DE1792357C3 - Thermoplastic molding compounds and processes for their production - Google Patents

Description

The invention relates to thermoplastic molding compositions for the production of impact-resistant, weather-resistant Moldings and a method for producing the same.

Various rubber-modified impact-resistant resins were previously known, such as acrylonitrile-butadiene-styrene resin, High impact polystyrene resin or the like, and there are also various procedures for making them Resins suggested.

According to a previously known procedure, for example, a styrene-acrylonitrile-graft copolymer was

³ 4

merisate was obtained by graft polymerization of styrene merisate, a very good impact

or styrene and acrylonitrile using a durability, however, this resin has the disadvantage

Polymerization initiator of the peroxide type in opposition to the fact that it is deteriorated by ozone and

Was a rubber-like polymer tending to conju- ultraviolet rays or a very bad one

gated Dio.Cxinart polymerizes, whereby an acrylic 5 windering resistance due to in the chewing

nitnl-butadiene-styrene resin or? in polystyrene resin, chuk-like polymer in the main chain

of high impact resistance, which has one which has unsaturated double bonds. To the

Structure with phase separation and interfacial affinity- Improvement of the weather resistance of one of the-

activity was. Under the imprint-like resin used here was, therefore, a process for

»Formation or structure with phase separation and io graft polymerisation of various vinyl mono-

Interfacial affinity "is a structure to be understood, meren on an essentially saturated rubber

in which proposed in the interface zone between a type of polymer. With this

rubber-like material and a hard resin will drive peroxide bonds in the polymer

a polymer with an affinity for both phases by oxidizing the rubbery polymer

is present, as a result of which both phases form a mutually exclusive 15 and react with the monomers of the

seem to have long-term affinity. Brought resin component. Furthermore, a procedure

There is also adopted a method of manufacturing a ren in which the rubbery

elastomer modified polymer darch dissolving polymer to react with the resin monomers

an elastomer, in a polymer of one using a polymerization initiator

Vinyl compound or a mixture of such 20 having a high hydrogen abstraction capacity

Monomers and polymerize the system in which is brought.

Mass by emulsion polymerization, suspension- However, since the rubber-like polymer

polymerisatiori or mass suspension polymer sat is practically in the saturated state and

sation known. It is also known that, accordingly, the number of graft-active points

occur a phase separation between a partial 25 or places is reduced, and also the affini-

elastomer phase polymerized in the bulk and did between the rubbery material and the

hard resin phase with stirring to achieve resin-like material due to the very low proportion

a high impact resistance, a high hardness that is grafted onto the rubber-like polymer

high tensile strength and good moldability of monomer is generally very poor, it is

is effective, with a small amount of a 30 difficult to establish a suitable interfacial affinity pha-

To create elastomers in the manufacture of an elastomeric mass release structure, and accordingly

modified polymer by graft polymerisation can be used impact-resistant resins after the

from styrene to a conjugated diolefinic syn- standingly described common working methods

thetic rubber by polymerization in which practically cannot be obtained.

Bulk or suspension polymerization 35 To overcome these difficulties,

is used. also a process for the production of an impact

However, the solid resin is not sufficiently efficient by polymerizing a vinyl compound

with regard to a high impact resistance in the case of bonding or of vinyl compounds in

obtained from a hard resin if an elastomer unit of an ethylene-vinyl acetate copolymer with

phase and the hard resin phase form a structure with Pha- 40 CH ₂ = CHCOO or CH, = C (CH ₃ ) COO groups

form separation. The above-described as a side chain and a dispersion of the ethylene-Vi-

Case in which the occurrence of a phase separation acetate copolymer with such side chain

formation, by simply mixing one acted in grains of 0.5 to 10 microns in a poly-

Can give the same impact resistance, an ausmethyl methacrylate resin is proposed. However, will

exceptional case, the solubility parameters of both 45 after such an improved process the

the phases are relatively similar to each other, phase separation structure with the interfacial affinity

as is not always obtained with a styrene-acrylonitrile copolymer, and even if the phase

sat and a butadiene-acrylonitrile mixed polymer separation structure with interfacial affinity

sat is the case. is aimed, a polymer with a good

In general, the solubility parameter of a 50 impact resistance is not always preserved,

hard resin from that of an elastome- In addition, according to the above-described

different, and in this case it is not always the most common ways of working.

for the achievement of an effective impact-resistant lymerisatartikel with a good surface

It is necessary to create a so-called structure with Pha properties. It is often the case

to create separation and interface affinity;> 5 that the surface of the polymer

d. H. in an interface zone in which a phage is roughened and the surface smoothness deteriorates

separation between a hard resin phase and, creating an appearance similar to that of matt-finished

an elastomer phase is present, a block mixing glass is obtained.

polymer or a graft copolymer, the object of the invention is to create thermal

probably the hard resin and the elastomer form thermoplastic molding compounds for the production of

containing components, with solid, weather-resistant molded body, the extra-

also for achieving improved ozone resistance and the Impact resistance the proportion of the block copolymer when molding objects with good surface merizate or the graft copolymer result in the smoothness. The invention also aims to

Interface zone is a very important factor. 65 Creation of a process for producing this

As described above, the resin possesses the thermoplastic molding material.

by graft polymerization using a material according to the invention are thermoplastic conical diolefinic rubber-like poly molding compounds for the production of impact-resistant, weatherproof

· ■ -

Resistant molded body created from (A) 0.5 methacrylic anhydride in the presence of a weak up to 80 percent by weight of a graft copolymer alkaline catalyst of an esterification reaction sats subjecting by graft polymerization from 20 to or

300 percent by weight of a vinyl monomer with (6) at least one elastomeric α-olefin vinyl ester

a content of more than 30 percent by weight of 5 vinyl alcohol copolymer or an elastomeric alkyl methacrylate with 1 or 2 carbon atoms in α-olefin-vinyl alcohol copolymer and little of the alkyl group on a graft-activated, elastomeric acrylic acid, methacrylic acid or their alkylmeres α-olefin vinyl ester Copolymer (main ester of an esterification reaction or ester interchange rubber polymer component) has been prepared by mixing the same with heating and at least one of the groups therein or by heating a mixture thereof in Ge-CH ₂ = CHCOO- and / or CH ₂ = C (CHg ) COO- as the presence of an alkaline or acidic catalyst, part of the side chains in a proportion of 0.05 to subject and the reaction product obtained in this way contains 1.0 mol percent of the binding units of the main chain with hydrochloric acid, sulfuric acid or an acid chloride, the proportion of which is mentioned - treated, with at least one of the groups of ten Main rubber polymer component 0.3 to 15 CH _{2 = CHOO- and CH 2} = CH ₂ = C (CH ₃ ) COO- as 30 percent by weight of the total composition contributes side chain to the elastomeric -olefinic mixture, and (B) 20 to 99.5 Percentage by weight of a polymer in a proportion of 0.05 to 1.0 molar polymer (resin component) of a radical polymer of the binding units of the main chain leads to vinyl monomers with a content of 0.3 to 30 parts by weight of this activated more than 30 percent by weight of a methacrylic acid - ao «-olefinic copolymer and 60 to 99.7 Geesters with 1 or 2 carbon atoms in the alkyl parts by weight of a radical polymerizable vinyl moiety exist, the graft rubber components with a content of more than 30 parts by weight (A) in the hard resin phase forming Resin percent of at least one alkyl methacrylate with component (B) is dispersed, the larger proportion 1 to 2 carbon atoms in the alkyl group z ur the rubber component (A) in the resin compo- »5 Creation of a solution of this copolymer in component (B) in the form of spherical hollow particles of the monomer mixture mixed, the activated from 0.05 to 0.5 micron, which is inside with the elastomer« -olefinic copolymer (chew resin component (B) are filled or in the form of chuk component) and the said vinyl mono-aggregations of these spherical particles are dispersed with stirring in the presence of a radical polymerized and the average wall thickness of the hollow part 30 polymerization initiator in the mass , until between 0.0025 and 0.125 microns and not more than the proportion of the total polymer in the poly- ¹ U of the mentioned mean grain size of this merizate system is increased by a phaseum over twice the proportion of the chewing material, chuk component According to the invention, a process of bringing about a reversal, and then partially in order to produce the above-described thermals Mass polymerized system of a Polymerisamoplastischen molding compositions described, which is characterized tion in the mass or a suspension polymerisage that one subjects either tion.

(1) an alkyl methacrylate and an elastomeric In den

Λ-olefin-vinyl ester copolymer of an ester series F i g. 1 to 5 are electron microscopic photo-exchange reactions in an alkyl methacrylate as solvent ♦ <> graphics (magnification 30,000) of very thin solvents in the presence of a solution of an alk- Sections of objects from the activated oxide of an alkali metal in a solution of ethylene vinyl acetate -Mischpolymerisat mixed agent shown as a catalyst at a lower temperature resin compositions, and in the
than the boiling point of the solvent for the catalyst F i g. 6 and 7 are in photographic representation

sator or 45 imprints of the surfaces of the objects of the with

(2) an alkyl methacrylate and an elastomeric resin compositions mixed with the activated ethylene-vinyl acetate copolymer olefin-vinyl ester copolymer of an ester composition are shown,
exchange reaction in a mixture of mixed poly examples of the merizable vinyl compound monomers used according to the invention, which are an alkyl methacrylate, methyl methacrylate and ethyl-alkyl methacrylate and an aromatic vinyl compound 5 ° methacrylate. The alkyl methacrylate may contain an alkali metal as a catalyst in the presence of an alkoxide of other radical polymerizable vinyl compounds or binding in an amount of less than 70% by weight

(3) an alkyl methacrylate and an elastomeric percent thereof are mixed. As a means of radical α-olefin-vinyl ester copolymer in a polymerizable vinyl compound, which with the algae over hydrocarbon methacrylate which is inactive in the reaction is to be mixed, e.g. solvent of an ester interchange reaction in anwe- alkenyl-substituted aromatic compounds of the Sness of an alkoxide of an alkali metal as Ka general formula

subject or

(4) an elastomeric α-olefin vinyl ester vinyl alcohol _
hol mixed polymer or an elastomeric «olefin 60, 1 ~~
Vinyl alcohol copolymer and at least one

Acrylic acid chloride or a methacrylic acid chloride

an esterification reaction by mixing under Rj

Subject to heating or χ

(5) an elastomeric α-olefin vinyl ester vinyl al 65 ^/
alcohol copolymer or an elastomeric a-oil

fin-vinyl alcohol copolymer and at least are used in which R 1 and R "are hydrogen of the compounds of acrylic anhydride or atom, a methyl group or a halogen atom

7 8

put. Practical examples of this are styrene and are used are compounds of general rt-methylstyrene. Other vinyl formulas can also be used

connections, e.g. B. acrylonitrile, methacrylonitrile,

Acrylic acid, methacrylic acid, an alkyl acylate (with 1. ,

to 8 carbon atoms in the alkyl group) and a 5 Il

Alkyl methacrylate (with 3 to 8 carbon atoms in CH ₂ = CH - O - CX

of the alkyl group).

Among the combinations of the above-mentioned vinyl compounds, the use of wherein X is a hydrogen atom gives an alkyl group of 1 Combination of 30 to 100 percent by weight alkyl ίο to 8 carbon atoms or an aroma ^ -che methacrylate (containing at least 30 Ge groups with 6 to 8 carbon atoms. Weight percent on alkyl methacrylate with some alkyl preferred examples are vinyl formate, vinyl group with 1 to 2 carbon atoms) and 0 bis acetate, vinyl propionate and vinyl benzoate. 70 percent by weight of alkyl acrylate a weather- The elastomeric copolymer of the α-ol

Resistant and impact-resistant resin with a very 15 fin and the vinyl ester can be used in a known manner good transparency as well as a high economic by copolymerizing the α-olefin and the lent utility in terms of hue and vinyl ester at a temperature of 1100 to 300 ° C of coloring power. In this case it is so produced and under an extraordinarily high pressure of made mixed polymer composition particularly good - 100 to 1000 at using a radical to show the weather resistance, e.g. resistance ao polymerization initiator, for example a Perdigkeit against discoloration and deterioration, oxyds. It is for the thread. That is, through the use of the above mention of a copolymer with a good one specific combination of vinyl-mechanical behavior that the content of Bonds can be an impact resistant resin with the best of the vinyl ester being less than 30 mole percent of the bin's weather resistance among the resin masses there is »5 formation unit in the main chain, can be obtained according to the invention. A copolymer of ethylene and one

In the case of using a mixture of vinyl esters other than vinyl acetate, herroi and methyl methacrylate and / or ethyl acrylate can be provided by introducing an ethylene-vinyl acetate the increase in the proportion of styrene to a down copolymer and a vinyl ester to an ester take the transparency of the polymer mass up to an exchange reaction in a solvent, e.g. Dizu a translucent behavior. If the oxane, use a sodium naphthalene fraction is further increased by styrene, the containing complex compound is subjected as a catalyst, tene polymer composition completely cloudy. On the other hand, an activated ethylene vinyl acetate can also be used but with an increase in the proportion of sty vinyl alcohol copolymer partly due to hyrene the moldability of the polymer composition is improved by the drolysis of an activated ethylene-vinyl acetate mixture. As vinyl compound monomers with polymerizats in an inactive solvent, e.g. B. the alkyl methacrylate to be mixed is toluene, using a methanol solution of Styrene with regard to the interpolymerizability and sodium hydroxide as a catalyst are produced, the most advantageous of the cost, "and practical will The proportion of that used according to the invention

chosen a composition in which the 40 elastomeric, -i-olefin-vinyl ester copolymer Sum of the proportions of methyl methacrylate and styrofoam with regard to the creation of a phase center roll is more than 60 percent by weight. voltage structure or a phase separation structure

