HU211069B - Process for producing grafted copolymers, composition of said copolymers and polyolefins and method for improvement of quality and compatibility polyolefins - Google Patents

Abstract

The present invention provides a novel process for preparing grafted copolymers by grafting at least one kind of methacrylate homopolymer or copolymer chain onto a nonpolar polyolefin strain in a ratio of 1: 9 to 4: 1 by weight of nonpolar polyolefin having a molecular weight of between 50,000 and 1,000,000 in a known solvent. and dissolving a monomer or monomer mixture of at least 80 wt% CH2 = C (CH 3) -COOR methacrylic acid ester, wherein R is C 1-8 alkyl and optionally up to 20 wt% of other copolymerizable acrylate monomer; this is polymerized by grafting at 60-200 ° C by addition of a free radical initiator to a chain having an average molecular weight of between 20,000 and 200,000. The invention also relates to mixtures of the graft copolymers prepared as above with polyolefins and their use for the production of extruded, calendered or cast products, and for improving the compatibility of the polyolefins elongation modulus and their resistance to sag and further polymers with different polarity levels. EN 211 069 B Description: 34 pages

Description

The present invention relates to a process for the preparation of a graft copolymer composition for improving the physical properties of polyolefins, optionally containing a non-grafted polyolefin additive; the invention also relates to a composition for improving the elastic modulus and resistance to sagging of polyolefins, and to the manufacture of shaped articles using the composition of the invention.

The grafted copolymers of the present invention are olefin copolymers which are covalently bonded to a high molecular weight methacrylate polymer chain. The methacrylate chain may have a weight average molecular weight of from 20,000 to 200,000, preferably from 30,000 to 150,000.

The graft copolymer composition of the present invention can be prepared essentially by incorporating an apolar polyolefin known per se, preferably polypropylene or polyethylene, in an inert hydrocarbon solvent. which dissolves (or swells) and then heated to a temperature such that the polyolefin dissolves. While stirring, the methyl methacrylate (MMA) monomer and initiator are added gradually with stirring to provide a constant low radical concentration to initiate polymerization of the monomer at the solution temperature and to form covalent bonds. The grafted side-chain polyolefin is then recovered from the solution by evaporation of the solvent, preferably using an evaporation extruder. Finally, the grafted polymer may be blended with a suitable polyolefin such as polypropylene or polyethylene and extruded to the desired shape.

Apolar polyolefins, in particular polypropylene and polyethylene, are mixtures thereof and have various low density. high density and linear low density versions are major commercial products for a variety of purposes. However, there are special needs on the market for which these materials have not yet been satisfactorily addressed. Among other things, they have not overcome the difficulties of thermoforming and, in particular, the processing problems of bulk polyolefins in bulk or semi-bulk form (well above the melting point); as the polymer is easily folded under its own weight, as it has a lower stiffness than desired, which results in a highly uneven wall thickness during thermoforming. This was overcome by increasing the molecular weight of the polymer; however, the processing of the high molecular weight polymer has presented difficulties which did not occur with the low molecular weight types.

Also known as polybutylene, the low melting point of the isotactic polybutene1 makes it difficult to crystallize the polymer after processing, to develop proper properties and ease of handling by crystallinity. Nucleation centers capable of repairing these have not yet been marketed.

Solutions are also being sought to improve toughness or impact resistance, for example in the case of polypropylene. The use of copolymers or polyethylene modified with ethylene / propylene rubber improves toughness, but at the expense of even less stiffness and reduced heat resistance. It would be desirable to combine the impact resistance of the copolymers with the stiffness and heat resistance properties of the polypropylene homopolymer.

The grafting of vinyl polymerization monomers, such as styrene, methyl methacrylate and the like, to polyolefins such as polyethylene, polypropylene, ethylene / propylene copolymers and ethylene / propylene / diene terpolymers has been under investigation almost since such methods have been practiced. Grafting to solid polymers has already been tried by vapor-phase polymerization, reaction in an extruder, peroxidation of the olefin backbone structure and subsequent grafting to the side group double bonds. However, there is a lack of a method which allows relatively high molecular weight grafting with relatively good grafting efficiency (i.e., low formation of non-attached polymer molecules), gel-free and efficient and inexpensive practical methods for producing and recovering the grafted polymer.

Mixtures of two or more polymers are often made, for example, to combine desirable properties of the individual polymers to be blended, or to create specific properties with the blend, or only to produce cheaper products by introducing cheaper or waste polymers. Compatible polymers form mixtures in which the individual polymers form small domains; In the case of "miscible" polymers, they are of molecular size and exhibit properties as if a single polymer were present, that is, they exhibit only a glass transition temperature and are optically pure. Such mixtures are often referred to as "alloys". However, compatible polymers that are not clearly miscible within the meaning of the above, however, form blends with properties that are close to miscible. Such property is the tensile strength, which is related to the adherence of the domains to one another and which does not deteriorate when compatible polymers are mixed.

Unfortunately, many polymers have poor compatibility with each other. Low compatibility is not necessarily predictable for particular polymer combinations, but in general, it is expected that apolar and more polar polymers will not yield compatible mixtures. Poor compatibility will be appreciated by the skilled artisan, as it usually exhibits low tensile strength and deterioration of other physical properties relative to the polymers of the blend. Low compatibility can also be confirmed by microscopic observation, since large, poorly adherent domains of each polymer component are visible in the continuous medium of the other polymer. More than one glass transition temperature occurs, and blends of otherwise transparent polymers become blurred because the size of the domains is such that it scatters visible light.

Considerable research has been devoted to increasing the compatibility of poorly compatible polymers to be blended. Thus, additional polymers were added to the mixture which were incompatible

EN 211 069 Β compatible with polymers; the polymers thus added act as bridges at the interfaces of incompatible components, which often reduces the size of the domains. Such polymeric additives are chlorinated polyethylene, in particular mixtures of polyolefins with other poorly compatible polymers.

When the incompatible polymer A is grafted onto polymer B, the grafted polymer promotes mixing of polymer A and B. Moreover, such grafted polymers can facilitate mixing of other incompatible polymer pairs (C and D) if A and C and B and D are compatible.

It is also difficult to predict in polymer science the extent to which such grafted polymer is effective in improving the desired properties of the mixture over the properties of the incompatible mixture. Therefore, the skilled artisan should also try all combinations of graft polymer and polymer components of a given mixture and experimentally determine, in a particular case, whether improvements in properties such as tensile strength can be achieved by adding a particular graft polymer to a particular mixture. .

No. 4,094,927. U.S. Pat. No. 5,123,195 discloses copolymers of longer-chain alkyl methacrylates with (meth) acrylic acid as additives in polypropylene, to increase melt strength, to improve foam stability, and to improve processing. However, these polymers are not fully compatible with polypropylene, and the additive tends to flake out and damage the equipment during operations such as calendering.

