DE2524472A1 - THERMOPLASTIC POLYBLENDS - Google Patents

Description

KECHTSSWWXITE DR. JUP. Γ. L-CHEM. WALTER BEIL Γ.2. June 1975

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AUaONXAS

Our no. 19 833

Stauffer Chemical Company Westport, Conn., V.St.A.

Thermoplastic polyblends

Rigid thermoplastics such as copolymers made from styrene and acrylonitrile are solid, hard plastics. In order to increase the impact resistance of these plastics, these copolymers were mixed with

made of preformed elastomers. The modified with elastomers Plastics have evenly distributed and stable elastomer particles within a continuous, rigid plastic matrix or Birase. , on. To the for the said Purpose-used elastomers include butadiene, butadiene / styrene, butadiene / acrylonitrile, and alkyl acrylate esters. Usually graft copolymers of those mentioned

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Elastomers for. Styrene / acrylonitrile used · These elastomers are used or grafted elastomers in a styrene / acrylonitrile matrix incorporated, so increase impact resistance and The strength of the resulting plastic can be seen from a Increase in impact strength (ASTM D-256) and appearance a yield point in the elongation curve of a sample (ASTM-638). In general, however, results in the thermoplastics modified in this way a decrease in tensile strength (ASTM D-638), hardness (ASTM D-2583), flexural strength (ASTM D-790), and deflection temperature under load (ASTM D-648), compared with the non-modified iced thermoplastics. Since these decreases are related to the elastomer content of the polymer, they lie in products with high impact strengths generally have lower values for the properties mentioned, compared to the unmodified styrene / acrylonitrile copolymer.

The invention relates to a polyblend containing a rigid copolymer of low impact strength as shown above, the excellent impact resistance and toughness with im general good tensile strength, hardness, flexural strength and Deflection temperature under load compared with the previously known ßlastomer-modified styrene / acrylonitrile copolymers with high impact strength values rigid plastic or the copolymer is provided.

The polyblend according to the invention contains (a) about 20 to 90 and preferably about 50 to 70% by weight of at least one rigid Plastic, (b) about 10 to 60 and preferably about 15 to 45 weight 56 of an emulsion polymer of an acrylate, for example Polybutylaerylat, which by a vinyl chloride suspension polymer has been overpolymerized, (c) about 1 to 30 and

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preferably about 5 to 20 wt. ^ of an interpolymer of polyvinyl chloride (PVC) particles with a methacrylate-containing Component, preferably a mixture of methyl methacrylate and butyl acrylate, has been overpolymerized, and (d) about 0 to 40, and preferably about. 15 to 25 wt. $ 6 one Vinyl chloride suspension polymers. By adding a few percent, for example up to about 10% by weight, of an inorganic flame-retardant Polyblend produces an unusually tough, impact-resistant, flame-retardant thermoplastic.

las additive ^^ SÄ responsible for improving the impact resistance of the rigid plastic and adding to it, contains about (a) 20 to 90 wt. <$> of a polyacrylate overpolymerized with suspension PVC, (b) about 10 to 75 wt . $ Polyvinyl chloride that has been over-polymerized with a polymethaerylate-containing component; and (c) about 0 to 35% by weight of polyvinyl chloride. In addition, about 0 to 20% of a conventional flame retardant agent can be present in the mixture. The percentages relate to the total weight of the additives in the polyblend that is to be added to the rigid plastic.

The presence of the suspension polymer with vinyl chloride overpolymerized The polyacrylate in the rigid plastic leads to elastomer particles that reduce the impact resistance properties of the increase the rigid plastic containing polyblends. The use of small amounts of the interpolymer from with the methacrylate-containing Component of overpolymerized polyvinyl chloride improves the impact resistance properties of such Polyblends in a dramatic Ϋ / ice, without the addition of large ones Amounts of elastomer to the mixture. The impact resistance properties of the the rigid plastic containing polyblends improved.

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Each component of the polyblend can be produced separately. The acrylate emulsion polymer with overpolymerized vinyl chloride suspension polymer, the vinyl chloride suspension polymer interpolymer with over-polymerized methacrylate component and the optional polyvinyl chloride component are then incorporated into mixed with the rigid plastic in a manner known to the person skilled in the art. For example you can get the rigid plastic and the Mix the individual components in resin or powder form in a conventional mixer, or you can use the powder mixture Feed it directly to the manufacturing machine to manufacture the finished parts. You can also use the dry resin mixture first process into pellets by extruding rods and cutting them into appropriate lengths. These pellets can then fed to the manufacturing machine that produces the finished parts. You can also use the rigid plastic mix in pellet form with pellets containing the other components and extrude and seal the pellet mixture Cutting up pellets which are then used to manufacture the products. You can also use the rigid plastic Mix in pellet form with pellets containing the other components and feed this mixture to the manufacturing machine. The possibility of preparing a mixture according to the last-mentioned method is particularly favorable because it increases the number of the intermediate mixing and storage corridors designed to be minimal. Furthermore, it allows the processor a large Scope with regard to the mixing ratio of rigid plastic and components according to the invention.

The mixtures of rigid plastic and components according to the invention can use all conventional plastics processing methods further.processed. The .mixtures can be calendered into foils and webs, furthermore by injection molding or compression molding into simple or complicated designs

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form deformed or into foils or webs or relief-like
Forms are extruded.

According to the present description, the "rigid plastics" include styrene / acrylonitrile copolymers. and by elastomers
modified styrene / acrylonitrile copolymers. Examples of preferred rigid plastics are:

(1) Copolymers of a styrene, for example styrene, '^ - methyl = styrene and / or tert. Butyl styrene and an acrylonitrile, for
Example acrylonitrile or methacrylonitrile, which are usually used as
"SAN" polymers are referred to;

(2) Acrylonitrile / butadiene / styrene resins, commonly referred to as "ABS" resins, and generally either a blend of 60 to 80:40 to 20 styrene: acrylonitrile copolymer and about 10 to 40 wt up to 40: 95 to 60 acrylonitrile: butadiene copolymers or a mixture of 60 to 80: 40 to 20 styrene /
Acrylonitrile copolymer and about 10 to 40% by weight of a graft polymer of the last-mentioned copolymer on polybutadiene;

(3) Acrylate / styrene / acrylonitrile resins, commonly referred to as "ASA" resins, made up of copolymers containing a major proportion of Cp-Cg alkyl acrylate ester elastomer,
to which about 65 to 95% by weight, based on the latter copolymer, of a 70 to 80:30 to 20 styrene: acrylonitrile copolymer are grafted;

(4) Methacrylate / butadiene / styrene resins, which are commonly referred to as "MBS" resins and have a minor proportion of a methyl = methacrylate / styrene / acrylonitrile Ierpolymeren that is grafted and / or mixed with polybutadiene or a
Copolymer of butadiene and smaller amounts of comonomers such as

Styrene and acrylonitrile, and,

,, / Rubber

(5) By ethylene / propylene / diene modified ene (EPDMJ / styrene /

/ modified

Acrylonitrile copolymers.