When using methyl methacrylate in one should not be too high and should be considered in terms of sheep quantity of 100%, the polymer composition does not have too low a function of high impact strength best transparency, tensile strength and hardness on, and 45 be. Accordingly, the proportion of the -olefin is if an acrylic ester with the methyl methacrylate-vinyl ester copolymer of the elastomer type (the is mixed, the hardness and tensile strength of the rubber used in the graft polymerization are deteriorated. like main polymer component) appropriate

Taking into account the above-described 0.3 to 30 percent by weight, preferably 1 to 20 genes To balance the properties, it is necessary - 5% by weight of the finished polymer mass, lent, the monomer mixture at least 30 Ge. According to the invention, a donut activating

percent by weight methyl methacrylate and / or ethyl and essentially saturated kaiitschukartimethacrylat for the achievement of the transparent or total elastomer with CH ₂ = CHCOO groups or translucent polymer mass with upright CH ₂ = C (CH ₃ ) COO groups as side chains chewing maintenance of an adequate tensile strength and 55 chuk-like components for the graft activation to incorporate hardness. the a-olefinic copolymer of the elasto-

Examples of that used according to the invention before the merenart, which so far as inactive chew-activation Λ-olefinic mixed polymer used with an extremely good elastomer The type of elastomer is a mixed polymer with weather resistance and ozone resistance α-olefin and a vinyl ester and an α-olefin had become known, and it was found that, fin vinyl ester vinyl alcohol copolymer, which if the grafting activity of the activated and im due to partial hydrolysis of the above-described essential saturated rubber elastomer benen copolymer is produced. Examples is and the proportion of introduced as the side chains Λ-olefins are ethylene, propylene, butene-1, pentene double bonds are large, a graft reaction in ten-1, Hcxen-1, Hepten-1, 3-methylbutene-1 or 65 takes place to a high degree when a solution of the 4-methylpentene-1, including ethylene in particular rubber-like elastomers in the monomer is preferred. The corresponding above is polymerized in the mass with stirring, woschribenen Vinyl ester, which occurs according to the invention by a crosslinking reaction and the sy-

stem is gelled. The gelation or gelation is a serious disadvantage in the manufacture of thermoplastic resins. Also finds even if the proportion of double bonds introduced as side chains is reduced to such an extent that causes no gel formation of the reaction system, is reduced if the proportion is above a certain Value, the graft polymerization reaction is too high in the case of polymerization in the Mass of a solution of the activated substantially saturated rubbery elastomer in the Monomers take place with stirring, whereby it is not always possible to combine the rubber-like elastomers in one granular state and maintain the phase separation structure and moreover, even if the greater part of the rubbery elastomer causes phase separation, part of it tends to be to remain dissolved in the hard resin phase. This tendency diminishes to a considerable extent the moldability of the polymer composition thus obtained. Therefore, it must be used in the manufacture of the impact resistant resin by dissolving the graft activated and substantially saturated rubbery elastomer in the vinyl compound polymer according to the procedure described above, the proportion of in double bonds introduced as side chains of the rubbery elastomer are less than 1 mole percent of the binding units of the main chain for the production of a polymer material with a good one Be malleable.

Moreover, it is useful for achieving good Impact resistance required a suitable phase separation structure with interfacial affinity too create, and for this purpose the graft percentage must be within a narrow range, namely to one Range from 20 to 300 percent by weight.

Taking into account the factors described above, the proportion of those introduced as side chains must Double bonds higher than 0.05 mol percent, preferably 0.2 to 0.9 mol percent of the bond units the main chain, the Λ-olefin-vinyl ester copolymer be of the elastomer type. The proportion of double bonds to be introduced can be determined by the reaction temperature and the reaction time and the amount of the catalyst can be regulated.

In addition, as described above, in the case of producing an impact-resistant resin, it is necessary to create the phase separation structure with the interfacial affinity; however, even at Realization of a phase separation structure with interfacial affinity with a polymer mass good impact resistance is not always obtained.

It has now been found that for the preparation of the impact-resistant resin composition, the combination of the rubber and the resin components and the shape of the particles of the rubber component dispersed in the resin component are very important, and that it is particularly necessary that the rubber component in the resin component constituting the hard resin phase is dispersed with the greater part of the rubber component in the continuous resin component in the state of spherical films having an average grain size of 0.05 to 0.5 microns containing therein the resin component or aggregations of the spherical films is present and wherein the mean thickness of this film is 0.0025 to 0.125 microns and not more than ¹ Å of the mean grain size thereof.

Investigations showed that if z. B. an acrylic

rubber (a butyl acrylate-acrylonitrile mixed polymer with a content of 12 percent by weight Acrylonitrile), which had been graft activated by introducing double bin fertilizers as side chains on a polymer component consisting mainly of styrene and / or methyl methacrylate

ίο was brought to a phase separation structure mi Interfacial affinity was formed, but as a method for realizing the formation of suitable Necessary forms of rubber particles for achieving impact resistance have not been found could, a polymer composition with a sufficient impact strength could not be obtained.

On the other hand, it is generally the elasto when applying a Λ-olefin copolymer merenart, that by introducing double bonds

[CH ₂ = CHCOO groups or

CH ₂ = QCHjJCOO groups]

as side chains had been graft activated, on the polymer mass with a content of more than al: 30 weight percent methyl methacrylate impossible the formation of the above-described more suitable Realize shapes of rubber particles required for impact resistance, albeit a phase separation structure with interfacial affinity can be formed. Only if the side chain double bonds into the -v-olefinic copolymer of the type of elastomer introduced under the specific conditions described below is and also the \ -olefinic copolymer of the elastomer type, the graft activation is, in a monomer mixture with a content of more than 30 weight percent methyl methacrylate is dissolved and then under the special polymerization conditions, as described below, is polymerized, however, the phase separation structure can be formed with interfacial affinity, and in addition, the rubber particles can be used for imparting high impact resistance the resin have required shapes, whereby the useful thermoplastic resin composition with a grien resistance to proliferation as well as a good one Impact resistance can be obtained.

The typical electron microscopic photographs of the very thin sections of objects made of the polymer masses produced by the application of the Λ-olefin copolymer of the elastomer type, which is obtained by introducing CH ₂ = CHCOO groups or CH., = C (CH.,) COO- Groups in a proportion of 0.05 "to 1.0 mol percent of the binding units of the main chain had been graft-activated as part of the side chains, on which polymer composition with a content of more than 30 percent by weight of methyl methacrylate was obtained, are shown in FIGS. 1 to 5 ( These results show that the phase separation structure with interfacial affinity was formed in all cases, but effective impact resistance was obtained only with the compositions of Figures 4 and 5. Figure 5 relates to the case in which the rubber component was dispersed in the state of spherical films, and Fig. 4 relates to the case where

which the rubber component in the state of aggregation of such spherical films was dispersed.

For the formation of the spherical films or the aggregations of spherical films of the Rubber component, it is necessary, as described above, the rubber component under to activate the specific conditions described below and also under the conditions below to polymerize specified specific polymerization conditions, and in particular are the activation conditions for the rubber component for the generation of the spherical Films of the rubber component are important.

In the polymer composition according to the invention, wherein a phase separation structure when dispersed of the rubber particles is formed in the hard resin phase, has the grain size of the rubber particles a close relationship with the surface condition of the molded articles of the polymer composition on. Thus, when the mean grain size of the dispersed rubber particles is greater than 0.5 microns is, the surface of the object is in a roughened state, and the surface smoothness is worsened. In order to create a molded article with a good surface condition, it is necessary the mean grain size of the rubber particles dispersed in the resin phase is less than 0.5 microns (preferably less than 0.45 microns) and if the mean grain size thereof is reduced If a transparent resin is desired, the surface smoothness of the object will be improved its transparency is also greatly improved.

The F i g. 6 and 7 show in photographic representation impressions (magnification 850x) of the surfaces of the objects which were produced from the resin composition containing the activated ethylene-vinyl acetate mixed polymer with an average grain size of 0.8 and 0.3 microns, respectively. It is clear from these results that the surface smoothness of the article largely depends on the mean grain size of the rubber component particles dispersed in the resin phase, and even if the mean grain size is about 0.3 microns, the mean smoothness is very good. As the mean grain size of the rubber particles dispersed in the resin phase becomes smaller, the impact resistance of the resin becomes lower, and therefore it is necessary for practical considerations of an impact resistant resin that the mean grain size of the dispersed rubber particles is larger than 0.05 microns, preferably larger than 0.1 micron. The average thickness of the spherical film of the rubber particles is most preferably 0.0025 to 0.125 microns and not more than V _{4 of} the mean grain size thereof, and a resin composition capable of forming articles with good surface smoothness can also be easily obtained.

Moreover, according to the invention, the grain size is determined according to the following procedure. First, the object of the polymer mass is cut into thin sections (500 to 1000 Å thick) with the aid of a microtome, and the cross section is measured with the aid of an electron microscope photograph. The photograph is copied onto a cabinet size photographic copier paper at a magnification of 10,000 to 30,000, and the shape size of the particles is measured around the whole particles of the photograph. Since the rubber particles are in various shapes and the cross sections are not always circular ring shapes but have deformed ring shapes, the grain size (or diameter of the particles) is measured according to the following conditions: The largest diameter of the rubber particle is referred to as (a), the length the diameter passing through the center of the longest diameter perpendicular to it is called (ft), and the mean of (a) and (fc) is called the mean diameter (d) . d _t = (a _f + ft,) / 2. The mean grain size (d) used according to the invention is determined by means of the following equation using the results obtained by measuring the diameters of the whole particles:

Ση, ά?

Ση, ά?

where n, - denotes the number of particles with grain size d _t .

Since it is believed that one of the reasons for obtaining the resin composition having high impact resistance according to the invention in relation to the affinity of the interface layer between the rubber phase and the hard resin, and also the shape of the rubber component, which is a feature according to the invention is a spherical film containing the hard resin component therein contains, the surface shape and surface area of the rubber phase are very remarkable Importance, and therefore the above-described mean grain size value becomes according to the invention as an appropriate value related to the area of the rubber particles.

The resin composition according to the invention can usually be prepared by the following procedure will. In the first stage, some of the side chains of the Λ-olefin copolymer are used It is elastomeric and has one or two vinyl groups with good radical polymerization reactivity to an alkyl methacrylate or styrene, for example

CH ₂ = CHCOO group

and

CH ₂ = C (CH ₃ ) COO group

in an amount of 0.05 to 1.0 mol percent, preferably 0.1 to 0.9 mol percent, of the binding unit de Main chain introduced under the specific reaction conditions given below.

