CA1048187A - Pvc moulding compounds with high dimensional stability to heat - Google Patents

Abstract

Abstract of the Disclosure Polymer mixtures useful ?? moulding compounds and copolymers of:
a) 20 - 90 % by weight of polyvinyl chloride or copolymers of vinyl chloride with up to 30 % by weight of other copoly-merisable vinyl compounds:
b) 10 - 80 % by weight of polycarbonate in which at lest 50 % by weight of the structural units have the formula (1):

(1) wherein X represents a single bond, -O-, -CO-. -SO2-. C1-C10 alkylene, C1-C10 alkylidene, C5-C15 cycloalkylene, C5-C15 cycloalkylidene, C5-C20 cycloalkyl alkylidene or

Description

1~48187 .
This invention relates to ~hermoplastic moulding compounds with high dimensional stability to heat and high impact strength produced from vi~yl chloride polymers and - certain polycarbonates. The mou1ding compounds may contain elastici~ing componen~s, such as rubbers and/or rubber modified thermoplastic resins, to increase their toughness and notched impact strength.
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The freezing temperature (glass transition temperature3 of polyvinyl chloride is about 80C so that its dimensional stabi-lity to heat (Vicat temperatures about 75 to 84C depending on the K-~alue and for~ulation)his insufficient for many purposes.
Attempts have therefore been made to improved the dimensional .,, ~. stability to heat by modifying the molecular structure (copoly-.~
merisation)~ carrying out chemical after-treatments or adding t.`' thermoplasts with a higher glass transition temperature (G. K~hne et al, Kunststoffe Volume 63 (1973) pages 139-142). Partial successe~ have been achieved by after-chlorination and cross-linking as well as by copolymerisation with maleic imides (Vicat tempera-`~ tures about 90 C). It has also been attempted to mix PVC wlth other thermoplasts. Technically valuable products, however, were obtained in only a few cases.
The moulding compounds according to the inventi~nl consist of:
- (a) 20 - 9o % by weight (based on a) and b)) of polyvinyl chlo-ride or copolymers of vinyl chloride and up to 30% by weight of one or more copolymerisable vinyl compounds;
(b} 10 - 80% by weight (based on a~ and b)) of a polycarbonate in which at least 50~ by weight of the structural units have the formula (1):

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loC~ x~3-c 1 (1) . .
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wherein X represents a single bond, -O-, -CV-, -S~2-, Cl - Cl~ alkylene, Cl ~ C10 alkylidene, C5 ~ C15 cyclo-alkylene, C5 - C15 cycloalkylidene, C5 - C~O cyclo-alkylalkylidene, ~ or -~ 10 C~3 - C ~ Cl-13 :~ C~3 and (c) O - 100~, by weight, based on the mixture of (a) and (b), of a rubber and/or a rubber-modified thermoplastic resin.
Particularly preferred moulding compounds consis-t of:
(a~ 30 - 90~, by weight, of a vinyl chloride homo- or co-polymer in which up to 30~, by weight, of other vinyl compounds have been polymerised;

2~ (b) 10 - 70%, by weight, of a polycarbonate of the formula (2);
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r C1~3~ ~3 -l ~ - 2 -.i~. . ;
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n = about 30 to 1000 . .- .
or a polycarbonate in which at least 50 % by weight of the struc-tural units have the formula (2) and -the remainder consists structural units of formula (2 a) CH
(2 a) _ -0 - C - ~ ~ -C ~ -and ; (c) 10 to 50 % by weight, based on the mixture of (a) and (b) of a rubber and/or a rubber-modified thermoplastic resin.
The moulding compounds according to the invention may be prepared by dissolving their polymer components in suitable ~ solvents and evaporating the solution or by mutual precipitation.
If desired, the components may also be mechanically mixed by conventional methodsO
Moulding compounds which have high impact strength and 1~ high notched impact strength, and in many cases, may also be transparent, may be obtained by the addition of rubbers or cer-.:
tain rubber-modified resinsO Without the addition of rubber or rubber-modified resins the moulding compounds obtained, which - may be transparent, have generally a lower impact strength.
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Suitable polycarbonates according to the invention are i~ homo- or co-polycarbonates and mixtures of various homo- and co-polycarbonatesO The polycarbonates generally have molecular weights of 109000 to 200,000 (weight average molecular weight), preferably 20,000 to 80,000. They may be prepared9 for example, by the interfacial polycondensation process from phosgene and `~ bisphenols (see German OS Nos. 2,063,050; 2,063,052; 1,570,703;
2,211,956; 2,211,957 and 2,248,817 and French PS No. 1,561,518).
The Polycarbonate units of formula (1) may, for example be based on the following bisphenols:
- Bis-(3,5-dimethyl-4-hydroxyphenyl) Le A 15 504 ~ 3 ~

