DE2014884A1 - Plastic compound based on a toughened vinyl aromatic polymer and process for its production - Google Patents

Description

Shell Internationale Research Maats0h.ap.pt3 N.V, Carel van Bylandtlaan 30, The Hague, Netherlands

concerning:

Plastic compound based on a toughened vinyl aromatic polymer and process for its production

The invention relates to plastics based on vinyl aromatic Polymers with improved toughness and impact resistance, e.g. toughened polystyrenes, as well as a process for the production of such plastic compounds and their use for the production of everyday objects, for example through deformation of fuel. Of the The term "vinyl aromatic" also includes the term "vinylidene aromatic".

It is known that the impact strength of polymeric vinyl-aromatic compounds, for example of polystyrene, can be improved by incorporating elastomer components into the polymer with the aid of processes such as, for example, polymerization of the vinyl-aromatic monomer in the presence of an elastomer, the proportion of which is usually 5 to 8 % of the monomer weight. The polymerization can be carried out in any way and leads to a plastic mass based on vinyl-aromatic polymers, in which the elastomeric component is present entirely or to a substantial extent as a gel, ie it forms an interpolymer or graft copolymer that is formed within the matrix vinyl-aromatic polymer forms a disperse phase.

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When i _{m the} following of "toughened compositions based on vinyl-aromatic polymers" or in the narrower sense of "toughened polystyrene" is mentioned, plastic compositions of this type are meant. It can be assumed that such interpolymers or graft copolymers are formed entirely or for the most part during the last stage of the polymerization; for the sake of simplicity, however, the term gel formation is used here simply, since the term “gel” is known to the person skilled in the art. Suitable elastomers for the production of toughened compositions based on vinyl aromatic polymers include natural and synthetic rubbers; Polybutadiene, acrylonitrile / butadiene / styrene and styrene / butadiene rubbers are particularly suitable. Any process in which at least the main part of the final polymer is produced using an interpolymerization technique in which gelation occurs can be used to produce the compositions mentioned.

It is also known that the flow properties of a polymeric vinyl aromatic compound can be improved if you add a small amount of one to the polymer Adding a lubricant such as a mineral oil or an ester-based lubricant such as butyl stearate; these However, improvement of the flow properties is at the expense of the softening point of the PoljTaer. The flow properties are of particular importance in the manufacture of small cross-section articles by injection molding, and it has been adopted previously indicated that the use of up to 6 to 7 wt .-% Lubricants represent the best compromise between improved flow properties and reduced softening point.

According to an earlier proposal (British patent application No. 46 5 ^ 4/67), the flow properties of a tough made mass on the basis of a toughened vinyl

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aromatic polymers improve when viewed as a lubricant additive at least 13% by weight of petroleum jelly (petroleum jelly) is given if incorporated together with a mineral oil, the mineral oil content not being more than 40% by weight of the petroleum jelly. If you produce thin-walled objects from such a plastic compound that are to be printed, it shows that the flow properties of the mass are improved without affecting the essential properties of the softening point and the printability required of such compositions are compromised. According to this application the petroleum jelly and the mineral oil that may be added to the toughened polymer mass can either be passed through, physically mixing the two ingredients or by introducing the lubricant additive during the polymerization of the vinyl aromatic monomer can be incorporated, for example by having monomeric styrene in the presence of a Polymerized elastomer component and lubricant additive; any particular difference in the physical The properties of the products were not ascribed to any of these methods.

In contrast to this view it has now been surprisingly found that by incorporating certain additives, such as lubricants, in amounts of at least 10% by weight in toughened plastics based on vinyl aromatic Polymers during the polymerization of the vinyl aromatic monomer in the presence of an elastomer plastics obtained, which have a much higher impact resistance than the products that are obtained by adding the additive merely physically mixed with a toughened mass based on vinyl aromatic polymers. Without this fact by any particular theory should be justified, it can be assumed that, if one ensures that the necessary additive in the polymerization mixture, is present before gel formation is complete

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and if the correct type of additive (described below) is chosen, the additive is preferred enters the dispersed phase and is retained there, so that there is an advantageous during gel formation can exert a modifying influence.

