DE2937718A1 - TRANSPARENT POLYMERIS MIXTURES - Google Patents

Description

1A-2963
27,382

AMERICAN CYANAMID COMPANY Wayne, New Jersey, U.S.A.

Transparent polymer mixtures

030013/0911

It is known that thermoplastic molding compositions are made from various Polymers and rubber latices can be produced by either the polymers with the grafted Mixing the rubber compound, or by adding the monomers used to prepare the polymers in the presence polymerized in the rubber compound. U.S. Patent 3,354,238 For example, such a molding compound is described in which the resinous phase consists of methyl methacrylate, styrene and acrylonitrile consists and the rubber phase consists of polybutadiene, on which methyl methacrylate, styrene and acrylonitrile are grafted on. Similarly, U.S. Patent 3,261,887 describes a molding composition similar to that of the above Patent is essentially identical with the exception that acrylonitrile is omitted. Also in U.S. Patent 4,085 describes a similar molding compound in which acrylonitrile is replaced by ethyl acrylate.

These products have acceptable properties when used as colored molding compositions, but are absent of a dye has defects. In the uncolored state, these products are not sufficiently transparent. As a result, their use as a packaging material is restricted.

Investigations have shown that the optical properties of the molding compositions are improved when rubber-like, reinforcing elastomers, such as the polybutadiene phase in the above patents, are more uniform in the resinous polymer phase is distributed and if the agglomerates of the elastomer, if any, are smaller than the wavelength of visible light. The smaller the agglomerates, the better the optical properties.

Π30013 / 0915

Although the visible light wavelength is about 4000 to 7000 % and the polybutadiene that has hitherto been used is generally on the order of less than 2000 Å in diameter, the resulting products have nevertheless not been entirely satisfactory because of their relatively poor quality Haze and gloss properties.

It has now been found that by modifying the procedure, with which the graft elastomer is produced, a improved molding compound obtained because the rubber phase is distributed more uniformly in the resin phase.

The graft elastomer layer is made using one of the following methods manufactured:

(a) sequential and controlled addition of monomers (SCAM) during graft polymerization;

(b) Mixture of two separately prepared graft polymers, the two graft polymers being different Have rubber to monomer ratios (MEG); or (c) a multiple grafting process in which a second Grafting is carried out in the presence of the product grafted in the first step (DGMAC).

According to the present invention, improved molding compositions for two-phase plastic systems are created. Examples for the rubbery, reinforcing part of such systems include those such as polybutadienes, poly (styrene / butadienes), Poly (methyl methacrylate / butadiene), polyisoprene, polyisobutylene, poly (isobutylene / isoprene) copolymers, Poly (acrylonitrile / butadiene), polyacrylate, polyurethane, Neoprene, silicone rubbers, chlorosulfonated polyethylene, Ethylene-propylene rubbers and other rubber-like Materials a.

030013/0812

Such monomers can be grafted onto the rubbers mentioned above which are mentioned in detail below for the resin phase. Monomers to be grafted on, must be compatible with the respective monomers that were used for the resin phase of a respective mixture be. The same monomers are preferably used in both components. The term “compatible” includes such polymers to understand who show a strong affinity for one another so that it is possible to contribute to the one in the other small domain size to disperse. The smaller the domains, the more compatible are the polymers. Further details regarding compatibility are found in Advances in Chemistry Series, Item 99, "Multi-Component Polymer Systems ", edited by R.F. Gould, 1971, named.

Any polymer or copolymer can be used as the resin phase, which can be used with the grafted rubber phase is compatible (compatible). Examples of suitable monomers include acrylates, methacrylates, nitriles, styrenes, vinyl ethers, vinyl halides, and others, the like Mono vinyl compounds. Particularly suitable monomers include methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, Ethyl methacrylate, polymethacrylate, acrylonitrile, methacrylonitrile, Styrene, α-methyl styrene, butyl vinyl ether and vinyl chloride a.

According to the invention, the rubber phase preferably consists of polybutadiene, methyl methacrylate, styrene and optionally a third monomer selected from methyl acrylate, ethyl acrylate or acrylonitrile are grafted on. The resin phase preferably consists of a polymer of methyl methacrylate, styrene and optionally a third Monomers selected from methyl acrylate, ethyl acrylate and acrylonitrile.

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In a particularly preferred embodiment, the molding compositions are used made from a graft polybutadiene phase and a polymeric resin phase, the polybutadiene portion the Pfropfpolybutadienphase 5 to 25 Gew.K, based on the entire molding compound. The polymeric resin phase contains 60 to 80 parts of methyl methacrylate, 15 to 30 parts Styrene and 0 to 15 parts of one of the components methyl acrylate, Ethyl acrylate or acrylonitrile. The graft polybutadiene phase consists of a polybutadiene latex on which methyl methacrylate, Styrene and optionally either methyl acrylate, Ethyl acrylate or acrylonitrile are grafted, the total ratio of polybutadiene to the graft monomers im Range from about 1: 1 to about 6: 1. The graft monomers are in a ratio of about 60 to 85 parts of methyl methacrylate, 15 to 30 parts of styrene, and 0 to 15 parts of either Methyl acrylate, ethyl acrylate or acrylonitrile are used.

The SCAM process, which is essentially a standard free radical initiated polymerization process is, at least the monomer which, as a polymer, has the best compatibility with the resin phase becomes added to the rubber latex, and all other monomers that are also to be grafted onto the rubber added gradually and in a controlled manner. Conventional initiators and other polymerization components are used. Since there is no valid theory, it can be assumed that the SCAM process results in a non-agglomeration occurs that a substantially uniform shell of resin is formed around the rubber particles, the outer Layer of the shell consists primarily of the monomers added in a controlled manner.

In the MEG process, a mixture of two rubber-like Graft polymers with different rubber to monomer ratios manufactured. One of the used

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-Jf-

Rubber phases have a relatively high rubber-to-monomer ratio e.g., greater than about 2.5 / 1, preferably greater than about 3/1, and most preferably about 3/1 to 5/1. This latex possesses an appreciable agglomeration of the rubber particles, whereby the good physical, however poor optical properties of such materials are caused. Older other latex has a relatively low level Rubber-to-monomer ratio, e.g., below about 2/1, preferably below about 1.5 / 1 and particularly preferably about 1/1. There are essentially none with this latex Agglomerates, creating excellent optical properties, but also exceptionally poor physical properties are conditional. By employing a mixture of the two rubber phases, one might expect a product to be created which in the best case has the physical and optical properties of the two rubber phases. It However, it has been shown that when using a smaller portion of that rubber phase with the small one Rubber-to-monomer ratio and a larger serving the other rubber phase is given a molding compound with only a slight deterioration in physical properties, however, has significantly improved optical properties.