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~ 811~7 Bis~(3,5-dimethyl-4-hydroxyphenyl)-e-ther ~is (3,5-~imethyl-4-hydroxyphenyl)-carbonyl Bis-(3,5~dimethyl 4-hydroxyphenyl)-~ulphone ; Bis-(3,5-dimethyl-4-hydro~yphenyl)-methane l,l-Bis-(3,5-dimethyl-4-hydroxyphenyl)-ethane l 9 l-Bis-(3,5 dimethyl-4-hydroxyphenyl)-propane 2,2-~is-~3,5-dimethyl-4-hydroxyphenyl~-propane 2,2-~is-(3,5-dimethyl-4-hydroxyphenyl)-butane ~,- 2,1~-Bis-(3,5-dimethyl-4-hydroxyphenyl) 2-methylt)utane . 2,4-Bi~-(3,5-dimethyl-4-hydroxyphenyl)-butane . 10 3,3-Bis-(3,5-dimethyl-4-hydroxyphenyl)-pentane `~ 3,3-Bis-(3,5-dimethyl-4-hydroxyphenyl)-hexane 4,4-Bis-~3,5-dimethyl-4-hydroxyphenyl)-heptane 2,2-Bis-(3 7 5-dimethyl-4-hydroxyphenyl)-octane 2,2-His-(3,5-dimethyl-4-hydroxyphenyl)-nonane ` 15 2,2-Bis-(3,5-dimethyl-~-hydroxyphenyl) decane . l,l-Bis-(3,5-dimethyl-4-hydroxyphenyl) cyclohexane . l,4-Bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane .- a,~'-B.is-(3,5-dimethyl-4-hydroxyphenyl)-~-diisopropylbenzene . ~,a'-Bis-(3,5-dimethyl-4 hydroxyphenyl~-m-diisopropylbenzene .~ 20 The following are pre~erred:
Bis-(3,5-dimethyl-4-hydroxyphenyl)-methane 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propane .~ 2D4-Bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane l,l-Bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane and ~,~'-Bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisoRropylben~ene.
2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)propane i~ particularly preferred.
In addition to units of formula (l), the polycarbonates may contain up to 50~, by weight, of units derived from other 3o bisphenols, ior example those in which at least one ortho-.

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~` position of the phenyl ~roups is no-t substituted or sub-- stituted by halogen (e.g. chlorine or bromine). The following . :.
are examples.
Hydroquinone 9 resorcinol, dihydroxydiphenyls, Bis-(hydroxyphenyl~-alkanes, Bis-(hydroxyphenyl)-cycloalkanes, Bis~(hydroxyphenyl)-~ulphides, -~ Bis-(hydroxyphenyl)-ethers, -~ 10 ~is-(hydroxyphenyl)-ketones, (hydroxyphenyl)-sulphoxides, ~is~(hydroxyphenyl)-sulphones and `. ~,~'-l~is-thydroxyphenyl3-diisopropylbenzenes.
The following are particularly preferred:
2,2-Bi~-(4-hydroxyphenyl)-propane, is-(4-hydroxyphenyl)-cyclohexane, - 2,2-Bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-Bis-(3,5-dibromo-4-hydroxyphenyl)-propane, ~,~'-Bis-(4 hydroxyphenyl)-p-diisopropylbenzene and 2,2-~is-(3-methyl-4-hydroxyphenyl)-propane.
- These and other aromatic dihydroxy compounds and the polycarbonates thereof have been described in US PS Nos,

3,028,365; 2,999,835j 3,14~9172; 3,271,~68; g,991,273; 3,271,367;
3,780,078; 3,014,891 and 2,999,846 and in German OS No.
~ 25 1,570,703.
The polyc~rbonates may be branched by incorpor~ting small quantities of polyhydroxyl ccmpound~, e.g. 0.05 to 2.0 mol ~ (based on the quantity of bisphenols used).
Polyc~rbonates o~ this type have been described, for example, in German OS Nos. 1,570,533; 2,116~974 and 2,113,347, :

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. .. , ' ' . . ' . .