U.S. Pat. No. 4,409,345. U.S. Pat. No. 5,102,125 discloses a polymerizable polyolefin modified with an unsaturated carboxylic acid ester, which improves the processing of blends of polypropylene, high density polyethylene and finely divided vegetable fibers. This patent appears only to demonstrate the reinforcing effect of the graft copolymer-bonded polyolefin. Each example is limited to grafted maleic anhydride or acrylic acid, where the molecular weight of the "graft" refers to a small number of monomer units.

No. 826,440. South Africa Patent Specification for Improved Melt Viscosity (higher viscosity under mild shear conditions, while maintaining low melt viscosity of unmodified polypropylene under high shear) and improved snow-forming properties of salts of polypropylene and certain acid modified propylene polymers.

No. 4,370,450. In the US patent, polypropylene is modified with polar vinyl monomers. It is prepared by polymerizing in an aqueous suspension containing a swelling agent above 85 'C with a radical chain transfer initiator having a half-life of between 80 and 135 ° C for at least 2 hours. The patent does not mention direct grafting in solution, it merely speaks of "only a relatively small degree of grafting". The examples list hydrocarbons as swelling agents.

No. 4,161,452. U.S. Pat. No. 4,192,115 describes the grafting of only unsaturated carboxylic acids or anhydrides and (meth) acrylic acid esters in ethylene / propylene copolymers in solution in the presence of free radical initiators capable of hydrogen removal at 60 to 220 ° C. The claim relates to an oil-soluble polymer.

No. 4,595,726. Patent U.S. C ₂ -C ₆ alkyl methacrylates polypropylene relates to graft copolymers which are made from solvent-free vapor-phase polymerization, in which the number and the molecular weight of the grafted chain is controlled so that the desired (although undefined) chain length and láncsürűség develop that makes it suitable for use as an adhesive between polypropylene and more polar substrates. According to the patent, similar graft copolymers can be prepared from methyl methacrylate but do not exhibit the desired adhesive properties. According to the patent, the polymerization should be conducted at temperatures below the softening point of the polypropylene, although this value is not given but is known to decrease in the presence of monomers and in the examples above 140 ° C does not occur under solvent-free conditions. There is no indication or indication that a relatively high molecular weight chain is covalently grafted onto the polyolefin. Moreover, the resulting root flux appears to be too large to form a high molecular weight chain, say greater than 20,000.

No. 4,692,992 of the ÚSA. Grafting is carried out between 60 and 160 ° C while the olefin polymer remains in solution in a solvent consisting of a mixture of hydrocarbon and ketone and the graft polymer only precipitates when the reaction mixture is cooled below 40 ° C. No mention is made of the reaction conditions required to achieve the high molecular weight, nor the advantage that the reaction is conducted only in the presence of a solvent with low chain transfer activity.

No. 3,862,265. In U.S. Pat. No. 4,600,440, polyolefins are melt-extruded and then grafted with unsaturated acids to achieve Improved Theology, in the sense described in U.S. Patent No. 826,440. South African patent.

U.S. Pat. No. 3,886,227. U.S. Patent No. 4,123,125 to Gillard discloses the grafting of unsaturated acids and esters (although no examples of esters are provided) for the preparation of a material that can be used as a polypropylene modifier. Grafting is carried out in an extruder. It is also reported that the molecular weight of the polypropylene backbone is reduced by decomposition during the grafting process above 200 ° C. The grafted product is mixed with polypropylene, which results in changes in properties such as nucleation, post-processing warping, and the like. Although improvements in thermal stability are reported, improved theological properties are not mentioned at the temperatures required for thermoforming or the like.

No. 59-164,347. Japanese Kokai Patent No. 6,198, which has led to very low grafting of unsaturated acids or derivatives (including their esters) (10-5 to 10-8 grams equivalents to 1 g of polyolefin), mixing these products with polyolefins and applying them to the surface tension of molten polyolefin.

EN 211 069 Β without changing its viscosity under high shear, which makes it suitable for eg. for blow molding of bottles.

Kallitis et al. [Eur. Polym. J. 27, 117 (1987)] reported the use of ethylene / propylene copolymers as a nucleating agent in polybutylene. There is no mention even of the utility of the polypropylene / methacrylate grafted products of the present invention.

No. 2,987,501. U.S. Pat. No. 4,125 discloses the grafting of polymers of Reike and Moore vinyl monomers onto polyethylene or polypropylene. The polyolefin is oxidized with fuming nitric acid or nitrogen tetroxide and the polyolefin thus activated is heated with the vinyl monomer. In the examples, methyl methacrylate is grafted onto polyethylene and polypropylene.

A 223 250/87. s. In Japanese Kokai Patent No. 6,198, the polyolefin and the polyamide are made compatible by injecting an unsaturated carboxylic acid or derivative thereof into a mixture of the polyolefin and the polyamide, and utilizing this reaction product in the presence of a mixture of two or more polymers. The amount of acid or acid derivative reacted with the parent polymer is less than 10% and the only example given is that low molecular weight units are attached or grafted using non-homopolymerizable unsaturated acids. These include reaction conditions that use a relatively small amount of unsaturated acid and a relatively large amount of peroxide, which does not bring it closer to the molecular weight of the grafted chain as in the individual cases described below according to the present invention. This patent discloses a specific modifier which is formed as such. that two non-polymerizable acids are reacted with a mixture of four core polymers and that affects the compatibility of the polyamide and the polyolefin. However, comparative data suggest that the reaction of the acids with polypropylene alone is not effective in improving the compatibility of the two polymers. Furthermore, low-molecular weight polymers grafted with an unsaturated acid or its derivatives are not effective enhancers of compatibility between polyamides and polyolefins.

No. 86,040/87. Japanese Kokai Patent Specification No. 3,600,125 relates to polymeric adhesives. Introduces an olefin polymer adhesive. which is modified with a carboxylic or carboxylic anhydride group, then reacted with an alcohol-functional polyolefin and finally reacted with an aromatic acid halide.

Boutevin et al., Angewandte Makromolecular Chemie, 162 (1988), p. 175] discloses the preparation of a poly (methyl methacrylate) copolymer for a polyethylene strain. The low density polyethylene is subjected to ozonolysis and the activated polyethylene is heated in the presence of methyl methacrylate. The grafted methyl methacrylate chain has an average molecular weight of up to 21,400. These grafted polymers are used as emulsifiers or as a compatibility additive for low density polyethylene and polyvinyl chloride mixtures. They reported a marked increase in the tensile stress of the compatible mixture and a decrease in the size of the domains in the mixture. A noticeable decrease in the molecular weight of polyethylene when treated with ozone prior to grafting is also reported. This publication does not address the higher molecular weights and does not provide any indication that the grafted polymer may be effective in reducing the deflection of the polyolefin matrix polymer, or that it would otherwise have the desired rheological effects on the polymer.