In the DGMAC process, at least two grafting steps are carried out in succession, namely in such a way that rubber and graft monomers are first combined and then further rubber and further graft monomers are added. The grafting process used in each reaction step consists either in reacting rubber with equilibrated monomer, as is known in US Pat. No. k 085 166, or in carrying out a successive and controlled addition of the monomers (SCAM -Procedure as described above). To the graft product obtained in the first reaction step, 0.5 to 1.0Jt (based on

030013/0913

on the weight of the rubber latex of the second reaction stage) a stabilizer, such as kallumlaurylarylsulfonate, is added to maintain latex stability during polymerization to ensure in the second reaction stage. Further stabilizers can be added in further reaction stages. The proportions of the monomers used in the individual graft reaction stages, preferably methyl methacrylate, Styrene and either methyl acrylate, ethyl acrylate or acrylonitrile, correspond to the ratios given above for the total graft mass. The rubber to monomer ratio in the individual grafting reaction steps, the overall composition of the graft polymers given above determined, i.e. is about 1: 1 to about 6: 1. The main compositional limitation on individuals Reaction stages consists in the fact that the graft product of each reaction stage weighs at least as much as the one before manufactured, grafted rubbers. In a two stage system, the second reaction stage preferably makes at least one 60) 4 of the product and is specifically about 65 to 95 #. When determining the weight of the by successive The graft rubber products obtained in the reaction steps are assumed that the graft rubber products obtained in successive reaction steps Monomers used are uniform between the rubbers from the previous and the new Reaction step, as well as between the resin (graft monomer) formed in the previous reaction step, distribute.

Regardless of how the grafted rubber was produced, the molding compositions can be obtained by a resin phase mixed with the rubber phase in suitable amounts. The resin phase can thereby by a with free Radical initiated reaction in the presence of a solvent and in a two-stage system in which the monomer mixture is placed in a first reactor and up to

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about 20 to 4094 solid fraction is polymerized, whereupon it is placed in a second reactor in which the full conversion is carried out .warn be produced.

Any of the known methods can be used to prepare the resin phase. Preferably, however, the resin phase is obtained by mixing together suitable concentrations of the monomers in a solvent such as toluene in a concentration of 60 to 80% of monomers. Then, for example, a suitable initiator, such as benzoyl peroxide, di-t-butyl peroxide, etc., is added in the presence of an additive for molecular weight control, such as an alkyl mercaptan, for example n-dodecyl mercaptan, n-octyl mercaptan, t-dodecyl mercaptan, benzyl mercaptan and the like. As mentioned above, this polymerization is preferably carried out in a two-stage system in which the monomer solution is input to the first stage reactor and polymerized at about 80 to 110 ⁰ C for about 12 to 24 hours. The conversion rate is preferably adjusted to about 1 to 3% solids / hour. The polymer obtained in the first reaction case is then preferably transferred to a second reaction step in a reactor, for example of the plug flow type, where a complete conversion of the monomers to the polymer is carried out. The final solids content is generally between 60 and 70 *. Initiators can be used in amounts of about 0.01 to 5.0% by weight , based on the weight of the monomers. Molecular weight control additives can be used in the same weight percentages, again based on the weight of the monomers.

During or after its formation, additives such as heat and light stabilizers, antioxidants, Lubricants, plasticizers, pigments, fillers, dyes, etc., can be added.

030013/0812

In the DGMAC process, each reaction step can either by a conventional grafting method or by the sequential and controlled addition method of monomers (SCAM). The SCAM method is preferably used in at least one of the reaction steps is used, and it is particularly preferred to carry out two process steps, each of these steps proceeds according to the SCAM procedure. Although the grafting reactions can be carried out in a series of reactors »it has proven advantageous to use a single reactor to use and to carry out the grafting reactions in successive steps.

With these methods, one obtains a large number individually grafted rubber particles which have essentially no agglomeration and / or aggregation of the rubber particles. This results in both improved optical properties and a mass with reduced taste and odor transmission properties.

With the SCAM procedure (or as part of the DGMAC procedure) one should proceed in such a way that the monomer, which is added gradually, over a period of at least 15 minutes, preferably at least 1 hour and particularly preferably during a period of about 1 to 3 hours » added, the grafting reaction taking place during the addition, and then preferably allowing the reaction to proceed for about 1 hour. The initiator, preferably from Redox type, can be included in the reactor from the start, it can either be added simultaneously with the monomer In the same stream or in separate streams; or ultraviolet light can be used. In general the initiator is used in an amount that is about four Times the standard amounts used in US Pat. No. 4,085,166. If a redox inflator

030013/0912

is to be added in a controlled manner (i.e. not to be present in the reactor from the start), either the oxidizing or reducing part are added to the reactor from the beginning, and it only has to be the other part can be added in a controlled manner. The reaction will take place in a pH range of about 6.0 to 8.5 and in a temperature range from about 20 to 65 ° C, although none of these ranges are critical for the present invention has proven.

Examples of suitable redox initiator systems include the following a: t-butyl hydroperoxide, cumene hydroperoxide, hydrogen peroxide or potassium persulfate-sodium formaldehyde sulfoxylate-iron; Hydroperoxide-tetraethylene pentamine or Dihydroxyacetone; Hydroperoxide bisulfite systems; and other such well known redox initiators.

The rubber-to-monomer ratios in the graft polymerizations, regardless of whether it is carried out using conventional methods or SCAM methods, from the point of view of that can be varied by adjusting the rubber-to-monomer ratios the desired balance of properties can be achieved in the final product. It is therefore the desired end product, which determines the actual proportions that occur when carrying out the graft polymerizations be used. In general, rubber to honey ratios should be in the range of about 1: 1 to as high as 6: 1, with materials with lower ratios having better optical properties show and materials with larger ratios have better physical properties. With the MEG and DGMAC process preferably has a portion of the graft products having a rubber-to-monomer ratio of at least 2.5: 1 and the other less than 2: 1. Particularly preferred

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2937719

is a ratio of about 2.5: 1 to 4: 1 for one portion and about 1: 1 to 2: 1 for the other.

The DGMAC process according to the invention results in more intimate mixing of the chewing rubber phases with different rubber-to-monomer ratios achieved than was previously possible. Different rubber-to-monomer ratios will be easily obtained even if rubber and nonomer are added in the same ratio in each reaction step because the first grafted rubber is in the reactor when the next grafting reaction is performed.