~8187 .....
GB PS Nos. 885,442 and 1,079,~21 and US PS No. 3,544,514. The ~ ~ollowing are some examples of suitable polyhydroxyl compounds: Phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene-(2), 4,~- dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethanev 2, -bis-~,4-(4~ di-hydroxydiphenyl)-cyclohexylJ propane, 2,4-Bi~-(4-hydroxy-phenyl-4-isopropyl)-phenol, 2,6-bis-(2'-hydroxy-5'-methyl-benzyl)-4-methyl-phenol, 2,4-di-dihydroxybenzoic acid, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane and 1,4-bis-(4',4"~dihydroxy-triphenyl-methyl)-benzene.
The mixtures according to the invention may contain vinyl chloride polymers which have been obtained by emulsion, suspension or mass polymerisation and which have K-values, : . .
according to Fikentscher, of ~rom 50 to 80 determined in cyclohexanone ~1~ solution at 23C). Suitable vinyl chloride polymers of this type are polyvi~yl chloride and copolymers of vinyl chloride obtained from at least 70~, by weight, of vinyl chloride and not more than 30~, by weight, of a vinyl compound. The following are examples of vinyl compounds which are suitable for copolymerisation with vinyl chloride: Vinylidene chloride and vinylidene fluoride, vinyl esters, such as vinyl acetate, vinyl propionate or vinyl benzoate, aorylic acid or methacrylic acid and alkyl esters thereo~, amides and nitriles of -~ acrylic an~d methacrylic acid, ~aleic acid esters and semi-esters, maleic imides, vinyl ethers and olerinically unsaturated hydrocarbons, ~uch a~ ethylene, propylene or butylene. Rechlorinated polyvi~yl chloride i~ ~lso r ~: ' "

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~L~41~87 suitable llubbers suitable for use according to the invention are, in particular, natural rubber and synthetic rubbers. The ~ollowing synthetic rubbers, for example, may be used:
Polypentenamer, ethylene-propylene-diene rubber (Diene e.g. l,5-hexadiene, norbornadiene, ethylidene norbornene), diene rubbers, i.e. homopolymers of conjugated dienes containing 4 - 8 c~rbon atoms, such as butadiene, isoprene, piperylene and chloroprene, copolymers of such dienes with each other and copolymers of such dienes with ~tyrene, acrylic or methacrylic compounds (e.g. acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, ; butyl acrylate or methylmethacrylate) or isobutylene.
Particularly pre~erred rubbers are the butadiene, butadiene-; 15 styrene, butadiene-methylmethacrylate, butadiene~butyl acrylate, ethylene-propylene-diene, polypentenamer and ; butadiene-acrylonitrile rubber~, any of which may still contain small proportions o~ other mono~ers condensed with them, e.g. divinylbenzene and methacrylic acid in the case Or the la~t-mentioned rubber. Elastomeric polyurethanes, silicone rubbers, polyether rubbers and chlorinated low pressure polyethylene with A ohlorine content of 20 to 50%, by weight, as well as copolymers of ethylene and vinyl acetate with a vinyl acetate content of 15 to 65~, by weight, prefer~bly 30 to 65%, by weight, are also suitable.
The following are rubber-modified thermoplastic resins which may be u~ed in accordance with the invention:
(A) Grart polymers of vinyl compounds (a) on rubbers (b); or (B) Mixture~ of gra~t polymers (A~ ~nd thermoplastic resins (c) ~hich are prepared by the polymerisation of vinyl ',', Le A 15 504 - 7 -.
, . , . , ~ . . .