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The elastomeric polyacrylic / PVC copolymer component is produced by suspension polymerization of vinyl chloride or a mixture of vinyl chloride and a smaller proportion of one or more comonomers, in the presence of an aqueous emulsion of a polyacrylate, for example polybutyl acrylate, according to a preferred embodiment is networked. The microscopic Examination of the resulting suspension / emulsion interpolymer (SEI) particles shows that the polymer of the suspension polymerized Vinyl monomers, i.e. polyvinyl chloride, is intimately mixed with the elastomer particles. This apparently results from the fact that the vinyl chloride monomer, which is used in the last suspension polymerization stage, the elastomer particles before the polymerization partially has swelled. The resulting particles, which have been produced by a suspension process, lie in FIG Form of agglomerates, the particle size of which is much larger is than that of the particles of the original rubber emulsion used in its manufacture.

The elastomer particles that are used to make the polymer parts Made of elastomeric polyacrylic and PVC are used by conventional aqueous emulsion processes made of emulsifiers and water-soluble catalysts.

In carrying out the aqueous emulsion polymerization of the copolymer of elastomeric acrylic and PVC is first prepared a Monomerbesehickung consisting of an aqueous emulsion which <$> contains about 10 to 50 wt. One or several animal described below monomers. About 0.05 to 2.0% by weight, based on the monomer mixture, of a water-soluble catalyst such as ammonium, sodium or potassium persulfate or hydrogen peroxide are added to the mixture

/"for the production

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or a Redoxsysterns, for example a mixture of a persulfate and an alkali metal bisulfite, thiosulfate or hydrosulfite, added, then approximately 0.5 to 8 hours to about 40 to 95 ⁰ C heated. The emulsion should also contain from about 0.2 to 2.0% by weight, based on the total monomer charge, of any known surfactant or surfactant mixture, resulting in elastomer particles of about 0.05 to 15, and preferably 0.1 lead to 0.8 microns. This class of surfactants includes the common soaps, the salts of long chain carboxylic acids and sulfonic acids, the alkylated aromatic sulfonic acids, and the salts of long chain amines.

It has also been found that, regardless of the particular emulsifier used, the polymerization is greatly simplified on an industrial scale if you change the monomer feed in the course of Introduce in about 3 equal servings for about 1 to 3 hours. If all of the monomer feed is added at once, so the resulting exothermic polymerization reaction is often actually uncontrollable, which leads to overheating, which in turn can cause coagulation of the resulting polymer latex. However, the monomer feed is subdivided and if it feeds in about 3 equal portions, the resulting polymerization reaction remains controllable; and overheating and fcoagulation can be prevented.

The for the production of the copolymer particles from elastomeric polyacrylic and PVC used polyacrylic elastomer particles consist of a polyacrylic copolymer with a glass transition temperature less than about 25 ° C. These acrylic polymers are made by free radical initiated emulsion polymerization at least one Cp-Cg alkyl aylate including n-butyl · = acrylate, 2-Äthylhexylaerylat and ethyl acrylate formed. Under the term "acrylic polymers" include copolymers from the

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The monomeric acrylates mentioned above and smaller proportions, for example up to about $ 25 to $ 30, of one or two vinyl monomers such as styrene, acrylonitrile, vinyl acetate, benzyl acrylate and methyl methacrylate, ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, Isoprene, chloroprene, ethylene and other common vinyl monomers. These polyacrylic elastomer particles are preferred networked so that they can be used during subsequent processing stages Maintain size and shape. This crosslinking can take place during the polymerization of the acrylic monomers by at least one polyethylenically unsaturated monomer is added to the polymerization batch. Under the name "networked" is understood to mean a polymer which at room temperature in organic »; Solvents such as tetrahydrofuran or cyclohexanone im is essentially insoluble.

The crosslinking is caused by the presence of small amounts, i.e. 0.05 to 10 $ (based on the weight of the acrylate monomers) of a polyethylenically unsaturated monomer, that is, a monomer with at least 2 ethylenically unsaturated monomers Groups such as allyl methacrylate, divinyl = benzene, diethylene glycol dimethacrylate, ethylene glycol dimeth = acrylate, trimethylolpropane trimethacrylate, methylene-bis-acryl = amide, diethylene glycol diacrylate, ethylene glycol diacrylate, Di = * vinyl ether, diallyl fumarate, diallyl phthalate, divinyl sulfone, Divinyl carbitol, triethylene glycol dimethacrylate, trimethylene = • glycol diacrylate, butylene glycol diacrylate, pentamethylene glycol diacrylate, Glyceryl triacrylate, octylene glycol diacrylate, tri = methylolpropane triacrylate, pentaarythritol tetraacrylate ester and various diallyl phosphonates. 1,3-Butylene glycol diacrylate is preferred for the present purpose.

The next stage in the preparation of the copolymer particles

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elastomeric polyacrylic and PVC consists in the suspension polymerization of a vinyl chloride-containing monomer charge in the presence of the aqueous emulsion of the elastomer particles, the preparation of which is described above. In addition to vinyl chloride, you can also use a monomer charge that contains a mixture of vinyl chloride and a smaller proportion of one or more additional vinyl monomers, for example vinyl esters such as vinyl acetate, vinyl phosphonates such as bis (ß-chlorine = ether _v l) vinyl phosphonate, vinylidene halides, olefins, Alkyl = vinyl ether and ethylenically unsaturated dicarboxylic acids, their anhydrides and C ..- Cg mono- and dialkyl esters. Preferably, vinyl chloride is used as the only monomer in this suspension polymerization.

The vinyl chloride, with or without a minor proportion of another vinyl comonomer, is preferably combined with a stabilizer and lubricant mixed. Bie ^ tight to stabilizer can from about 0.1 to 10/5 based on the weight of the vinyl chloride, and the amount of lubricant can range from about $ 0.1 to $ 10. Examples of suitable lubricants are Stearic acid and its barium, calcium and lead salts, waxes based on petroleum or paraffin, oils, low molecular weight polyethylene = oil waxes, stearic acid amides, montan wax, modified Montan wax, synthetic waxes and stearic acid esters such as glyceryl monostearate. Examples of suitable stabilizers are the phenyl salicylates, benzophenones, benzotriazoles, basic lead compounds such as dibasic lead phosphate, dibasic Lead stearate, lead sulphate, lead chlorosilicate and dibasic lead phthalate, organic tin compounds such as dibutyltin maleate, Dibutyltin dilaurate, di (n-octyl) tin maleate polymer, n-butyl = * stannic acid, thiol / lauric acid or its anhydride, dibutyltin lauryl mercaptide, Dibutyltin isooctylthioglycollate, dibutyltin mercaptopropionate and di (n-octyl) tin-S, S'bis (isoctylmercapto = acetate), the barium, cadmium, calcium or zinc salts orga-

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nic acids such as barium-2-ethylhexoate, barium-nonylphenate, Cadmium-2-ethylhexoate, zinc-2-ethylhexoate and the barium, cadmium, Calcium or zinc laurates and stearates, polyols such as pentaerythritol and sorbitol, nitrogen compounds such as melamine, Benzoguanamine and dicyandiamide, epoxy compounds such as epoxidized Soybean oil, epoxidized linseed oil, epoxidized tallow ester, and butyl and octyl epoxystearate, organic phosphites such as diphenyldecyl phosphite, phenyldidecyl phosphite and Tris-no = nylphenyl phosphite, as well as liquid phenolic compounds such as butylated hydroxytoluene and the like. Regarding · a For a more complete list of lubricants, stabilizers and other functional additives, refer to "Polyvinyl Chloride" by H. A. Sarv-etnick, Van Nostrand Reinhold Co., New York, N.Y. Referenced in 1969.