For example, you can create an intimate mix of a 3s1 and a 1: 1 rubber: monomer from two 2: 1 graft polymerizations manufacture as follows:

For graft polymerization 1, a total of 3 parts by weight of reactants is used - 2 parts of rubber and 1 part Monomers - to get a 2: 1 product. A second graft reaction is then carried out by adding 9 parts of reactants - 6 parts rubber and 3 parts monomers - used together with the first graft product. The second The new monomers are grafted onto the first product and the newly added rubber grafted on in substantially the proportion in which they are present in the reactor. Consequently, in this example, 6/9 of the 3 parts of newly added monomers are grafted onto the new rubber, i.e. 6 parts rubber per 2 parts monomer - a 3: 1 ratio, and 3/9 are grafted onto the earlier graft, i.e. 2 parts of rubber per 1 part of the first monomers plus 1 part of the new monomer - a 1: 1 ratio. In this way, the resulting mixed graft polymer 4 parts of a 1: 1 graft polymer and θ parts of a 3t1 contain graft polymers which are intimately mixed are.

030013/0912

ORIGINAL INSPECTED

In the MEG process, there are two graft polymer parts preferably in each case from polybutadiene, on the methyl methacrylate, styrene and optionally either methyl acrylate, Ethyl acrylate or acrylonitrile are grafted on. One part makes 95 to 60 wt. * Of the grafted polybutadiene phase and has a ratio of the polybutadiene to the graft monomers ranging from about 2.5: 1 to about 6: 1. The other part consists of 5 to 40% by weight of the graft polybutadiene phase, the ratio being from polybutadiene to graft monomers in the range of about 1: 1 to about 2: 1. The graft monomers of both parts have the same proportions of about 60 to 85 parts of methyl methacrylate, 15 to 30 parts of styrene and 0 to 15 parts of either methyl acrylate, ethyl acrylate or acrylonitrile.

Resin phase and rubber phase can be made however they are in conventional manner such as using a ball mill, hot rollers, emulsion mixing processes o.a., are mixed together.

Preferably, the mixing process is as described in column 3, lines 3 to 72 of the above-mentioned U.S. Patent 3,354,238, using a Devolatllizer extruder carried out.

As mentioned above, the field of use is that of the invention Masses where toughness, rigidity and transparency are necessary, and the masses can therefore be used in injection molding of highly stressed parts in blow molding and thermoforming processes from containers or other desired objects.

The invention is explained in more detail below with the aid of examples. All information about partial quantities and the percentage

030013/0912

ORIGINAL INSPECTED

given are amounts by weight, unless otherwise stated. the Examples 1 to 40 show the SCAM process; Examples 41 to 50 the MEG process; and Examples 51 to 63 das DGMAC procedure.

example 1

It becomes a 71.5 / 23.5 / 5/0 methyl acrylate / styrene / ethyl acrylate terpolymer composition prepared by polymerizing the following monomer-solvent mixture: methyl methacrylate 51.6 parts Styrene 17.0 parts

Ethyl acrylate 3.6 parts Toluene 27.5 parts

n-dodecyl mercaptan 0.022 part di-t-butyl peroxide 0.30 part

The polymerization is carried out in a two-stage system, ie the monomer-solvent mixture is placed in the first-stage reactor and polymerized for about 15 hours to a solids content of 28 to 30 ° at 90 to 95 ° C. The conversion rate constant is about 2% solids / hour. The reaction product of the first stage is then transferred to a plug flow reactor, where the complete conversion of the monomers into a polymer is carried out. The final solids content is close to 72%.

A grafted rubber compound is made by adding 79.19 parts of polybutadiene-tex (43.3% solids, 34.29 parts Polybutadiene) and 7.46 parts of desalinated water inen Reactor and with 1.5 # aqueous ammonia the pH sets about 8.3. To this, 2.29 parts of styrene are added with stirring and the uniform mixture with nitrogen purged to create an almost oxygen-free atmosphere. Thereafter, 1.51 parts of sodium formaldehyde sulfoxylate chelate solution are added the following composition:

030013/0912

ORIGINAL INSPECTED

96.269 (deionized water 3.51 * sodium formaldehyde sulfoxylate

0.19 * ethylenediamine tetraacetic acid tetrasodium salt

0.04 * iron (III) chloride hexahydrate

10096

After 5 minutes and with constant stirring, 9.14 parts of methyl methacrylate and 0.39 parts of tert-butyl hydroperoxide solution are added (5.85% t-buty! Hydroperoxide and 94.15 * demineralized water) pumped into the reactor. The methyl methacrylate is at a rate of 0.0508 parts / min within Added 3 h. The rate constant for the t-butyl hydroperoxide solution is 0.0195 parts / min for 10 minutes, then 0.00108 parts / min for 180 minutes, 1 hour after completion the addition of honey amounts to conversion into polymer 98 to 99 *.

20 parts of the above grafted rubber are then mixed together with 80 parts of the above terpolymer, a final polybutadiene content of 15 * is achieved. The mixing is done on a devolatilizer extruder at a temperature on the inlet side of about 120 ° C and on the DU side of about 29o ° C in a vacuum from 635 to 685mmHg.

The transparent wetness obtained then becomes different Test specimen formed and examined. The results are given in Table I below along with the results obtained for products made by conventional methods.

As can be seen from Table I, the process provides the sequential and controlled addition of monomers a product with equivalent impact strength and significantly superior optical properties (high gloss,

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2937719

lower haze and reduced transmission) with material made in conventional catfish.

Table I.

Notched impact Shine. F. Long shot TrUbun *. * ⁰ Y % toughness Izod ^a
ft.lbs / in 20 ° 60 ° Y Z Trans
mission Belsp. 1 1.6
Comparison 1.6 64
47 86
81 13.0
17.0 7.8
10.0 90.5
89.8

^a ASTN 0-256, method A; molded specimens 1/4 χ 1/2 5 inches (0.635 x 1.270 χ 12.70 cm); 1 ft. X lbs./inch = 5.437 kg.cm/cm.

^b ASTM D 2457-70, molded discs, 1/8 inch (0.317 cm) thick.

^c ASTM D 1003-61, molded discs, 1/8 inch (0.317 cm) thick.

Examples 2 to 6

The procedure of Example 1 is repeated with the exception that the rubber-to-monomer ratio of the graft polymer is varied and the pumping time is 1 h instead of 3 h. The comparison products are obtained using conventional methods. Molding compositions are produced in which the ratio of the resin phase to the rubber phase is varied so that products are obtained which contain a constant proportion of 14.5% polybutadiene.

Table II below shows the results for injection moldings and in the following Table III the results for those produced by Theraoforming methods are given Moldings of 0.012 inch (0.5 mm) thick are listed.

