 I a~ ~ I I I
h O O
O
U~_ I ~ I I I I
O o ~r . I ~ ~ I
U~ o U~
I oo ~ I I ' o o O ~
., X
E ,1 o o o a~
S ' : ::
~ ~ ~ ~ ~ ~1 ~
o ~ ~c a:i ~' c,) O
O O V~
Z ~
.,, ~ ~ .
O ~ O :
Q U ~ , E~ ~ ;
LeA , 7: 476 ~ ~
:, :
: .
~3 U~
~J
~ u) ~ r r A~ ~
a~ o u~ u~
.c ~o ~ r s~ ~ ~ I I I I ,_ W ~AJ
O
C~ l I I I C~
rl .~
Q N N Ntn ~,A, 1-- ~ W~
A
O N Ul U) R
~: x x r tn ~ r--~ I I I ~ w ~, N N N
I
,AJ X ~ ~1 I I ~ Q
C U~
~I) N N U~ N U~ ~
U~ X X X X ~ W
U~
AJ
~) O O O O ~
~1 E~ O O o o r.
IY; ~1 I I
x 1~ o ~
LeA 27 476 ,.
.
.
.. . .
' ' - .: : ~ . , .. - : . . . .
~7~ ~
~r . ~r .
~ h 0 > ~ O r4 0 Q
tn ~ ~ .
E ~ h ~
O ~q O Q
X
U~ ~,~ o h ~ ~r . ~r .
~) h ~
O Q O Q
h O . 'r Q
9 h -1 R N ~
~r . ~ . ~:
.~, o L~
Q O Q
oQ. ~r R
N N ~ N S::
h ..
o . ~ Q
o h ,_1 --1Q N
~ ` ~::
Q~ ~I o\O ~
Il) O h -- ~ Q~ C o l ~ Z~) h ~:: O h ~: Q
N a~ ~~ rl U ~ S: -1 U
~ U~ a~ O ~ h fl~ O Xu~ o ~o) QJ O
C/~ WH m u~ H Ei m ~ Q ~
~.
,:
--19- .~: .
.
LeA 2 7 4 7 6 ~.
2 ~ 3 '~
As Table 2 shows, the addition of graft polymer/hydrogenated nitrile rubber or of graft polymer/ethylene-vinyl acetate copolymer to polycarbonates based on substit~ted cyclo-alkanes results in a marked improvement in notched impact strength at room temperature and at lower temperatures. In addition, the solvent resistance of injection moulded parts is increased.
LeA 27 476 - .. :
.
, :
... . .
.. ~
'~
.
' ~ ' ' '
Claims (5)
1. A thermoplastic molding composition comprising A) 20 to 97 parts by weight of a polycarbonate based on substituted dihydroxydiphenyl cycloalkanes corresponding to wherein R1 and R2 denote, independently of one another a member selected from the group consisting of a hydrogen atom, a halogen atom, C1-8 alkyl, C5-6 cycloalkyl, C6-10 aryl and C7-12 aralkyl, m stands for an integer from 4 to 7, R3 and R4, which are selected individually for each X, denote, independently of one another, a hydrogen atom or C1-6 alkyl radical, and X denotes carbon, under the condition that on at least one carbon atom denoted by X, R3 and R4 are both alkyl radicals, B) 3 to 80 parts by weight of a graft polymer of resin-forming monomers on a rubber and C) 1 to 50 parts by weight of an agent selected from the group consisting of (i) a hydrogenated, randomly structured nitrile rubber and (ii) a copolymer of ethylene/vinyl acetate, the sum of A + B + C amounting in each case to 100 parts by weight.