When carrying out the suspension polymerization, the vinyl chloride or the mixture of vinyl chloride and one or more comonomers is added to the previously prepared aqueous emulsion of the elastomer particles in a concentration of about up to 90% by weight, based on the elastomer particles. Furthermore, the aqueous emulsion of the elastomer particles must contain a suspending agent in a concentration of about 0.01 to 5 and preferably about 0.05 to 1 $, based on the total weight of vinyl chloride monomer or monomer mixture that was added to the aqueous emulsion of the elastomer particles, are added, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, talc, clay, polyvinyl alcohol, gelatin and the like being mentioned as suspending agents. Hydroxypropylmethyl = cellulose is preferred, which should preferably have a viscosity of at least about 3000 and preferably about 15000 cP (at 2O ⁰ C, 2 percent by weight aqueous solution of the polymer, measured in the Ubbelohde viscometer according to ASTM D-1347-64 and D- 2363—

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It has been found that the latter suspending agent gives an extremely clean reaction system. In particular, the use of hydroxypropylmethylcellulose with the above molecular weight corresponding to the formation of a Skin or a film of polymer on the reactor wall largely stopped, while other suspending agents often do so Skin formation takes place to a considerable extent. This skin creates serious problems as it is subject to any further use the reactor must be removed, otherwise a corresponding heat transfer is disturbed during the polymerization.

When using a hydroxypropylmethyl cellulose with above The properties described achieved'exerdem a satisfactory bulk density and satisfactory particle size distribution the resulting co-polymer parts consist of elastomeric materials Polyacrylic and PVC.

A monomer-soluble catalyst or initiator, for example azo-bis-isobutyronitrile, lauroyl peroxide, benzoyl peroxide or Isopropyl peroxydicarbonate, should also be obtained at a concentration of about 0.01 to 3, and preferably about 0.2 to 1 $ on the monomeric vinyl chloride or mixture of monomers added to the elastomer emulsion. Further it has been found that by adjusting the pH of the polymer latex to a value of about 3 to 9, its mechanical Stability is improved and a clean reaction is also achieved during the subsequent suspension polymerization. the The pH can be easily adjusted by adding the required amount of a basic solution to the emulsion, for example an aqueous sodium carbonate, sodium bicarbonate or sodium hydroxide solution.

The polymerization can then be initiated by heating the above batch to about 45 to 75 ^° C. and about 2

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holds at this temperature for up to 12 hours with agitation. That resulting product consists of an aqueous suspension of copolymer particles made of elastomeric polyacrylic / PVC, in which the supernatant liquid of the original rubber polymer emulsion is completely exhausted. The total solids content of these Suspension is about 20 to 50 wt. $. Each of the so obtained Polyacrylic / PVC copolymer particles actually contain an elastomer particle formed by emulsion polymerization with a vinyl chloride suspension polymer obtained by suspension polymerization was grafted onto the elastomer particle to form the crosslinked acrylic elastomer emulsion polymerization particle surrounds and / or is homogeneously dispersed therein. The extent to which this vinyl chloride suspension polymer the The mass of the crosslinked polyacrylic elastomer emulsion polymer particles surrounds and / or is dispersed therein, of course, depends of the monomers used in suspension polymerization and the polymer that is used in the crosslinked polyacrylel " stomer polymer fraction is present, from.

In these polyacrylic / PVC copolymer particles, the polyacrylic elastomer emulsion polymer can thus be present in a concentration of 2.0 to 80 wt of the polyacrylic / PVC copolymer particles. Preferred products should contain about 30 to 55 weight percent of a crosslinked polyacrylic elastomer emulsion polymer and about 55 to 70 weight percent vinyl chloride suspension polymer, the latter surrounding the bulk of the elastomer emulsion polymer and / or homogeneously dispersed therein .

The polyacrylic / PVC copolymer particles resulting from the process should expediently have a particle size of about 10

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up to 200 microns and can therefore be easily insulated for example by filtration on a Buchner filter or similar device, after which simply in the air is dried. Expensive and time consuming spray drying or coagulation processes involved in isolating the rubber polymer particles, from which the present polyacrylic / PVC copolymer particles are produced, on an industrial scale are usually required are thus superfluous here. The particles should also have a bulk density of at least about 0.2 and preferably about 0.3 to 0.4 g / cm (according to ASTM D-1895 determined).

The PVC / methacrylate interpolymer is an interpolymer made from polyvinyl chloride and a polymethacrylate-containing component composed of methyl methacrylate and optionally another Consists of acrylate. Under the designation "Methaerylat" and "polymethacrylate" in this context means both methyl methacrylate alone and also containing methyl methacrylate Copolymers understood.

The interpolymer is made in a preferred process by suspension polymerization of vinyl chloride among them Conditions that the polyvinyl chloride in a certain particle size range receives. For this purpose, a conventional, free-radical initiated suspension polymerization is also controlled Stirring speed and carried out in the presence of a certain concentration of a suspending agent, unreacted Removing vinyl chloride from the system after polymerization has occurred at least 60 $ gives the system a effective concentration of a chain transfer agent, a minor proportion, i.e. up to about $ 50 based on that Weight of total solids, one containing methyl acrylate (MMA) Methacrylate ester monomer feed and up to about

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25? ° of their weight of one or more optional comonomers as described below, and an initiator added, the polymerization continued until the added methyl methacrylate and at the same time any comonomers added in and / or on the particles of the previously polymerized PVC were polymerized, and the polymethacrylate-modified polyvinyl chloride interpolymer thus obtained was isolated. Apparently the monomer methacrylate added in this way, that is to say the methacrylate plus any comonomers, is different from the initially generated PolyvinylchloridyXeilchen absorbed and polymerized in and / or on these, so that a polymethacrylate-modified PVC resin is preserved.

According to the preferred embodiment of the method, the Methaerylate ester monomer, i.e. the MMA and any optional ones Monomers, based in the system at a concentration of about 20 to 100, and preferably from about 25 to 66 weight percent on the previously polymerized PVC. Thus about 10 to 60, and preferably about 20 to 40 wt of the resulting polymethacrylate-modified polyvinyl chloride product Contributed by shares from the monomeric methacrylate ester, i.e. the MMA and any comonomers, while the polyvinyl chloride is about 40 to 90 and preferably makes up about $ 60 to $ 80 of the total weight of this product. It is important that the methaerylate ester monomer used contain about 80 to 100% by weight of MMA, but may be smaller 'Component in addition to the MMA preferably up to about 20 wt. 56, based on the total weight of the methacrylate ester monomer, one or more optional monomers are present.

In other words, the polymethacrylate ester portion of the polymethacrylate modif icated polyvinyl chloride can be made from polymethyl methacrylate or preferably from copolymers of methyl meth =

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-AS "

acrylate and up to about 20% by weight of at least one ethylenically unsaturated, that is to say vinyl comonomer _; exist. As already mentioned, this polymethacrylate ester component, which preferably consists of a methyl methacrylate copolymer, is in the polyvinyl chloride particles overpolymerized by polymethacrylate in a concentration of about 10 to 60 and preferably 20 to 4-0 $, based on the polyvinyl chloride component of the interpolymer particles , before.