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Rubber-to- Monomer

ratio

Table II nz %
60 ° Long shot
Y TrUbun «#
Z Y % Trans
mission Sch1agz8hle ^ke1 *
Izod
(ft.lbs./inch) _Gla
20 ° 89 6.4 7.3 86.4 0.41 69 83 11.8 13.6 78.4 0.47 58 86 8.7 10.7 84.3 0.54 62 84 9.0 10.3 84.1 0.81 59 86 9.5 11.1 83.8 2.1 60 85 12.9 13.8 83.1 1.9 58 83 10.2 11.0 86.0 2.0 54 83 15.9 17.3 77.0 1.6 57 81 11.3 12.0 84.7 1.7 52

Example 2
comparison
Example 3
comparison
Example 4
° comparison
° Example 5
" Comparison
Example 6

1/1 1/1 2/1 2/1 3/1 3/1 4/1 4/1 5/1

.4 < lanz 60 ° 7th - 4t - Z 29377K S. 2tV 3 89
87 4.2
4.2 Y % transmission 61
51 Table III
Total haze % Ex
Cf. D 1 e 1 e Y 92.5
92.7 at 3.0
3.1 until 24

The procedure of Example 1 is repeated with the following changes: (1) the rubber to monomer ratio of the grafted Rubber, (2) the pumping times, (3) placing the t-buty! Hydroperoxide in the reactor from the start, and (4) the Amount of each part of the initiator system (the amounts given in Example 1 serve as the standard STD).

In the following Table IV the changes together with the properties of the resulting molding compositions are listed in which Each adjusted to a polybutadiene content of 14.5% is summarized. In the table:

MMA methyl methacrylate TBHP t-butyl hydroperoxide SFS chelate sodium formaldehyde sulfoxylate chelate solution KSZ notched impact strength

030013/091

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030013 / 091Ϊ

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Examples 25 to 29

The procedure of Example 1 is repeated except that the initiator and pumping times are varied. The equimolar amount, based on the t-butyl hydroperoxide, is used as a guide for the standard concentration (STD) of each starter of Example 1. The results are shown in Table V below.

. initiator Tabel Pumping To, tale cloudy % Z 20th V SFS KSZ Gloss 5 f 60 ° E.g. times (h) y 10.4 Starter- Chel. Izod
(ft.Ib / 20 ° No. mMA start 9.6 12.8 conc. HOURS in.) 81 CHP ^ 12.6 - begin HOURS 1.5 56 82 H ₂ O ₂ 1 1 - 12.1 HOURS 1.8 55 80 25th H ₂ O ₂ 1 1 10.2 10.0 HOURS , 5 HOURS 1.8 49 84 26th (NH ₄ J ₂ S ₂ O ₈ 3 3 9.5 Cumene hydroperoxide HOURS , 5 HOURS 1.7 57 83 27 K ₂ S ₂ O ₈ 1 1 1 s ρ 1 e 1 HOURS 1.5 59 28 1 1 STD 0, 29 Table V (continued) STD O ₁ Y transmission
* E.g.
No. 25th 26th 27 28 29 ΤΪΤ B e 85.6 84.6 - 82.6 83.3

The procedure of Example 1 is repeated with the exception that the t-butyl hydroperoxide is added to the reactor and controlled the sodium formaldehyde sulfoxylate chelate solution is admitted. For both the methyl methacrylate and the Solution, the pumping time is 1 hour. The starter is used in standard quantities. The resulting product (14.5 *

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Polybutadiene) has the following properties: Notched Impact Strength Izod (ft.lb / in.) 2.1

Gloss, % 20 ° 47

60 ° 81

Total haze, 96 Y 13.4

Z 15.5

Y transmission, % 83.8

Example 31

The procedure of Example 1 is repeated except that a mixture of methyl methacrylate and styrene monomer is used is added to the reactor in a controlled manner. The pumping time for both the monomers and the starter is 1 hour. The resulting composition with 14.5 * polybutadiene has the following Features on:

Notched Impact Strength Izod (ft.lb / in.) 2.2

Gloss, % 20 ° 58

60 ° 84

Total haze, % Y 8.5

Z 9.4

Y transmission, % 86.4

Example 32

The procedure of Example 1 is repeated except that a portion of the methyl methacrylate is controlled is added, replaced by ethyl acrylate and the pumping time is 1 h. The resulting mass, with 14.5 * polybutadiene, has the following properties:

Notched Impact Strength Izod (ft./lb/in.) 2.0

51 81 11.1

15.3

Y Transmission, * 84.8

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Shine, % 20 ° * Y 60 ° Z Long shot Cloudiness,

Examples 33 to 35

The procedure of Example 1 is repeated with the exception that molding compositions are prepared in which the amounts of polybutadiene in the end product. The results are summarized in Table VI.

Table VI

__ ,. . 1 gloss

Mr. dien (ft.lb/in.) zoo oQo YZ slon. % Ex. % Polybuta- KSZ Izod Gloss.Jt Tot. Turbidity. * Transais-

33 14.5 2.2 59 86 10.1 12.1 84.9 34 12.5 2.0 58 86 9.3 11.3 84.1 35 10.5 1.7 64 87 8.0 9.6 86.2

Examples 36 and 37

The procedure of Example 4 is repeated to produce thermoformed molded articles with a thickness of 0.1-0.165 mm. The shaped bodies are compared with material produced in a conventional manner with regard to their optical properties assessed. Table VII shows the results.

Table VII

iz. % Toti dien zo »" oTF γ ζ 'sion. %

E.g. % polybuta gloss. % Total TurbidityΛ Y Transmis

36 14th , 5 20th 67 20th , 0 26th , 7 91 , 5 37 12th , 5 32 76 15th , 5 17th , 2 91 .7 Cf. 14th , 5 9 58 23 ,1 30th , 9 91 , 3

Examples 38 and 39

The procedure of Example 4 is repeated; with the mass obtained are 453 g capacity Margarinebehfilter from a 0.9 mm thick film obtained by extrusion produced by means of a thermoforming process at r75 to 185 ° C. the

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Rubber phase has a rubber-to-monomer ratio of 3: 1 and the total mixture contains 14.5 # polybutadiene. The results are summarized in Table VIII.

E.g. Pumping times star
ter Tabel
0.5mm thick 40 VIII Shine. ooo * 60 ° No. HNA I Ul I O Impact resistant
ability (ft. Ib / in Side part -
.) 0.28 mm thick 65
36
55
30th 82
61
81
63 I Ul I Ul i e 1 25.2
30.3
29.6
30.0 2ÖÖ Bottom part -
O.43 mm thick 38
See.
39
See. i S P 19th
2
10
2 2o ° B e 42
19th
45
17th

The procedure of Example 38 is repeated except that the mold temperatures in making the Margarine container can be varied. The results shown in Table IX show that in the inventive thermoformed masses the visual clarity is essentially insensitive to changes in the mold temperature, whereas in the case of materials produced by conventional methods with an increase in temperature, a deterioration in the visual clarity occurs.