The inventive method for making a toughened one Plastic based on vinyl aromatic Polymers is characterized in that one has a vinyl aromatic Compound polymerized in the presence of an elastomer to form a polymer composition which is composed of an elastomeric disperse phase and a continuous phase in the form of a polymeric vinyl aromatic compound and contains at least 10% by weight of an additive which is an organic substance, preferably a hydrocarbon is of low volatility (as defined below), a particularly good compatibility for the disperse phase and is present in the polymerization mixture, before the gel formation in the mixture is complete, but this addition is not in 13 or more wt .-% Vaseline or in a lubricant made from Vaceline and up to 40% by weight should consist of a mineral oil.

By the term "an organic substance of low volatility" is meant a substance, preferably a hydrocarbon meant, their boiling point or boiling range (apart from low, practically meaningless low boiling fractions) is above 300 ° C. With an organic substance that is particularly well tolerated for the aforementioned Has disperse phase, of course, is a substance genoint, which is primarily in the disperse Phase distributed. Preferably at least 60, if possible at least 75% by weight of that used according to the invention should be Distribute additives so far in the disperse Phaco that these quantities enter the disperse phase and, as can be assumed, are retained by it. The distribution

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degree can be determined by using a reaction mixture * in which the degree of conversion for the vinyl aromatic monomer is 25 "to 30 % ; the distribution of the lubricant additive of the disperse phase and the continuous phase can then be determined by taking a sample of the Takes styrene monomer diluted prepolymer and introduces it to separate the phases in a 100 ml measuring cylinder, which is optionally kept at a slightly elevated temperature (for example 40 to 60 ⁰ C) to ensure that the solubility of the lubricant in the styrene monomer is maintained .wird After standing for a short time, a sharp interface will form between the two phases and one can then estimate the percentage of lubricant that is present in the disperse phase.

The hydrocarbon additives that are used according to the invention can find single compounds or mixtures be of different types of hydrocarbons, however, hydrocarbon polymers or hydrocarbon Geraische which contain such polymers can be used. Those paraffinic hydrocarbons can also be used as additives serve as lubricants for polymeric vinyl aromatic Compounds are known or suitable; many such hydrocarbons are common lubricants for these compounds, which means that they are from the literature are known to be suitable or already used in the art for this purpose.

According to a further aspect of the invention, contains a toughened plastic based on vinyl aromatic Polymers, as described above, at least 10, preferably at least 13 wt .-%, of an additive dispersed represents an organic substance of low volatility (as defined above) and particularly good compatibility for the disperse phase of the plastic aufx ^ eist, where

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the main part of the additive is located within the disperse phase, with the restriction that the Addition should not be 13 or more wt .- # of petroleum jelly or a lubricant made of petroleum jelly and up to 40 wt .- # of mineral oil.

The invention also encompasses a method of making Objects, especially thin-walled objects, such as thin-walled containers, which consists in the fact that the relevant Articles by injection molding from a toughened plastic obtained according to the invention on the basis made of vinyl aromatic polymers.

Since the incorporation (either by physical mixing or by interpolymerization) of at least 13% by weight of a lubricant made from petroleum jelly or petroleum jelly along with $ 40) mineral oil in a toughened plastic based on vinyl aromatic polymers in British patent application 46 544 / 67 is described and claimed, the use of this lubricant in the specified amount in the preparation of the originally toughened composition is not covered by the present application. However, it is 10 to 13 wt .- ^ Vaseline or 10 to 13 wt .- ^ a mixture of vaseline and up to 40 wt -% of a mineral oil are used, and in general, the upper limit for this and others in carrying out the. Additives used in the method according to the invention are determined by the fact that no toughened plastic compound may form in which an oil phase is deposited in addition to the continuous (polymer) phase and the disperse (elastomer) phase. Generally speaking, the effectiveness of the additive as an agent promoting the utilization of the rubber content is greater and the problem of phase separation is lower, the better the additive is compatible with the dispersed phase. Consequently, any other