Suitable vinyl comonomers which can be used together with the methyl methacrylate to form the preferred polymethacrylate ester fraction of these particles are C ₂ -C alkyl methacrylates, 2.3, ethyl, n-propyl and isopropyl methacrylates, the glycidyl esters of Acrylic acid and methacrylic acid, for example glycidyl methacrylate and glycidyl acrylate, and preferably the C ^ -C ₁ p-alkyl acrylates with a straight-chain or branched alkyl radical, for example methyl, n-propyl, η-butyl, isobutyl, tert. Butyl, hexyl, 2-ethylhexyl, deeyl and dodecyl acrylate or mixtures of two or more of these optional monomers. Particularly preferred is a polymethacrylate-modified PVC interpolymer, the particles of which contain about 60 to 80% by weight of polyvinyl chloride and about 40 to 20% by weight of a copolymer of about 86 to 93% by weight of methyl methacrylate and 7 to 14% by weight of butyl acrylate contain.

The process for making the interpolymer consists in that you have the appropriate amount of methacrylate ester monomer from methyl methacrylate and optionally one or more optional Comonomers to an aqueous suspension of a previously polymerized polyvinyl chloride, in particular one polyvinyl chloride formed by suspension polymerization. The polyvinyl chloride can be any of the compounds contain lubricants and stabilizers mentioned with the polyacrylic / PVC component. When performing such a

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Suspension polymerisation for the production of polyvinyl chloride is the monomeric vinyl chloride or a mixture of vinyl chloride and a smaller proportion of a comonomer such as vinyl acetate or a lower alkyl acrylate, at about $ 0.01 to $ 5.0, based on the weight of the total monomer mixture, a suspending agent such as methyl cellulose, hydroxy « ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, talc, clay, polyvinyl alcohol, gelatin or the like mixed. It has been found that the particle size of the resulting PVC particles depends on the concentration of the suspending agent in the System is affected. It is therefore necessary to use a suspending agent concentration which is within that indicated above Moving boundaries. For example, if the upper limit is exceeded significantly, the resulting PVC particles are be below the required particle size range of about 5 to 150 microns. If the lower limit is reversed not observed, the resulting PVC particles will be too large.

Furthermore, a monomer-soluble, free radical should be in the system Catalyst or initiator such as 2,2'-azobis-isobutyronitrile, Lauroyl Peroxide, Benzoyl Peroxide or Iso * propyl peroxydicarbonate in a concentration of about 0.01 to 3 $ »based on the weight of the total monomer charge, can be used to polymerize PVC or vinyl chloride copolymers.

The polymerization of the subsequently added monomer Meth = Acrylate ester is by usual monomer-soluble, that is Oil-soluble, free radical initiators initiated. To the suitable catalysts include 2,2'-azo-i) isobutyronitrile, Lauroyl peroxide, benzoyl peroxide, t-butyl peroxypivalate and Iso = propyl peroxydicarbonate. The catalyst can either be premixed with the methacrylate prior to its addition to the from the

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DT-PA P 24 22 688.8 known warm PVC suspension medium, or both methaerylate and non-premixed catalyst can be added to the PVC suspension when the latter is cold, as described in CA-PS 9 ² Jl 085, whereupon heat is added to the suspension will. The former process with the addition of methaerylate plus initiator is preferred.

During the polymerization of methaerylate and optional Comonomers are used to chain transfer agents Properties to be controlled additionally, for example the flow properties the melt of the resulting methacrylate-modified PVC particles. The chain transfer agents can come from the following groups of substances:

(1) Chlorinated aliphatic hydrocarbons such as carbon tetrachloride, Chloroform, methylene chloride, butyl chloride, methyl = »chloroform, propylene chloride and trichlorethylene;

(2) Aromatic hydrocarbons such as toluene, xylene, mesitylene, Cumene, ethylbenzene, t-butylbenzene and chlorobenzene;

(3) aldehydes such as acetaldehyde, propionaldehyde, benzaldehyde and crotonaldehyde;

(4) Aliphatic and cyclic ketones such as methyl ethyl ketone, Acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone

(me t hylät hylke t on);

(5) Cyclic ethers such as dioxane and tetrahydrofuran;

(6) Alkyl esters of aliphatic carboxylic acids such as methyl isobutyrate and ethyl acetate;

(7) Aliphatic alcohols such as sec-butyl alcohol, n-butyl alcohol, Isobutyl alcohol and t-butyl alcohol;

(8) Aliphatic carboxylic acids such as acetic acid;

(9) Cyclic hydrocarbons such as methylcyclohexane, and especially preferred

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(10) Mono-, di- and polymercaptans including monomercaptans such as methyl mercaptan, ethyl mercaptan, propyl mereaptan, η and t-butyl mercaptan, η- and t-phenyl mercaptan, hexyl mercaptan; n- and t-heptyl mercaptan; n- and t-octyl mercaptan; n- and t-Dee ^ lr · -r cap "tan; n-dodecyl, i.e. lauryl, and t-dodecyl mercaptan; n- and t-i-detradecyl mercaptan; n- and t-hexadecyl mercaptan; n- and t-octadecyl mercaptan; n- and t-eicosyl mercaptan; n- and t-penta = cosyl mercaptan; n- and t-octacosyl mercaptan, n- and t-triconyl = mercaptan and mixtures thereof. Lauryl mercaptan is preferred among these monomercaptans »

Other useful monomer captans are thioacetic acid, 1-mercap = to-2-butanone, methyl mercaptoacetate, ethyl mercaptothioacetate; 1-mercapto-2-ethoxyethane; Diethyl-mercaptoethyl-phosphoro = trithioate; 2-mercaptoethyl acetamide; Dimethylaminomethylmercap = tan; Gysteamine; Mercaptomethylthiopropane, monomericaptocyclohexane; Benzyl mercaptan; Cysteine and mercaptoethanol.

Suitable dimercaptans are, for example, ethanedithiol, 2,3-Di = mercaptopropanol, decanedithiol-1,10 and the like.

Polymercaptans which are suitable as chain transfer agents and have more than 3 mercaptan groups per molecule are pentaerythritol tetra (7-kidneycaptoheptanoate), mercaptoacetic acid triglyceride, penta = erythritol tri (β-mercaptopropionate); Pentaerythrl-tetra (β-mer = captopropionate); Cellulose tri- (o (mercaptoacetate); 1,2,3-propanetrithiol; 1,2,3,4-neopentane tetrathiol; 1,2,3, 4,5,6-mercapto = poly (ethyleneoxy) - ethyl (sorbitol); 1,1,1-trimethylpropyn ~ tri (Q (mercaptoacetate); Dipentaer.ythritol-hexa (3-mercaptopropionate); 1,2,3-tris (Of -mercaptoacetypropane); Thiopentaerythritol-tetra (Of mercaptoacetate ); 1,6, 10-trimercaptocyclododecane, 1,2,3,4,5,6-hexamercaptocyclohexane; N, N ¹ , N ¹¹ N ¹ ' ^f- tetra- (2-mercaptoethyl) pyromellitamide; tri- (2 -mercaptoethyl) nitrilotriacetate; Penta = erythritol-tri (Of -mercaptoacetate); Pentaerythritol-tetra (O (-mercap =

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toacetate); Tri (p ~ mercaptomethylphenyl) methane; 2,2,7 »7-tetrakis- (mereaptomethyl) ~ 4,5-dimercaptooctane; 5.5 »5-tri (mercaptoethyl) phosphorotrithioate, Xylitol pentaiß-mercaptopropionate) and the like.