Thus, the present state of the art includes the realization of graft copolymers of methyl methacrylate grafted onto polyolefin substrates, but the graft polymers of the present invention have not yet been prepared. Moreover, the advantages of the polymerization process described herein for the rapid and efficient preparation of high molecular weight, new graft polymers without gel formation and easy product isolation have not been recognized. It appears that some graft polymers can be blended with polyolefins, but the unexpected utility of new graft polymers in improving low-shear melt rheology and solid state properties has not been recognized, in particular that high-shear behavior is hardly or at all affected. . It has also not been discovered or discovered that the graft polymers of the present invention can advantageously influence the tendency to sag.

It is therefore an object of the present invention to provide an improved process for the preparation of new polyolefins grafted with methacrylate esters. Another object of the present invention is to provide at least one graft copolymer having a relatively high, i.e. at least 20,000 average molecular weight methacrylate polymer chain, on a polyolefin homo- or copolymer backbone. It is a further object of the present invention to provide graft copolymers which can be used as a compatibility additive for blends of otherwise poorly compatible polymers. It is another object of the present invention to provide graft copolymer blends having a polyolefin matrix which improve the physical properties of the melt during cooling and even in the solid phase.

The foregoing objects and advantages of the present invention may be achieved by inoculating at least one polymer chain having a weight average molecular weight greater than 20,000 and a weight ratio to polyolefin in the range of from 1: 9 to 4: 1, in solution in the apolar polyolefin stock polymer. The grafted polymer moiety comprises at least 80% of methacrylate ester monomer units represented by the formula CH ₂ = C (CH ₃ ) COOR, wherein R represents a C 1-8 alkyl group, and up to 20% of this grafted polymer moiety may be any methacrylate. ester copolymerizable styrene or other acrylate monomer. This synthesis can be accomplished by adding the methacrylate monomer to the solution of the polyolefin together with an initiator which has a constant low radical concentration and / or lower concentration. provides root flux at the temperature of the solution. These radicals initiate polymerization of the monomer and form covalent bonds with the parent polymer.

The resulting copolymer product is hereinafter referred to as a "concentrate". This may blend with the polyolefin directly as a result of the preparation, or it may be blended subsequently. The mixture can be extruded to the desired shape either directly or by granulation

EN 211 069 Β. In each case, the resulting product advantageously combines the favorable tensile modulus and reduced tendency to sag with good melt viscosity compared to the corresponding un grafted polymers, i.e., with the high molecular weight chain or chains covalently bonded to the polyolefins.

The concentrate may also be mixed with other polymers of a non-polyolefin type, in particular a mixture of two or more polymers which are poorly compatible with each other and which may also contain a polyolefin, in order to improve the compatibility of the resulting mixture.

The invention also relates to a process for the production of graft polymers according to the invention. Briefly, the process according to the invention is as follows: The polyolefin is dissolved or swelled in an inert hydrocarbon solvent and then heated to a total dissolution of the polyolefin, i.e., at least 140 ° C. Monomer is added to the solution with constant stirring, together with an initiator which provides a constant, low root flux at the solution temperature; the radicals initiate the polymerization of the monomer and the formation of covalent bonds with the polyolefin backbone. The reaction mixture is brought to a solid state by evaporation of the solvent. The product thus obtained, the concentrate, comprises a polymer chain grafted polyolefin, an unreacted polymer, i.e., un grafted polyolefin, and a methacrylate ester polymer uncoupled from the parent polymer. This system can be granulated, blended with additional polyolefin and extruded to the desired shape. Alternatively, the reaction mixture may be extruded directly by means of an evaporation extruder from which the solvent and monomer residue may be removed; it can then be blended with additional polyolefin and extruded into a mold, such as sheet, tube or similar profile.

Further, low density polyethylene (LDPE) is generally branched, having a density ranging from 0.91 to 0.94 g / cm ³ ; high density polyethylene (HDPE) has a density of about 0.95 g / cm ³ ; linear low density polyethylene (LLDPE) has a density of 0.91 to 0.95 g / cm ³ : a rubber terpolymer of EPDM ethylene, propylene and non-conjugated diene such as 1,4-hexadiene or ethylidene norbomene.

The term "polar substrate" or "apolar polymer" as used below is difficult to quantify. "Apolar" refers to polymers that are predominantly composed of mono- or diolefin monomer units; "Polar monomers that have oxygen, nitrogen or sulfur functionality are generally considered polar in the art. Thus, methyl methacrylate, acrylonitrile or vinyl phenyl sulfone is a "polar" monomer, while polypropylene is an "apolar" polymer.

The graft modified polymers are apolar olefin polymers and copolymers such as polypropylene, polyethylene (HDPE, LDPE and LLDPE), polybutene, ethylene / propylene copolymers in any ethylene / propylene ratio, and EPDM terpolymers in any ethylene / propylene ratio of 10% and containing by weight not more than 25% of poly (butene-1), poly (methyl-pentene), ethylene / vinyl acetate copolymers, ethylene / methyl acrylate copolymers, ethylene / methyl methacrylate copolymers and ethylene / ethyl acrylate copolymers and mixtures of any of these.

Useful graft copolymers are those in which the weight ratio of polyolefin to acrylate polymer or copolymer ranges from 20:80 to 80:20.

The molecular weight of the olefin polymer constituting the core polymer of the graft copolymer should be high enough to yield a large amount of apolar polymer after grafting, but small enough to predominantly acrylate polymer chains on each polyolefin chain of the core polymer. It is particularly preferred that the weight average molecular weight M _{w of the} parent polyolefin is 20,000-800,000, but also polyolefins having a molecular weight of 800,000-1,000,000 and 50,000-200,000. In general, the graft copolymer improves the melt rheology properties of the high molecular weight polyolefin. This is especially true if the molecular weight of the graft polymer polyolefin strain is relatively low.

It is known that the melt flow rate (MFR) is well correlated with the weight average molecular weight. The polyolefin stock polymers used in the preparation of the grafted polymers of the present invention preferably have an MFR of between 20 and 0.6 g / 10 min. In ASTM D-1238. measured according to the standard.

Methacrylate monomers are particularly preferably used as methyl methacrylate, but also preferably esters of methacrylic acid containing a C2-C4 alkyl group. However, good results may also be obtained with methacrylate mixtures containing methacrylic acid alkyl esters with some or all, but preferably up to 20% by weight, of a longer chain with C5-C8 alkyl groups.