compounds (a); or ~ (C) Mixtures of rubbers (b) with thermopl~stic resins (c)~
; The following are examples of suitable vinyl compounds (a):
l. Styrene and its derivatives, e.g, ~-methylstyrene, chlorostyrene, ~-chlorostyrene, 2,4-dichlorostyrene9 ~-methylstyrene, 3,4-dimethylstyrene, o- and ~-divinyl benzene, ~-methyl-~-methylstyrene and ~-chloro-~-methylstyrene.
.~.
2. Acrylic and methacrylic compounds, e.g, acrylic and methacrylic acid, acrylonitrile, methacrylonitrileg methylmethacrylate, ethylacrylate, n- and iso-propyl-acrylate, n~ and iso-butylacrylate, 2-ethylhexylacrylate9 - methylmethacrylate, ethylmethacrylate9 n~ and iso-propyl-methacrylate, n- and iso-butylmethacrylate, cyclohexyl methacrylate and iso-bornylmethacrylate.
,"
. 3. Vinyl chloride or vinyl monomers which may be copolymerised ; with vinyl chloride.
The resins and graft polymers may be prepared by con-ventional radical polymeris~tion, e.g~ by solvent-free ~- solution9 solution/precipitation, suspension or emulsion ~ polymerisation. The graft poly~ers or rubber and the resins ; may be mixed by conventional method~, e.g. on rollers or kneaders or by mixing suit~ble latices and then isolating the products ,~ 25 by mutual precipitation.
; The following rubber-modifled resins are pre~erred:
Graft polymers of styrene, ~methylstyrene, acrylonitrile, methacrylic acid esters or mixtures thereof on a rubber, e.g. polybutadiene or a butadiene copolymer and mixtures of such gra~t polymers with polystyrene or styrene copolymers.
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~ ln p~rticular, the preferred rubber-modified resins ;~ have the following compositions:
I. Urflft polymers of:
: ~l l) 5 - 90%, by weight9 pr~fer~bly lO - ~%, by weight, . of ~I rubbery elastic biutadi0ne polymer or copolymer .. containing up to 50%, by weight, of copolymerised styrene, acrylonitrile and/or alkylesters of acrylic or methacrylic acid containing l to lO ~ atoms in the alcohol group as graft basis; und ~ 10 (I 2) l~ - 95~, by weight, p~eferably 4~ - 90%, by weight, of a monomer mixture of:
(I 2.1) 50 - lO0 parts, by weight, of styrene, ~-methylstyrene, : Cl - ClO alhyl esters of acrylic and methacrylic acid or mi~tures thereof;
(I 2 2) 0-50 parts, by weight, of acrylonitrile, methacrylo-nitrile, Cl - ClO alkyl esters o~ acrylic or methacrylic acid or mixtures thereof which are i~ polymerised in the presence of (I 1).

II~ Mixtures of:
. 20 (II l) 5 - 80%, by weight, of polymer (I); and .~ (II 2) 20 - 95~, by weight of a thermoplastic polymer or copolymer of the monomers (I 2).
III, Mixtures of:
(III l) 5 - 60%, by weight, of a rubber according to (I l); and - 25 (III 2) 40 - 95~9 by weight, of a thermoplastic polymer according to (Il 2).
~ Polyc~rbonates containing structural units of formul~
.. (l) are surprisingly highly compatible with polyvinyl -~ chloride, with the result that the moulding compounds . 30 according to the invention have excellent physical "'', '~'' ' ~ _ g _ .';
:' .':

~ . . ~ . ,. ' ' .' . ' :' . " .; ' . ~ ' ' ' ~.~4~l87 :.;
properties. Some of the moulding compounds are surprisingly also transparent, p~rticularly when polycarbonates based on ~,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane or 2,4-bis-(3,5-dimethyl-4-hydroxypl1enyl)-2-methylbutane are used.
~olycarbonates containin~ structural units o~ formula (l), for example~ those based on 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane and294 -bis-(3,5-dimethyl-4-hydroxy-phenyl~-2-methylbutane, may be dissolved together with ~ PVC in a PVC solvent. No phase seyaration takes place.
~` 10 Polycarbonates based on bisphenol A do not have these properties.
Another surprisin~ 4uality of the moulding compounds accordin~ to the invention is the ease with which they may be worked-up; thus, mixtures ol polyvinyl chloride and, for example~ polycarbonates based on o~O70l ,O~-tetralnethyl-- substituted bisphenols may be worked-up thermoplastically ~ at 24~ - 260~C whereasthe pure polycarbonate may be worked-up - only at temperatures upwards of about 300 - 330C.
The moulding compounds accordin~ to the invention - 20 have surprisingly high heat distortion temperatures.
Yicat temperatures according to ~IN 53 460 l5 kp) of 130 -l35~C are obtained with polycarbonate contents of about 50~, by wei~ht. Compared with polyvinyl chloride, the ~ moulding compounds are distinctly improved in their hardness, - 25 tensile str~ength, flexural strength and E-modulus.
:.
- Hegardless o~ the proportions in which the components are mixed,some moulding compounds are to a large extent ; transparent, particularly when polycarbonates based on 2,2~bis-(3,5-dimethyl-4-hYdrXyphenyl)-propane and 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane are used.