Examples of low molecular weight polymers with at least three Side-group mercapto groups per molecule are homo- polymers and copolymers of vinyl thiol, for example polyrinyl thiol. Other polymeric thiols such as glycerine / ethylene glycol polyether polymer mercaptan can also be used as chain transfer agents are used in the process according to the invention.

However, best results will be obtained when using low molecular weight Polymercaptans with 3 to 5 mercapto groups per molecule such as pentaerythritol tetrathioglycolate, pentaerythritol tetra- (3-mercap = topropionate); Trimethylolethane tri (3-mercaptopropionate); Xylitol penta (β-mercaptopropionate); Irimethylolethane-trithio " glyeolate, trimethylolpropane tri (3-mercaptopropionate) and tri methylolpropane trithioglycolate. Using the The latter polymercaptans are preferred because they are most effective in terms of the rate of polymerization that can be achieved are.

Those involved in the manufacture of the polyvinyl chloride / methacrylate interpolymer The amount of chain transfer agent to be used depends largely on the particular chain transfer agent chosen. In most cases, concentrations of about 0.025 to 7> $ 5 based on the total weight of the methacrylate ester monomer feed, that is, the total weight of MMA and any optional monomers present, applicable. In general Mercaptans and especially polymercaptans are more effective and they can therefore be used in concentrations corresponding to the The lower end of the specified range can be used while

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less effective chain transfer agents such as the aromatic hydrocarbons in concentrations accordingly the upper end of the range.

By using a chain transfer agent in the manufacture of the interpolymer particles to be used in accordance with the invention it is possible to more control the molecular weight higher than the maximum value of the range given below that part of the finished polymer product that consists of MMA and any comonomers that were introduced together with it, originates. This affects the molecular weight of the product as a whole. The PVC / methacrylate interpolymer should - preferably a molecular weight, given in values of the relative viscosity did a 1 percent strength by weight solution of the polymer in cyclohexanone at 25 ° C from about 1.50 to 2.80 and preferably about 2.30 to 2.60. It has been found that products with a relative viscosity within this range give the best properties. As is well known, the relative is calculated Viscosity according to the following equation:

Relative viscosity »T ₁

where T- is the time taken for a standard volume of the polymer solution to pass through an orifice of the viscometer and Tp that is necessary for the passage of a standard olumen of the solvent mean time taken by opening the viscometer.

The polymerization of the methacrylate ester monomer, i.e. clay MMA and any optional comonomer, takes place with heating of the system, i.e. the chain transfer agent, the previously prepared PVC polymer and the mixture of catalyst and MMA and optional comonomers, to a temperature of about 40 to 100 ⁰ C during one to complete

609809/0956

Polymerization of the MMA and any comonomers in and / or on the PVC particles sufficient time-r usually must no fresh suspending agent is introduced into the system, since a sufficient amount has already been obtained from the first polymerization of the polyvinyl chloride is present.

Catalyst, temperature, reaction time and the other operating conditions are of course chosen depending on each other; they can as with the polymerization of methyl = methacrylate be common. Further modifications of the polymerization technique are obvious to the person skilled in the art.

The process is particularly satisfactory when ea with polyvinyl chloride homo polymer as initially produced polymer performs. However, as already mentioned, conventional copolymers can also be used from vinyl chloride and smaller amounts of one or more ethylenically unsaturated, i.e. vinyl comonomers can be used provided the resulting vinyl chloride copolymers within the prescribed part size ranges and the prescribed ranges of the - Increase viscosity.

Examples of vinyl copolymers which can be copolymerized with vinyl chloride are Φ -olefins such as ethylene, propylene and butylene, carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl stearate, Cj-CpQ-alkyl esters of acrylic and methacrylic acid such as methyl methacrylate, methyl acrylate, ethyl acrylate , Butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate, aryl, halogen and nitro-substituted benzyl esters of acrylic and methacrylic acid such as benzyl acrylate and 2-chlorobenzyl acrylate, ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, ethylenically unsaturated dicarboxylic acids, their anhydrides ₂₀ ~ mono- and dialkyl esters such as aconitic acid,

603809/0958

Fumaric acid, maleic acid, itaconic acid, citraconic acid, maleic anhydride, Dibutyl fumarate and mono- and diethyl maleate, amides Ethylenically unsaturated carboxylic acids such as acrylamide and methacrylamide, vinylaryl compounds such as styrene and Oi-methyl = styrene, nitriles of ethylenically unsaturated carboxylic acids such as acrylonitrile and methacrylonitrile, vinyl pyrrolidones such as N-vinyl 2-pyrrolidone, Cj-C ^ Q-alkyl vinyl ethers such as methyl vinyl ether, Ethyl vinyl ether and stearyl vinyl ether, dienes such as isoprene and Butadiene and glycidyl esters of acrylic and methacrylic acids such as glyeidyl acrylate and glycidyl methacrylate and the like.

In this process, the polyvinyl chloride or vinyl chloride copolymer initially prepared by a suspension process until the reaction is at least 60 and preferably $ 80 or more has ended. Unreacted vinyl chloride must are then removed by relaxing the system before adding MMA and any comonomers and then polymerizing will. If this is neglected, the remaining monomer vinyl chloride undergoes an undesired copolymerization with the subsequent one added MMA, resulting in non-reproducible results and the formation of a soft, rubbery product leads, which often hardens before it can be removed from the reactor. The measure of sequential polymerization, that is, the polymerization of vinyl chloride first and then MMA, is an important stage in the process for the production of methaerylate-modified polyvinyl chloride, to be used in the polyblend.

The polymerization of the methacrylate ester, that is, of MMA and optionally one or more optional monomers, can be added in the same vessel directly after the end of the suspension polymerization of the vinyl chloride are carried out, or with previously prepared polyvinyl chloride, that is, vorgangsi

609809/0958

polymexized, then stored and only later to be carried out polyvinyl chloride used in this second process stage The polymerization of the monomeric methacrylate ester takes place in situ directly after the PVC polymerization system has been depressurized and removed made of unreacted monomer, the addition of a further catalyst may be superfluous.

A polyvinyl chloride produced by suspension polymerization should be provided as an optional polyvinyl chloride component of the polyblend. Processes for its production are known. In this context, the term "polyvinyl chloride" means polyvinyl chloride with up to about 25% of a compound known to polymerize with vinyl chloride, for example a vinyl ester, vinyl phosphonate, vinylidene halide, olefin or the like. The suspension polymerization is carried out by adding the monomer to about 0.01 to 5 and preferably about 0.05 to 1 $, based on the weight of the monomer, of a suspending agent such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carb = oxymethyl cellulose, talc, clay, Polyvinyl alcohol, gelatin or the like and about 0.01 to 3.0 and preferably about 0.2 to 1.0 $, based on the weight of the monomer, of a monomer-soluble catalyst such as azo-bis-isobutyronitrile, lauroyl peroxide, benzoyl peroxide or isopropyl peroxydicarbonate containing aqueous medium is added. The polymerization is initiated by heating the mixture to 45 to 75 ^° C. for about 2 to 12 hours. The optional PVC component can contain any of the lubricants or stabilizers described above.