Table IX Example mold temperature ( ⁰ C '

standard temperature (C)

174 180 182

No. 149 T55 174 180 182 193 199

40 good good good good-

moderate

Cf. moderately moderately bad bad bad

D30013 / 0912

Examples 41 to 48

A. A mixture of monomers containing 51.6 parts of methyl methacrylate, 17.0 parts of styrene and 3-6 parts of xethyl acrylate, in the presence of 0.30 parts of di-t-butyl peroxide, 27.3 parts of toluene and 0.022 parts of n -Dodecyl mercaptan polymerized in a two-stage system, ie the monomers are added individually to a reactor for the first reaction stage and polymer-free conversion rate up to a solids content of 28 to 30% at 90 to 93 ° C. for 16 to 20 h is about 2,096 solids / hour. When the appropriate solids content is reached, the reaction material of the first stage is transferred to a plug-flow reactor, where the complete conversion of the monomers into a polymer is carried out. The final solids content is 68 to 70Ji.

B. A rubber composition is prepared by mixing 75.0 parts of polybutadiene in latex form with 19.6 parts of methyl methacrylate and 5.4 parts of styrene. The rubber to monomer ratio is 3: 1. The monomers are then grafted onto the polybutadiene in a polymerization initiated with a redox initiator using, based on the monomer, 0.05 part t-butyl hydroperoxide, 0.06 part sodium formaldehyde sulfoxylate, 27 ppm iron (III) - Chloride. 6H ₂ O and 127 parts per million of ethylenediaminetetraacetic acid. 4Na salt at room temperature for 2 to 5 hours.

C. A second rubber compound is prepared by adding 50.0 parts of polybutadiene in latex form, 10.8 parts of styrene, 0.12 part of sodium formaldehyde sulfoxylate, 54 parts per million of Elsen (III) -chlorld.6H ₂ O and 254 parts of ethylene diamine-tetraacetic acid .4Na-SaIζ mixed together. A graft polymerization is then carried out by, independently of-

03 0013/0912

each other, in the above mixture controlled 39.2 parts Methyl methacrylate and 0.05 part t-buty! Hydroperoxide over adds a period of 3 h. The rubber to monomer ratio is 1: 1. The reaction is continued for an additional hour and the grafted rubber is obtained.

Six mixtures are then prepared, the polymer A being mixed with the rubber compositions B and C in such a way that each of the mixtures has a final polybutadiene content of about 14.5%. Table X contains the proportions of the graft rubbers B and C. The mixing is carried out in a devolatilizer-extruder at a temperature at the inlet side of about 120 ⁰ C and at the DUsenseite of about 293 ° C at a vacuum of 635-686 mmHg . The resulting mixtures are then molded into various test specimens and examined to determine their physical properties. In addition, the gloss is determined in accordance with ASTM D2457-70 and the haze in accordance with ASTM D1003-61. The results are detailed in Table X below.

From the results, it can be seen that when the ratio of rubber to graft price monomers is 3/1, the mixture has good impact properties but high levels of haze and low gloss. If the percentage of the 1/1 graft copolymer in a mixture of the rubber phases is increased to about 35% , a decisive improvement in the haze and gloss characteristics is observed, while at the same time there is only a slight decrease in the impact resistance, which is still good.

Examples 47 and 48 show the tremendous improvements in optical properties of blends starting at 176 to 185 ° C were thermoformed.

030013/0912

Tabel X

Example ratio of the number mixed, grafted Rubbers m

KSZ Izod Gardner-Schlag- Total Opacity (ft.Ib / Strength (2) T "^ ^ in.) (In.lbs./mil)

Gloss valuea

5L

Front back

20 *

- 1: 1 rubber chuk 60 ^c

20 ^BC

60 ^c

41
42
43
44
45
46
47 ⁺

100
90
80
65
50
O

100
65

O 10 20 35 50 100

0 35

1.8

1.8

1.8

1.6

0.57

0.51

0.52 0.51 0.49 0.48 0.38 0.31

14.9 11.0 10.4 10.9 14.9 8.7

19.2 36 76 44 77 13.7 42 79 41 76 13.2 45 81 44 80 14.8 47 81 52 81 19.3 58 83 64 86 11.9 59 85 57 83 15th 71 28 87

μ thermoformed moldings

(Dd.r G. « _a « t-Polybut.di _hurry . _Stop in _all , u _schungea ,,. Carries 14.5 <* ". *.

(2) 1 inch lbs / mil)

453 kg cm / cm

-β5-

Example 49

The procedure of Examples 41-48 is repeated except that the 1: 1 rubber-to-monomer material is used de · conventional way is established for the 3: 1 material has been described. Similar results are obtained.

Example 50

The procedure of Examples 41 to 48 is repeated except that the ethyl acrylate is immediately replaced with acrylonitrile will. Again, similar results are obtained.

Example 51

It becomes a 71.5 / 23.5 / 5.0 methyl methacrylate / styrene / ethyl acrylate terpolymer composition prepared by polymerizing the following monomer-solvent mixture:

Parts

Methyl methacrylate 51.6

Styrene 17.0

Ethyl acrylate 3.6

Toluene 27.5

n-dodecyl mercaptan 0.022

Di-t-butyl peroxide 0.30

The polymerization is carried out in a two-stage system, ie the monomer-solvent mixture is placed in a reactor for the first reaction stage and polymerized to a solids content of 28 to 30 ° at 90 to 95 ° C. for about 15 hours. The conversion rate is about 2% solids / hour. The reaction product of the first stage is then transferred to a plug-flow reactor, where complete conversion of the monomers to the polymer is carried out, the final solids content is close to 72 *.

030013/091 *

ORIGINAL INSPECTED

"XL-

A grafted rubber compound is produced in a two-stage graft polymerization as follows! A first grafted rubber composition obtained by mixing 100 parts of polybutadiene Indea in latex form with UO parts of methyl methacrylate and 10 parts of styrene. The chew to monomer ratio is 2: 1. The monomers are then grafted onto the polybutadiene by a polymerization initiated with a redox starter, 0.1 part of t-duty hydroperoxide, 0.23 part of sodium maldehyde sulfoxy let, 27 ppm, based on the monomer (III) chloride.6H ₂ 0 and 127 ppm ethylenediamine tetraacetic acid.4Na salt starts at room temperature for 1 to 3 5 hours.

The second graft copolymer is produced in that the first, above-described graft polymer is placed in a reactor, 6.7 g of potassium laurylarylsulfonate are added and then 300 parts of polybutadiene in latex form, 120 parts of methyl methacrylate, 30 parts of styrene and the same amounts of the starter system described above. The ratio of the second rubber to the second monomer is at this level 2: 1. The grafting reaction is carried out at room temperature carried out for 1 to 5 hours with constant stirring.