Then, in the second stage, the above-described activated α-olefin-vinyl ester mixture polymer alkyl methacrylates with 1 to 2 carbon atoms in the alkyl group and required if less than 70 weight percent of another copolymerizable vinyl compound monomer ren added, and the so mixed liquid mass <is adjusted so that the ratio of the activating th Λ-olefin-vinyl ester copolymer to de Total liquid 0.3 to 30 weight percent un <the ratio of vinyl compound monomers

Mixture to the total liquid 70 to 99.7 Ge ethanol, n-propanol, isopropanol, n-butanol and t

weight percent to the polymerizing isobutanol. It can also be used as a solvent for ι

To yield liquid. Then the system is against- these catalysts also use another alcohol-

if necessary, can be used after addition of a radical polymer. '

initiator. a chain transfer agent and 5 In the combination of, for example, the mixed (

other additives partially polymerized in the mass polymer (I) and the alkyl ester (c) can '<-

until the double bonds present in the polymerization system in the compound (I) as a side t

entire polymer a phase reversal in a chain with direct execution of the ester exchange ι

Ratio of at least 2 times the weight reaction using sodium methylate 1

the activated rubber component and io are introduced and also in the combination of the r

then, if necessary, a radical copolymer (II) or (III) with an acid ι

Polymerization initiator, a chain transfer mitchloride (d), can form the double bonds to the £

Tel and other additions to the system in addition to the side chain of the copolymer through a ver ι

leads, and the system undergoes a bulk polymerization reaction without the use of a catalyst

sated or suspension-polymerized to be introduced into the final gelling agent. In addition, c

to get cured polymer. Furthermore, if a combination of copolymer (II) or (III) c

the resin component monomers proportionally and acrylic acid (a) or methacrylic acid (b) the Dop-1

are small, the resin composition according to the invention may have pelbindungen to the side chain of the mixed polymer

by mixing a separately polymerized poly- sate by carrying out the esterification reaction and f

merisats that the above-described Vinylver- »o ter use of p-toluenesulfonic acid as Kata- j

Binding monomer mixture (A) contains, prepared lysator are introduced. Furthermore, in the

will. In this case, the system can be combined with mixed polymer (II) or (III) ν

using a common mix and an acid anhydride (c) the double bonds 1

are, for example, a heating roller, one in the side chain of the copolymer under verse

Bunbury mixer and / or an extruder mixer, using a weakly alkaline catalyst, 5

As described above, z. B. of pyridine, are introduced. c

As described above, if the An ι

Bination of rubber components and the shape of the double bonds to be introduced too high \

of the particles of the rubber components which is in the polymerization system during the manufacture λ

Phase of the resin component are dispersed, very 30 ment of the impact-resistant resin gelled and forms a 1

important, and also it is necessary that the three-dimensional networked structure, with the image

Rubber components in which the hard resin phase becomes difficult to form the phase separation structure. {

constituent resin components are dispersed and even if a phase separation structure in,

the greater portion that can be formed in the continuous resin - in this case, is the moldable -;

component phase dispersed rubber compound of the resin composition is extremely reduced. For t

nents in the form of spherical films or the achievement of a resin mass with a good 2

Shells are present that have the Harzkom impact resistance mentioned therein, it is necessary that the resin composition I

contain components, and for obtaining a suitable phase separation structure with

such a shape is formed by spherical films or a green surface affinity and the degree \

The envelope of the rubber components is the reaction of the grafting in the range of 20 to 300 weight- \

tion conditions for the introduction of the CH., ^ percent, preferably 50 to 250 percent by weight, ₍

CHCOO group or CH., = C (CHjcOO group. From these factors the necessary ₍

in the α-olefin-vinyl ester copolymer, the proportion of double bonds is 0.05 to 1.0 mol per-I

Type of elastomer very important. cent, preferably 0.1 to 0.9 mole percent, of the bin c

The graft-activated elastomeric α-olefin mixture unit of the main chain of the elastomeric oleic polymer, which is produced by the introduction of the dopinic copolymer. The proportion of double t pel bonds in the side chains is graft activated, bonds can be used in the implementation of mixed poly; can be prepared by adding (I) the pre-merisat (I), (II) or (III) and component c mentioned α-olefin-vinyl ester copolymers (a), (b), (c), (d) or (e) through the reaction temperature, (II) the volefin-vinyl alcohol mixed polymer temperature, reaction time and the amount of catalyst
sat, which can be regulated by complete hydrolysis of the micchpoly-. <merisats (I) has been produced, or (III) the As stated above, these graft α-olefin-vinyl ester-vinyl alcohol copolymers, activated elastomeric α-olefin copolymers f that by partial hydrolysis of the copolymer! - are not always for dispersing the rubber parts; sats (I) has been made with (a) acrylic acid, 55 chen in it in the form of spherical films of the
(b) Methacrylic acid, (c) an acid anhydride thereof, the rubber components containing resin components, acid chloride or an alkyl ester thereof, or converts aggregations of such spheres. In this case, if necessary, a shaped film which is a feature of the invention is acidic catalyst, for example hydrochloric acid, sulfur, is suitable. B. the activated rubber,
Flaic acid, p-toluenesulfonic acid or the like, an alkaline ⁶ ° of the active catalyst described below, z. B. an alkoxide of an alkali metal, approximately conditions was prepared for use
for example sodium, lithium or potassium, it is usually difficult to get the rubber
and a weakly alkaline catalyst, for example pyrite particles in the resin component phase in the form of
din. spherical films or shells or the aggregate

Practically, the alcohol component is used ^{to disperse the alk- 6} 5 ions of the spherical films.

oxides of the mentioned alkali metals a lower Al- If the activated ethylene-vinyl acetate mixed

Alcohol with fewer than 4 carbon atoms polymerized with CH ₂ -C (CH.,) COO groups as

turns. Practical examples of this are methanol, part of the side chains made by one

Ethylene-vinyl acetate copolymer and methyl methacrylate of an ester exchange reaction at high temperature, for example 8O ⁰ C, significantly higher than the boiling point of a solvent for the catalyst (Methanoi in this example '), in methyl methacrylate as the only solvent in the presence of a methanol solution of sodium methoxide as a catalyst It is difficult to disperse the particles of the rubber component in the activated copolymer in the form of spherical films or collections of spherical films. However, in this case the above-mentioned purpose can be achieved by previously modifying (denaturing) the activated a-olefin copolymer of the elastomer type with hydrochloric acid, sulfuric acid or an acid chloride, such as acetyl chloride, prior to graft polymerizing the monomers to form the copolymer. This modification process can be performed under the following conditions:

0.5 to 100 parts by weight, preferably 1 to 70 parts by weight, of the active ethylene-vinyl acetate copolymer are dissolved a solvent in 100 parts by weight, and the solution is treated with hydrochloric acid, sulfuric acid or an acid chloride at a temperature of 20 to 12O ⁰ C, preferably 40 to 100 ^° C. for more than 10 minutes, preferably 30 minutes. Examples of the solvent used in the above-described treatment are hydrocarbons such as benzene, toluene, xylene, η-hexane, n-heptane, cyclohexane and styrene, organic halides, ζ. Β. Chloroform and ethylene tetrachloride, esters, e.g. B. methyl acetate, ethyl acetate, methyl propionate, methyl methacrylate, methyl acrylate and ethyl acrylate and organic acids, e.g. B. methacrylic acid, acrylic acid, acetic acid, propionic acid or the like.

When hydrochloric acid is used in the denaturing or modifying treatment described above, hydrogen chloride gas can be introduced directly into the reaction system can be blown, but it is more advantageous to use an alcohol (preferably Methanol) solution of hydrochloric acid, which has been produced by saturating the alcohol with hydrogen chloride gas is to use. The amount of hydrochloric acid is 1 to 50OmMoI, preferably 10 to 30OmMoI, given as hydrogen chloride, per 100 parts by weight of the activated ethylene-vinyl acetate copolymer.

When using before »sulfuric acid, as when using hydrochloric acid, it is more advantageous to use a Alcohol (preferably methanol) solution of sulfuric acid to be used by dissolving concentrated Sulfuric acid in which alcohol is produced. The amount of sulfuric acid is 1 to 50OmMoI, preferably 10 to 30OmMoI, expressed as sulfuric acid, per 100 parts of the activated Ethylene-vinyl acetate copolymer.

Furthermore, when using an acid chloride, an acid chloride such as acetyl chloride, acrylic acid chloride, Methacrylic acid chloride and propionic acid chloride, are used. The amount of the acid chloride is 1 to 5 mmol, preferably 10 to 50Ommol per 100 parts of the activated ethylene-vinyl acetate copolymer.

For obtaining the activated α-olefin copolymer the type of elastomer that easily removes the rubber particles in it in the form of the above :) spherical films or the agglomerations or aggregations of the spherical films can disperse, the activation of the elastomeric α-olefin copolymer can also be among the under the following conditions:

(1) An α-olefin-vinyl ester copolymer and Methyl methacrylate undergoes an ester interchange reaction in a single solvent, namely methyl methacrylate, at a much lower one

ίο Temperature as the boiling point of a solvent for the catalyst in the presence of a methanol solution of sodium methoxide as a catalyst to create an α-olefin-vinyl ester mixed polymer with CH ₂ = C (CH ₃ ) COO groups as part of the

Subject to side chains.

(2) An α-olefin vinyl ester copolymer and methyl methacrylate undergo an ester exchange reaction in a mixed solvent of methyl methacrylate and a hydrocarbon solvent such as toluene or styrene which is inactive for the reaction, in the presence of a methanol solution of sodium methoxide as a catalyst to create an α-olefin vinyl ester -Mischpolymerisats with CH ₂ = C (CH ₃ ) COO groups as part of the side chains.

(3) A Λ-olefin-vinyl ester-vinyl alcohol copolymer and methacrylic acid chloride are converted into toluene and / or methyl methacrylate by creating an α-olefin-vinyl ester-vinyl alcohol copolymer with CH ₂ = C (CH ₃ ) COO groups as part of the side chains implemented.

(4) an α-olefin vinyl ester copolymer and methyl methacrylate undergo an ester exchange reaction in methyl methacrylate as the only solvent at a temperature significantly higher than the boiling point of a solvent for the catalyst in the presence of a methanol solution of sodium methoxide to create an α-olefin vinyl ester Subjected mixed polymer with CH ₂ = C (CH ₃ ) COO groups as part of the side chains, whereupon the mixed polymer is treated in toluene with hydrochloric acid, sulfuric acid or an acid chloride.

(5) A ft-olefin-vinyl ester-vinyl alcohol copolymer and methacrylic acid undergo an esterification reaction in a solvent mixture of toluene and methacrylic acid in the presence of p-toluenesulfonic acid as a catalyst to create an α-olefin-vinyl ester-vinyl alcohol copolymer with CH ₂ = C (CH ₃ ) COO groups as part of the

Subjected side chains, whereupon the copolymer in toluene with hydrochloric acid, sulfuric acid or acetylene chloride is treated.

The particularly preferred procedure for introducing the double bond is that under Procedure (1) and procedure (2) shown activation process, but the ethylene-vinyl acetate copolymer an ester interchange reaction in a mixed solvent of interpolymerizable Vinyl compound monomers containing at least one alkyl methacrylate in the presence of one Is subjected to alkoxide of an alkali metal as a catalyst, and this procedure is special effective with regard to the implementation described below.

If namely without the need for recovery the activated elastomeric ^ -olefinic copolymer by, for example, precipitation than other ways of working, vinyl compound rrono-

mers of the activation reaction according to the above procedure described, solution

ren in the figures provided above ^ ^"e n Bere.ch egt 1, the solution thus prepared can be used as before * o lymensaüonsverfahren dem_lo in the second stage supplied ^ ^ ^ ^ _{Methacrylsäureest>} ^

or another mischpo.ymeris.erbaren Vi " _yl . connection, üie in essence no opposite of

^ _{0n inactive solution element emhä |}
y _{after the donkey exchange is over} ,

£ iu ^ ^ ^ _{der Einste]} , _{ung the concentrate} ^{jo n} _{n of} the rubber component and the composition

monomers that are in the form of a mixture with a

to be incorporated into a concentration that leads to none Precipitation of the ethylene-vinyl acetate copolymer leads

The characteristics of the ester interchange reaction of the above-described olefin-vinyl ester copolymer and the methacrylic acid ester are explained in detail below.

(1) Only part of the methacrylic acid ester, 5 takes part in the ester interchange reaction, and the vinyl groups of the remaining methacrylic acid ester are maintained in the active state throughout the reaction.

(2) Even if other copolymerizable yinyl compounds are present in the reaction system, the vinyl groups of the vinyl compounds become not inactive during the activation reaction if it has no adverse effects on the Exercise ester interchange reaction.

(3) The major proportions of the methacrylic acid ester and other copolymerizable vinyl compounds act as a good solvent for the x-olefin-vinyl ester copolymer.

(4) In the activation reaction (ester exchange reaction), the amount of by-products is very small and, after the activation reaction is finished, if necessary, the resulting solution in the subsequent polymerization stage with the addition of copolymerizable vinyl compounds can be treated without significantly disrupting the polymerization.

(5) The activation reaction (ester exchange reaction) can take place at a relatively low temperature be carried out, the extent of the reaction in the activation reaction up to such The extent to which is rapid is that the reaction reaches equilibrium within 30 minutes to 1 hour and even if so a vinyl compound (e.g. styrene) capable of polymerizing under heating without the presence of a catalyst capable of existing in the reaction system, the polymerization percentage of the vinyl compound during the activation reaction can be reduced to an extent substantially below eight can be left (for example, the reaction temperature is kept at 50 to 80 ° C, and 5 to 200 parts / million of a polymerization inhibitor can be incorporated into the system).

Since the ester interchange reaction has useful advantages or features, it is possible to do the above described expedient and acceptable direct process for the production of the weather-resistant weatherproof thermoplastic resin compositions

z. B. Styrene, ^^?}.?
chlorostyrene, or various Vmylmonorneren, z. B. vinyl chloride, are mixed. These can expediently be selected according to the solubility of the-olefin vinyl ester polymer polymer used Nylon compounds which are a good solvent and which are used in a concentration with which no precipitation of the olefin-vinyl ester mixed polymer is formed. As the solvent inactive with respect to the polymerization, among the solvents inactive with respect to the activation reaction which are used in the activation method (2) described above, hydrocarbon compounds or their derivatives capable of dissolving the elastomeric olefin copolymer, e.g. B. toluene, η-hexane, cyclohexane, heptane, benzene and xylene are used.