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re substances, preferably those hydrocarbons used as lubricants in polymeric vinyl aromatic compositions such as polystyrene, for purposes of the invention. Normally hydrocarbon polymers with low molecular weight, for example polybutenes and polypropylenes "and components are the oil and Waehsfraktionen of oil suitable. Examples of such lubricants which are suitable according to the invention as additives are. Especially good as mineral and paraffin wax results were followed by _r the additions Achieved: white oil of a type such as "Eisella" oil ^; 33 ("Eisella" is a registered trade mark) or Lobitos WAI white oil; another combination mentioned here is Amopol C-60 and Lobitos WAI oil. Amopol C-60 is a low molecular weight polypropylene (average 800). ''. ■. ■

Even so, it has been known that increasing the amount of lubricant within the conventional range of 6 to % By weight often leads to an increase in the toughness of a polymer vinyl aromatic compound has not existed so far Incentive to increase the amount of ßclimiermittel * as this affects would affect the softening point of the polymer and also because of the extrusion problems with a higher content of Sehmiermittel would occur. The possibility of improvement toughness can be achieved by having concentration Choosing the lubricant higher than usual has only been the case until now of academic interest. Has a defining characteristic The present invention consists in the surprising finding that, when using the correct lubricants in higher proportions, i.e. in amounts of more than 10 % By weight, the type of incorporation of the lubricant additive is decisive for the properties of the polymer end product. When incorporating the "lubricants" in the usual proportions (e.g. 6%), the one used for incorporation was used Method generally viewed as merely a matter of practice, of little if any

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Influence on the physical properties of the final obtained polymer - an opinion which has been established by the research work of the applicant within this additional area could be confirmed *) .. However, if the lubricant additive is increased to 10% by weight and more and in particular to Increased 13 wt .-% and more of the polymer composition, it was surprisingly found that the type of incorporation of the lubricant is of great importance for the physical properties, especially for the impact resistance of the End polymers and that products with extraordinarily high impact resistance can be obtained by using one of these additives described, e.g. a hydrocarbon-based lubricant, at the correct stage during the polymerization the vinyl aromatic compound incorporated.

As noted above, the so-called "interpolymerization" process for the manufacture of toughened polymeric vinyl aromatic plastics involves the formation of chemical bonds between the vinyl aromatic chains and the dispersed elastomer phase in the final stages of the polymerization. Since, as far as it was ascertained, the additives according to the invention bring about a desirable modification of this process, the additive must be incorporated into the reaction mixture at the correct stage of the polymerization process. For example, it can be added to the monomer and elastomer storage solution, or to the prepolymerizer, or even the final polymerization reactor, provided that the addition is made before golf formation is complete; and preferably before any noticeable gel formation occurs. However, the lubricant additive is often not completely soluble in the monomer solution to be fed in at ambient temperature and difficulties arise when it comes to maintaining a corresponding homogeneity in the storage vessels. If necessary, the supply knows L-ur at a slightly increased tempo. around 40 to 60 ⁰ CjEe-

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im make sure the lubricant additive completely resolved "remains. Instead, the either of the other two possibilities can be used, whether the lubricant additive to the prepolymerizer or to the Reaction gel during its transfer from the prepolymerizer in the actual reactor is generally preferred, as it is sometimes difficult to add the To mix the reaction mixture intimately when it is only added in the actual polymerization reactor itself.

In the manufacture of toughened plastics on the It is the main one based on vinyl aromatic polymers Puncturing the elastomer component to increase the impact resistance of the vinyl aromatic polymer; However, since the elastomer is generally one of the most expensive raw materials of the procedure, it naturally appears to be desirable to achieve a certain predetermined shock resistance with as little elastomer as possible. To make comparisons in this insight To enable between products with different elastomer content, the term "Kautschiikausnützung" ("rubber utilization "). This expression denotes the quotient that is obtained when the impact resistance is divides the rubber content (i.e. the elastomer content) and therefore, the higher the rubber utilization, the lower is the need for rubber to achieve a given impact resistance value. Those in those manufactured as above toughened plastics based on vinyl aromatic High values for impact resistance are found to be achieved with only conventional polymers Kengen (i.e. at 5 to 8% by weight) of rubber, from which It is clear that these masses have a higher rubber utilization have than the usual substances; quantitative comparisons on this point are given in the examples. It is a particularly 'valuable consequence dor in the inventive Higher rubber content observed in plastics

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Use that a certain value for the impact strength, as it is required for a specific product , can be achieved with smaller amounts of rubber than with the usual materials with the same impact strength. This effect can of course be used in the polymerization of the vinyl aromatic compound by the process according to the invention to use a significantly smaller amount of elastomer (for example 2 to 4% by weight) than in the known processes.