In this example, the mixed, grafted polybutadiene phase contains calculated, 1 part of a 1: 1 graft copolymer to 2 parts each of a 3: 1 graft copolymer, the graft copolymers being intimately mixed. The overall ratio from rubber to monomer is 2: 1.

21.75 parts of the above grafted rubber are then mixed with 78.25 parts of the above terpolymer to create a final polybutadiene content of 1 hour, 5% . The mixing is carried out on a devolatilizer extruder

Π30013 / 0915

a temperature at the inlet side of about 120 ⁰ C and at the nozzle side of about 29o C under a vacuum ⁰ 635-686 mmHg performed.

The resulting Polymerisatmlschungen can then in different specimen shapes and their physical and examine optical properties. Superior optical properties are observed compared to those after products manufactured by the conventional method according to US Pat. No. 4,085,166, wherein the grafted rubber is contained in a single stage reaction from a 3: 1 rubber-to-monomer mixture.

Example 52

The process of Example 51 is repeated except for the graft polymerizations, which are carried out as follows: A first, grafted rubber compound is prepared by mixing 325 parts of polybutadiene in latex form with 133 parts of methyl methacrylate and 33 parts of styrene. The rubber to honey ratio is 1.963: 1. The monomers are then grafted onto the polybutadiene by a polymerization initiated with a redox starter, 0.33 part of t-butyl hydroperoxide, 0.66 part of sodium formaldehyde sulfoxylate and 88 parts per million of iron (III) chloride being added, based on monomers. 6H ₂ 0 and 408 ppm of ethylenediamine-tetraeaetic acid. 4Na salt is used at room temperature overnight. The maximum exothermic heat dissipation was reached within 36 minutes. The solids content in the first reaction stage is 45.1 *.

This first graft copolymer is placed in a reactor together with 17.48 parts of sodium lauryl aryl sulfonate and then with 1646 parts of polybutadiene in latex form (44.8Ji Solids, 737 parts polybutadiene) and deionized water

030013/0913

offset. The pH is raised with 1.596 aqueous ammonia set about 8.3. 56 parts of styrene are added with stirring and the equilibrated mixture is flushed with nitrogen. to create an almost oxygen-free atmosphere. 37 parts of sodium formaldehyde sulfoxylate chelate solution are then added the following composition added:

96.2 ^ 96 desalinated water

3.5156 Sodium formaldehyde sulfoxylate 0.1996 Ethylenediamine tetraacetic acid tetrasodium salt 0.049 t iron (III) chloride hexahydrate 10096

After 5 minutes, 222 parts of methyl methacrylate are added with constant stirring and 32.8 parts of tertiary butyl hydroperoxide solution (1.796 t-buty! Hydroperoxide and 98.396 deionized water) in pumped the reactor. Nethyl methacrylate is fed in at a rate of 1.85 parts / min for 2 hours. The rate constant for the t-butyl hydroperoxide solution is 1.64 parts / min for 10 minutes and then 0.1367 parts / min for 120 minutes Monomer ratio in this second reaction stage is 2.666: 1. 1 h after the end of the monomer addition the conversion to polymer 98 to 9996. The final solids content is about 4796.

In this example the grafted polybutadiene phase contains arithmetically 1 part of a 1.13: 1 graft copolymer on each 2 parts of a 4: 1 graft copolymer, which are intimately mixed are. The total rubber-to-nonomer ratio is 2.45: 1.

20.4 parts of the above grafted rubber are then mixed with 79.6 parts of the above terpolymer, whereby creates a final polybutadiene content of 14,596. The mixing is done on a Devolatillzer extruder at one

0300 13/0912

Inlet side temperature of about 120 ° C and about 290 ° C the DUselt was carried out at a vacuum of 635 to 685 mmHg. The resulting, transparent polymer mixture is then shaped into various test specimens and tested. The physical and optical properties are as follows:

Notched Impact Strength Izod, ft.Ib./in. 2.14 gloss, % 20 ° 56

60 ° 81.

Examples 53 to 56

The procedure of Example 51 is repeated with the exception that 0.4 parts of sodium formaldehyde sulfoxylate, 89 parts per million of elena (III) chloride.6H ₂ 0 and 407 parts of ethylene diamine tetraacetic acid. 4 Na salt are used in the second graft polymerization, and the first Graft polymerization is carried out with a SCAM process in the following manner: A grafted rubber mass is prepared by adding 225 parts of polybutadiene latex (44.596 solids, 100 parts of polybutadiene) and 25 parts of deionized water to a reactor and adding 1.596% aqueous ammonia to the adjusts pH to about 8.3. 10 parts of styrene are added to this with stirring, and the squilibrated mixture is flushed with nitrogen in order to create a virtually oxygen-free atmosphere. Then 6.6 parts of sodium formaldehyde sulfoxylate chelate solution according to Example 2 are added. After 5 minutes, 40 parts of methyl methacrylate and 4.69 parts of a tert-butyl hydroperoxide solution (2.1396 t-butyl hydroperoxide and 97.87H of deionized water) are pumped into the reactor with continuous stirring. Methyl methacrylate is introduced at a rate of 0.6667 parts / min for 1 hour. The rate constant for the addition of the t-butyl hydroperoxide solution is 0.235 parts / min over 10 minutes and then 0.0391 parts / min over 60 minutes.

630013/091 *

The above procedure is repeated with the exception that the styrene is now pumped in along with the methyl methacrylate will.

21.75 and 24.75 parts of each of the grafted rubbers described above are then mixed with 78.25 and 75-25 parts, respectively, of the terpolymer described above to give final polybutadiene contents of 14.5 * and 16.5 *. The mixing is carried out in a devolatilizer-extruder at a temperature at the inlet side of about 120 ⁰ C and of about 29o ° C on the nozzle side at a vacuum from 635 to 685 mmHg.

The resulting, transparent masses then become different Test specimen formed and examined. The results are detailed in Table XI.

Table XI

Ex. % Polybuta- styrene KSZ Izod gloss, no. Dien in the (ft.Ib./

Mixture pumps in.) (I) 20 60

53 14.5 no 1.5 51 81

54 16.5 no 2.0 48 80

55 14.5 yes 2.1 47 79

56 16.5 yes 2.4 46 70

(1) ASTM 256, Method A.

