DE1445228B2 - PROCESS FOR THE PRODUCTION OF BLOCK PLUG POLYMERS FROM POLYMERIZED VINYLAROMATIC MONOMERS AND OLEFINPOLY MERIZEDS - Google Patents

Description

1 ²

The present invention relates to a method with the high and low pressure polymerization of olefin

whose help is incompatible with one another or only fineness, such as ethylene, propylene and butylenes, such as

Olefin polymers with limited compatibility with one another isobutylene, 1-butene and 2-butylene have been produced

be made compatible. One receives modi can. Preferred olefin polymers are poly

ficated olefin polymers, which are opposite to the ethylene, polypropylene, polyisobutylene. The olefin

chemical and physical polymerizates with improved gear components have a melting point at 190 ° C

have calic properties. indices between 0.05 and 25, preferably between

It is known that various mixtures of 0.1 and 20 g / 10 minutes.

Olefin polymers are difficult to homogenize The suitable polymers are vinylaromatic can and that, after shaping, optionally io monomers can by the customary processes of segregation occurs very quickly. The hetero block, emulsion and suspension polymerization The nature of such mixtures can be determined with microscopes made of vinyl aromatic compounds such as styrene, can be easily recognized: the moldings contain methyl styrene and vinyl toluene, or mixtures thereof larger particles in the mixture side by side. of the substances mentioned. Preferred In addition, the surface of such shaped bodies is 15 polymers of vinyl aromatic monomers mostly scaly and shows severe stress whitening. Polystyrene and styrene-acrylonitrile copolymers. The mechanical properties are also special, as are organic substances which form radicals especially the tensile strength, decreases. Distinguish those at temperatures between 50 and 350 ° C the mixture components in their solubility, disintegrate into radicals, which have a medium life so one can easily possess them by extracting the one for 20 from about 10 seconds up to 20 minutes, Separate component. From the USA patent such as, in particular, organic peroxides, for example 2,528,523 it is known, molded articles made of polyethylene cumene hydroperoxide, dicumyl peroxide, tertiary butyl mit modified properties by adding hydroperoxyd ^ i-tert.-butylperoxydAS-di-tert.-butyl-polyethylene at temperatures between 110 and 180 ° C peroxy-2,5-dimethyl-hexane, dibenzoyl peroxide, lauromite tertiary peroxides mixed and these mixtures 25 yl peroxide, tert-butyl perbenzoate, and azo-bis-nitrile, after shaping by heating to temperature such as azo-bis-isobutyric acid nitrile, and azodisulfonates. doors over 180 ° C, d. H. between about 190 and 210 ° C, such catalysts can be crosslinked in the invention. In this known method, methods according to the invention can also be used in the form of their solutions the polyethylene also elastomers and resins, such as in suitable solvents, such as Polyisobutylene and polystyrene, together with the 30 benzene, toluene, xylene, dioxane, cyclohexane, butanone, Peroxides are added. Dimethylformamide, carbon tetrachloride and tetra-elastomers are obtained, which are not used hydrofuran after the crosslinking process. Generally sets are more thermoplastically deformable. You can also use 0.05 to 10, preferably in the process you no longer with one of the starting components 0.1 to 5 percent by weight, based on the amount of mix. 35 Mixture of all components, on catalysts

From the Belgian patent specification 576 200 it is a.

also known, under irradiation from olefinically un- The components of the type mentioned are saturated Monomers and olefin polymers are intensively kneaded according to the invention. For this are employed Graft polymers with olefin polymers special single- or multi-screw screw presses and to mix. However, the Pfropfpoly- 40 disk kneader is obtained in a suitable manner. In such snail merchandise In a technically very difficult press or disk kneader, large shear guides occur radiochemical process in very low stresses in the crevices by the wall Space-time yield under the snail chamber and the snail or through

the cylinder wall and the kneading disks are formed

Liters of reaction product. These shear stresses can be up to

1.5 · 10 ³ kg / cm ² and more. Machines this

Liters of reaction space · hours / _{type are the} same for the process according to the invention

lies. more suitable, the greater the achievable in them

Also from the French patent it is shear stresses. The resulting genes

1 229 660 known, mixtures of high and low speed gradients G are expediently between

printing polyethylene, polypropylene or polyisobutylene see 10 and 200 · 10 ² sec " ¹ oHer above,

with the addition of peroxides, for example in Ka- The residence time of the mixtures to be kneaded intensively