Although the reasons for the surprisingly high rubber utilization are not exactly known in the method according to the invention, it should be mentioned that the research work of the applicants have led the view that the additive, which participates in the reaction in favor of the disperse phase, acts as a crosslinking inhibitor in the stage of gel formation. This is also evident from the much higher source indices of the toughened plastics according to the invention based on vinyl aromatic polymers in comparison with similar ones Plastics with the same original rubber content, in their production under otherwise identical conditions of the Additive was omitted or manufactured under the same conditions, but only with the usual amounts of lubricant became. The type and amount of the additive used according to the invention therefore appear to be conditions in the disperse phase to create, which favor the gel formation, but are unfavorable for the coupling together during the gel formation vinyl aromatic polymers formed on the rubber molecules side chains; the result is then that the disperse phase shows a more elastomeric lead and can therefore better absorb shock and impact loads.

The mentioned "swell index" is determined by adding a known weight of polymer plastic at 25 ° C with Treated toluene until completely dispersed, centrifuged the dispersion and the clear supernatant liquid - - 11-

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deducted, after which the residue with a cold air stream, blown to remove the solvent retained on the surface to remove, and this residue then weighs * The source index is then calculated as the ratio of the final weight (i.e. weight of the plastic swollen in the toluene) Starting weight (i.e. dry weight).

It has also been found (and is also a feature of the invention) that the high rubber utilization of the toughened plastics according to the invention based on vinyl aromatic polymers are also maintained remains if the products are made with a non-toughened poly-

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mers or copolymers of a vinyl aromatic compound be mixed or blended. That means that the in the case of the plastics according to the invention with the usual Rubber etching achieved particularly high impact resistance can be reduced to a conventional value, if you the products according to the invention with a corresponding Amount of non-toughened polymer (e.g. crystalline

■ - "1 ■ ■ - ■

■ Polystyrene) -, "diluted". '

In accordance with the invention, a method is therefore also provided for the production of a toughened plastic on the Basis of vinyl aromatic polymers, which are stands that you have a vinyl aromatic "compound in the presence of an elastomer polymerized to a polymer plastic, which in addition to an elastomeric disperse phase and a polymeric vinyl aromatic compound as a continuous Phase contains at least 10 wt .-% of an additive that has a organic substance, preferably a hydrocarbon of low volatility (as explained above) and is particularly compatible with that in the polymerization mixture disperse phase present before completion of gel formation, with the restriction that the addition is not 13% by weight -yo or more is petroleum jelly or a lubricant that is a

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a mixture of petroleum jelly and up to 40% by weight mineral oil. The special feature of this process variant is that the tough polymer obtained as above with a Polymer or copolymer of a vinyl aromatic compound mixed, the latter in the absence of an elastomer and was usually also prepared in the absence of the additive mentioned, although during the formation of the polymer or Copolymers can also be a lubricant present. The crystalline used as above for mixing or blending Polystyrene can itself be a lubricant, e.g. up to 15 Contain% by weight Vaseline if a toughened plastic with a high lubricant content is to be produced, which e.g. suitable for shaping very thin-walled objects in a rapid shaping cycle.

As plastic mixtures based on vinyl-aromatic polymers, especially styrene polymers \ suitable -copolymerisate ind, for example copolymers of styrene with acrylonitrile or acrylonitrile, styrene and butadiene (ABS). Accordingly, when the invention is further described with particular reference to toughened polystyrene plastics and their production, it is to be understood that the invention can also be used for the production of polymers and copolymers of other vinyl aromatic monomers.