As already mentioned, this can contain a rigid plastic Polyblend according to the present invention contain conventional inorganic or organometallic flame retardants, if you are aiming for a flame-retardant polyblend.

6098 0 9/0956

Antimony oxide, barium metaborate, zinc borate, magnesium borate, mixtures of antimony oxide and one of the borates and known metallocene flame retardants, for example ferrocene ( ^ü 2 ^H 5 ^ 2 Pe β The amount of flame retardant to be added to the polyblend should be up to about 10 wt. ^ In the additive mixture which is intended to be added to the rigid plastic, the amount should be up to about 20% by weight.

The polyblend according to the invention has good impact resistance, while maintaining the flexural properties, as on the flexural module evident. The processing properties of the rigid plastic s are surprisingly retained, despite the presence of the polyvinyl chloride containing additives, of which a less favorable heat stability would be expected. By adding substantial amounts of methacrylate elastomer to the polyblend instead of the conventional butadiene or butadiene copolymer additives the weather resistance of the resulting polyblend is improved.

In the following examples, parts are by weight, unless otherwise stated.

Example I.

About 1090 kg of distilled water, 1738 g of the bis (tridecyl) ester of sodium sulfosuccinic acid (Aerosol TR-70), 1250 g of potassium persulfate and 500 g of sodium bicarbonate are poured into a reactor with a capacity of 1895 l, which is equipped with means for moderate stirring . 10.12 kg of butylene glycol diacrylate and 500 kg of butyl acrylate are mixed and 91 kg of the mixture are introduced into the "reactor. This is then closed and ^{heated to 70 °} C. As soon as the exothermic reaction begins to subside, the remainder of the mixture becomes straight

609809 ^ 0956

pumped into the reactor so quickly that the exothermic reaction is maintained. After the end of the monomer addition, the temperature is ^{held at 70 °} C. for a further 30 minutes, then the reactor is allowed to cool to room temperature. The latex is poured into a template, it has a solids content of $ 31. Two further approaches were carried out in order to obtain the amount of latex required for the following suspension step.

A reactor with a capacity of 15,140 l is charged with 2950 kg of the above latex. 6.35 kg of methyl cellulose (Methocel HG 90 15000 cP) are dissolved in a portion of a water charge of 7203 kg and added to the reactor along with the remaining water. 2.27 kg of azo-isobutyronitrile (Vazo 64) are then added and the reactor is closed. "£ r is then evacuated to 38 to 51 cm Hg and this pressure is maintained for 15 minutes. The reactor pressure is then allowed to rise to normal pressure by adding gaseous monomeric vinyl chloride. The evacuation is repeated for 5 minutes, and a total of 2860 kg of monomeric vinyl chloride is added. with stirring, the mixture is heated to 6O ⁰ C and kept at this temperature has fallen until the reactor pressure by 2.67 kg / cm. at this time 2.49 kg of butylated Hy = droxytoluol added and the unreacted vinyl chloride monomer The mixture is allowed to cool to 30 ° C. and the product is isolated.

Example II

The components listed in the following table, with the exception of sodium bisulfite, are poured into a polymerization reactor:

€ 09309/0956

-26- Respondents 2524472 Parts by weight Butyl acrylate 100 "■ - '.. Butylene glycol diacrylate 2 least. water 730 Aerosol TR-7O (bis / iridecyl7-
esters of sodium sulfobers
stinic acid 32 Potassium persulfate 0.42 NaHCO ₃ 0.2 Peso 0.004

The reactor is evacuated to a pressure of 26 cm Hg and the vacuum is released with nitrogen. The evacuation and purging with nitrogen are repeated. The reactor is then ^{heated to 30 °} C. with stirring and the sodium bisulfite is added. The temperature is raised to 5O ⁰ C and maintained until the end of the polymerization at this value. The reactor is then cooled to 30 ° C. and opened, and 227 parts by weight of distilled water, 45 parts by weight of "Methocel 1242" as a suspending agent and 0.16 parts by weight of lauroyl peroxide are added. The reactor is then closed, a vacuum is applied for 10 minutes and 158 parts by weight of monomeric vinyl chloride are added. The reaction mixture is stirred and heated to 6O ⁰ C. The temperature is held at this value until the pressure in the reactor has decreased by 2.46 kg / cm. About 11 parts by weight of butylated hydroxy toluene are then added, unreacted vinyl chloride monomer is drained off and the reactor is cooled to room temperature, whereupon the granular resin is isolated.

Example III

About 0.089 part by weight of "Methocel 1242" (methyl cellulose suspending agent) are dissolved in one part of 248 parts by weight of water and together with the remaining water and 0.038

609809 / 09S8

Parts by weight of azo-bis-isobutyronitrile (Vazo 64 initiator) are introduced into the polymerization reactor. The reactor is cooled and evacuated and the vacuum is released with nitrogen. Then it is evacuated again and then 100! 'Rush monomeric vinyl chloride are added. The mixture is ^{heated to 71 °} C. with vigorous stirring and the temperature is maintained until the pressure has dropped by 1.41 kg / cm. Unreacted vinyl chloride monomer is vented and the reactor is cooled to 25 ⁰ G. Then 0.081 part of "Vazo 64" is added. About 0.005 parts by weight of lauryl mercaptan are dissolved in 29.6 parts by weight of methyl methacrylate and this mixture is added to the reactor along with 4.96 parts by weight of butyl acrylate. Pb * mixture is heated to 75 ⁰ G and held for 4 hours at this temperature and then cooled, is isolated after which the resin.

Example IV

The following table I shows three polyblends according to the invention which from a commercially available ABS plastic and according to the examples 1 to 3 manufactured components were formed. The table also shows the physical properties of these Mixtures:

609809/0356

Table I. component

ABS (Gycolac DH-10000) ⁺
Example I.
Example II
Example III

Tensile strength, yield point (kg / cm *)

Test procedure

Elongation, yield point
Tensile strength, break (kg / cm) elongation, break

Izod impact strength 3 »2 mm (m.kg/cm)

0.77

Impact tensile strength (m.kg/cm) 10.3

Tensile modulus (kg / cm ² x10 ~ ^) 0.079

Flexural modulus (kg / cm ^{2 x10 ~ 5} ) 0.206

_? DTL ⁽⁰ C, 6 4 mm - sample at

18.5 kg / cm fiber tension) 82.5

70

20 10

485 7

373 39

0.25

8.1

0.082

0.203 85.5

70

25 5

464 7

366 34

0.29 8.1 0.080 0.189

85.5

ASTM D-638 ASTM D-638 ASTM D-638 ASTM D-638

ASTM D-256 ASTM D-1822 ASTM D-638 ASTM D-790

ASTM D-648

Manuf. Borg-Warner Corp.