When the activation treatment for the x-olefin-vinyl ester mixed polymer carried out in a solvent which is inactive towards the polymerization it is necessary that after the activation reaction has ended, a non-solvent (Precipitating agent) is added to the product, and after recovery of the activated, in this way precipitated A-olefin-vinyl ester copolymer the copolymer is washed, dried, again in a certain polymerizable vinyl compound dissolved and the solution polymerized in the mass or suspension polymerized. The extraction of the activated vinyl polymer in the process described above leads to very large Losses in terms of solvent and non-solvent consumption and losses Due to the set-up costs for the extraction process, personnel and time expenditure. Therewith is the weather-resistant, impact-resistant, thermoplastic resin compound finally produced with Costs burdened, and therefore the economic value of the weather-resistant, impact-resistant, thermoplastic Resin mass greatly reduced. Accordingly, it is convenient and desirable in the activation step not to use a solvent which is inactive with respect to the polymerization. If necessary is, after the activation reaction, impurities such as residual catalyst in the rubber and Solvent (alcohol) to completely remove the catalyst solution can of course also be used in the case

19 20

the use of an inactive solvent that The calculation of the value in mol percent units

activated copolymer is obtained once and th is based on the component ratio

in the polymerization reaction in the second stage from α-olefin to vinyl ester in the previous

using wcrder .. measuring sample carried out.

As the ester used in the ester exchange reaction for the 5 As described above, the Dispercie application, methacrylic acid esters having the particles of the rubber component in the an alkyl group of 1 to 8 carbon atoms in the resin component can be used by a suitable selection of. Examples of this are achieved by methyl polymerization conditions. In the case of methaci-ylate, ethyl methacrylate or butyl methacrylate. Production of the impact-resistant resin by emulsion-For the introduction of the CH, = CHCOO groups io polymerisation using a Kauw, the execution of the ester exchange reaction under Tschuklatex with the desired grain size the latex use of the above-described acrylic particles in the polymer in almost the same way ester is not so much preferable, rather the grain size is dispersed, and therefore the grain use of acrylic acid chloride and acrylic acid size of the dispersed rubber particles may easily be anhydride preferred. _{15 are} regulated. In the way of working, in which

The ratio or proportion of the ester-a solution of the rubber-like material in the

exchange reaction introduced as a side chain vinyl monomers polymerized in the mass or suspen-

groups can be ionized according to the procedure described below, but it is impossible to pre-

Operation according to the invention can be measured. the rubber component in the form of

A toluene solution to disperse a sample of the \ -olefin-vinyl 20 particles. Therefore, there is a working ester mixed polymer with incorporated therein, which acrylic acid groups or acrylic acid groups are necessary for the formation of a phase separation, in which the particles of the rubber particles are added to a large amount of methanol to disperse the solvent in the resin phase in a solution to coagulate, and the coagulate is repeatedly polymerized a solution of the rubbery with methanol and washed for 2 days at 25 material in the monomer, the solution of the 20 to 30 ° C, whereby a sponge-like rubbery material is partially obtained with stirring sample. Then a 200 ml alder is prepolymerized until at least one phase Meyer flask equipped with a reflux condenser takes place in the mass,
tet and with 1000 g of the sample prepared in this way and with The phase inversion generally takes place about 15 ml of dioxane and takes place in a bath of 90 ° C 30 when the portion of the total polymer is immersed in, the sample being uniformly in that of the polymerization system twice as much as the Ge-dioxane is dissolved. weight of the rubber-like polymer,

Then 10.0 ml of a methanol and it is therefore necessary to use a partial polymer

solution of 1 n-KOH is added to the solution, whereupon sation is carried out in the mass, the stirring

Maintained under reflux for 10 minutes and then speed until the phase reversal occurs

50 ml of distilled water are also added.

and then again for 5 minutes under the term used here »phase reflux is held. After that, the reversal ”is to be understood as follows: When the mono-giving Solution cooled to room temperature, with one containing the rubber component in solution, is polymerized by means of a standard solution of 1 η-hydrochloric acid under 40 with stirring, this is used Vinyl polymer newly formed by Phcnolphthalein as an indicator from the rubber compotralized and after adding 15 ml of an aqueous component due to the poor affinity of this ge solution separates from 2 η-hydrochloric acid and 10 ml of an aqueous one; however, because the proportion of vinyl polymer With a solution of 40 g / l KBr, the resulting solution is initially less than the amount of rubber un- 45 component by suction in a Büchner funnel, forms the one dissolved in the monomer The use of some filter papers for sheep rubber has a continuous phase, and that fung of a colorless and transparent aqueous vinyl copolymer dissolved in the monomer Solution filtered. A discrete dispersion phase is added dropwise to the filtrate. If the anonymous Solution of 0.1 n-KBrO., Added until the part of the vinyl copolymer in the further Solution turns yellow, and the system is closed. 50 Polymerization proceeds to a certain point and during 15 minutes, in the case of the determination, its extent increases, the inversion or dei occurs the proportion of methacrylic acid groups and during the transition of the polymerization phase, d. h., the 2 hours in the case of determining the proportion of vinyl copolymer phase present in the monomers Acrylic acid groups left to stand. is dissolved, forms the continuous phase, and the

Then, after adding 10 ml of an aqueous rubber phase, the discrete dispersion phase is formed

Solution of 20 g / l KJ the solution by means of a Stan- The transition of the phases is called phase reversal

Standard solution of 0.1 n-Na., S., O., titrated (where in the denotes.

In this case, the titer "of the standard solution of The grain size of the rubber component part

0.1 11-Na ₀ S ₂ O ₃ , which is added, can be designated as α ml due to the prepolymerization conditions

net is) "A blank value will also be regulated in the mass under execution 60. The control or Re

the same procedure without adding the sample gel conditions are achieved by combining «

measured (in which case the titre is determined by various factors, e.g.

0.1 n-Na., S ₂ O _{3 is} referred to as h ml). by the prepolymerization time, the shape de

The proportion of double bonds in the sample becomes the polymerization vessel, the shape of the stirrer determined by the following equation: 65 direction, the speed of the stirrer and the end poly

merization percentage, but in particular

Double bond = ^{h ° '· 0.1 · 10 ~ «mol / g. ^the prepolymerization percentage is important, and

τ therefore it is necessary, as described above, ie

21 22

Prepolymerization is applied until phase retirement occurs in the second stage,

to perform reversal. is usually an oily radical polymerization

The degree of stirring or the stirring speed initiator, and it may e.g. B. a peroxide initiator such as in the prepolymerization depends on the scale benzoyl peroxide, DUert.-butylperoxide, lert.-butylder Polymerization, the dimensions and the perbenzoate, lauroylproxyd, methylethylketonperstalt the stirrer and the type and amount of chain oxide, cyclohexanone peroxide, p-methane hydroperoxide, Transfer agent, the degree of stirring cumene hydroperoxide or the like, and an initiator however, to provide at least one for that of an azo compound, e.g. B. azobisisobutyronitrile or 2.2'-Azobis-2-methylbutyronitrile required to apply the shear force to effect the phase inversion must be suitable. This is how long the stirring process is.

usually measured in the range of 50 to 1000 U-sec " ^1. As is well known, it is preferably 70 to 500 U-s.ec- ¹ in the manufacture of an impact-resistant resin by forming a graft-average shear force rate the type of chain transfer required, the speed is lower than the specified range is a peroxide initiator with a high hydrogen, a phase inversion does not take place in sufficient peelability, such as benzoyl peroxide or di-tert-the extent, or the grain size of the disperbutyl perbenzoate, However, in the yawed rubber particle is greater than 0.5 Mi. the case of the invention, in which a graft mixed polymer, while if the shear rate is higher merisat of the type of copolymer, a range than the specified range, the grain size of the sufficiently effective or usable graft poly rubber particles undesirably smaller ao merisat can be obtained nn by not only being 0.05 microns. the peroxide initiator with a high

The temperature for the previous polymer removal capacity, but also an Azoverbinsation The mass is usually from 30 to a formation initiator that has almost no dehydrogenation-250 ° C, preferably 45 to 220 ° C. If the poly possesses, for example, azobisisobutyromerization temperature lower than the specified 25 nitrile, used. Since according to the invention one of the range can be a practical level of such initiator that has almost no dehydrogenation polymerization are not obtained, while if has the capacity, such as azobisisobutyronitrile, deserve Polymerization temperature higher than that can be used, in particular, can be any given range, the polymer deteriorates to the nature of a mercaptan chain transfer agent, which is not beneficial. 3 ° can be used together with the initiator, wherein

In the previous polymerization in the composition also contained in the case of the preparation of the acrylonitrile there is a tendency that when the poly-tending polymer composition there is a tendency to a gelation time long discoloration can be avoided after the phase reversal, whereby according to is, the stirring time is then extended and the invention creates a particular advantage, according to the grain size of the rubber particles gradually- 35 The amount of used according to the invention borrowed becomes smaller. Therefore, the length of time or the elastomeric, -x-olefin-vinyl ester copolymer Point in time at which the prepolymerization is allowed for the formation of the phase separation structure will break, in accordance with the grain, not be too large and allowed for the extraction of a size of rubber particles that is desired. The high impact strength should also not be too low. So selects, whereby it is necessary, however, the prepoly- 40 expediently lies the amount of the elastomeric -v-olefimerisation carry out until at least the phase-niche copolymer in the range from 0.3 to reversal takes place. In the practical version, 30 percent by weight, preferably 1 to 20 percent by weight of the invention are based on the result percent, the finally obtained copolymers an exact observation of the electron mass.

microscopic analysis of the samples obtained after 45 In suspension polymerization in aqueous

different combinations of prepolymerization phase, a water-soluble high molecular weight

conditions were established, the conditions so binding, e.g. B. polyvinyl alcohol, a styrene-malcine

chosen that the mean grain size of the rubber-acid mixed polymer and sodium salts of poly-

particle becomes 0.05-0.5 microns. The temperature methacrylic acid, and an inorganic compound,

the polymerization in bulk or in the suspension 5 ° z. B. a water-insoluble carbonate, a sulfate

sion, which is used in the second stage after the prepolymer - phosphate and a hydroxide

sation running is usually at 30 to gen.

250 ° C, preferably 45 to 220 ° C. Taking into account the composition of the

In the case of the polymerisation in the mass carried out in the second stage according to the procedure described above, the degree of stirring or the polymer mass produced according to the invention must be kept at the same level as the degree of grafting of the vinyliTioncrnercrikompowerden necessary to bring about a shear of the nenten with a content of more than 30 weight rubber phase is not sufficient, and preferred percent methacrylic acid ester, based on which the polymerization system is not essential Range from 20 to 300 is chosen so that it is less than 50 ^{seconds "1.} percent by weight, preferably 30 to 250 percent by weight, on the other hand, it is percent in suspension polymerization - the invention 0.5 to 80 percent by weight, The preferred alloying of the beads of the copolymer is 1 to 70 percent by weight, of the graft polymer, and the top rate is preferably used (the proportion of the main rubber polymeric flow rate of the screw being higher than 30 m / min. sat component 0.3 to 30 percent by weight, preferably

The polymerization initiator, which is 1 to 20 percent by weight of the total mass in the polymer

sation in the mass and the polymerization in suspension), and 99.5 to 20 percent by weight, preferred

wise 99 to 30 percent by weight, of the polymer radical polymerizable vinyl monomers (resin component) containing more than 30 percent by weight methacrylic acid ester contain.

If the degree of grafting exceeds 300% by weight (the proportion of double bonds in the activated rubber mass more than 1 mol percent of the binding units of the main chain is), the affinity between the rubber component and the resin component becomes too high, and accordingly, the grain size of the dispersed rubber particles is reduced too much, whereby the Impact resistance and the moldability of the polymer composition is reduced.

On the other hand, when the degree of grafting is less than 20% by weight (where the proportion of the double bonds in the rubber component is less than 0.05 mol percent of the bond units of the main chain), the affinity between the rubber component and the resin component are insufficient, thereby preventing the dispersion of the Rubber component in the form of spherical films is made difficult.

As described above, the degree of grafting can be increased by the introduction of the double bonds regulated in the α-olefin-vinyl ester copolymer will.

Further, when the composition ratio is out of the range according to the invention, are the mechanical properties such as impact resistance are poor, and the desired polymer composition can will not be echoed.

Conjugated diolefinic synthetic rubber materials are used as rubber components, and these are in terms of Weather resistance as well as ozone resistance due to the in the main chain of the rubber component existing unsaturated bonds very inferior, and accordingly such Common resins are rarely used as materials for outdoor use.

In contrast, the invention successfully leads to the production of useful, striking, impact-resistant Resins by using the α-olefin copolymer the type of elastomer with particularly good weather-resistant behavior and a particularly good ozone resistance as a rubber component. Thus, according to the invention, there is a resin With excellent impact resistance and weather resistance created on a large scale for Materials for outdoor use as well as for electrical purposes can be used.

The degree of grafting is determined according to the invention by the following method.

Determination of the degree of grafting

A 300 ml Erlenmeyer flask was filled with 1000 g a sample and 10 ml of toluene, and after attaching an upright condenser to the upper one At the end of the flask, it is immersed in a bath at 11 ° C. While stirring the mixture occasionally the sample is uniformly dissolved in toluene in about 30 minutes. Then 9OmI acetone or dimethylformamide is slowly added to the system through the condenser and the system is turned on Heated 110 ° C for 30 minutes. In this case it is it is necessary to increase the effect in terms of obtaining the graft polymer, acetone or dimethylformamide according to the composition of the sample. On the basis of research it has been found that acetone is advantageously used when the resin component is made more than 80 percent by weight methacrylic acid ester, while dimethylformamide is advantageous for Used when the proportion of methacrylic acid ester in the resin component is 30 to 80 percent by weight amounts to.