As already noted, are suitable as elastomer components for incorporation into the toughened polystyrene besides Synthetic rubbers are also natural, but the synthetic rubbers such as polybutadiene, acrylonitrile / butadiene / styrene and styrene / butadiene preferred. Possibly For example, these rubbers can be used in the oil-extended form provided that the extending oil contains a represents a suitable additive for the purposes of the invention. This has been heretofore used in the manufacture of toughened polystyrene not considered feasible. Preferably, however, '

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the necessary additive is added as a separate component, ^% The amount of elastomer incorporated into the styrene is normally 5 to 12% by weight of monomer and is, for example, in the usual range of 5 "to 8% by weight, although higher amounts (up to 15%) can be used when it comes to the manufacture of specialty products or in connection with extensive "dilution" of the product with non-toughened polystyrene Polystyrenes can be added, is largely determined by the impact resistance that the end product is supposed to have and by the rubber content of the toughened polystyrene ^ Y / a toughened polystyrene, for example, is made by polymerizing styrene in the presence of 6% rubber and 15 % one Lubricant additive, it was found that a product with acceptable impact resistance combined with a conventional lubricant ff content can be obtained if such a toughened polystyrene is blended with the same amount of crystalline polystyrene. If larger amounts of rubber are incorporated into the toughened polystyrene, a higher ratio of crystalline to toughened polystyrene can be used when blending; so it is at Kautschukan ^r beilen 10 to 15 wt .-%, for example, often possible to produce useful products by reacting to verschneidet the toughened polystyrene to 4 times its weight of crystal polystyrene. · A further advantage of blending- with crystalline polystyrene is that one can influence the properties of the final product by careful selection of the crystalline poly used for blending. styrene. - €> £ ν ~~ is · - & s— -ρβ ^ & β ^ ι Often, for example, a crystalline polystyrene with a molecular weight can be produced without further ado, which, although desirable, is not readily achievable in the production of tough polystyrene, is; the polystyrene matrix of the cut end product can then be modified by using the

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like polystyrenes as a blending component. In addition, it is frequently found in the addition of such crystalline polystyrene that a modification of the polystyrene increases the impact resistance of the final product, with the result that the blending with crystallized polystyrene virtually increases the overall utilization of the rubber.

The polymer compositions according to the invention, regardless of whether they are the above mixtures with crystalline polystyrene or not, can optionally contain further additives beyond those according to the invention, for example dyes, antioxidants for rubber and antistatic additives, such as those known to the person skilled in the art. For example, the polymer plastics can contain up to 2%, preferably 1 to 1.5% by weight of an alkanolamide, such as lauric acid diethanolamide, as an antistatic agent; additionally or instead of this, a phenolic rubber antioxidant may be present, which has expediently been added during the last part of the polymerization.

For the practical implementation of the traversed invention for preparing toughened polystyrene from styrene monomer, rubber and the Kautschukausnütsung enhancing additive is to say the following: The method may be performed in any system is w carry overall in the care that first of all a dispersion from rubber to styrene monomer up to a monomer conversion of 25 to 35 % can be prepolymerized with stirring and that this prepolymer is then polymerized to a degree of conversion of 96 to 97 % essentially without stirring. The remaining, unreacted monomer is then separated from the resulting product and the product is converted into particles which are then made available to the plastics molding industry; These two measures are expediently carried out in a devolatization extruder, with further additives, for example antistatic

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corner means that can be added. The method is advantageous carried out continuously, a solution of rubber in styrene monomer with a stirrer · and Jacketed vessel is added in which the prepolymerization is carried out and in which the .Dwell time and the temperature can be controlled so that one desired, predetermined degree of conversion of the monomer obtained. The reaction mixture is continuously withdrawn from this vessel and introduced into a tower from above, in which the final polymerization takes place. The one fed to the tower The reaction mixture moves downwards therein, the conditions being chosen so that the mixture is as possible Remaining close to the pour point and taking into account the temperature profile and the speed of movement of the contents of the tower controls so that in it, usually in the lower part of the Tower, a gel formation takes place in which the reaction mixture reaches the final stage of polymerization represented by a conversion of 80 to 96% and gel formation or at least the majority thereof occurring. The addition necessary according to the invention can be in the supplied. Mixture of rubber and monomer may be present or it can be introduced into the prepolymerization vessel or with the mixture resulting from the intermediate reaction be mixed before the latter is fed to the tower. An immediate introduction of the addition to the tower is preferably avoided, since there is no possibility of adding the additive by stirring accordingly in.dem viscous Distribute reaction mixture. If, on the other hand, the tower has a contains upper boiling zone, in which the conditions for a effective distribution of the additive can exist possibly also be given up in the tower. Be it pointed out that the method according to the invention is in no way restricted in its implementation to the use a polymerization system of the type just described. Rather, any system can be used in which a toughened plastic based on a