-29 «■■ - ■■■ -252U72

Example V

The procedure of Example III is repeated with the difference that that the following reagents are used for the first polymerization:

Reactant parts by weight vinyl chloride monomer 100

least. Water 257

Methocel 1242 0.093

"Vazo 64" initiator 0.022

The following reagents are used for the second polymerization worked:

Reactants methyl "Vazo 64" initiator lauryl mercaptan

Example VI

Several polyblends are produced using a commercially available ABS resin, the acrylic resin / PVC copolymer component according to Example I and the PVC / methacrylate interpolymer according to Example V. The mixtures and the results achieved with them can be seen from Table 2:

Weight Parts 36 , 9 0 , 11 0 , 05

9 80 9/0956

"ν ο to

! Table 2 422 70 2 28 3 , 04 4th 56 J ₅ , 57 6th , 58 7th 5 8th component 1 21 15th 70 27 50 , 61 90 065 90 , 097 90 , 076 70 , 5 70 $ ABS (Cyclolac DH-10Q0) 100 2, 13th 30th 29 50 , 18 9.5 070 9 , 14 8th , 12 28, 27 $> Example I. - O, - - 0.5 1 2 1, 3 $ Example V - O, 17th 499 92 415 , 95 555 66 570 , 58 443 , 45 513 506 Tensile strength b. Yield strength (kg / cm) 598 78 373 345 380 408 218 366 , 33 380 Tensile strength b. Breakage (kg / cm) 5, 50 17th 25th 38 56 37 , 10 52 Elongation at break ($) 2, 2 2, 2 2 2, , 17th 2.37 Flexural modulus (kg / cm χ 10) 0, 0 0, 0 0 0, 0.17 ^ Notched impact strength-Izod (m.kg/cm) 0, 0 0, 0 0 0, , 02 0.24 ' Notched impact strength-Charpy (m.kg/cm) 73 68 75 75 77 72 71 TVPT ( ^Ο ίΜ 4, 1 5, 7th 7th 9, 10.3D ' Impact tensile strength (m.kg/cm)

Continuation of table 2

Component 9 10 11 12 13 H 15

io ABS (Cyclolac DH-1000) ° / o Example I ⁰ Jo Example V

~, Tensile strength at yield point (kg / cm) 520

°? Tensile strength b. Breakage (kg / cm)

tß elongation at break ($)

ö flexural modulus (kg / cm χ 10 * " ⁴ ")

Notched impact strength-Izod (m.kg/cm) Notched impact strength-Oharpy (m.kg/cm) DTL ( ⁰ C) Impact tensile strength (m.kg/cm)

70 70 , 0 70 , 95 70 70 70 13th 60 I.
Previous year 24 21 , 12 18th , 081 15th 12th 9 049 47.5 T 6th 9 , 23 12th , 20 15th 18th 21 097 2.5 20th 541 , 5 548 555 570 562 5 422 80 394 , 48 401 , 59 408 408 408 63 84 56 49 59 52 41 65 57 2.46 2 1 2.05 2, 10 2, 2.08 0.15 0 0 0.065 0, 060 0, 0.78 0.20 0 0 0.16 O, 146 0, 0.26 73 72 72 70 72 73, 67.0 9.95 5 6th 6.59 6, 73 6, 6.92

Table 2 continued

Component 16 Π 38 19 20 21 22

i * ABS (Cyclolac DH-1000) $> Example I # Example V

(yes tensile strength at yield point (kg / cm)

% Tensile strength at break (kg / cm ² ) ^ elongation at break (#)

ο flexural modulus (kg / cm ² χ 1O * " ⁴ ) cn notched impact strength-Izod (m.kg/cm) notched impact strength-Charpy (m.kg/cm) DTL ( ⁰ G)

Impact tensile strength (m.kg/cm) 7.31 10.42 8.06 8.74 7.29 7.68 6.71

50 18th 50 29 50 ■ 50 , 93 50 97 50 , 07 50 45 70 40 65 35 30th , 18 25th 097 20th , 070 15th 5 59 10 68 15th 20th , 60 25th 40 30th , 16 35 570 5 471 5 492 520 534 5 548 , 5 562 394 309 373 387 401 408 408 28 45 58 68 94 96 31! 2, 2, 1 , 87 1 1, 2 2.08 O, 0, 0 , 37 0 0, 0 0.060 O, 0, 0 , 64 0 0, 0 0.15 68, 68, 67 , 2 ■ 69 68, 67 69

The above values show that with mixtures with constant Amount of ABS, but increasing amounts of product: according to Example -V compared to product according to Example I (see formulations 3 and 15 to 22 ($ 50 ABS) and formulations and 7 to 14 ($ 70 ABS)) the Izod impact strength in general decreases with increasing amount of product according to Example IV, but the Sehlagzerreißfätiigkeit increases to a maximum and then falls off. If the quantitative ratios of product according to Example V to product according to Example I are approximately 1: 3 to 4 »as observed one gets the best values of the impact tensile strength.

Example VIl

All the components listed in the following table are filled into a keactor with a capacity of 15,140 1, whereby the sodium bisulfite is added last:

Respondent crowd

Butyl acrylate 1130 kg

2-ethylhexyl acrylate 4860 kg

Butylene glycol diacrylate 31.8 kg

least. Water 6600 1

Aerosol TR-70 (Bis / tridecyl7 ~

ester ~ - the sodium sulphate

succinic acid) 5.44 kg

Aerosol MA (dihexyl ester of

Sodium sulfosuccinic acid) 4.76 kg

Potassium persulfate 10.2 kg

Sodium bisulfite 5.1 kg

Ferrous sulfate 40 g

Sodium bicarbonate 3.06 kg

⁺ Aerosol TR-70 and MA were dissolved in 946 liters of distilled water.

609809/0 9

-34-. 252U72

The reactor was evacuated twice and refilled with nitrogen each time. The stirrer was switched on and the reaction medium was heated to 45 ° C. and kept at this temperature until the end of the polymerization, that is to say about 3.5 hours. The reactor was then cooled to 29-5 ° O and, with stirring, 9.3 kg of Methacel HG 90, dissolved in 2575 l of deionized water, were added to the latex thus formed. The agitation was switched off and 1.25 kg of "Vazo 64" (initiator) were added. The reactor was then sealed and evacuated to 51 cm Hg for 10 minutes. The reaction mixture was placed under normal pressure with nitrogen and then evacuated again for 5 minutes. Were then fed into the reactor 1930 kg of monomeric vinyl chloride and the mixture was stirred and heated to 60 ⁰ C. The temperature was kept at 60 ^° C. until there was a pressure drop of 5.62 kg / cm in the reactor. About 2.72 kg of butylated hydroxytoluene was then added and the unreacted vinyl chloride was drained. The reactor was opened and then 6.7 kg of aluminum sulfate was added. After cooling, the product was isolated.

Example VIII

Two polyblends were produced which contain a commercially available ABS resin, the component according to Example VII, the component according to Example VII Example III and a commercially available PVC suspension resin (SCC-616, sold by Stauffer Chemical Co.). Flame retardants (SbpO-z) and zinc borate hydrate have also been used. Table 3 shows the composition of the polyblends, while Table 4 shows the physical properties are.