~ - 10 --. - ': , , , ' '''~ '' ' ' " ' .' ' :' ;' 8~37 .
Moulding compounds prepared from polyvinyl chloride : .
and the polycarbonates described above, however, have not a sufficient impact strength for all purposes.
The toughness and notched impact strengthg may, however, be considerably improved by adding rubber-~odified thermoplastic resins.
~., - ~ The addition of such resins normally destroys the trans-; parency of a moulding compound so that more or less opaque products are obtained. In the transparent moulding compounds according to ` 10 the invention it is surprisingly found that the transparency is - preserved after the addition of rubber-modified resins which in fact have pEactically the same refractive index as the moulding - compound.
The moulding compounds according to the invention are considerably more flame resistant than pure polycarbonates and !':' substantially resistant to acids, alkalies and solvents.
In the polymer mixtures according to the inven~ion, the rubber generally forms a separate phase which is finely divided in the polymer mixture.
The rubber may be in the form of individual pellets or agglomerates of pellets or in the form of other regular or irregular particles and agglomerates or also in the form of network-like particles in which another polymer .
is embedded. The particles generally measure 0.01 to 20 ~m, preferably 0.03 to 10 ~m. They-maY consist of one or more different types, depending on the method employed for preparing the polymer mixture and the choice of individual components, and the individual types of particles ~ may differ very substantially from each other in form, :' - :' ' ' , ' .. . .. . .

1~4B3L87 si~e and distribution of particle size. Two polymer mixtures having the same rubber content and otherwise identical in composition may differ substantia:Lly from each other in their - properties due to differing rubber phases, for example they may differ in their toughness and surface gloss.
- Whereas the rubber content generally forms a separate phase in the polymer mixtures according to this invention~ the ; other polymer components of the mixture may form a common phase ~- in which the vari-ous polymers may be almost molecularly dispersed or ~they may ~orm several phases. Each of these several phases may consist of an almost molecularly dispersed mixture of various polymersO
The moulding compounds according to the invention may be obtained by mixing the polycarbonate with polyvinyl chloride with the addition of a oonYentional stabilizer system followed by homogenisation on ~ixing apparatus, such as rollers, mixing screws, mixing extruders~
internal mixers or kneaders. ~wing to the operating temperature of up to 260C employed, it is advisable : 20 to add the total quantity of stabilizer required to the polyvinyl chloride and mix vigorously in a high speed mixer (temperatures up to 150C) before the polyvinyl chloride is mixed with the polycarbonateO For example, the polyvinyl chloride may be added as a stabilized gran-ulate to the usually pulverulent or granular polycarbonate, and this mixture may then be homogenized. Alternatively, the two polymers may be melted separately~ for example in extruders, and the two melts may then be combined, OI`
the polycarbonate or polyvinyl chloride may first be ' ' :