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vinyl aromatic polymers, preferably by polymerization in bulk, provided that means are provided by which the necessary addition can be made Can disperse completion of gel formation. In principle, any polymerization technique can be used, but is bulk polymerization under the action of heat is preferred. If necessary, however, "can also be catalytically promoted bulk polymerization was applied and also the use of an inert solvent for convenience the heat dissipation during the first stages of polymerization, in which most exothermic heat occurs is not excluded. Other changes to the system described above can also be made; for example, the prepolymerization can be effected in two vessels connected in series, or between the prepolymerizer and the tower another one with a stirrer Switch on the provided vessel as "intermediate polymerizer"; the prepolymer can also be partially polymerized Styrene (i.e. with a solution of polystyrene in styrene) must be mixed before it is fed into the tower.

The mixing or blending of the toughened plastic mixture based on vinyl aromatic polymers with other vinyl aromatic polymers, e.g. crystallized Polystyrene according to the above-described particular embodiment of the process according to the invention can be applied to any V / can be done. Mixing is preferably carried out while the toughened polymer is still in the form of a Schi ·, el ze is present, which has accrued in the mass from the polymerization, in which case the non-toughened polymer before adding it softens in the heat. However, you can also mix the ingredients in the cave or they in the solid state to an extruder in which they softened by heating and mixed thoroughly; also common mixers, for example a Bu3s ~ co-

Kneader'l can be used.

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The toughened polymers according to the invention with improved impact strength can be used for many purposes, for which toughened polymers are already being used, but also for other purposes for which the impact strength of the previously known plastics on the basis of tough made vinyl aromatic polymers was not sufficient ".

The same applies to the toughened polymers according to the above embodiment were still blended, but these mixtures are particularly suitable for production of thin-walled objects that have a corresponding breaking strength and effective antistatic behavior should have.

The examples serve to explain the invention in more detail. Example 1_

A mixture of monomeric styrene "Gariflex" S-1006 styrene / butadiene-ko-uchuk (the word "Cariflex" is a registered trade mark) and a lubricant additive was poured into the bottom center of a cylindrical glass reactor vessel at 130-160 ml / h abandoned with a round bottom and a working volume of 1000 ml, the latter being stirred by a uniaxial twin turbine stirrer - in which each turbine had six plates and which rotated at 3 ^ 0 rpm. The temperature of the reactor was kept at 114 to 118 ° C. and a prepolymer was withdrawn from a side arm in the vicinity of the upper end of the reactor in such a way that an average residence time for the reaction mixture of 7 to 8 1/2 h and a degree of conversion for the polymer of 21 to 2 '}% resulted. At this continuous, uniform Vorpolyi; icrisation a 22-hour polymerization joined at 180 G ⁰ in the storage vessel to 'to obtain the finished product!.

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The polymerization process was carried out according to the invention with a charge made up of 79-3% by weight of styrene, 6.9% by weight of S-1006 SBR and 13.8% by weight of Lobitos WAI white oil as a lubricant additive duration. A product named "A" was obtained, the properties of which are shown in Table I, which also contains, for comparison purposes, the properties of Products ¹¹ B "and" G ";Product" B "was obtained from a mixture which contained only 3.8% by weight .-% of the lubricant mentioned, while the product "C" was obtained by physically mixing a commercially available SBR toughened polystyrene with a content of 3.8 % Lobitos WAI white oil, the W also 11.5% by weight petroleum jelly (Shell) The mixing was carried out in a Banburry mixer, and the resulting mixture was particulate by extrusion molding and cutting the strands into small pieces.