809/0956

Table 3

Component _I II

Yyy ⁺ White Star 101-1 / 4

⁺⁺ Humphrey 2B-112
⁺⁺⁺ du Pont ß-900

SECTION. (Oyclolac DH-1000) 52 2 1.5 48 Example VI 33 1.5 30th Example III 2 5 PVO (SCG-616) 8th 13th Sb ₂ O ⁺ 8th : ^; . Zinc borate hydrate ⁺⁺ - TiO ₂ ⁺⁺⁺ -

both non-flammable in the ASi ¹ M D-635 test procedure

PR-ABS

Table 4

j—-

mixed pellets not thermally treated (UNANNEALED)

I II

rorpelletisiert mixed pellets not therm. not therm. therm.be- treated therm.be- treated treated delt treated

(UNANNEALED) (ANNEALED) (UNANNEALED) (ANNEALED)

Tensile strength or stretch
border 485 464 464 485 478 492 © Tensile strength b.
fracture 323 366 366 401 373 394 a ©
CD
■ "** $> Elongation at stretch
border 6th 7th 7th 7th 7th ViJ
T. "Ι O
ς £ » io elongation b. fracture 21 34 32 28 41 30th cn Flexural module χ 10 0.16 0.144 ' 0.148 0.148 0.154 0, 1Ö? Izod impact strength
3.2 mm 0.14 0.32 0.35 0.27 0.44 0.35 Impact tensile strength 6.53 8.1 7.78 7.61 10.7 9.07 DTL 6.4 mm ( ⁰ C) 82.5 86 85.0 102.5 83.5 99.5.

Borg Warner Cyclolac KJB was used in the flame retardant ABS

NJ)

Claims (26)

Patent claims 1. Thermoplastic poly blend with improved impact strength, marked by (a) about 20 to 90 weight percent of a rigid plastic, (b) containing about 10 to 60 wt. ^ of a copolymer overpolymerized by a vinyl chloride suspension polymer Aerylat, (c) about 1 to 303 of an interpolating containing a through a methacrylate component overpolymerized polyvinyl chloride suspension polymer and (d) about 0 to 40 wt.> Polyvinyl chloride. 2. Polyblend according to claim 1, characterized in that The rigid plastic is an aeryl nitrile / butadiene / styrene resin, a styrene / acrylonitrile copolymer, an aerylate / styrene / aeryl nitrile resin »methacrylate / butadiene / styrene - March or styroJ / acrylonitrile copolymer, which is modified by ethylene / propylene / diene Modified rubber is _f contains. 3 «polyblend according to claim 1, characterized by about up to 70% by weight of the rigid plastic. 4 · polyblend according to claim 1, characterized in that the copolymer according to (b) about 13 to 45% by weight of the polyblend digs out 5. Polyblend according to claim I _9, characterized in that the interpolymer according to (c) makes up about 5 to 20 wt. 54 of the polyblend. 6 · polyblend according to claim 1, characterized in that the acrylate copolymer in the copolymer according to (b) with a «Very much as a monomer containing an ethylenic double bond is networked. 7-polyblend according to claim 6, characterized in »that the crosslinked acrylate has a glass transition temperature of less than about 25 ° C. 8 «polyblend according to claim 7 * characterized in that exn the acrylate in the copolymer at least C 1 -C 4 -alkyl acrylate UiBf ate * 9 «polyblend according to claim 1, characterized in that the vinyl chloride suspension polymer in the copolymer and in the Interpolymer according to components (b) and (c) and in component (d) of polyvinyl chloride or copolymers of vinyl chloride and a minor proportion of at least one further vinyl monomer. 10. Polyblend according to claim 1, characterized in that component (d) is about 15 to 25 wt. ^ Of the polyblend matters. 11. Polyblend according to claim 1, characterized in that the interpolymer according to (c) about 60 to 80 wt. ^ Polyvinyl chloride and about 40 to 20% by weight of the methacrylate component. 12. Polyblend according to claim 1, characterized in that the methacrylate component in (c) and methyl methacrylate Contains n ^ butyl acrylate. 13 · polyblend according to claim 12, characterized in that the methacrylate component about 86 to 95 wt.} 6 methyl meth = » 609809/0956 aerylat and about 7 to 14 percent by _e $ n ~ butyl acrylate. 14. Polyblend according to claim 1, characterized by approximately 0 up to $ 10 of a flame retardant substance ", 15 · Polyblend according to claim 14, characterized in that it contains antimony trioxide, barium metal as the flame-retardant substance. borate, zinc borate, magnesium borate, mixtures of borates or Contains metaborates with antimony trioxide or metallocenes. 16. Polyblend according to claim 1, characterized in that in the polyvinyl chloride about 0.1 to about 10 $ of a lubricant, based on the weight of the polyvinyl chloride. 17β polyblend according to claim 1, characterized in that There will be about 0.1-10 $ of a stabilizer in the polyvinyl chloride based on the weight of the polyvinyl chloride. 18. Multi-component mixture, which is used for mixing with a rigid plastic in order to improve the impact strength of this Plastic is indicated by (a) About 25 to 90% by weight of a copolymer containing an overpolymerized by a vinyl chloride suspension polymer Acrylate, (b) Containing about 10 to 75 percent by weight of an interpolating overpolymerized by a methacrylate component Polyvinyl chloride suspension polymer and (c) from about 0 to 35 percent by _e $ polyvinyl chloride. 19 · Multi-component mixture according to claim 18, characterized in that that the acrylate copolymer in the copolymer according to (a) with one containing more than one ethylenic double bond Monomer is crosslinked. 609809 ^ 0956 20. A multicomponent mixture as claimed in claim 19, characterized in that the crosslinked acrylate has a glass transition temperature of less than 25 ⁰ C. ~ - 21. Polyblend according to claim 20, characterized in that the acrylate in the copolymer is at least one Cp-Cg-alkyl acrylate having. 22. Multi-component mixture according to claim 18, characterized in that that the vinyl chloride suspension polymer in the copolymer according to (a), in the interpolymer according to (b) and in component (c) composed of polyvinyl chloride or copolymers of vinyl chloride and a minor proportion of at least one other vinyl monomer. 23 · Multi-component mixture according to claim 13, characterized in that shows that the interpolymer according to (b) about 60 to 80 wt. ^ polyvinyl chloride and about 40 to 20 wt. $ of the meth » contains acrylate component. 24. Multi-component mixture according to claim 18, characterized in that the methacrylate component in the interpolymer according to (b) contains methyl methacrylate and n-butyl acrylate. 25. Multi-component mixture according to claim 24, characterized in that that the acrylate mixture contains about 86 to 93 wt. ^ Methyl methacrylate and about 7 to 14 $ n-butyl acrylate. 26. Multi-component mixture according to claim 18, characterized in that that it also has about $ 0 to $ 20 of a flame retardant Contains substance. 27 · Multi-component mixture according to claim 26, characterized in that 609809/0958 252U72 is characterized by the fact that antimony trioxide, zinc borate, magnesium borate, barium metaborate, mixtures are used as a flame retardant substance the borates or metaborates and antimony trioxide or ferocene contains. 28ο Multi-component mixture according to claim 18, characterized in that ^P in the ^y vinyl chloride contains about 0.1 to 10 $ of a lubricant, based on the weight of the polyvinyl chloride. 29 · Multi-component mixture according to claim 18, characterized in that that in polyvinyl chloride about 0.1 to about 1096 a stabilizer, based on the weight of the polyvinyl chloride. For: Stauffer Chemical Company WestpoKt, / fconn., V.St.A. Dr. ». J. WoIff Lawyer 609809/0956