! to change, to knead. The products obtained in the kneading machines are expediently between

can, however, generally not with polymers 10 seconds and 10 minutes, preferably between

vinyl aromatic compounds such as Polysytrol, 55, 30 and 240 seconds. The modified ones are obtained

be mixed homogeneously. Olefin polymers in general in a space-time

There has now been a method of producing yield of about
Masses containing block graft polymers , _τ · ■
found. The process is characterized by _{50 to 200} / liter reaction products \ ^
that a mixture, the polymers vinylaro- 60 y liter reaction space · hours / '
containing matic monomers, olefin polymers and organic radical formers, at temperatures the ratio between the olefin poly between 80 and 350 ° C kneads intensively until a merisate and the polymers vinylaromatic at least partial crosslinking of the components of the monomers can occur in the intermingling according to the invention. ⁶ 5 driving can be varied within wide limits, i.e.

For the purposes of the invention, olefin polymers are the proportion of a specific olefin polymer in the in particular high molecular weight polymers, which in the reaction mixture can be between about 1 and 99 usual Way, for example, according to the procedure weight percent.

3 4

In the process, the components can add up to 1.05 g / cm ³ and have a K value of 67, and are sprayed on

next in the usual mixing machines, such as this mixture at 0 to 20 ⁰ C 0.7 parts of a 70%

vortex or impeller mixers, premixed aqueous cumene hydroperoxide solution. This peroxide

and using conventional metering devices, the containing mixture is then continuously fed through a

such as vibrating chutes, conveyor belts, dosing screws S Dosing device (vibrating chute or feed screw)

and weighfeeders, the machines in which a commercially available twin-shaft disc mixer

their implementation will be carried out. fed and therein 40 to 150 seconds at 210 to

However, the components can also be kneaded intensively at 250 ° C. and then kneaded in the usual way

feed separately. The process according to the invention is granulated in a manner. A block graft poly-

can be discontinuous and with advantage also continuously, which has a density of 1.01 g / cm ³ , according to DIN.53453

must be carried out naturally. In addition, a. Impact strength of 32 cmkg / cm ² and after

the components also include additives, such as. for example DIN 57302 has a ball indentation hardness of 800 kg / cm ^a .

wise pigments, fillers and such dyes and its softening range is 142 to 155 ° C. his

and stabilizers are added, the dielectric constant is according to DIN 53483

the radicals used. forming substances at. 15 ε - 2.6, its dielectric loss factor according to

do not respond to intensive kneading. DIN 53483 tg <5 = 0.001 and its water absorption

In the process, products are obtained in which 0.07 percent by weight.

it is essentially block graft polymers from B. A mixture of 30 parts of the components in question prepared according to A, with a block graft polymer, 42 parts of a commercial certain amount uncrosslinked present as a mixture of 20 polyisobutylene and 28 parts of polyethylene, which can. Density 0.918 g / cm ³ and according to DIN 57302 the ball-products manufactured according to the invention have a compression hardness of 40 kg / cm ² , the valuable properties of a commercially available rubber kneader (roller mill) with slag-like high-molecular starting components are generally 190 to 230 ° C intensively kneaded, then 60 to nenten. In addition, their properties are, for example, their solution properties, their softening aftertreatment and then granulated in the usual way, their gas permeability, their coloring and which has a density of 0.960 g / cm ³ printability, its resistance to aging, its compression and ball indentation hardness 400 kg / cm ² . It holds up against stress corrosion and its viscoplastic properties, uniformly fine-grained mechanical and electrical properties, counter-structure, can be rolled out into pelts and is advantageously modified over unmodified polyolefins because of its impermeability to water as an insulating way. The products can be made according to the material.

customary processes, for example by injection molding, C. A mixture of 1 part of the prepared according to A.