The present invention therefore relates to a novel process for the preparation of a graft copolymer composition for improving the physical properties of polyolefins, optionally containing a non-grafted polyolefin additive, wherein

a) introducing into the reactor vessel an inert solvent and an apolar polyolefin having a weight average molecular weight of between 50,000 and 1,000,000, comprising one or more monomers, namely ethylene, propylene, butylene and / or 4-methylpentene; it contains monomeric units;

b) dissolving the apolar polyolefin mentioned in a) in the solvent by heating to the extent necessary for dissolution;

c) adding to the mixture obtained by stirring at least 80% by weight of a methacrylic acid ester of the formula CH ₂ = C (CH ₃ ) COOR, wherein R is a C 1 -C 8 alkyl group, and optionally up to 20% by weight of other copolymerizable acrylates; a monomer or a mixture of monomers containing a monomer;

d) grafting the monomer or monomer mixture added in step c) to a strain having an average molecular weight of 20,000 to 200,000 such that

By adding an oil-soluble free radical initiator having a half-life of 1 hour at a temperature of 60 ° C to 200 ° C, the reaction mixture is maintained at a reaction flux of 0.0001 to 0.0005 equivalents / liter / min. and calculated to maintain this initiator addition and temperature until the graft polymerization is complete, and

e) removing the solvent from the polymerization mixture and, if desired, adding an additional olefin polymer to the copolymer prepared physically.

It is also advisable to pay attention to the practical implementation of the procedure. to minimize the chain transfer to the polymer of the polymerization chain relative to the polyolefin chains. This is necessary to efficiently produce a homogeneous, non-gelling, graft polymer in good yield.

The molecular weight of the grafted acrylate chain was determined. to measure the weight average molecular weight of the uncoated acrylate polymer prepared with it. This should preferably be between 20,000 and 200,000, more preferably between 30,000 and 150,000.

The graft polymerization process of the monomer results in the formation of graft and graft material. The percentage of graft material is 5-50% of the total acrylate polymer or copolymer formed. The graft copolymer is prepared by a process which polymerizes the monomer in the presence of an apolar polyolefin. The process is conducted in a solvent that dissolves or swells the apolar polymer. The solvent should also not exhibit a significant chain transfer effect. For example, non-branched or branched aliphatic hydrocarbons, benzene, chlorobenzene, tert-butylbenzene, anisole can be used. cyclohexane, petroleum products and dibutyl ether. Preferably, the solvent is easily removed by extrusion evaporator. therefore, it is advantageous to have a boiling point below 200 ° C, preferably below 150 ° C. However, in order to avoid too much pressure, it is advantageous to have a boiling point above 100 ° C.

The final solids content (polyolefin and acrylate polymer together) depends on viscosity and good miscibility. The practical limit is between 20% and 70%, but the solids content may be as high as good mixability requires economically. Preferably the solids content is between 35 and 60%.

It is advisable to add the monomer gradually or in portions. If necessary, the amount of monomer need not be uniform throughout, for example, the last 0-20% may contain all small amounts of monomer used to be concentrated in a single portion on the polymer.

During polymerization, the temperature may be between 110 and 200 ° C, but more preferably between 130 and 175 ° C, particularly preferred between 145 and 160 ° C. The pressure may be atmospheric or higher up to 2100 kPa or whatever is required to maintain the reaction mixture in the liquid phase at the temperature of polymerization.

The concentration of unreacted monomer should be kept low during the reaction. This can be controlled by balancing root flux and monomer delivery.

An oil-soluble initiator providing thermal free radicals is used for polymerization. In this process, they have a half-life of between one hour and 60 ° C to 200 ° C. Preferably, in the range of 90 to 170 'C, the half-life is one hour. Suitable free radical initiators include: peroxy initiators such as tert-butyl peroxy pivalate, lauryl peroxide, 1,1,3,3-tetramethyl butyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2, 5-bis (2-ethylhexanoylperoxy) hexane, acetyl peroxide, tert-butyl peroxy isobutyrate, succinic acid peroxide, tert-butyl peroctoate, benzyl peroxide, tert-butyl peroxy maleic acid, hydroxy-1-hydroperoxydicyclohexyl peroxide, 1,1-bis (tert-butyl peroxy) -3,3,5-trimethylcyclohexane, tert-butyl peroxycrotonate, 2,2-bis (tert-butyl) peroxybutane), tert-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, tert-butyl peracetate, methyl ethyl ketone peroxide, di ( butyl) diperoxyphthalate, tert-butyl perbenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, 2,4-pentanedione peroxide, di (tert. butyl) peroxide,

2,5-dimethyl-2,5-di (tert-butyl-peroxy) -hexine-3, 1,1,3,3-tetramethyl-butyl-hydroperoxide, cumene-hydroperoxide,

2,5-dimethyl-2,5-di (hydroperoxy) hexane, tert-butyl hydroperoxide, tert-butyl cumyl peroxide, p-menthane hydroperoxide and azobisobutyronitrile.

The initiator is introduced along with the monomer during the polymerization so as to provide a sufficiently constant root flux for most of the polymerization period. This is required for the desired high molecular weight, high grafting efficiency, required molecular weight distribution and gel-free.

The root flux is the calculated rate of formation of free radicals in root equivalent / liter / min. Since this cannot be measured experimentally, it can be calculated from the instantaneous concentration and known rate of degradation of the free radical initiator present at that time. The decomposition rate of the initiators can be found in the literature, and the concentration is either constant when the initiator is added uniformly or can be calculated (per initiator charge) from the known decomposition rate constant and from the time of feeding.

Good results are obtained when a uniform root flux is maintained and the calculated root flux is between 0.00001 and 0.0005 root equivalent / liter / min, preferably 0.00002 and 0.0002 root equivalent / liter / min. The radical flux depends on the material quality, concentration, and rate of decomposition of the particular initiator, as well as the reaction temperature chosen. The decomposition rates can be found in tables, such as those in the 2nd edition of The Polymer Handbook (ed. Brandrup and Immergut, Wiley and Sons, New York, 1975), unless otherwise provided by the manufacturers. Even if the exact velocity constant at the temperature in question is not known, activation energies are often available, from which velocity can also be calculated. The root flux calculation equation:

Root flux = 2 (k _d ) (60) (I) where k _{d is} the decay rate constant of a given initiator in reciprocal seconds and I is the initial

EN 211 069 Β tor concentration in moles / dm ³ . In a batch reaction, I continuously decreases starting with I _o , which is the value at the time of loading, so the root flux is not constant. If the initiator is continuously added, the concentration of the initiator at a given time will be calculated, but may be maintained at a much more constant level than in the batch reaction, especially if the addition of the initiator is carefully controlled.

The process can be performed in semi-continuous or continuous mode. The monomer, solvent and initiator may be added in the same manner as described above. The polymer has to be dissolved separately in the solvent and can be introduced at a rate equivalent to product removal, or it can be introduced into the reaction in melt or solid form by means of an extruder.

After polymerization, after some time, the solvent and a portion of the unreacted monomer are removed by evaporation. An acceptable evaporator may be an evaporator extruder, a rotary film evaporator, or any other convenient quick evaporator. The polymerization reaction mixture may be introduced batchwise or continuously into the evaporator.