(2) ASTM 2457

Example 57

The procedure of Example 51 is repeated to prepare the resinous polymer. The grafted rubber is obtained as follows:

A first grafted rubber compound is produced, by adding 151 parts of polybutadiene latex (44.8 * solids,

030013/0913

67.65 parts of polybutadiene) and 19.5 parts of deionized water are added to a reactor and the pH is adjusted to about 8.3 with 1.5% aqueous ammonia. 6.8 parts of styrene are added with stirring and the equilibrating mixture is flushed with nitrogen in order to create a virtually oxygen-free atmosphere. Then 4.48 parts of a sodium formaldehyde sulfoxylate chelate solution according to Example 2 are added. After 5 minutes, 27.1 parts of methyl methacrylate and 10 parts of a tert-butyl hydroperoxide solution (0.678% t-butyl hydroperoxide and 99.32.2% deionized water) are pumped into the reactor with constant stirring. Nethyl methacrylate is introduced at a rate of 0.3985 parts per minute over 66 minutes. The rate constant for the addition of the t-butyl hydroperoxide solution is 0.5 parts / min over 10 minutes and then 0.0833 parts / min over 60 minutes The ratio of rubber to first monomer is 2: 1. This product has a solids content of approximately 46 #.

To the first graft copolymer are added, with stirring, 18.5 parts of a 23 # strength aqueous solution of potassium lauryl aryl sulfonate and 36 parts of deionized water and then 453 parts of a polybutadiene latex (44.896 solids, 203 parts of polybutadiene). The pH is adjusted to about 8.3 with 1.5% aqueous ammonia. 20.3 parts of styrene are added with stirring and the equilibrating mixture is flushed with nitrogen in order to create a virtually oxygen-free atmosphere. Then 13.4 parts of a sodium formaldehyde sulfoxylate chelate solution according to Example 2 are added. After 5 minutes, 81.2 parts of methyl methacrylate and 10 parts of t-butyl hydroperoxide solution (2.03 * t-butyl hydroperoxide and 97.97 * deionized water) are pumped into the reactor with continuous stirring. Methyl methacrylate is introduced at a rate of 1.3533 parts / min for 1 hour. The rate constant of addition of the t-Butyl hydroperoxide 0.5 part / min for 10 min and then O _(O33 parts / min while

030013/0912

1 h. The ratio of the second rubber to the second monomer in the second reaction stage is 2: 1. The final one Solids content is 47.5%.

In this example, the mixed, grafted contains polybutadiene phase arithmetically 1 part of a 1: 1 graft copolymer to 2 parts each of a 3: 1 graft copolymer, which are intimately mixed. The total ratio of rubber to monomer is 2: 1.

21.75 parts of the above grafted rubber are then mixed with 78.25 parts of the above terpolymer to provide a calculated final polybutadiene content of 14.5%. The mixing is carried out in a devolatilizer-extruder at a temperature in the EinlaBseite of about 120 ° C and about 29o C ⁰ at the DUsenselte at a vacuum from 635 to 685 mmHg.

The transparent mass obtained is then shaped into various test specimens and examined. The results are listed in Table XII below along with the results for products made by conventional processes with a rubber to monomer ratio of 3: 1 and according to the MEG process described above by mixing a 3: 1 graft rubber with a 1: 1 rubber became. The percentages for polybutadiene found in the analysis correspond to 80 to 85% of the polybutadiene, the In the polymer blends is present, and the numbers are merely intended to compare the relative amounts of the actual enable contained polybutadienes.

As can be easily seen from the results, results
The DGMAC process shows an improvement in the optical properties compared to both the sample produced according to the conventional process and the sample produced according to the

030013/0911

-η-

HEG process (mixed, elastomeric graft copolymers) obtained sample. The DGMAC process also provides a product whose impact resistance is almost identical to that is from material made by conventional methods. The outstanding optical properties can be

Tabel XII Example 57 On conventional
Way here
posed pro
duct MEG (mix
of elastomer
Graft copoly-
merisats) 11.7 % Polybutadiene
(according to analysis) 14.3 12.8 Cast samples 1.4 KSZ Izod, ft.lb / in. 1.8 1.1 39.3 Dart Impact Resistant
capacity, ft.lb / in. (1) 41.5 34.8 8.1 Total turbidity, Jt (2)
Z 8.1 10.8 65 Gloss, % 20 ° 55 61 86 60 ° 82 85 Thermoformed
Samples (3) 15th Gloss, % 20 ° 2 13th 65 60 ° 32 59

(1) ASTM 3029m, modified TUP

(2) ASTM 1003

(3) Samples thermoformed at 176 to 185 ° C, in shape of margarine containers with a wall thickness of 0.27 mm.

example

58

The procedure of Example 57 is repeated except that now the ratio of first rubber to first Monomers to 1.963: 1 and the ratio of the second

030013/0912

Rubber to the second monomer is adjusted to 2.666: 1. Hence, the mixed polybutadiene phase arithmetically contains 1 part of a 1.13: 1 graft copolymer to 2 parts each a 4: 1 graft copolymers that are intimately mixed. The total rubber: monomer ratio is 2.45: 1.

The resulting transparent mass is then shaped into various test specimens and examined. The results are as follows:

Notched impact strength Izod, Ft.Ib./in. 2.1 gloss, % 20 ° 57

60 ° 82.

Example 59

The procedures of Examples 51 to 57 are repeated except that the ethyl acrylate in the resin portion is through Methyl acrylate is replaced. Similar results are observed.

Example 60

The procedures of Examples 51 to 57 are repeated except that the ethyl acrylate is in the resin portion is omitted and the proportions of the monomers varied accordingly in order to achieve the resulting change in Compensate for refractive index. Similar results are obtained.

Example 61

The procedures of Examples 51 to 57 are repeated with the exception that the polybutadiene latex is replaced by a polyisoprene latex is replaced and that the monomer ratios in both the graft copolymer phase and the resin phase can be varied in order to

030013/0913

compensation index. Comparable results are obtained.

Example 62

The procedures of Examples 51 to 57 are repeated with the exception »that 3 parts of methyl methacrylate in the graft polymerizations be replaced by 3 parts of ethyl acrylate. Similar results are observed.

Example 63

To determine the taste, transmission and smell characteristics of the to determine masses according to the invention and to be able to contrast the previously known Hassen and Glas Bottles made from each material to be tested.

In the taste transfer test, water is added to each bottle and left in it at room temperature for one week. After that, a water sample from each bottle is poured into individual glass beakers by a jury consisting of 6 participants, drunk and "best" by each participant between the limits (lowest transfer of taste) rated to "worst" (most flavor transfer). The procedure is repeated and gave the results, which are summarized in Table XIII below.

For the odor test, a new bottle is taken from the respective Allow material to stand uncapped overnight, then sealed and stored at room temperature for one week. Each bottle is then opened and each of the six participants rates the bottles from "best" (low odor) to "worst" (strong odor). The results are in summarized in the following Table XIII.