TABLE I:

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Per-

Composition of the batch Izod impact

strength (mkg / 1 inch notch)

T A BE L LE I.

chaften Zugeigens

Gel content

Parts by weight

Weight ·· * - %

O ⁰ C

speed
(kg /

tion

Swelling rubber index utilization

rubber

00 ■ C-lsi

Styrene

S-1006F

VAI oil

Styrene

S-1006F

WAI-Ö.1

Styrene
S-1006?
V / Al oil
SVPJ

92

.8th

16

92 8

4 ·

92 8 4

12th

79

6.9 13.8

88.5 7.7

3.8

79.3 6.9

■ 10.4

Physically. Mixture made of tough. styrene + 11.5 % SWPJ

0.29 0.32 91 98

0.23 0.22 169 162

0.1? 118 104

70

42

77

18.0 13.5

18.0

9.3

13.8 11.7

33.5

20.5

17.5

• Yield stress see ASTM, E6

*. ·, Ultimate stress see ASTM, D638

ro

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- 20 Example 2

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The polymer produced according to Example 1 and designated "A" was intimately mixed in various proportions of two grades of crystalline polystyrene which have the trade names "Carinex" SB 61 and "Carinex" HEM; the properties of the various blends are shown in Table II.

TABLE II:

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TAElLE

II

Additional information on the batch

Izod impact strength (mkg / 1 inch notch)

Tensile properties

23 ⁰ 0 ° C flow, tensile strength at break. capacity (kg / cm ² ) (kg / cm ² ) (kg / cm ² )

Styrene 79.3% by weight)

. S3R S-1006F 6.9% by weight)

VAI-Ol 13.8% by weight)

= X

98

70

Rubber utilization Izod "at 23 ⁰ C x 10 ² /% rubber

33.5

X
SB61

Geiaischbestand parts

Genisch- styrene

SBE 3-1006? WAI oil

ZUS--

■ sir.

Parts by weight

75 25

84.5

5.18 10.32,

121

113

64

Mixture inventory
share ' '

Mixed styrene
additional - SBR S-1006F set zg. WAI oil

50 50

Wt% 89.65 3.45 6.90

179

157

43

32

Mixture- X
stock- SB61
share

ro
ro

Mixture-

add.

setzg.

"Styrene
SBR S-1006F WAI oil

Parts by weight

25 0.10

75% by weight

94.83 1.72

277

221

13th

43.5

Ports. TABLE II:

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OO 9 8 Λ 2/1805 BAD ORIGINAL

Claims (1)