Extrusion, melt spinning or deep drawing, to block graft polymer, 100 parts commercially available

Moldings, such as threads, fibers, bristles, foils, 35 polystyrene, which has a K value of 66, the density 1.05 g / cm ³

Pipes, injection molded articles, as well as adhesives, and the notched impact strength is 18 to 19 cmkg / cm ² ,

Paints or cable sheathing are processed. is in a commercial kneader 1 to 2 minutes

They differ from those kneaded according to the Belgian at 200 to 220 ° C and then in more common

Patent specification 576 200 manufactured products in their way granulated. A molding compound is obtained in

Constitution as well as advantageous chemical and 4 ° of which the components are evenly finely distributed

Physical Properties. This can be derived from the density 1.04 g / cm ³ , the K value 67.5 and

French. Patent specification 1 229 660 not derived from DIN 53453 the impact strength 21 to 22 cmkg /

will. . cm ³ has

; It is a particular advantage of the invention. -19
manufactured products that you can use them both with 45 U e 1 s ρ 1 el 2
Olefin polymers as well as with polymers A mixture of 10 parts of the polyisobutylene and polyhomogeneous mixture described in Example 1, A bevinylaromatic monomer, especially in kneaders. This gives new ethylene, 90 parts of polystyrene, which has a density of 1.05 g / cm ³ molding compounds based on olefin polymers or and the K value of 67, and 0.5 part of di-tert-butyl from polymers of vinyl aromatic monomers, 50 peroxide is kneaded intensively in a commercially available screw with its mechanical properties and dyeing and press for about 40 to 150 seconds at 210 to 250 ° C printability compared to the contained therein and then in the usual way olefin polymers or granulated to the contained therein. A block graft polymer is obtained, polymerizates of vinylaromatic monomers in advantageous fashion, which looks like mother-of-pearl, which have changed in an adhesive manner on storage for 8 days. Such homogeneous 55 in water absorbs 0.18% water, the density molding compounds can be processed in the usual way to form 1.01 g / cm ³ , according to DIN 53483 the dielectric bodies of the type mentioned above. constant E = 2.6 and at 10 ⁶ Hz the dielectric The parts mentioned in the following examples has a loss factor tg = 0.0005. The product is suitable are parts by weight. The K values were used to manufacture molded structures.
H. F ike η tscher, Cellulose Chemie, 13 (1932), 60. .
P. 58, determined. Example

. A. A mixture of 25 parts of polystyrene containing the

13 ei game 1 has a density of 1.05 g / cm ³ and a K value of 68, 75 parts

A. 25 parts of a homogeneously kneaded mixture of high-pressure polyethylene, which has a density of 0.918 g / cm ³ ,

from 60 parts of polyisobutylene and 40 parts of poly- 65 the softening point 105 ⁰ C and at 190 ° C den

ethylene, which has a density of 0.918 g / cm ³ and an Er melt index of 1.3 g / 10 minutes, and 0.5 parts

has a softening range of 149 to 172 ° C, it is mixed with di-tert-butyl peroxide in a commercially available

75 parts of commercial polystyrene, the density of twin-screw disk kneader 40 to 150 seconds

5 6

Kneaded intensively at 210 to 250 ° C. The product is intensively kneaded for 150 seconds at 210 to 250 ^° C., then granulated in the usual way. It is obtained and then granulated in the usual way. Man

a block graft polymer with a density of 0.93 g / cm ³ a thermoplastic block graft polymer,

and at 190 ° C. the melt index 0.4 g / 10 minutes, the density 1.00 g / cm ³ , the dielectric constant

and that is much more dimensionally stable than unmodified 5ε = 2.6, at 10 ^e Hz the dielectric loss factor