Le A 27 476 - 21 -
Le A 27 476 - 21 -
2. The thermoplastic molding composition of Claim 1 wherein said graft polymer used as component B is obtained by the polymerization of B.1) 5 to 90 parts by weight of a mixture of B.1.1) 50 to 95 parts by weight of at least one member selected from the group consisting of styrene, a-methyl styrene, styrene substituted with halogen or methyl in the nucleus, methyl methacrylate or mixtures of these compounds and B.1.2) 5 to 50 parts by weight of at least one member selected from the group consisting of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic acid anhydride, C1-C4-alkyl- or phenyl-N-substituted maleimide or mixtures of these compounds in the presence of B.2) 10 to 95 parts by weight of a rubber having a glass transition temperature below -10°C.
3. The thermoplastic molding composition of Claim 1 wherein said hydrogenated nitrile rubber is the hydrogenation product of a random copolymer comprising 90 to 45% by weight of at least one conjugated diene and 10 to 55% byweight of at least one unsaturated nitrile and from 0 to 10% by weight of at least one other monomer which is copolymerisable with conjugated dienes and unsaturated nitriles.
4. The thermoplastic molding composition of Claim 1 wherein said ethylene/vinyl acetate copolymer contains 10 to 90% by weight of vinyl acetate.
5. A molded article comprising the thermoplastic molding composition of Claim 1.
LeA27 476 -22-
LeA27 476 -22-
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4008463.9 | 1990-03-16 | ||
| DE19904008463 DE4008463A1 (en) | 1990-03-16 | 1990-03-16 | Low temp. impact resistant polycarbonate moulding compsn. - contg. polycarbonate based on substd. di:hydroxy:di:phenyl:cycloalkane and grafted rubber plus hydrogenated nitrile rubber or EVA |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2037182A1 true CA2037182A1 (en) | 1991-09-17 |
Family
ID=6402378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2037182 Abandoned CA2037182A1 (en) | 1990-03-16 | 1991-02-27 | Impact resistant polycarbonate moulding compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0446443A3 (en) |
| JP (1) | JPH04222850A (en) |
| CA (1) | CA2037182A1 (en) |
| DE (1) | DE4008463A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10392506B2 (en) * | 2015-07-06 | 2019-08-27 | Covestro Deutschland Ag | Polycarbonate compositions for galvanic applications having a high requirement for heat distortion point |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2102262T3 (en) * | 1994-04-15 | 1997-07-16 | Bayer Ag | COMPATIBILIZED MIXTURES FROM ABS PLASTICS, POLYOLEFINES, AND IN CASE GIVEN AROMATIC POLYCARBONATES. |
| JP6696928B2 (en) * | 2017-03-23 | 2020-05-20 | 日本エイアンドエル株式会社 | Polycarbonate modifier, modified polycarbonate resin, and method for producing modified polycarbonate resin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3324906A1 (en) * | 1983-07-09 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS |
| DE3712116A1 (en) * | 1987-04-10 | 1988-10-20 | Bayer Ag | THERMOPLASTIC MOLDING MATERIAL WITH IMPROVED TENSION crack behavior |
| DE3844633A1 (en) * | 1988-08-12 | 1990-04-19 | Bayer Ag | Dihydroxydiphenylcycloalkanes, their preparation, and their use for the preparation of high-molecular-weight polycarbonates |
| CA1340125C (en) * | 1988-10-06 | 1998-11-10 | Dieter Freitag | Mixture of special new polycarbonates with other thermoplastics or with elastomers |
-
1990
- 1990-03-16 DE DE19904008463 patent/DE4008463A1/en not_active Withdrawn
- 1990-12-07 EP EP19900123539 patent/EP0446443A3/en not_active Withdrawn
-
1991
- 1991-02-27 CA CA 2037182 patent/CA2037182A1/en not_active Abandoned
- 1991-03-13 JP JP7211091A patent/JPH04222850A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10392506B2 (en) * | 2015-07-06 | 2019-08-27 | Covestro Deutschland Ag | Polycarbonate compositions for galvanic applications having a high requirement for heat distortion point |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0446443A2 (en) | 1991-09-18 |
| EP0446443A3 (en) | 1992-01-02 |
| DE4008463A1 (en) | 1991-09-19 |
| JPH04222850A (en) | 1992-08-12 |
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