A certain amount of methanol is added to the mixture and the system becomes during Refluxed for 30 minutes. The amount of methanol will be according to the kind of the resin component varies and is one by which the hard resin component is not precipitated, however the rubber component and the graft polymer containing the rubber component and the hard resin component grafted on the rubber component is precipitated. The amount Methanol, which is used to determine the degree of grafting in the examples according to the invention is shown in the table below, for example.

.

example

Amount of
Methanol (ml)

(1.1) - (1.10)

(2.1), (2.2), (4.1-4.4)

(6), (7.1) - (7.8), (8.1), (8) } 120

(8.2), (9.1), (9.2)

(10.I) - (ICO), (12.1) - (12.4) J.

(3.11), (3.2), (II) 90

(3.3), (5.1) - (5.5) 50

After the treatment described above, the flask is closed, allowed to cool, and Left to stand at 23 ° C overnight. Then the white one made the previous day becomes cloudy Liquid subjected to centrifugal separation for 2 hours at 3200 rpm. The protruding Liquid is slowly removed by suction from above, leaving the precipitate behind.

Then a washing liquid with the same composition as the mother liquor is in the Flask containing precipitate is introduced, and the system undergoes centrifugal separation during Subjected for 2 hours at 3200 rpm. After repeating the treatment twice (where no further white precipitate is formed if a large amount of methanol is added to the supernatant Liquid is added) the precipitate at the bottom of the flask is washed with methanol and filtered with a glass filter (1 G 4) to collect the precipitate. The percentage of graft is calculated according to the following equation:

Degree of grafting = - ^ - ~ - ⁾ ■ 100
B.

(A): amount of precipitate;

(B): amount of rubber in the sample (calculated value).

Note: The amount of rubber in the sample is the amount of activated Λ-olefin vinyl ester

Copolymer containing double bonds in the sample before the graft polymerization.

In addition, the result of the determination of the accuracy of the above Method for measuring the degree of grafting confirmed by means of nuclear magnetic resonance spectroscopy, that the separation of the graft polymer is complete and the reliability of the determination the degree of grafting is sufficiently high,

Example A.

Manufacture of activated
Ethylene vinyl acetate copolymer (1)

A 7-liter reactor equipped with a stirrer and a condenser became one with 1,000 g Ethylene-vinyl acetate copolymer and 4000 g of distilled and purified methyl methacrylate (Water content 400 parts per million) using dry nitrogen to one touch To avoid air exposure of the ingredients, the mixture was allowed to stir for about 30 minutes Stirred creating a homogeneous solution. After adjusting the reaction system to the table A specified activation temperature became an alcohol solution of an alkoxide of an alkali metal was added as a catalyst, and the system was reacted for one hour with stirring. After the completion of the reaction, the reaction system was made by adding acetic acid in one the admitted. Alkali equivalent amount neutralized, using a methyl methacrylate solution a content of 20 percent by weight of active

tem ethylene-vinyl acetate copolymer was obtained.

The ethylene-vinyl acetate mixed polymer used in the activation reaction consisted of a content of 33 or 28 percent by weight vinyl acetate.

The catalyst used in this experiment was as follows:

(1) A methanol solution of sodium metoxide (alkali concentration 3.03N).

(2) An ethanol solution of sodium ethoxide (alkali concentration 1.77 n).

(3) An n-propanol solution of sodium n-propoxide (alkali concentration 1.81N).

(4) An n-butanol solution of sodium n-butoxide (alkali concentration 1.79N).

(5) A methanol solution of
(Alkali concentration 1.52 n).

(6) A methanol solution of lithium methoxide (alkali concentration 1.13N).

The activation reaction conditions and the proportions or ratios of double bonds in the activated ethylene-vinyl acetate copolymers produced in this way are listed in Table A below.

Potassium methoxide

Table A. Evaflex Activation Catalyst solution Additional Proportion of doubles Methyl methacrylate No. temperature Amount of bindings in acti solution of activated catalyst fourth ethylene Ethylene vinyl acetate solution Vinyl acetate mixed Mixed polymer polymer (° C) (cm3) (Mole percentage) 150 60 Methanol solution of 28 0.021 A-I Sodium methoxide 150 60 Methanol solution of 36 0.28 A-2 Sodium methoxide 150 60 Methanol solution of 38 0.42 A-3 Sodium methoxide 150 60 Methanol solution of 42 0.72 A-4 Sodium methoxide 150 60 Methane solution of 50 1.55 A-5 Sodium methoxide 150 70 Methanol solution of 38 0.55 A-6 Sodium methoxide 150 70 Methanol solution of 45 1.21 A-7 Sodium methoxide 150 80 Methanol solution of 36 0.43 A-8 Sodium methoxide 150 60 Ethanol solution of 80 0.25 A-9 Sodium ethoxide 150 60 n-propanol solution of 50 0.30 A-10 Sodium n-propoxide 150 60 n-butanol solution of 100 0 "> 7 A-Il Sodium n-butoxide 150 60 Methanol solution of 100 0.36 A-12 Potassium methoxide

7th 27 1 7 92 357 28 Proportion of doubles
bindings in acti
fourth ethylene
Vinyl acetate mixed
polymer
(Mole percent) 0.41 Table A. Evaflex
No. Additional
Amount of
catalyst
solution
(cm") 0.33 Methyl methacrylate
solution of activated
Ethylene vinyl acetate
Mixed polymer 150 Activation
temperature
(• C) Catalyst solution 100 0.031 A-13 250 60 Methanol solution of
Lithium methoxide 38 0.37 A-14 250 60 Methanol solution of
Sodium methoxide 75 0.59 A-15 250 60 Athanol solution of
Sodium ethoxide 90 1.33 A-16 250 60 Ethanol solution of
Sodium ethoxide 103 Ethyl methacrylate
Butyl methacrylate A-17 250 60 Ethanol solution of
Sodium ethoxide 125 A-18 Example B. 60 Ethanol solution of
Sodium ethoxide B-2, B-3 Example BI,
25 and B-4 Example B-5

Ethylene-vinyl acetate copolymer (2) Production of activated

A 7 liter reactor equipped with a stirrer and a cooler was loaded with 1000 g of an ethylene-vinyl acetate copolymer, a vinyl acetate content of 33 percent by weight, 2000 g Methyl methacrylate (water content 150 to 400 parts per million) that has been distilled and purified, and 2000 g of an alkyl methacrylate or a copolymerizable vinyl compound as follows indicated, with a supply of dry nitrogen, and the system was run for about Stirred for 1 hour at 60 ° C. in order to obtain a homogeneous solution.

Table B.

Examples B-6 and B-7 styrene

Then, after adding a methanol solution of sodium methoxide (alkali concentration 3.03 n) as a catalyst, the system reacted for 1 hour at 60 ° C. with stirring. After completion of the implementation the reaction system was treated with acetic acid in an amount equivalent to the alkali added neutralized, a solution containing 20 percent by weight of activated ethylene-vinyl acetate copolymer was obtained.

When the amount of catalyst was varied as indicated in Table B below is, the activated ethylene-vinyl acetate copolymers with double bonds in the in Table B amounts given.

Activated ethylene-vinyl acetate copolymer solution

Composition and weight ratio of the activation reaction solvent

Additional amount
of catalyst
solution
(cm") Proportion of doubles
bindings in acti
fourth ethylene
Vinyl acetate mix
polymer
(Mole percent) 40 0.044 55 0.35 60 0.82 65 1.22 60 0.37 58 0.41 68 0.65

BI
B-2
B-3
B-4
B-5
B-6
B-7

Methyl methacrylate / butyl methacrylate (50/50) methyl methacrylate / butyl methacrylate (50/50) Methyl methacrylate / butyl methacrylate (50/50) methyl methacrylate / butyl methacrylate (50/50) Methyl methacrylate / butyl methacrylate (50/50) methyl methacrylate / styrene (50/50) methyl methacrylate / styrene (50/50)

Example C

Production of activated ethylene-vinyl acetate copolymer (3)

The same activation reaction as in Example A was carried out at 60 ° C, using 3000 g of toluene and 1000 g of methyl methacrylate were used in place of 4000 g of methyl methacrylate. Then became the polymer solution poured into a large amount of methanol to coagulate the solution to form an activated To obtain ethylene-vinyl acetate copolymer. When a methanol solution of sodium

methoxide (alkali concentration 3.03 · 10 ~ ^s mol / ml) was used as the catalyst and the amount of the catalyst was changed to 40, 50 and 60 ml, the proportions of double bonds in the activated ethylene-vinyl acetate copolymers were shown in the following Table C are obtained (mole percent in the linking unit of the main chain).

Table C. Table D.

Solution of
Vinyl acetate-vinyl benzoate copolymer

? t1c "S £ * ζ.2Χ2ΐ ^χ '53 Χ0Τ

(ml)

Mpnop at

Double bonds in
Mixed polymer

(Mole percent)

Methanol solution of
Sodium methoxide

(ml)

Share of
Double bonds

(Mole percent) DI
D-2
D-3

D-4

1.2
1.8

2.0
2.7

0.016
0.27
0.33
1.70

40 ispiel D. 0.035 50 0.43 60 1.77 Be

Manufacture of activated
Ethylene-vinyl acetate-vinyl benzoate copolymer

A 3 liter flask equipped with a stirrer and a condenser was filled with 250 g of an ethylene-vinyl acetate copolymer (33 percent by weight vinyl acetate content), 300 g of dioxane, 300 g of tetrahydrofuran and 800 g of methyl benzoate charged, and the system was stirred at 80 ° C to obtain a homogeneous solution. After cooling the system 250 ml of a catalyst solution (a solution of 84 g of naphthalene and 15 g metallic sodium in 500 ml of tetrahydrofuran) dropwise to the system with vigorous stirring admitted what nacl. Implementation of the system for 5 hours at 60 ° C, the alkali in the mixture was neutralized by adding 160 ml of 2N hydrochloric acid. When pouring the solution thus obtained An ethylene-vinyl acetate-vinyl benzoate copolymer was then added to a large amount of methanol receive. By analyzing the copolymer, it was confirmed that the vinyl benzoate content Was 8.2 mole percent.

A 300 ml flask that comes with a stirrer and a cooler was equipped with 50 g of the ethylene-vinyl acetate-vinyl benzoate copolymer, which had been prepared as above, and 200 g of methyl methacrylate (water content 150 to 400 parts / million), which had been distilled and purified, was charged, whereupon the mixture took about 30 minutes was stirred at 70 ° C for a long time to obtain a homogeneous solution. After cooling the reaction system at 60 ° C a methanol solution of sodium methoxide (alkali concentration 3.03 n) was added as a catalyst, and the system was reacted with stirring. After completion of the implementation the reaction system was neutralized by adding acetic acid to make a solution with a content of 20 percent by weight of activated ethylene-vinyl acetate-vinyl benzoate copolymer to obtain. When the amount of the catalyst to be added was varied as in the following Table D is given, were ethylene-vinyl acetate-vinyl benzoate copolymers obtained with double bonds in the amounts given in Table D.

Example E.

Production of activated ethylene vinyl acetate vinyl alcohol copolymer (1)

Each of the activated ethylene-vinyl acetate mixtures

ao polymers A-4, B-3 and B-7 were each in

poured a large amount of methanol, and the coagu-

Lated copolymer was removed therefrom and dried in vacuo at 30.degree. C. overnight.

Then a 1 liter flask equipped with a stirrer and a cubic meter was charged with 160 g of the activated ethylene-vinyl acetate mixed polymer and 800 g of toluene dried above. and the mixture was stirred at 70 ° C to obtain a homogeneous solution. Then, after cooling the reaction system to 40 ° C., 70 ml of a methanol solution of 0.3N sodium hydroxide was added to the solution, and the system was stirred at 40 ° C. for 5 hours to carry out partial hydrolysis. After the completion of the reaction, the reaction system was neutralized by adding 14 ml of 2N hydrochloric acid. The solution was poured into a large amount of methanol to coagulate the activated ethylene-vinyl acetate-vinyl alcohol copolymer, the two days was dried at 3O ⁰ C and then removed in vacuo long. The hydrolysis percentage of the activated ethylene-vinyl acetate copolymer and the proportion of double bonds in the activated ethylene-vinyl acetate-vinyl alcohol copolymer obtained are given in Table E below:

Table E.

Activated Activated (A + 1 (B +) Ethy'.cn vinyl Ethylene vinyl acetate vinyl acetate mixed alkahol mixed polymer (Mol polymciisat ( ⁰ Zo) percent)

EGG
E-2
E-3

A-4
B-3
B-7

33
34
30th

0.41
0.45
0.37

(A): percentage of hydrolysis;

(B): Proportion of double bonds in the activated ethylene-vinyl acetate-vinyl alcohol mixed poly

merisat as received.