Polyethylene and much more elastic than unmodified tg <5 = 0.0035 (DIN 53483) and at 190 ° C the melt polystyrene is. The product has a uniform fine-particle index of 2.71 g / 10 minutes and that for 8 days Structure and is suitable for the production of form storage in water 0.19 percent by weight water

bodies. records. 100 parts of the product dissolve up to

B. A mixture of 5 parts of the io prepared according to A to a small remainder of about 1 percent by weight Block graft polymer and 95 parts of high pressure in 1500 parts of boiling dioxane.

polyethylene, which has a density of 0.918 g / cm ³ and, for comparison, a mixture of polystyrene at 190 ° C. has a melt index of 1.5 g / 10 minutes, and polypropylene in the absence of radicals

in a commercial kneader for 1 minute with 200 bis forming substances under otherwise identical conditions

21O ⁰ C intensively mixed. A stable 15 is obtained, which is intensively kneaded to obtain a product from

Molding compound based on olefin polymers, which is subject to the aforementioned conditions

the density 0.921 g / cm ³ and at 190 ° C the melting with boiling dioxane only the poly contained therein

index 1.1 g / 10 minutes. In contrast to styrene, it can be removed.

Mixing of polystyrene and polyethylene is shown in B. A mixture of 20 parts of the substance derived from A

Molding compound with a magnification of up to 400 times a thermoplastic block graft polymer

evenly fine distribution of the components. and 80 parts of polypropylene (modified olefin

C. A molding composition based on a polymer is obtained which has a density of 0.895 g / cm ³ and, in the case of styrene polymer with a uniformly fine distribution, 190 ° C. has a melt index of 0.43 g / 10 minutes, of the components if 5 parts of the after A is intensively kneaded for 1 to 2 minutes in a commercially available two-screw disk block graft polymer with 50 parts of a kneader and then granulated in the customary manner after a block graft polymer in the customary manner. Polystyrene produced by a sation process is obtained which has a molding composition based on olefin polymers, a density of 1.05 g / cm ³ and a K value of 66, 1 to 0.921 g / cm ³ and a melt of 2 minutes at 190.degree at 200 to 220 ° C in a commercial index 0.90 g / 10 minutes and which is homogenized in a plastic state after the kneader. The 30 conventional injection molding processes to form moldings ver molding compound has a density of 1.04 g / cm ³ . lets work.

D. A mixture of 1 part of the prepared according to A. .
Block graft polymer and 10 parts of a conventional example 5

Manner from 76 parts of styrene and 24 parts of acrylonitrile A mixture of 92 parts of one in a conventional manner

Copolymer produced, the copolymer produced from 75 parts of styrene having a K value of 72.5 35

and the density has 1.08 g / cm ³ , in one hand ice and 25 parts of acrylonitrile the density 1.08 g / cm ³ , the

usual plasticizing device 2 to 4 minutes with a K value of 71 in dimethylformamide, 8 parts

about 200 ⁰ C intensively kneaded and then in polypropylene of density 0.896 g / cm ³ , the after

usually peeled off as a tape. An ASTM D 1238-T is obtained at 190 ^° C. with a melt index of 0.3 g /

homogeneous molding compound based on a styrene poly- 4 ° 10 minutes, and 0.7 parts of azo-diisobutyric acid

merisats, which has the density 1.06 g / cm ³ and the impact nitrile is about 55 seconds at 190 to 230 ⁰ C in

Has a viscosity of 38 cmkg / cm ² and that for 1 hour a multi-shaft disk mixer in which

Storage in boiling water 0.2 percent by weight velocity gradients of 19 800 seconds " ¹ occur,

Absorbs water. The homogeneous mixture can after an energy consumption of the kneader of 0.4 to

the usual methods, for example the injection 45 0.5 kWh per kilogram of mixture intensively kneaded.

casting or deep-drawing, processed into molded bodies. An impact-resistant product of uniformity is obtained

will. opaque appearance, for example after the

For comparison, a mixture of injection molding and extrusion molding processes is kneaded to form moldings

10 parts of the aforementioned styrene-acrylonitrile mixture can be processed. Plates made from it

Polymer, 0.25 parts of polystyrene with a K value of 68 50 can be shaped by the deep drawing process.

and 0.75 parts of high pressure polyethylene of density The product has the density of 1.06 g / cm ³ and after

0.918 g / cm ³ in the absence of DIN 53371, which forms free radicals, the tensile strength is 500 to 620 kg / cm ² .