Prior to, during or after the evaporation step, the necessary additives may be added to the graft copolymer solution or to the solution. suspension to be introduced into the isolated graft copolymer. If the additive does not interfere with the grafting reaction, it may be added before, during or after the polymerization process. Such additives can also be added when the graft copolymer is already mixed with the parent polymer. Such additives may be light or heat stabilizers. Thus, benzothiazoles, inhibited amines, alkyl polysulfins, such as dialkyl disulfides, lubricants or plasticizers, and flame retardants. Preferably, the amount of added disulfide such as di (n-dodecyl) disulfide or di (tododecyl disulfide) is from 0.001 to 0.05% by weight based on the total weight of the grafted copolymer and the parent polymer to stabilize the acrylate portion of the grafted copolymer during melt processing. against thermal decomposition during mixing with the matrix polymer and extrusion.

Another group of stabilizers are tris (polyalkylhydroxybenzyl) -s-triazintrions. Preferably, tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine (1H, 3H, 5H) -trione may be used in an amount of 0.001 to 0.1% by weight based on the total weight of the polymer .

The stability of the acrylate portion of the graft copolymer can also be achieved by incorporating alkylthioalkyl (meth) acrylate, preferably ethylthioethyl methacrylate, together with the acrylate monomer or monomers.

The product is finally recovered by extrusion, cooling, slicing and drying, and then bagged or otherwise formulated.

The polyolefin and the graft copolymer concentrate may be mixed by extrusion of the dry mixture, either directly in the form of a film, sheet or the like. either by collecting the mixture and recycling it to the desired article, or the polyolefin may be added during evaporation.

Polyolefins are often manufactured with one or more stabilizers to preserve the appearance and physical properties of the polymer during processing and / or end use. Such stabilizers include metal salts such as metal stearates which act as acid scavengers, inhibited phenols as antioxidants, sulfur-containing organic esters or derivatives thereof as snow stabilizers. For example, these additives, which are commonly marketed by formulators, include metal stearates, 2,6-dimethylphenol derivatives and thiodiester esters of long chain alcohols. The polyolefins may also contain light stabilizers such as inhibited amines, benzthiazoles and the like. All polyolefins used in the examples of the invention are believed to contain small amounts of such self-formulated stabilizers.

In one aspect of the preferred blend compositions, at least 0.2% by weight of the total composition (polyolefin and graft copolymer together) should be graft polymer or copolymer according to the invention. Preferably, the maximum amount of graft polymer according to the invention is 10% by weight, more preferably up to 5% by weight, which optimizes the mixture in terms of both cost and most properties.

The mixture of concentrate and polyolefin may be further modified by the addition of inorganic or organic fillers, fibers, impact enhancers, dyes, stabilizers, flame retardants and / or blowing agents.

The blowing agents may be gases, such as nitrogen or carbon dioxide, which are admixed to the polymer melt in the extruder and cause the melt to foam at the end of the extrusion. However, in most cases, the blowing agents are solids which release gas only at a specific melt temperature, usually nitrogen, and are incorporated into the melt, possibly in the form of a premix dispersed in the polymer matrix. Polyolefins typically have a melting temperature of 200-230 ° C, although other temperatures may be used depending upon the particular blowing agent. Solid blowing agents include azo compounds such as azo-dicarbonamides, azo-isobutyronitriles, hydroazo compounds or nitroso compounds.

Mixtures of graft copolymer and polyolefin are suitable for thermoforming, main production (especially by blowing and extrusion), blow molding, fiber drawing, acidic and basic dyeing, foaming, extrusion (sheet, tube and profile), co-extruding, molding and molding, , with or without bonding layers), as a hotmelt adhesive, for calendering and extrusion coating (to produce polymer / textile combinations, carpets, foils and other multilayer structures). Such grafted copolymers, especially with small amounts of copolymerized acid functionality, are useful if they are to be mixed to improve the printability of the polyolefins. Graft polymers can be used on their own as binding layers for otherwise incompatible polymers.

HU 211 069 Β

For extrusion, especially for LLDPE, the graft copolymer is useful as it reduces melt fracture without affecting the flow rate of the melt. Unlike 4,094,297. The additives used in the US patent do not disintegrate when the modified polyolefin is extruded for an extended period of time.

Modifying polypropylene with the graft copolymer of the present invention makes it useful for the manufacture of a number of useful articles, such as extruded or injection molding foodstuffs, aqueous solutions such as infusion liquids or hot-filled products such as sauces for bottles, for the manufacture of doors and windows and the like. Foamed articles can be used to replace wood, as packaging material, as insulating or sound absorbing materials, as food wrappers and other rigid articles. Foils can be used as a variety of protective and wrapping materials, such as food wrapping, blister wrapping, wrapping utility items, and the like.

The graft copolymers of the present invention are suitable for the production of polyolefin fibers, in particular for polypropylene fibers, especially when the graft copolymer is made from a polypropylene core polymer. Polypropylene is relatively easy to process into high-strength tough fibers.

Polypropylene fibers have certain disadvantages, which make them difficult to dye and have low long-term shape stability. However, germinated chains containing functional sites become paintable. These can be prepared by the process according to the invention by incorporating small amounts of colorant uptake monomers such as methacrylic acid. dimethylamino-ethyl methacrylate. N-vinylpyridine or the like is incorporated into the graft chain. The lower tendency of the graft polymer of the invention based on the polypropylene matrix necessarily improves the creep properties of the fiber.

Polypropylene filament formation can be accomplished by cutting extruded film into high denier coarse fibers; filament extruded filaments of controlled cross-section, also of high denier value; multiple fiber extrusion through a fiber extrusion head to fine fiber bundles. In each case, the texture of the fibers bears traces of pull. For example, low denier polypropylene fiber bundles can be extruded with a 25.4 mm, single screw extruder having a 24: 1 screw to length ratio, such as a Killion extruder from Cedar Grove (New Jersey) with a static mixer, metering pump and equipped with a threading head. Using such a machine, the extruded polypropylene first enters a cooling bath and then passes through a series of triangular metal cylinders which are heated and cooled. to create orientation in the polymer and freeze it.

Polypropylene fibers include, but are not limited to, knitting, netting (for example, fishing nets), slitting, rope, twine, sacks, carpeting.

used as loosened ribbons, upholstery, blankets, tarpaulins, swimming pool covers, sailcloths, garden furniture braids, screens, brushes, sewing threads, cigarette filters, beans, ruffles and drapes .

The graft copolymer of the present invention can also be used to improve the compatibility of polymers in mixtures where they would otherwise be incompatible. The grafted copolymer is preferably incorporated in such mixtures at a level of from 0.2 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 0.8 to 2.5% by weight, to achieve the desired improvement in compatibility. More graft copolymers may be used, but amounts above the indicated levels will only slightly improve Compatibility.