Example F

Manufacture of ethylene-vinyl acetate-vinyl alcohol mixed polymer (2)

A 15 liter reactor was stirred at 70 ⁰ C with 9000 g of toluene and 1200 g of an ethylene

Vinyl acetate copolymer (Evaflex No. 150) was used, a homogeneous solution being obtained. After cooling the system to 40 ° C., a solution of 0.3% sodium hydroxide was added, and the system was reacted for 30 minutes at 40 ° C. with stirring. After completion of the reaction, the reaction system was neutralized with an aqueous solution of 2N acetic acid, and a large amount of methanol was added to the product to precipitate the polymer, an ethylene-vinyl acetate-vinyl alcohol copolymer being produced. In this case, the content of OH groups 1.24 · ΙΟ- ³ mol / g. ^vv

In a 2-liter flask equipped with a stirrer and a condenser, 120 g of the so produced ethylene - vinyl acetate - vinyl alcohol copolymer dissolved in 1200 g of a toluene dehydrated with active aluminum oxide, and after addition of 21.6 g of methacrylic acid chloride the system reacted for 6 hours at 50 ° C. with stirring. Then a large amount of methanol added to the system to precipitate the polymer, the activated ethylene-vinyl acetate-vinyl alcohol - Copolymer with introduced therein

H ₃ -C

Ii

CH ₂ = C - C - O groups

as side chains. The proportion of double bonds in the activated one thus produced Ethylene-vinyl acetate-vinyl alcohol copolymer was 0.51 mol percent.

Example G

Production of activated ethylene-vinyl acetate-vinyl alcohol copolymer (3)

A 2-liter flask equipped with a stirrer and a condenser was charged with 250 g of the ethylene-vinyl acetate-vinyl alcohol copolymer prepared in Example F, 500 ml of toluene, 500 ml of methacrylic acid, 10 g of p-toluenesulfonic acid and 5 g of hydroquinone, and while using and slowly feeding nitrogen gas, the system was stirred for 3 hours. The product in the flask was then poured into a large amount of methanol to recover the polymer, the activated ethylene-vinyl acetate copolymer having CH ₂ = C (CH ₃ ) COO groups introduced therein being obtained. The proportion of double bonds in the polymer was 0.35 mol percent.

Example H

Production of activated ethylene-vinyl acetate-vinyl alcohol copolymer (4)

Repeating the same procedure as in Example G, but using acrylic acid instead of Methacrylic acid was used, an activated ethylene-vinyl acetate-vinyl alcohol copolymer was used receive. The proportion of double bonds introduced in this way was 0.15 mole percent.

Bet game I

Production of activated ethylene-vinyl acetate-vinyl alcohol copolymers (5)

Repeating the same procedure as in Example G, but using 250 ml of methacrylic acid and 250 ml of acrylic acid were used in place of 500 ml of methacrylic acid, an activated one was used Ethylene-vinyl acetate-vinyl alcohol copolymer receive. The proportion of double bonds thus introduced was 0.22 mol percent.

Example J

Production of activated ethylene-vinyl acetate-vinyl alcohol copolymer (6)

A 1 liter flask equipped with a stirrer and a condenser was charged with 70 g of that in Example H activated ethylene-vinyl acetate copolymer produced and 400 g of pyridine charged, and the mixture was stirred at 80 ° C, whereby a homogeneous Solution was obtained. After adding 200 ml of a mixed solution of acetic anhydride and pyridine (weight ratio 1: 1) was subjected to acetylation for 10 hrs Subjected to stirring at 80 ° C. After completion of the reaction, the polymer solution was in a Poured a large amount of methanol to cause coagulation, whereupon the activated ethylene-vinyl acetate copolymer was won. During the acetylation, the proportion of double bonds in the activated ethylene-vinyl acetate-vinyl alcohol copolymer, as obtained in Example H, introduced, did not vary.

Example L

A 1 liter flask equipped with a stirrer and a condenser was filled with 500 ml of toluene and 100 g of the polymer obtained by pouring the activated ethylene-vinyl acetate copolymer prepared in Example A (A-6 or A-8) and coagulating the same was charged, and the mixture was stirred at 70 ° C to obtain a to obtain homogeneous solution. Then 25 ml of a methanol solution of 2.59 N HCl were added, and the system was stirred at 70 ° C for 4 hours. The polymer solution thus formed in the flask was poured into a large amount of methanol to recover the polymer. The proportion of Double bonds in the polymer are given in the table below.

Activated ethylene Share of Vinyl acetate mixed Double polymer ties (Mole percentage)

L-I A-6 iel M. 0.53 L-2 A-8 0.40 Ex

The same procedure as in Example L was repeated, but with 6.0 ml of acetyl chloride Instead of the methanol solution of HCl was used and a reaction temperature of 60 ° C Place of 70 ° C is used. Dc: proportion

609 608/89

of double bonds that are obtained in the polymer as are present as side chains, is in the given in the table below.

masses were in the
Way determined:

Measurement conditions ..

given below

23 ° Cun & 55 ", o relative humid

Activated ethylene

Vinyl acetate mixed

polymer

Proportion of double bonds

(Mole percent)

A-6
A-8

0.52 0.41

Example N

The same procedure as in Example L was repeated, except that 17 ml of an ethanol solution of 30 percent by weight H ₂ SO _{4 were used} in place of the methanol solution of HCl and a reaction temperature of 55 instead of 70 ° C. was used. The proportion of double bonds which are present as side chains in the polymer obtained is given in the table below.

Activated ethylene

Vinyl acetate mixed

polymerisai

Proportion of double bonds

(Mole percent)

A-6
A-8

0.46 0.35

35

example 1

A 1 liter flask equipped with a stirrer and a condenser was filled with 375 g of methyl methacrylate, 125 g of the activated ethylene-vinyl acetate copolymer solution prepared in Example A, namely the copolymer A-2, A-3, A-9, A-10, A-II, A-12, A-13, A-14, A-16 and A-17, respectively Charge 1.5 g of azobisisobutyronitrile and 2.0 g of n-dodecyl mercaptan, and under flowing nitrogen gas the system was polymerized in bulk with stirring for 2 to 3 hours at 55 ° C. This amounted to the proportion of the total polymer in the partially polymerized product is about 23 percent by weight. Then, a 2-liter flask equipped with a stirrer and a condenser of 500 g of the above-mentioned partial polymer product, 100 g of water, 10 g of sodium polymethacrylate and 10 g of sodium dihydrogen phosphate were charged, and the system was started with stirring at 400 rpm suspension-polymerized for 3 hours at 70 ° C. and then for 2 hours at 90 ° C., a granular Polymer was obtained.

The physical properties of the moldings of the granular polymer produced in this way and the Results of electron microscopic observation of thin sections thereof are shown in FIG Table 1-1 below. In this case, it was the surface smoothness of the molded articles well, the transparency was improved, and therefore, as a measure of the surface smoothness, the Turbidity value used.

The physical properties of the polymerizability Izod impact strength

(Score)

(kg · cm / cm notch) ASTM D 256-56

Yield strength (kg / cm ² ) .... ASTM D 638-58 T

(Tensile strength 5 mm / min.)

Elongation at Break ("Vo) ASTM D 638-58 T

Haze value ASTM D 1003-52

(3 mm thick plate)

Each of the test pieces was obtained by injection molding the polymer composition at 230 ° C.

As can be clearly seen from Table 1-1 below the structures of the samples obtained were of the kind shown in Figs. 4 and 5 shown wherein the rubber particles are in the form of spherical films with an average grain size from 0.05 to 0.5 microns; the impact resistance was very high, and the surface smoothness was excellent.

Comparative example 1

Repeating the same procedure as in Example 1 with the modification that the activated Ethylene-vinyl acetate copolymer A-6 or A-8 was used, a sample was obtained. On Hand of electron microscopic examination of a very thin section of an object In this sample, it was found that the structure of the sample differs from that shown in FIG. 3 was the type shown; the rubber particles were not in the form of spherical films but in the form of fine fragments dispersed. In addition, the impact strength of the sample was 1.2 to 2.2 kg · cm / cm notch, which is for the practical use was too low.

From these results, it was found that even if the proportion of in the activated ethylene vinyl acetate - The vinyl groups introduced into the copolymer are in the range from 0.1 to 1.0 mol percent. The rubber particles in the sample are not in the form of spherical films that are necessary for the creation a high impact resistance is suitable, dispersible were. It was thus found that the reaction conditions for the introduction of

_ O - C - C = CH ₂ groups

O CIi ₁

as side chains of the. • v-olefin-vinyl acetal copolymer, in particular the reaction temperature used, a significant factor here Harstell. The critical point for determining the reaction temperature depends on the Sicdepunk of the solvent (alcohol) for the catalyst

Comparative example 2

If the same way of working as ^; m Example ] was repeated with the modification that a solution of the activated ethylene-vinyl acetate copolymer, namely from A-5. A-7, A-18 or B-4, ode 475 g of methyl methacrylate and 25 g of the activated

Ethylene-vinyl acetate-vinyl benzoate copolymer (D-4) or the activated ethylene-vinyl acetate copolymer (C-3) instead of 125 g of the solution of the activated ethylene-vinyl acetate copolymer used in Example 1 were used, the polymerization system was used in the stage of partial prepolymerization at the start of polymerization gelled. These results show that the activated ethylene-vinyl ester copolymer, the Vinyl groups in a proportion greater than about 1 mole percent of the binding units of the main chain for the preparation of the thermoplastic impact-resistant resin according to the invention was extremely unsuitable.

the dispersion of the spherical films of the rubber particles was realized to obtain a polymer composition with a high impact resistance became that, however, when the mean grain size increased to a high value of about 0.76 microns became, the surface finish of the mold body was extremely deteriorated and related on the transparent resins the haze value has been increased to such an extent that there? transparent Appearance was almost lost, as was the case in the present comparative example.

Example 2 (2.1)

Comparative _{Example 3 The same} procedure as in Example 1 was used

The same procedure as in Example 1 was repeated with the modification that a solution of the repeated with the modification that the activated activated ethylene-vinyl acetate copolymer Ethylene - vinyl acetate - copolymer A-I, A-15 A-3 and 225 g of methyl methacrylate and 150 g of methyl or. B-I (in Example 1) or 475 g of methyl methacrylate 20 acrylate instead of 375 g of methyl methacrylate lost and 25 g of activated ethylene vinyl acetate were used. Copolymer C-I, of the non-activated Ethy- ρ -η

len-vinyl acetate-vinyl benzoate copolymer DI ^V ~

or the · unactivated ethylene vinyl acetate - The same procedure as in Example 1 was carried out

Copolymer instead of 375 g of methyl meth- 25 repeated with the modification that a solution of the acrylate and 125 g of the solution of the activated ethylene-vinyl acetate copolymer len-vinyl acetate copolymer, as in Example 1
used, were used, with a
Sample was created. The structure of the sample was
in their electron microscopic nature 3 °
of the in the Fi g. 1 or 2, and
there was no resin composition in which the rubber particles in the resin component were in the form of spheres

shaped films were obtained. Except-

A-3 and 225 g of methyl methacrylate and 150 g of ethyl acrylate instead of 375 g of methyl methacrylate were used.

The physical properties of the samples obtained are shown in Table II below and the state of dispersion of the rubber particles was from that in FIG. 4 and 5 shown Type, whereby polymer masses with an excellent

have been preserved.

so was the impact strength of the 35 th surface smoothness thus obtained and a high impact strength specimen of quite a low value, namely 1.0 to
2.7 kg · cm / cm notch, which is extremely useless.
From these results it was confirmed that,
if the proportion of the vinyl groups introduced into the activated ethylene-vinyl ester copolymer
was less than about 0.05 mole percent, no polymer composition was obtained in which the rubber particles in the resin phase were in the form of spherical ones
Films were dispersed.

Example 3 (3.1)

Comparative example 4

The same procedure as in Example 1 was repeated with the modification that 3.0 g of n-dodecyl mercaptan instead of 2.0 g of n-dodecyl mercaptan

A 1 liter flask equipped with a stirrer and a condenser was filled with 250 g of methyl methacrylate, 125 g of styrene, 1.5 g of azobisisobutyronitrile, 1.0 g of n-dodecyl mercaptan and 125 g of a solution 45 of an activated ethylene-vinyl acetate copolymer (A-3), whereupon the system was partially polymerized in bulk with stirring at about 300 rpm and flowing nitrogen gas over the reaction system at 60 ° C until used, the stirring speed at 5 ° total solids 37% by weight fraud. The partial polymerization in the mass 50 to after was a 2 liter flask with 500 g of the partially 100 rpm and the proportion of the total poly-polymerized product, as prepared above in the prepolymerization product at the end, 1000 g of water , 10 g of sodium polymethacrylate of the polymerization in the mass 13 to 15 weight and 10 g of sodium dihydrogen phosphate charged. An percent, a sample was prepared. The system was then closed for 5 hours when examined by an electron microscope
of the sample, it was found that although the state of dispersion of the rubber particles was different from that in
Fig. 4 or 5 and a structure
was formed by a dispersion of spherical films, the mean grain size (3) 0.76 microns
was causing a considerable decrease in smoothness

Polymerized in the mass at 70 ° C, 1 hour at 80 ° C and 2 hours at 90 ° C.