Fabrics for 2 to 4 minutes at about 200 ° C in the same. .

Plasticizing device, an inhomogeneous example is obtained

Mixture that has an impact strength of only 30 to 55. A mixture of 25 parts of polystyrene that has the

31 cmkg / cm ² and that, according to the injection molding density 1.05 g / cm ³ and the K value 68, has 75 parts

Process processed, molded body with flaky high-pressure polyethylene, which has a density of 0.918 g / cm ³ ,

Surface results. the softening point 105 ⁰ C and at 190 ⁰ C den

. . Has melt index 1.3 g / 10 minutes and 0.5 parts

ispie 60 Di-tert-butyl peroxide comes in a single-wave

A. A mixture of 90 parts one after a screw machine in which the rotational movements

conventional block polymerization process produced the screw shaft by a reciprocating

Polystyrene on which the density 1.05 g / cm ³ and the K-value movement in the axial direction are superimposed

67 has 10 parts of polypropylene, which has a density of 90 to 120 ° C intensively kneaded. The product is

0.892 g / cm ³ , the softening point 115 to 118 ° C 65 closing in the usual way, and one

and at 18O ⁰ C the melt index 0.38 g / 10 minutes gives a modified olefin polymer containing the

and 0.5 parts of di-tert-butyl peroxide has a density of 0.93 g / cm ³ and the melting point at 190 ^{° C.}

commercially available twin-screw disk kneader has 40 to 0.7 g / 10 minutes.

Example 7

A mixture of 25 parts of polystyrene, which has a density of 1.05 g / cm ³ and a K value of 68, 75 parts of high-pressure polyethylene, which has a density of 0.918 g / cm ³ , a softening point of 105 ° C. and at 190 ° C. the melt index 1.3 g / 10 minutes has, and 0.5 parts of di-tert-butyl peroxide is kneaded in a commercially available single-shaft screw press, which has an adjustable gap between the worm shaft and worm chamber intensively at about 34O ⁰ C. The worm shaft rotates at 2000 revolutions per minute and the distance between the worm shaft and the screw chamber is 2.5 mm. The mean residence time of the reaction mixture in the screw machine is 3 seconds, and in the intensive kneading occurs a velocity gradient of 20,000 to see ^1. The product is then granulated in the usual way after the intensive kneading. A block graft polymer is obtained which has a density of 0.92 g / cm ³ and, at 190 ° C., a melt index of 11.8 g / 10 minutes.

Claims (6)

Patent claims: 1. Process for the production of plastic compositions containing block graft polymers, characterized in that a mixture containing the polymers is vinylaromatic Contains monomers, olefin polymers and organic radical formers, at temperatures between 80 and 350 ° C knead intensively until an at least partial crosslinking of the components with one another entry. 2. The method according to claim 1, characterized in that one is a polystyrene and olefin polymer containing mixture kneads. 3. The method according to claim 1 or 2, characterized in that there is a styrene-acrylonitrile copolymer and the mixture containing olefin polymer is kneaded. 4. The method according to any one of claims 1 to 3, characterized in that there is a mixture kneads that as olefin polymer is a homo- or copolymer of ethylene, propylene or Contains butylene. 5. The method according to any one of claims 1 to 3, characterized in that there is a mixture kneads, the olefin polymer is a copolymer of ethylene and / or propylene with acrylic or vinyl ester. 6. Use of the compositions prepared according to one of the preceding claims for production of molded bodies. 109 534/373