!'i', melted separately, e.g. on rollers, and the second com~
- ponent may then be added.
. ,.
.:
` The moulding compounds according to the inventionmay also be prepared from solutions by dissolving their components in a solvent or solvent mixture and then ~: isolating them together by the addition of a non~solvent `;:
or by pouring the solution dropwise into a precipitating ` agent or by evaporating the solvent.
The moulcling compounds may be worked-up as powders or granulates to produce shaped products of all kinds by the conventional thermoplastic processing methods.
~; Rubber-modified resins are in most cases obtained. ~ in a pulverulent crumbly form and may be used as sueh without - special preliminary measures for the mixing or bhermoplastic homogenization process. If desired, however, the polyvinyl chloride or polycarbonate may first be mixed with the resin.
The moulding compounds according to the invention ma~ be sta-bilized by means of the eonventional polyvinyl chloride stabilizers based on lead, barium/eadium, calcium/zinc, organo tin compounds or organic PVC stabilizers used either singly or in combination. The choice of lubricants also depends - on the requirements of the PVC. The stabllization of PVC is particularly important because~ depending on the proportion of polycarbonate used7 the working-up temperatures of the ;` moulding compounds lie close to the upper tolerance limit of PVC. In many cases, it will be necessary to use a higher total concentration of stabilizer than for pure PVC.
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The addition of colour pigments, fillers, glass fibres, antistatic agents, fire retarding agents and plasticizers is possible in principle for achieving particular properties or effects.
-~ Physical or chemical blowing agents may also be added .~ to the moulding compounds accord~ng to the invention in order - to produce a foam structure under suitable operating conditions.
~ The op~rating temperatures re~uired for the premixing -~ process, i.e. the incorporation of PVC stabili~er and if indicated homogenization of the total mixture before it is subjected to heat in the high speed mixer, lie within the range of 20 *o 150C. The subsequent working-up of the product into a granulate or finished parts should preferably ; be carried out at temperatures not higher than 260 C~ the tem-,: -perature required depending both on the viscosity of the poly-carbonate used and on the quantity thereof. With relatively low polycarbonate contents of up to about 30%~ the product may be worked-up in much the same way as PVC with a high K-value~
but if the proportion of polycarbonate is high the temperatures employed are likely to be higher. Owing to the resulting higher thermal stress, the total time empl~oyed for working-up the product should be kept as short as possible even if the product has been satisfactorily stabili~ed.
The moulding compounds according to the in~ention constitute a class of chemical materials which have the widest practical applications. As examples may be mentioned the manufacture of plates, sections and tubes, particularly for the building industry, where the high ':~
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heat distortion temperature is particularly important.
In this field, not only is it possible to compensate for the deleterious effect on the heat distortion temperature of-~VC by using impact strength modifiers but also the inclusion of the polycarbonate opens up new fields of application for PVC which, while having the ad~antage of low cost, could previously not be used on account of the : low dimensional stability to heat. The material may - also be used in the packaging industry in the form~of -; 10 bottles, containers and foils which~ in contrast to PVC
may be brought into contact with hot contents. There are also numerous possible uses of the material in the form of injection moulded articles for particular purposes where -extreme dimensional stability to heat is required in addition to high transparency. The high resistance of the moulding compounds to hydrol~sis enables them to be used in the construction of chemical apparatus~ as storage containers for acids and alkalies and ventilating systems for corrosive wast~ gases. In the electrical field, the high tracking resistance of the m~terial comes into its own. The application of the material from solution by casting9 spread coating or printing for the manufacture of coatings or foils should also be mentioned as a possible use.

~.

: . ' ' ' ' ': ' ' ;
lq~481B7 ExamE~es:
~- To produce the moulding compounds described in the ; Examples, a stabilized polyvinyl chloride mixture is first prepared and then worked-up into a homogenous mass with the polycarbonates or other components on rollers. The individual - pro~1cts are prepared as follows:
~; A, ~ rl~vl c~l~ri~e 100 ~rts, by w~ight, of suspension polyvinyl chloride ~ ,. .
with a K-value of 68 are mixed for 5 minutes in a high speed mixer at 2000 revs/min with the addition of a stabilizer system consis*ing of:
6 parts, b~ weight, o~ di-n-octyl-tin-dithioglycollic acid ester, :
1.5 parts, by weight~ of stearyl stearate, 1.0 parts, by weight, of diste~rylphthalate, 0.3 parts, by weight~ of montanic acid ester and 0.2 parts~ by weight, of polyethylene wax.
The temperature rises to 120C. The mixture is then cooled to room temperature while the speed of the mixer is reduced (about 500 revs/min).
- 20 The resulting polyvinyl chloride mixture is found to have the following mechanical properties;
Ball pressure hardness DIN 53 456 kp/cm2 1317 Impact strength DIN 53 453 cmkp/cm RT 10 samples not broken -20C 3/10 broken r' ~40 C "