(3.2)

The same procedure as in example (3.1) was repeated with the modification that 300 g Methyl methacrylate and 75 g styrene instead of 250 g methyl methacrylate and 125 g styrene and 125 g of the activated ethylene-vinyl acetate copolymer

the surface of the moldings of this resin composition, a remarkable deterioration in transparency

and an increase in the friction value caused 65 sats (B-6) instead of 125 g of activated ethylene. The properties of the thus obtained sample of vinyl acetate copolymer (A-3) used are shown in Table 1-2 below.
From these results, it was confirmed that if

ypy ()

the; a sample of the resin copolymer according to the invention was prepared.

37 38

merisats (A-3) and 330 g of ethyl methacrylate and 45 g of ^ ³ * ³ ) acrylonitrile instead of 375 g of methyl methacrylate

The same procedure as in example (3.1) was used to prepare the mixed polymer sample was repeated with the amendment that in place of manufacture.

of 250 g of methyl methacrylate and 125 g of styrene 75 g of 5 The physical properties and the result methyl methacrylate, 230 g of styrene and 70 g of acrylonitrile nisse of the electron microscopic examination and 1.0 g of the samples obtained above in place of 1.0 g of n-dodecyl mercaptan are used in the night-dodecyl mercaptan, Table IV listed below, which shows a sample of the polymer composition according to the invention that the state of dispersion of the rubber particles was prepared. ^l ° in these samples from the in F i g. 4 or 5 shown

The physical properties and the type of result was and that a transparent mass with fail the electron microscopic examination of drawn surface smoothness and a high of the sample thus prepared are obtained in the following impact strength. Table IH listed; the state of dispersion of the

Rubber particle was of that in Figure 4 or 5is Example 5

type shown, and the surface smoothness and impact {5 \}

strength were excellent. The resin mass was
translucent. The same procedure as in Example 1 was used

Vereleichsbeisoiel 5 ^{with the amendment} 8 repeats that 125 g of the

vergieicnsoeispiei d _{λο sm} ^ _{deg acüvierten} ethylene-vinyl acetate mixed poly-

The same procedure as in Example (3.1) merisate (A-3) and also 305 g of methyl methacrylate

was repeated with the modification that 375 g and 70 g of acrylonitrile instead of 375 g of methyl meth-

Styrene instead of 250 g of methyl methacrylate and acrylate to create the polymer sample according to

125 g of styrene and also 125 g of a solution of the invention were used, activated ethylene-vinyl acetate copolymer as

(B-6) were used to obtain a sample of the resin * ■ ■ '

to produce copolymer. The formed parts work in the same way as in the example (5.1)

Articles of the sample were very cloudy and this was carried out with the modification that 70 g

Impact resistance thereof was as low as methacrylonitrile in place of 70 g of acrylonitrile

2.8 kg · cin / cm notch, so that the economic creation of the polymer sample according to the invention

Value of this resin was low. It is thus envisaged that

lent that the monomer composition, the overall ^ - ^) measure of the invention is used, at least

30 percent by weight of methyl methacrylate contained The same procedure as in Example 1 was

got to. 35 repeated with the amendment that 125 g of the

Example 4 solution of the activated ethylene-vinyl acetate mixed poly

.- ₄ jx merisats (A-3) and 185 g of methyl methacrylate,

* · '' 140 g butyl methacrylate and 50 g acrylonitrile instead

The same procedure as in Example 1 indicated by 375 g of methyl methacrylate to create the poly

ben, was repeated with the modification that 40 merisate samples were used. 125 g of the activated ethylene vinyl acetate solution

tat copolymer (A-3) and 230 g of methyl meth- (5.4) acrylate and 145 g of ethyl methacrylate instead of

375 g of methyl methacrylate were used to perform a procedure The same as in Example 1 was followed

Produce mixed polymer sample. 45 repeated with the modification that 125 g of the solution of activated ethylene-vinyl acetate mixed poly-

v ⁴ · ² ) merisats (B-5) and 235 g methyl methacrylate, 90 J

The same procedure as in Example 1 was butyl methacrylate and 50 g of acrylonitrile on Steile voi

repeated with the modification that 125 g of the lo- 375 g of methyl methacrylate to create the polymer

Solution of the activated ethylene-vinyl acetate mixed polymer 50 risatprobe were used according to the invention merisats (B-2) and 280 g of methyl methacrylate and

95 g of ethyl methacrylate instead of 375 g of methyl (5.5) methacrylate were used to prepare an interpolymer sample. The same procedure as in Example 1 was

55 repeated with the amendment that 125 g of the Lo

ν * · ³ ) solution of the activated ethylene-vinyl acetate mixed poly

The same procedure as in Example 1 was merisats (A-3) and .18Og methyl methacrylate, 125

repeated with the modification that 125 g of the methyl acrylate and 70 g of acrylonitrile instead of 375

solution of the activated ethylene-vinyl acetate mixed poly methyl methacrylate to create the polymer merisats (A-3) and 90 g of methyl methacrylate and 60 sample were used.

285 g of ethyl methacrylate instead of 375 g of methyl- The physical properties and the results

methacrylate were used to make the interpolations of electron microscopy examinations

to produce merisate sample. of the samples are in the table below V au!

guided. The state of dispersion of the rubber parts

v ⁴ -v 65 surfaces in these samples was different from that shown in FIG. 4 and

The same procedure as in Example 1 was shown, and transparent pol}

repeated with the modification that 125 g of the Lömerisatmassen with excellent surface smoothness

solution of activated ethylene-vinyl acetate mixed poly and a high impact resistance.

IL

Example 6

The same procedure as in Example 1 was repeated with the modification that 125 g of the solution of the activated ethylene-vinyl acetate copolymer (A-3) and 280 g of methyl methacrylate and 95 g Acrylic acid were used to create the polymer sample of the invention.

Example 7

The same procedure as in Example 1 was repeated with the modification that instead of 125 g of the solution of the activated ethylene-vinyl acetate copolymer from Example 1 the activated ethylene-vinyl acetate-vinyl alcohol mixed powder E-I (example 7.1), F (example 7.4), G (example 7.5), H (example 7,6), E (example 7.7), J (example 7.8), E-2 (Example 7.2) or E-3 (Example 7.3) and also 475 g of methyl methacrylate instead of 375 g of methyl methacrylate were used to create the polymer compositions according to the invention.

Example 8

The same procedure as in Example 1 was repeated with the modification that the solution of the activated ethylene-vinyl acetate-vinyl benzoate copolymer D-2 (Example 8.1) or D-3 (Example 8.2) instead of the activated ethylene-vinyl acetate copolymer from Example 1 to create the Polymer sample according to the invention was used.

Example 9

The same procedure as in Example 1 was repeated with the modification that 475 g of methyl methacrylate instead of 375 g of methyl methacrylate and 25 g of the activated ethylene-vinyl acetate copolymer prepared as in Example C-2 (Example 9.1) or 25 g of the activated obtained in Example K. Ethylene-vinyl acetate copolymer (Example 9.2) instead of 125 g of the solution of the activated Ethylene-vinyl acetate copolymer from Example 1 to create the copolymer sample were used according to the invention.

Example 10

The same procedure as in Example 1 was repeated with the modification that 475 g of methyl methacrylate instead of 375 g of methyl methacrylate, as in Example 1, and 25 g of the activated ethylene-vinyl acetate copolymer L-I, L-2, M-I, M-2, N-I or N-2, as in the examples L, M or N produced, in each case in place of 125 g of the solution of the activated ethylene-vinyl acetate copolymer of Example 1 was used to create the polymer sample according to the invention.

Example 11

A 1 liter flask equipped with a stirrer and a condenser was filled with 125 g of the solution of the activated ethylene-vinyl acetate copolymer, as prepared in Example A, 255 g of methyl methacrylate, 70 g a-methylstyrene, 50 g acrylonitrile, 1.5 g of azobisisobutyronitrile and 1.0 g of tert-dodecyl mercaptan were charged, and the system became partial polymerized in the mass with stirring at 300 rpm at 79 ° C under a stream of nitrogen gas, wherein part of the acrylonitrile was refluxed until the proportion of the total polymer in the polymerization system was 25 weight percent. Then there was one with a stirrer and one 2 liter autoclave equipped with a condenser containing 500 g of the one obtained above in the bulk polymerization Product, 1.0 g azobisisobutyronitrile, 1000 g distilled water, 10 g sodium hydrogen phosphate and 10 g of sodium polymethacrylate were charged, and the system was run at 79 ° C for 3 hours with stirring suspension polymerized at 400 rpm, some of the acrylonitrile being held under reflux would. After further adding 1.0 g of azobisisobutyronitrile, the system was then continued during suspension polymerized for about 6 hours. Thereafter, 0.8 g of azobiscyclohexanenitrile was added to the system and after closing the autoclave, the temperature of the system was increased to an extent of 10 ° C per hour, and after the temperature reached 130 ° C, the system became at this Maintained temperature for 2 hours. After removing the remaining vinyl compound monomers the polymer sample according to the invention was then obtained from the product.

The physical properties and the results of electron microscopic observation of the samples obtained in Examples 6 to 11 above are each given below Tables VI to XI given. The state of dispersion of the rubber particles in the resin compositions is of the in Fig. 4 or 5 shown type, and the polymer compositions obtained have a excellent surface smoothness and excellent impact resistance.

The result of Example 10 shows the effect of after-treatment of the activated ethylene-vinyl acetate Mischpotymerisats compared with Comparative Example 1, and in particular, the sample obtained in Example 11 by 8 was up to 10 ⁰ C in the Wärmedeformierungstemperatur according to the BS method is higher than that of the sample, obtained in Example 3, and thus was excellent in heat resistance.

Example 12

(12.1)

The same procedure as in Example 1 was repeated with the modification that 410 g of methyl methacrylate, 40 g of methyl acrylate and 50 g of the activated ethylene-vinyl acetate copolymer solution sats (A-3) instead of 375 g of methyl methacrylate unc 125 g of the solution used in Example 1 of the active fourth ethylene-vinyl acetate copolymer were used ver.

(12.2)

The same procedure as in Example 1 was repeated with the modification that 260 g of methyl methacrylate, 40 g of methyl acrylate and 200 g of the activated fourth ethylene-vinyl acetate copolymer (A-3 instead of 375 g of methyl methacrylate and 125 g of the activated solution used in Example 1 Ethylene-vinyl acetate copolymer was used.

(12.3)

The same procedure as in Example 1 was repeated with the modification that 200 g of Methy

609 608/8

methacrylate, 50 g methyl acrylate and 250 g of the solution of the activated ethylene-vinyl acetate copolymer (A-14) instead of 375 g of methyl methacrylate and 125 g of the solution of the activated ethylene-vinyl acetate copolymer used in Example 1 were used.

(12.4)

A 1 liter flask equipped with a stirrer and a condenser was filled with 120 g of methyl methacrylate, 135 g of styrene, 45 g of acrylonitrile, 1.50 g of azobisbutyronitrile, 1.0 g of tert-dodecyl mercaptan and 200 g of the activated ethylene solution. Vinyl acetate copolymer (A-3) was charged, and the system was partially polymerized in bulk with stirring at 60 ° C. under a nitrogen gas stream until the total amount of solid components became 30% by weight. Then, a 2-liter flask equipped with a stirrer and a condenser was charged with 500 g of the partially polymerized product thus prepared, 1,000 g of water, 10 g of sodium polymethacrylate and 10 g of sodium dihydrogen phosphate. The system was then to the Polymerisatmasse to obtain with stirring at 400 rpm / min for 5 hours at 7O ⁰ C, for 1 hour at 8O ⁰ C and for 2 hours at 90 ° C suspension-polymerized according to the invention.

The physical properties and the results of the electron microscopic examination of the samples are shown in Table XII below, and the state of dispersion of the rubber particles was of the in Fig. 4 or 5 type shown; there were polymer compositions with excellent Obtained surface smoothness and high impact resistance.

Example 13

35

A 5-liter autoclave equipped with an induction stirrer was charged with 1350 g of methyl methacrylate, 150 g of methyl acrylate, 3 g of azobisisobutyronitrile, 3 g of n-dodecyl mercaptan, 2000 g of distilled water, 30 g of sodium polymethacrylate and 30 g of sodium dihydrogen phosphate and, after the autoclave was closed, the system polymerized under stirring at 400 r / min for 3 hours at 70 ° C, 1 hour at 8O ⁰ C and 2 hours at 120 ⁰ C, wherein the granular hard polymer was obtained.

The granular hard polymer obtained in this way was mixed with the polymer composition obtained in Example 12.2 or 12.3 mixed in a weight ratio of 1: 1, and after mixing the mixture by a

Peüctiereinrichtung was the mixture after Injection molding process molded.

The physical properties of the moldings are listed in the table below. the Moldings had good surface smoothness.

characteristic

unit

(D

(ID

Izod impact kg · cm / cm notch 4.3 4.8

strength

(Score)

Yield strength kg / cm ² 520 565

Elongation at break ° / o 400 43

Haze value - 14.0 12.4

(I): Mixed polymer, obtained in a similar manner,

as shown in example 12.2.
(II): Mixed polymer obtained in a manner similar to that shown in Example 12.3.