As mentioned above, compatibility is not easy to predict in advance. As a general rule, apolar polymers are poorly matched to more polar polymers, but there is also a poor compatibility between mixtures of experimentally polar and apolar polymers. Apolar polymers include polyolefins such as high and low density polyethylene, linear low density polyethylene, polypropylene including atactic polypropylene, polybutene-1, polyisobutylene, ethylene / propylene rubber, ethylene / acrylic acid copolymer, ethylene / propylene / diene terpolymer rubber, ethylene / vinyl acetate copolymer. ethylene / propylene copolymers, poly (methylpentene) and ionomers such as ethylene copolymer with a metal salt neutralized with acrylic acid.

More polar polymers, hereinafter referred to as polar polymers, are: acrylonitrile / butadiene / styrene polymer, acetal polymers, polyarylates, acrylate / styrene copolymers, acrylonitrile / styrene / acrylate polymers, ethylene / propylene modified copolymers, cellulose derivatives, polyester / polyether block copolymers, polyesters such as poly / butylene terephthalate), polyethylene terephthalate) and liquid crystal polyesters, polyether amides, polyether ether ketones, polyetherimides )-wedge. poly (ether sulphones), ethylene / vinyl alcohol copolymers, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride and fluoride, styrene polymers such as polystyrene, impact resistant polystyrene, copolymers of styrene / acrylonitrile, copolymers of styrene / butadiene, copolymers of styrene / maleic anhydride, copolymers of alkyl-substituted styrenes with either the styrene itself or other phenols listed as poly ( sulfide), polysulfone, polyurethane, polyamides, i.e. nylons such as nylon-6, nylon-6.6, nylon-6.9, nylon-6.10, nylon-6.12, nylon-11, nylon-12, amorphous nylons, poly (amide imide), poly (caprolactone), polyglutarimide, poly (methyl methacrylate) and other poly [(C 1 -C ₈ ) alkyl (meth) acrylates]. The acrylate polymers of particular interest referred to above, at least

Or more preferably acrylic acid and / or methacrylic acid (hereinafter collectively referred to as (meth) acrylic acid) or ester, preferably alkyl ester, more preferably 1-8 carbon atoms, most preferably 1-8 carbon atoms. They contain an ester monomer unit with an alkyl group containing 4 carbon atoms. The remainder consists of monomer (s) that can be copolymerized with (meth) acrylic acid or ester by free radical polymerization, preferably vinyl aromatic monomers, vinyl esters, vinyl nitriles, most preferably styrene or acrylonitrile.

Polar / apolar combinations that are particularly important for compatibility with the graft polymers of the invention include: (a) ethylene / vinyl acetate copolymer and polyvinyl chloride and / or acrylate polymer; (b) a mixture of ethylene / propylene / unconjugated diene terpolymer and acrylate polymer and / or polyester, in particular poly (ethylene terephthalate) and / or polyvinyl chloride and / or polycarbonate and / or polycarbonate / polyester; (c) high density polyethylene and ethylene / vinyl alcohol copolymer and / or polyester, in particular poly (ethylene terephthalate) and / or polyvinyl chloride and / or polyvinylidene chloride.

In the examples, the polymer concentrates and polymer blends were certified according to the following standard procedures.

The unreacted monomer in the reaction mixture was determined by gas chromatography before the solvent was removed or after extrusion evaporation.

The volatiles collected were analyzed by gas chromatography with a 25 m long wall wetted with CP wax 57 CB. bulk quartz capillary column at 40 ° C. By comparing the main solvent peak with the MMA peak, the amount of residual monomer in the reactor was determined and the conversion was measured directly. In order to measure the conversion more accurately, C, H, O analysis of the graft polymer was performed. The carbon content was used to calculate the EPDM or polypropylene content by interpolating between the carbon content of EPDM (85.49%) or polypropylene (85.87%) and the acrylate polymer (60.6%).

The grafted copolymers were analyzed by solvent extraction to remove the un grafted (meth) acrylate, the molecular weight of which was then determined by gel permeation chromatography. We did not have a process by which the graft copolymer could be separated from the un grafted polyolefin. For the concentrate, 0.8 to 1.3 g of polymer and 17 cm ^{3 of} xylene were weighed into a centrifuge tube, shaken overnight and placed in a 138 ° C oil bath, from which it was occasionally removed and shaken until the polymer dissolved. . Complete dissolution indicated that no crosslinking occurred. The tube was cooled. while the polypropylene-containing material precipitated. After centrifugation at 15,000 rpm for two hours, the xylene solution was carefully discarded without removing the float. The molecular weight of the xylene-extracted acrylate polymer was determined by gel permeation chromatography. The procedure was repeated with the solid residue. to extract the remaining (meth) acrylate. The composition of the solid residue was determined by determining the carbon content.

The polypropylene concentrate and the required additives were blended in a melted 7.6 x 17.8 cm electrically driven rolling mill with a minimum slit of 3.8 mm at 190 ° C. Rolling was continued for 3 minutes after melting. For materials with higher viscosity, higher temperatures were selected (e.g., 195 to 210 'C for MFRs of 0.5 to 2). The material was still hot or pressed or cut into small pieces (1-2 cm in each direction) for granulation (5 mm filter size). Interestingly, the additives according to the invention help to detach from the hot metal surface, including the balls of the Haake Rheocord ball mill.

Polyethylene was similarly rolled except that HDPE blends were rolled at 200 ° C and LLDPE blends rolled at 170 ° C.

A 2.5 cm Killion extruder was used for extrusion mixing. The two-speed auger was driven at 150 rpm. The temperature of each of the three zones was set at 190 ° C. The one-way tool was also controlled to the same temperature. The volatiles were removed in a vacuum outlet. The fiber was cooled with water and granulated. The extrusion yield was 4.5 kg / h.

The melt mixing was performed in a Haake Rheocord batch melt mixer on 50 g samples at 190 or 210 'C at 100 rpm in air. Stirring was stopped 3 minutes after reaching the maximum torque. The sample size was 50 g.

The polyolefin blends were extruded in an electrically heated 15 x 15 cm Carver press or a 30.5 x 30.5 cm Farrel press. The samples were extruded between aluminum sheets using a suitable filler to provide the desired thickness of 0.25 to 3.8 mm. One method was to transfer the hot melt directly from the ball mill between the two aluminum plates and place it in a 190 ° C press machine where it was extruded at high pressure (68-91 on a Farrel machine and 6820 kg on a Carver press) ). After three minutes, the mold was placed in an unheated press and high pressure applied for three minutes. Alternatively, the granulated or pasteurized material made by extrusion, Haake or milling was extruded after drying. The process was the same as melt extrusion, except that a five minute pre-heating was used, during which only a small amount of pressure was applied to the press. This was followed by high pressure pressing in the heated and cold presses. The hot press at 190 'C was generally suitable for polypropylenes with an MFR of 4, but higher viscosity polypropylenes split during the shrinkage test if their extrusion temperatures were not higher (195-210'C).

Polyethylene was pressed in the same way except that HDPE-1 was pressed at 170 'C, LLDPE was pressed at 150' Con.