Notched impact strength DIN 53 453 cmkp/cm2 Vicat DIN;~ 53 460 C 1 kp 86 . ~ .
, ~ 8~87 5 kp 74 Bending stress DIN 53 452 950 Sagging mm 3.8 Tensile strength DIN 53 455 kp/cm2653 ~longation DIN 53 455 % 4 B. Pol~carbonate Polycarbonate based on 2,2-bis-(3,5-dimethyl-4-hydroxy-phenyl)-propane in powder form. The relative vi~cosity is ~Iel =
1.30 (de-termined on a so~ution of 0.5 g of the polycarbonate in 100 ml of methylene chloride).
C. Rubber~modified resin I.
A graft polymer of 50 parts, by weight, of polybutadiene, 36 parts, by weight, of styrene and 14~parts~ by weight, of acrylon-itrile.

. ~3:~- , Graft polymer of 30 partsg by weight9 of polybutadiene, 45 parts, by weight, of styrene and 25 parts, by w~ight, of methyl methacrylate.

Example 1 .:
80 ~arts, by weight~ of polyvinyl chloride mixtura A are first mixed with 20 parts, by weight, of polycarbonate B for one minute in a high speed mixer at about 1500 revs/min and then homo-genized on laboratory rollers for a total of 5 minutes. The roller tempera*ure is 260 C. A continuous transparent sheet is obtained.
This sheet is then preheated without pressure in a high pressure press at 210C for 3 minutes and then pressed for a further 3 minutes under pressure to form a plate from which test samples are formed. The plates obtained are transparent. Their mechanical data are given in Table 1.

.. . : ' , . '' ' : ' Examples 2 - 5 Mixtures are prepared f`rom the following components as described in Example 1:

.:
`- 65 parts, by weight, of A +

- 35 parts, by weight, of B (2) ' ~
50 parts, by weight~ oX A -~

- 50 parts, by weight3 of B (3) `,".~
35 parts, by weight~ of A ~

65 parts, by weightg of B (4) ~ .
20 parts, by weight~ of A ~

80 parts, by weight, B (5) `~ Moulding compounds of high transparency are obtained ~,:
,.
in all cases. The mechanical properties are shown in Table 1.

` Example 6 - 50 Parts, by weight~ of polycarbonate A are dissolved in methylene chloride and 50 parts, by weight~ of suspension poly-. .~
vinyl chloride with a K-Yalue of 68 are dissolved in cyclopentanone.
The solutions are combined with stirring. The polymer mixture is precipitated by introducing the solution drop~ise into methanol.
The finely divided polymer m~xture is dried for 20 hours at 60C
~r and 15 hours at 80C under vacuum~

To work-up the product~ 100 parts, by weight, of the precipitated polymer mixture is mixed with the stabilizer and lubri-cant system described in Example 1 in the high speed mixer also described in Example 1 and the resulting ,.~ .
.:
-t~-,~, .

~L~)4~187 - mixture is homogeni~ed on a roller for 5 minutes at 240C.
~ The rolled sheet obtained is transparent and is worked-up .~ into pressed plates as described above The mechanical :~
properties of the plates are shown in Table 1 Examples ? - 12 : Polyvinyl chloride (A), polycarbonate (B) and resin (D~
. are mixed as follows by the method described in Example 1:
- 40 Parts, by weight, of A ~
. 50 parts~ by wei~ht5 of B +
10 parts~ by weight~ of D ~7) 43 parts, by weight, of A +
45 parts, by weight, of B +
. 12 parts, by weight~ of D (8) . 35 parts~ by weight~ of A t . i. . .
~ 50 parts, by weight~ of B ~
15 parts~ by weight, of D (9) il 30 parts~ by weight~ of A ;~ .
~: 50 parts~ by weight, of B +
20 parts, b~ weight, of D (10) 1 20 65 parts~ by weight~ of A ~
-. 23 parts, by weight, of B +
~i 12 parts, by weight, of D (11) 23 parts~ by weight~ of A
:~ 65 parts, by weight, of B ~
:~ 12 parts, by weight~ of D (12) The resulting moulding compounds are transparent and in addition to the gre~t hardness and flexural strength 1~81~