Example 14

The granular polymer obtained in Example 12.4 was mixed with a methylmethacrylaKY-methylstyrene copolymer (Bavic, trade name of Baker Co., analyzed content of -methylstyrene 22.5 percent by weight) in a weight ratio of 1: 1, and the mixture was through a Pelletizing device molded by injection molding. The molded articles obtained thereby possess the following physical properties and excellent surface smoothness.

Izod impact strength

(Notch) 4.2 kg · cm / cm notch

Yield strength 539 kg / cm ²

Elongation at break 55%

When the extremely thin sections of the molded articles according to Examples 13 and 14 were examined using an electron microscope, it was found that the grain sizes and the Shapes of the rubber particles to those in the polymer compositions obtained in Examples 12.2, 12.3 and 12.4 were almost the same.

From the above results, it was confirmed that by simply mixing of the graft copolymer with another hard polymer, the polymer composition with the useful properties could also be obtained.

Properties and results of electron microscopic examination Table I-1

example 1") 2 ») 3 *) 4 ») 5 ») 6 *) 7 *) 8th*) 9 *) 10 ») 11 ·) (1.1) A-2 0.28 5.0 495 45 0.36 0.03 25.3 115 10.8 89.2 (1.2) A-3 0.42 5.1 499 40 0.28 0.03 13.6 138 11.9 88.1 (1.3) A-9 0.25 4.8 508 46 0.30 0.04 25.7 106 10.3 89.7 (1.4) A-10 0.30 5.6 500 51 0.31 0, u3 18.5 98 9.9 90.1 (1.5) A-Il 0.27 5.4 501 45 0.35 0.03 26.6 150 12.5 87.5 (1.6) A-12 0.36 5.6 512 44 0.30 0.03 15.1 122 11.1 88.9 (1.7) A-13 0.41 5.1 516 39 0.25 0.04 13.8 166 8.3 91.7 (1.8) A-14 0.33 4.5 559 40 0.28 0.03 17.3 103 10.2 89.8 (1.9) A-16 0.37 4.2 564 36 0.22 0.04 15.3 86 9.3 90.7 (1.10) A-17 0.59 4.3 556 40 0.29 0.04 12.4 97 9.9 90.1

43 44

table 1-2 1*) II 1*) III 1*) IV 1 *) V 1") VI 1*) VII 1") 2 *) 3 *) 4 *) 5 *) 6 *) 7 *) 8th·) 9 ») 10 ») 11 ·) comparison 15- A-2 A-3 A-3 A-3 A-3 A-3 EGG 0.28 6.0 488 46 0.76 0.04 48.3 - - - example A-3 B-6 B-2 A-3 E-2 4th A-3 A-3 A-3 E-3 2 *) 3 ·) 4 *) 5 *) 6 *) 7 *) 8th") 9 *) 10 ») Π *) table A-3 B-5 F. 0.42 4.8 435 73 0.40 0.04 15.6 173 13.7 86.3 example A-3 G 0.42 4.6 423 77 0.36 0.04 14.4 160 13.0 87.0 (2.1) H (2.2) I. 2 *) 3 *) 4 *) 5 *) 6 *) 7 *) 8th") 9 ») 10 ») Π ·) table J 0.42 4.4 470 36 0.42 0.04 120 11.0 89.0 example 0.41 4.3 466 39 0.30 0.04 - 108 10.4 89.6 (3.1) 0.42 5.1 440 90 0.31 0.04 - 100 10.0 90.0 (3.2) (3.3) 2 ») 3 ») 4 *) 5 *) 6 *) 7 *) 8th") 9 *) 10 ·) 11 *) table 0.42 4.6 435 47 0.33 0.03 15.6 132 11.6 88.4 example 0.35 4.1 436 50 0.22 0.03 21.8 145 12.3 87.7 (4.1) 0.42 4.9 410 65 0.30 0.04 13.6 168 13.4 86.6 (4.2) 0.42 5.5 350 160 0.28 0.03 18.5 150 12.5 87.5 (4.3) (4.4) 2 *) 3 ») 4 ») 5 *) 6 *) 7 *) 8th*) 9 *) 10 *) 11 *) table 0.42 5.6 450 100 0.26 0.03 92 9.6 90.4 example 0.42 4.5 500 25th 0.31 0.04 - 85 9.3 90.7 (5.1) 0.42 4.4 410 66 0.26 0.03 - 58 7.9 92.1 (5.2) 0.37 4.7 395 58 0.40 0.03 103 10.2 89.8 (5.3) 0.42 5.8 432 120 0.41 0.03 - 121 11.1 88.9 (5.4) (5.5) 2 *) 3 ») 4) 5 *) 6 *) 7 *) 8th*) 9 *) 10 *) U *) table 0.42 4.8 520 42 0.33 0.03 - 150 12.5 87.5 example (6) 2 *) 3 ») 4 ») 5 *) 6 *) 7 *) 8th*) 9 ·) 10 *) 11 *) table 0.41 4.5 480 53 0.29 0.03 13.2 120 4.4 95.6 example 0.45 4.7 503 46 0.31 0.03 17.9 130 11.5 88.5 (7.1) 0.37 4.8 496 46 0.32 0.04 23.6 106 10.3 89.7 (7.2) 0.51 4.6 506 48 0.33 0.03 13.5 113 10.7 89.3 (7.3) 0.35 4.8 488 48 0.29 0.03 25.1 98 9.9 90.1 (7.4) 0.15 4.1 490 52 0.36 0.04 30.9 56 7.8 92.2 (7.5) 0.22 4.6 491 50 0.38 0.04 28.8 77 8.9 91.1 (7.6) 0.42 4.7 496 48 0.36 0.03 21.2 106 10.3 89.7 (7.7) (7.8)

Table VIII

45

46

example 1*) 2 ») 3 ·) 4 «) 5 *) 6 ») 7 *) 8th") 9 ») 10 ») 11 ") (8.1) D-2 0.27 4.8 503 40 0.25 0.03 23.3 88 9.4 90.6 (3.2) D-3 0.33 5.1 490 45 0.37 0.03 25.1 103 10.2 89.8 Table IX example 1·) 2 *) 3 *) 4 *) 5 ») 6 ») 7 ») 8th·) 9 ·) 10 ») 11 ») (9.1) C-2 0.43 5.2 501 42 0.37 0.03 21.1 95 9.8 90.2 (9.2) K 0.15 4.2 490 53 0.33 0.04 28.4 55 7.8 92.2 Table X example 1*) 2 *) 3 *) 4 *) 5 ») 6 ») 7 ·) 8th*) 9 *) 10 ») 11 ») (10.1) L-I 0.53 4.6 489 48 0.29 0.03 18.7 122 11.1 88.9 (10.2) L-2 0.40 4.5 493 45 0.32 0.03 20.5 90 9.5 90.5 (10.3) M-I 0.52 4.6 480 52 0.31 0.03 14.0 109 10.5 89.5 (10.4) M-2 0.41 4.3 496 43 0.32 0.03 15.6 117 10.9 89.1 (10.5) N-I 0.46 4.7 502 40 0.35 0.03 17.3 95 9.8 90.2 (10.6) N-2 0.35 4.6 496 48 0.31 0.03 17.2 86 9.3 90.7 Table XI example 1") 2 *) 3 *) 4 ») 5 ·) 6 ») 7 *) 8th*) 9 *) 10 ·) Π *)

A-3

0.42 4.2 450 33 0.27 0.03 -

180

14.0 86.0

Table XII example

1*)

2 »)

3 *)

4)

5 »)

6 *)

7 »)

9 »)

10 »)

Π ·)

(12.1) A-3 0.42 3.2 606 28 0.36 0.03 9.7 151 12.6 87.4 (12.2) A-3 0.42 8.2 477 78 0.40 0.03 24.9 144 19.5 80.5 (12.3) A-14 0.33 8.8 450 80 0.38 0.03 21.0 108 20.8 79.2 (12.4) A-3 0.42 8.9 480 110 0.32 0.03 _ 140 19.2 80.8

Note on the above tables:

1 *) Activated ethylene-vinyl ester copolymer. 2 ·) proportion of in the polymer as side chains e ^; Listed vinyl residues (mole percent).

3 *) Izod impact strength (kg · cm / cm notch).

4 *) Yield strength (kg / cm «).

5 ·) Elongation at break (Vt).

6 *) Average grain size of the spherical films of the rubber particles (microns). 7 ») Average film thickness of the spherical film of the rubber particles (μ). 8 ») turbidity value. 9 ·) Degree of grafting of the rubber component (percent by weight).

10 *) Amount of graft polymer (percent by weight).

11 ·) Polymer or mixed polymer for the hard resin phase (percent by weight).

4 sheets of drawings

Claims (3)

Patent claims: 1. Thermoplastic molding compounds for the production of impact-resistant, weather-resistant molded bodies, consisting of (A) 0.5 to 80 percent by weight of a graft copolymer, which is obtained by graft polymerization of 20 to 300 percent by weight of a vinyl monomer with a content of more than 30 percent by weight of alkyl methacrylate with 1 or 2 carbon atoms in the alkyl group has been produced on a graft-activated, elastomeric α-olefin-vinyl ester copolymer (main rubber polymer component) and in it at least one of the groups CH ₂ = CHCOO- and / or CH ₂ = C (CK ₃ ) COO- as part of the side chains in a proportion of 0.05 to 1.0 mol percent of the binding units of the main chain, the proportion of said main rubber polymer component being 0.3 to 30 percent by weight of the total composition, and (B) 20 to 99, 5 percent by weight of a polymer (resin component) of a radical polymerizable vinyl monomer with a content of more than 30% by weight of a methacrylic acid ester having 1 or 2 carbon atoms in the alkyl group, the graft rubber component (A) being dispersed in the resin component (B) forming the hard resin phase, the greater proportion of the rubber component (A) in the resin component (B) in the form of spherical Hollow particles having particle sizes of 0.05 to 0.5 microns internally filled with the resin component (B) or dispersed in the form of aggregations of these spherical particles and the mean wall thickness of the hollow particles from 0.0025 to 0.125 microns and not more than ¹ U of said mean grain size thereof. 2. Process for the production of thermoplastic molding compositions according to claim 1, characterized in that that one either (1) an alkyl methacrylate and an elastomeric ft-olefin-vinyl ester copolymer of an ester interchange reaction in an alkyl methacrylate solvent in the presence of a solution of an alkoxide of an alkali metal in a solvent as a catalyst at a lower temperature than the boiling point of the solvent subjects for the catalyst or (2) an alkyl methacrylate and an elastomeric (X-Üiefin-vinyl ester copolymer of an ester exchange reaction in a mixture of copolymerizable vinyl compound monomers that are an alkyl methacrylate and an aromatic Vinyl compound contained in the presence of an alkoxide of an alkali metal as a catalyst subject, or (3) an alkyl methacrylate and an elastomeric α-olefin-vinyl ester copolymer in one hydrocarbon solvents inactive to the reaction of an ester interchange reaction in Presence of an alkoxide of an alkali metal as a catalyst or subjects (4) an elastomeric α-olefin-vinyl ester-vinyl alcohol mixed polymer or an elastomeric Λ-olefin-vinyl alcohol copolymer and at least an acrylic acid chloride or a methacrylic acid chloride is subjected to an esterification reaction by mixing with heating or (5) an elastomeric α-olefin-vinylester-vinylalkchol copolymer or an elastomeric α-olefin-vinyl alcohol copolymer and at least one of the compounds of acrylic anhydride or methacrylic anhydride in the presence subjecting a weakly alkaline catalyst to an esterification reaction or (6) at least one elastomeric a-OIefin-Vinylester-vinyl alcohol copolymer, or an elastomeric a-OIefin-vinyl alcohol copolymer and at least acrylic acid, methacrylic acid or alkyl esters thereof to an esterification reaction or Esteraustauschreaktion thereof by mixing them unte ^r heating or by heating a mixture in Subjected to the presence of an alkaline or acidic catalyst and the reaction product thus obtained treated with hydrochloric acid, sulfuric acid or an acid chloride, with at least one of the groups of CH ₂ = CHCOO- and CH ₂ = C (CH ₃ ) COO- as a side chain in the elastomeric Λ- olefinic copolymer is introduced in a proportion of 0.05 to 1.0 percent by weight of the binding units of the main chain, 0.3 to 30 parts by weight of this activated α-olefinic copolymer and 60 to 99.7 parts by weight of a radical polymerizable vinyl monomer with a content of more than 30 Weight percent of at least one alkyl methacrylate with 1 b If 2 carbon atoms are mixed in the alkyl group to create a solution of this copolymer in the monomer mixture, the activated elastomeric olefinic copolymer (rubber component) and the vinyl monomers mentioned are polymerized in the mass with stirring in the presence of a radical polymerization initiator until the proportion of the total polymer in the Polymer system is increased over 2 times the proportion of the rubber component in order to bring about a phase inversion, and then the partially polymerized system is subjected to a polymerization in the mass or a suspension polymerization. 3. The method according to claim 2, characterized in that the radical polymerization initiator is used Azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile or azobiscyclohexanenitrile is used.