Polypropylene was injection molded into a tool from the ASTM family using a Newbury injection molding machine. The up9

The workpiece was dried at 60 ° C for 16 hours. The first zone of the auger was set at 204 ° C, the other two zones and the nozzle were set at 218 ° C. The injection time was 3 seconds, the injection cycle was 15 seconds and the total cycle time was 45 seconds. The injection pressure was 2100 kPa and the tensile pressure was 690 kPa. The auger speed was 100 rpm. The temperature of both mold halves was set at 60 ° C.

The sagging test was performed on a 10x10x0.15 cm pressed plate. The plate was mounted on a 7.6 cm ² frame. There are metal rulers on the front and back of the frame to measure the deflection. The frame was placed with the plate in a heated air circulation thermostat (typically 190 ° C). The deflection of the center of the plate is recorded as a function of time. Typically, the deflection was first recorded when it reached

2.5 cm, but for slow-sagging materials it was already 16 mm. Data were measured up to 10.2 cm deflection and 30 minutes, if any, after that time.

"Directional tangent" is the slope of a line given by the natural logarithm of the deflection in cm. A large directional tangent indicates a rapid descent and a small directional tangent indicates a slow descent. The advantage of this comparison of directional tangents is that it eliminates the difference in cooling in the thermostat when the sample is introduced (due to the opening time of the thermostat, room temperature, or other differences).

Danube thermoforming was performed in the laboratory to illustrate the effect of melt strength. The polypropylene or modified polypropylene plate was heated in an air circulation thermostat to 190 ° C, then removed from the thermostat, stretched over a female mold, and vacuum-molded.

Capillary flow was measured with a Sieglaff McKelvey rheometer. The flow rate was determined at ten shear rates (1 to 100 reciprocal seconds) at each temperature. The results fit the power function, ie viscosity = k (temperature) ^x (shear rate) ^Y. Values for 1 and 1000 reciprocal seconds were calculated using the best fit equation. Viscosity between parallel plates was measured with a Rheometrics Dynamic Spectrometer at 5% elongation.

Scanning calorimetry (DSC) measurements of melting and nucleation were performed on a duPont instrument. The heat of crystallization was considered to be 59 cal / g and the percentage of crystallinity was corrected for the presence of a flow enhancer. The nucleation temperature was determined in an experiment in which polypropylene was thawed at 200 ° C for 2 minutes and then cooled at 10 ° C / min. The temperature at which the crystallization peak appeared was called the nucleation temperature. The isothermal crystallization time was measured by rapidly cooling the polypropylene melt to 127 ° C and exothermizing as a function of time.

The physical properties of the polypropylene homopolymer and the "medium impact" copolymer were determined on extruded and injection molded samples, although similar results were obtained for rolled and extruded samples. In some of the examples below, special apparatuses are provided for producing foamed sheets, rods or profiles, extruded rods or tubes, fibers, cast foils, unidirectional and bidirectional films and injection molding bottles or hollow packaging.

The examples illustrate the invention in more detail, but are not limiting. All percentages are by weight unless otherwise stated. All reagents are of good technical quality unless otherwise stated.

Example 1

This example illustrates the preparation of graft copolymer (GCP) of polypropylene (PP), methyl methacrylate (MMA) and ethyl acrylate (EA).

The grafted polypropylene / acrylate copolymer is prepared by polymerization of a mixture of 5% ethyl acrylate (EA) and 95% methyl methacrylate (MMA) monomer in the presence of 430,000 average molecular weight polypropylene (weight ratio of polypropylene / monomer 0.67: 1). The radicals are formed from di (tert-butyl peroxide) (DTBPO)

0.00010 mol / dm '/ min (radical flux). The monomer and initiator were added over 60 minutes. At the end of the reaction, 55% of the theoretical solids (corresponding to 100% conversion) was found.

Equipped with dual spiral mixer (115 rpm)

A 6.6 dm ³ reactor was charged with 1780 g of an inert hydrocarbon mixture of 6-12 carbon 2-methylalkanes and 880 g of polypropylene (MFR = 4) and heated to 175 ° C. After 2 hours, the temperature is lowered to 155 [deg.] C. and the charge is stirred for an additional hour. Two solutions are then administered within two minutes. The first, 1.04 g of di-tert-butyl peroxide in 21 g of hydrocarbon solvent, the second, a mixture of 0.06 g of di-tert-butyl peroxide, 2.1 g of ethyl acrylate and 42 g of methyl methacrylate. In the next 58 minutes, a mixture of 1.87 g of di-tert-butyl peroxide, 62 g of ethyl acrylate and 1215 g of methyl methacrylate was added at the same feed rate as the second addition. This injection program produces 0.00010 root fluxes over time. After the addition was complete, the reaction was heated at 155 ° C for an additional 15 minutes and then concentrated in a 30 mm extruder with vacuum degasser, Werner-Pfleiderer, at 200-250 ° C. The concentrated product (concentrate) is a mixture containing 56% (meth) acrylate by elemental analysis. The extraction results show a grafting of 15.9% of the polymerized (meth) acrylate monomer and the M _w of the (meth) acrylate polymer is 91,300. The concentrate can be mixed with other thermoplastic polymers such as polypropylene.

The following table shows the efficacy of the above concentrate when mixed in varying amounts with a polypropylene homopolymer having a melt flow number (MFR) of 4 if it reduces the tendency to sag.

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/. spreadsheet

The weight% of the concentrate in the mixture Migration Directional Agent (min ^-1 ) Mintavas- membership (Mm) Bending after 17 minutes (mm) 2.5 cm bending time (min) 0 0.18 1.75 > 10 8.0 1.5 0.12 1.45 6.16 9.3 2.5 0.12 1.70 4.6 9.8 3.3 0.06 1.78 3.0 14.9 5.0 0,045 1.73 1.3 19.2 7.5 0,030 1.75 1.0 > 33

2-51. examples

An acrylate-grafted polypropylene copolymer was prepared by polymerizing a mixture of 5% ethyl acrylate (EA) and 95% methyl methacrylate (MMA) in the presence of polypropylene (polypropylene / monomer weight ratio 0.67: 1). The radicals are supplied by di (tert-butyl) peroxide (DTBPO) at a rate of 0.00010 mol / dm ³ / min (radical flux). The monomer and initiator were added over 60 minutes and 52.5% of the theoretical (100% conversion) solid was formed at the end of the reaction.

1880 g of hydrocarbon solvent and 840 g of poly20 propylene were charged to a 6.6 dm ³ reactor equipped with a matching stirring turbine stirrer (375 rpm). The mixture, heated to 155 ° C, was stirred for 3 hours. Two solutions were added over two minutes. The first consisted of 1.06 g of di (tert-butyl) peroxide and 21 g of hydrocarbon solvent, as in Example 1. In the second, 0.06 g of di-tert-butyl peroxide is dissolved in a mixture of 2.1 g of ethyl acrylate and 40 g of methyl methacrylate. An additional mixture of di-tert-butyl peroxide (1.87 g), ethyl acrylate (61 g) and methyl methacrylate (1157 g) was added over the next 58 minutes at the same rate as the second solution. This addition program results in a root flux of 0.00010 mol / dm ³ / min over time. After complete addition, the reaction mixture was heated at 170 ° C for another 15 minutes and then passed through a 30 mm Wemer-Pfleiderer extruder at 200-250 ° C through a vacuum degassing opening in the extruder. 51% of the concentrate thus obtained is acrylate.