The following materials were examined:

030013/0912

A. Product of Example 58, except that methyl methacrylate was pumped in for 1 hour.

B. The same product as A, but made on a different day.

C. Conventionally made in accordance with U.S. Patent 4,083,116 Material.

0. Conventionally made material according to US Pat. No. 3,354,238, where ethyl acrylate is substituted for acrylonitrile replaces 1st.

E. Product by example

F. Glass.

G. Same material as C, but a different sample.

The results clearly show that the inventions Masses (A, B and E) compared to conventionally made material of the same composition (C and G) as well as a greatly reduced flavor transfer compared to compositions containing acrylonitrile (D) and have reduced odor.

Table XIII Results from Example

Flavor transferred

Enough

B E

B A 0

X ·

worst

G C

G C

0300 13/0915

(1) Samples summarized in the table were either in flavor transfer or in Odor indistinguishable.

(2) The participants indicated that Samples C and G had particularly bad taste.

030013/0912

Claims (20)

Claims 1. Molding compounds with superior optical properties containing: (A) a major amount of a resinous polymer Phase, and (B) a lesser amount of a rubbery phase, the rubbery phase being composed of rubber and one or more monomers which are grafted onto the rubber and which are made with the resinous Phase are compatible in which the rubbery phase is substantially uniformly distributed and substantially does not form agglomerates and contains essentially no particles greater than about 1 micron in diameter, and the weight ratio of rubber to monomers being about 1: 1 to 6: 1. 2. Molding composition according to claim 1, characterized in that the rubber-like phase by successive steps and controlled addition of the monomers, and that at least the monomer that is used as a polymer has the best compatibility with the resinous phase over a period of at least 15 minutes added and the grafting reaction takes place during this addition. 3 · Molding compound according to claim 2, characterized in that a redox starter is used and either the reducing or the oxidizing portion of the initiator simultaneously with the monomer, which is added in a controlled manner is added. 4. Molding composition according to claim 2, characterized in that the weight ratio of rubber to monomer in the rubbery phase is in the range of about 2.5: 1 to 4: 1. 0013/0912 ORIGINAL INSPECTED 5. Molding compound according to claim 2, characterized in that that you can do the addition over a period of at least 1 hour. 6. Molding composition according to claim 1, characterized in that the rubber-like phase is a mixture of two separate ones is rubber-like phases, each of these rubber-like phases composed of a rubber and one or more Monomers are made which are grafted thereon and which are compatible with the resinous phase, wherein one of the rubbery phases has a rubber to monomer weight ratio of at least 2.5: 1 while the other of the rubbery phase has a rubber to monomer weight ratio of less than about 2: 1, and wherein the rubbery phase having the higher rubber to monomer weight ratio over those with the lower rubber-to-monomer weight ratio in excess is present. 7. Molding composition according to claim 6, characterized in that the higher rubber-to-monomer weight ratio is about 3: 1 to 5: 1, the lower rubber-to-monomer ratio is less than about 1.5: 1 and that the rubber-like phase with the lower rubber-to-monomer weight ratio makes up about 5 to 10% by weight of the total rubber-like phase. 8. Molding compound according to claim 1, characterized in that that the rubber-like phase consists of a mixture of two rubber-like Phases, each made of a rubber and one or more monomers, which are grafted thereon and which are compatible with the resinous phase, one of the rubbery phases being one Rubber to monomer weight ratio of at least 2.6: 1 while the other of the rubbery phases 530013/0911 a chew to monomer weight ratio of less than about 2.0: 1, and wherein the rubbery phase with the higher rubber-to-monomer weight ratio is opposite those with the lower chewing gum to monomer weight ratio is present in excess and in the presence of the phase with the lower rubber-to-monomer weight ratio will be produced. 9. Molding composition according to claim 8, characterized in that at least one of the rubber-like phases is characterized prepares that at least the monomer with the best compatibility with that of the resinous phase during the Grafting reaction gradually successive and controlled adds and this addition over a period of at least 15 minutes. 10. Molding composition according to claim 8, characterized in that the grafting is carried out in two stages and the rubber-like phase contains two parts with different rubber-to-monomer weight ratios. 11. Molding composition according to one of claims 8 to 10, characterized in that each stage of the grafting through stepwise successive and controlled addition during the grafting reaction of at least the monomer with the best compatibility with that of the resinous phase and that each addition is carried out over a period of takes place for at least 15 minutes. 12. Molding composition according to one of claims 1 to 11, characterized in that a polymer is used as the resinous phase from about 60 to 80 parts by weight of methyl methacrylate, about 15 to 30 parts by weight of styrene, and about 0 to 15 parts by weight of one Monomers used, the monomer from the group ge 030013/0612 is selected, which consists essentially of methyl acrylate, ethyl acrylate or acrylonitrile. 13. molding compound according to any one of claims 1 to 12, characterized characterized in that the rubber used is polybutadiene in latex form and the rubber is about 5 to 25% by weight of the molding compound matters. 14. Molding composition according to one of claims 1 to 13, characterized in that the rubber-like phase is polybutadiene uses, on the methyl methacrylate, styrene and optionally a monomer consisting of methyl acrylate, ethyl acrylate and acrylonitrile is chosen, are grafted on. 15. A process for the production of an easily distributable, grafted rubber which does not form agglomerates, thereby characterized in that (1) a rubber latex is added to a reaction vessel; (2) one or more monomers for the same, which are to be grafted onto it, added; (3) equilibrates the rubber latex; (4) to the equilibrated Rubber latex adds at least one monomer to be grafted onto it in a controlled manner, the addition of the monomer taking at least 15 minutes, a grafting reaction taking place in this space. 16. A method of making an improved, non-agglomerating, readily spreadable mixture of grafted Rubbers, characterized in that a series of graft polymerization reactions is carried out, wherein Any subsequent reaction in the presence of the product from the previous one Reactions is carried out. 17. The method according to claim 15, characterized in that at least one of the graft polymerizations is carried out 030013/0013 gradually successive and controlled addition of monomers carried out and the controlled addition at least Lasts 15 minutes, during which time the graft polymerization takes place. 18. The method according to any one of claims 15 to 17, characterized in that polybutadiene is used as the rubber latex, methyl methacrylate is used as the controlled added monomer and the reaction is carried out at a pH of about 6 to 8.5 and at a temperature of about 20 to 65 ⁰ C performs. 19. The method according to any one of claims 15 to 18, characterized characterized in that a redox starter is used and either the reducing or the oxidizing part of the starter is added in a controlled manner, at the same time, like the monomer, which is added in a controlled manner. 20. The method according to any one of claims 15 to 19 »characterized in that one or more other graftable Add monomers together with the rubber latex to the reaction vessel, with one other than other graftable monomers Styrene and optionally a monomer selected from the group consisting essentially of methyl acrylate, Ethyl acrylate and acrylonitrile. 030013/0915