Claims 1. Toughened plastic compound on the basis of a vinyl aromatic polymer containing an elastomer, characterized in that therein additionally at least 10% by weight of an organic substance of low volatility and particular compatibility with the disperse phase of the mass are dispersed, with the main part of the additive is located within the disperse phase, with the limiting provision that the additive not 13 or more percent by weight of petroleum jelly or a lubricant made of petroleum jelly and up to $ 40 the weight of petroleum jelly in mineral oil. 2. Plastic compound according to claim 1, characterized in that the additive is a hydrocarbon or is a mixture of several hydrocarbons. 3. Plastic compound according to claim 1 or 2, characterized in that the additive is a substance which is customary as a lubricant in plastic and is based on vinyl aromatic polymers. 4 | 4 · Plastic compound according to claim 3 »characterized in that the lubricant is a polymer of a Is a low molecular weight hydrocarbon. 5. Plastic compound according to claim 3, characterized in that g e ken n is characterized that the lubricant is part of the lubricating oil or wax fraction of petroleum - 2 4, -009842 / 1805 6. Plastic compound according to claim 2, characterized in that the additive is a white oil on hydrocarbon basis is. 7. Plastic compound according to claim 2, characterized in that the additive is a mixture of petroleum jelly with more than 40 # of the weight of petroleum jelly in mineral oil. 8. Plastic compound according to one of claims 1 to 7, characterized in that they.weniger than 13 wt .- ^ Addition contains. 9 · Plastic compound according to one of claims 1 to 8 in P form of toughened polystyrene. 10. A process for producing a plastic mass on the basis of a toughened vinyl-aromatic polymer, ζ labeled in characterized eichn.et by polymerizing a vinyl-aromatic compound in the presence of an elastomer to a plastic mass, the disperse of an elastomeric phase and the polymeric vinyl-aromatic compound exists as a continuous phase and to which at least 10 Ge \ i.-fo of an organic substance of low volatility are added, which has a special compatibility with the disperse phase and in the polymerization fc mixture is present before gel formation is complete is, with the limiting provision that as an additive neither 13 or more wt .-% petroleum aceline nor 13 or more wt .- $ of a lubricant from petroleum vaBeline and up to 40 wt .- ^ Mineral oil can be used. 11. The method according to claim 10, characterized in that the additive is a hydrocarbon or is a mixture of several hydrocarbons. 009842/1805 12. The method according to claim 10 or 11, characterized ge - ke η η ζ eic h η et that the additive is a substance common as a lubricant additive in plastics based on vinyl aromatic polymers. 1-3. A method according to claim 12, characterized Eke g η η - η ζ ei ch et that the lubricant is a polymer of a hydrocarbon of low molecular weight. Η. Method according to claim 12, characterized in that the lubricant is a constituent of the lubricating oil or wax fraction of petroleum. 15 · The method of claim 11, characterized geke ηη - ζ η et verifiable that the additive is a white oil hydrocarbon base. ' 16. The method according to claim 11, characterized in that g e k e η η - ζ e i e h e t that the additive is composed of a petroleum vaseline with more than 40% by weight, based on the petroleum jelly, of mineral oil represents. .. "'" 17. The method according to any one of the preceding claims, characterized / geke η η ζ. calibration et η, that the addition in an amount of less than 13 percent is present. -fo. . 18. The method according to any one of the preceding claims, characterized geke η η I show η etj that the polymerization as. Polymerization in the mass carried out in at least two successive stages, namely a prepolymerization stage which takes place with stirring, in which the conversion of the vinylaromatic monomer reaches 25 to 35 ° / <> , and a final polymerization stage to be carried out without substantial movement of the mass, in which the Conversion of the YinylaromatxBchen monomer reached at least 90 ^, and that the additive is present in the polymerization mixture fed to the final stage. . ■ '... ". _ ■> ■ .... -. - ■ ".-..:. -: ■ .- 26 -Ö09842 / 1805 ■ '" "■. 19. Process according to Claim 18, characterized in that the additive is mixed with the polymerization mixture in the prepolymerization stage. 20. The method according to claim 18 or 19, characterized in that a phenolic antioxidant for the elastomer is added to the polymerization mixture when it enters the final stage or within this final stage. 21. The method according to any one of the preceding claims, characterized in that the proportion of elastomer in the presence of which the polymerization of the vinyl-aromatic monomer is started is between 5 and 12 $ of the monomer weight. 22. The method according to any one of the preceding claims, characterized in that the vinyl aromatic The monomer is styrene. 23 · Modification of the method according to one of the claims 10 to 15 for the production of a plastic mixture on the Basis of a toughened vinyl aromatic polymer, thereby it indicates that you can use a vinyl aromatic compound in the presence of an elastomer to form a plastic compound polymerized, consisting of an elastomeric disperse phase and a polymeric vinyl-aromatic compound as a continuous Phase consists and at least 10 wt .-? S of an organic Contains substance of low volatility as an additive, which is particularly compatible with the disperse phase and in the polymerization tank. is included before in it the gelation is complete, whereupon the resulting Polymerization product with a vinyl aromatic Polymer or copolymer mixed, with the restrictive provision that neither 13 or more Gow .- # petroleum-petroleum jelly as an additive 13 or more percent by weight of a lubricant Petroleum jelly and up to 40 wt .- $ mineral oil can be used. - 27 Ö09842 / 1805 24. The method according to claim 23, characterized geke η η ze i ο h η et that the addition between 10 and 13 Ge: iür.i- # a white petroleum jelly or a white petroleum jelly> e ^ - ^; ^^ with up to 40 # of their weight in white oil. 25.. Process according to Claim 23, characterized in that the proportion of elastomer is between 5 and 12 ia of the weight of the vinyl-aromatic monomer. 26. The method according to any one of claims 23 to 25, characterized g e k e η Ji ze rejects that the vinyl aromatic The monomer is styrene. 27. The method "according to any one of claims 23 to 26, characterized ^ marked that the vinyl aromatic Polymer is mixed. with the polymerization product in Presence of up to 15% by weight of a lubricant for vinyl aromatic polymers. 28. Modification of the method according to claim 23, characterized in that one according to one of the claims 10 to 22 produced mixture blends with a vinyl aromatic polymer or copolymer. 8647 00 9 8 4 2/1 80 5 ORiQiNAt INSPECTED