described aoove they are distinguished by high toughness and notched impact strength. The mechanical properties are shown in Table 2.
Exam~les 13 - ~
Opaque moulding compounds are produced in the same way as in Examples 7 - 12 but us.ing ~osin C:
40 Parts, by weight, of A +
; 50 parts, by weightg of B ~
: 10 parts~ by weight, of C (13) : .~
: 35 parts, by weight, of A +
:
50 parts, by weight, of B +
15 parts, by weight, of C (14) 30 parts, by weight9 of A +
50 parts, by weightg of B +
20 parts, by weight, o~ C (15) , 23 parts, by weight, of A ~
65 parts7 by weight, of B +
12 parts, by weight, of C (16) 70 parts, by weight~ of A ~
. 18 parts~ by weight~ of B t 12 parts, by weight~ of C
The mechanical properties are shown in Table 3.

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Claims (9)

CLAIMS:

1. A polymer mixture comprising:
(a) from 20 to 90 % by weight, based on the mixture of (a) and (b) of polyvinyl chloride or a copolymer of vinyl chloride with up to 30 % by weight, based on the copolymer of at least one other copolymerisable vinyl compound;
(b) from 10 to 80 % by weight, based on the mixture of (a) and (b), of a polycarbonate having at least 50 % by weight of structural units of the following general formula (1):

(1) wherein X represents a single bond, -O-, -CO-, -SO2-, C1-C10 alkylene, C1-C10 alkylidene, C5-C15 cycloalkylene, C5-C15 cyclo-alkylidene 9 C5-C20 cycloalkyl-alkylidene or the group and (c) from 0 to 100 % by weight, based on the mixture of (a) and (b) of a rubber and/or a rubber-modified thermoplastic resin.

2. A mixture as claimed in claim 1 comprising:
(a) from 30 to 90 % by weight of a vinyl chloride homo- or co-polymer which contains up to 30 % by weight of at least one other vinyl compound;
(b) from 10 to 70 % by weight of a polycarbonate corresponding to the following general formula (2):

(2) wherein n = 30 - 100 or of a polycarbonate having at least 50% by weight of structural units of formula (2), the remainder consists of structural units of formula (2a) (2a) and (c) from 10 to 50% by weight, based on the mixture of (a) and (b) of a rubber and/or a rubber-modified thermoplastic resin.

3. A mixture as claimed in claim 1 or claim 2 in which the poly-carbonate (b) contains exclusively structural units of formula (1).

4. A mixture as claimed in claim 1 or 2 in which X represents

5. A mixture as claimed in claim 1 or 2 in which up to 50% of the structural units of the polycarbonate (b) are derived from the following bisphenols: 2,2 bis-(4-hydroxyphenyl)-propane; 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane; 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane;
1,1-bis-(4-hydroxyphenyl)-cyclohexane; .alpha.,.alpha.'-bis-(4-hydroxyphenyl)-p-diisopro-pylbenzene; and 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane.

6. A mixture as claimed in claim 1 or 2 in which component (a) has a K-value of from 50 to 80.

7. A mixture as claimed in claim 1 or 2 in which component (a) contains up to 30% by weight of one or more of the following: vinyl acetate, vinyl propionate, vinyl benzoate, acrylic or methacrylic acid ester containing 1 - 10 carbon atoms in the alcohol group, maleic acid esters or semi-esters, ethylene propylene, vinyl ethers, acrylonitrile, maleic imides or vinylidene chloride.

8. A mixture as claimed in claim 1 or 2 in which the rubber-modified thermoplastic resins used are graft polymers which have been prepared by polymerisation of styrene, .alpha.-methylstyrene, acrylonitrile, methacylonitrile, acrylic or methacrylic acid alkyl esters containing 1 - 10 carbon atoms in the alcohol group or mixtures thereof in the presence of polybutadiene or copolymers of butadiene with styrene, .alpha.-methylstyrene, acrylonitrile, meth-acrylonitrile, acrylic or methacrylic acid esters containing 1 - 10 carbon atoms in the alcohol group.

9. Moulded products when produced from a polymer mixture as claimed in claim 1 or 2.