By the procedure of this Example, additional acrylate-grafted polypropylene copolymers (Examples 2-51) are prepared and evaluated for their melt consolidation action by 3.5% admixture with melt flow number 4 polypropylene. II. Table 1 shows the polymerization conditions of the concentrate and the percentage of acrylate polymer present in the concentrate, as well as the pile strength of its blend with polypropylene.

II. In Table I, DTBPO refers to di-tert-butyl peroxide, TBPB to t-butyl perbenzoate and DDBH to 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane.

II. spreadsheet

! Example Descent directional tangent (min ^-1 ) Acrylate in Concentrate (%) initiator Solid material (%) Polymerization temperature ('C) Intake) time (Min) Gyökfluxus EA-% MMA Ref. * 0.15-0.18 - - - - - - - 1 0.03-0,05 56 DTBP 55 155 60 0.00010 5 2 0.06 61 DTBP 52.5 155 60 0.00010 5 3 0.06 52 DTBP 55 155 60 0.00010 5 4 0045 55 DTBP 55 150 60 0.00010 5 5 0.08 57 DTBP 55 145 60 0.00010 5 6 0.05 57 DTBP 57 150 60 0.00010 5 7 0.10 49 DTBP 55 150 60 0.00007 5 8 0.06 53 DTBP 55 150 60 0.00015 5 9 0.06 55 DTBP 55 150 60 0.00010 10 10 0.11 53 DTBP 55 150 60 0.00010 0 11 0,056 48 DTBP 55 155 60 0.00010 10 12 0.07 51 DTBP 50 150 60 0.00010 5 13 0.11 58 DTBP 55 145 120 0.00007 5 14 0.10 57 TBPB 55 145 120 0.00007 5 15 0:09 56 TBPB 55 150 120 0.00010 5 0.12 54 TBPB 55 150 120 0.00007 5

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Example Descent directional tangent (min * ¹ ) Acrylate is concentrated. Tumba (%) initiator Solid material (%) Temperature of polymerization (° C) feed time (Min) Gyökfluxus EA-% MMA 17 0.13 55 TBPB 55 150 120 0.00015 5 18 0.06 55 DTBP 55 150 120 0.00007 5 19 0.06 49 TBPB 55 150 60 0.00010 5 20 0.10 51 TBPB 55 150 120 0.00010 5 21 0.14 57 TBPB 56 150 120 0.00010 5 22 0.13 51 TBPB 55 150 60 0.00010 5 23 0.15 55 TBPB 55 150 120 0.00010 0 24 0.15 56 DDBH 55 150 120 0.00010 5 25 0.14 57 TBPB 55 150 120 0.00015 5 26 0:09 51 TBPB 55 150 60 0.00010 5 27 0.15 54 DDBH 55 150 120 0.00010 0 28 0:11 51 DDBH 55 155 120 0.00010 5 29 0:10 53 DTBP 50 150 120 0.00007 5 30 0.10 54 DTBP 50 150 120 0.00005 5 31 0:15 53 DTBP 50 150 120 0.00005 5 32 0:10 51 DTBP 55 150 120 0.00007 5 33 0:12 55 TBPB 55 150 120 0.00007 5 34 0:18 55 DDBH 55 150 120 0.00007 5 35 0:07 53 DTBP 55 150 120 0.00005 5 36 0.09 51 DTBP 55 150 120 0.00010 5 37 0:14 51 TBPB 55 150 120 0.00005 5 38 0:10 37 DTBP 55 155 60 0.00010 5 39 0:11 43 DTBP 55 155 120 0.00007 5 40 0:08 48 DTBP 55 155 120 0.00005 5 41 0:10 47 DTBP 55 155 120 0.00007 5 42 0:07 48 DTBP 55 155 60 0.00010 5 43 0.10 43 DTBP 55 155 120 0.00005 5 44 0.10 50 DTBP 55 155 120 0.00007 5 45 0.10 54 DTBP 55 150 120 0.00010 5 46 0.10 54 DTBP 55 150 120 0.00007 5 47 0.07 54 DTBP 55 150 120 0.00005 5 48 0.08 56 DTBP 55 150 120 0.00007 5 49 0.08 55 DTBP 55 145 120 0.00007 5 50 0:09 56 DTBP 55 145 120 0.00005 5 51 0.08 55 DTBP 55 145 120 0.00010 5

“Control = without PP concentrate

The calculated percentage of grafted acrylic polymer and the weight average molecular weight ojtatlan acrylates _(Mw) are set in the table 111 together with certain selected samples from which ojtatlan acrylate polymer were recovered from the concentrate by extraction.

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III. spreadsheet

Example Graft% of acrylate polymer to PP M _w 2 12.3 107,000 10 10.6 119,000 11 29.8 71,800 45 14.8 43,000 46 10.7 62,600 47 21.7 87,300

Note: M _w = average molecular weight.

52-54. examples

This example demonstrates the larger scale production of an acrylate-grafted polypropylene copolymer by polymerization of a mixture of 5% ethyl acrylate (EA) and 95% methyl methacrylate (MMA) in the presence of polypropylene (polypropylene / monomer weight ratio 0.67: 1). The radicals are supplied by di (tert-butyl) peroxide (DTBPO) at a rate of 0.000065 mol / dm-1 / min (radical flux). The monomer and initiator are fed over 122 minutes and 47% of the theoretical (100% conversion) solid is formed at the end of the reaction.

Equipped with reciprocating blade turbine mixers,

102.3 kg of hydrocarbon solvent and 36.4 kg of polypropylene homopolymer 4 having a melt flow rate of 4 were charged to a 380dm ³ reactor and stirred at 150 ° C for 4 hours. Two solutions were added over 20 minutes. The first consists of 82 g of di (tert-butyl) peroxide and 828 g of hydrocarbon solvent. The second was 454 g EA and

Contains 8.6 kg of MMA. The addition of the first solution is continued, with additional 82 g of di-tert-butyl peroxide and 826 g of hydrocarbon solvent being added to the system over 90 minutes. Simultaneous addition of 2.3 kg EA and 47.5 kg MMA monomer was continued for 102 minutes (i.e., 12 minutes after completion of the initiator feed). After a further 15 minutes at 150 ° C, a further 23 kg of hydrocarbon solvent was pumped in over 30 minutes. The reaction mixture is then concentrated by passing through a 20 mm twin screw extruder made by Welding Engineers at 200-250 ° C at 200 rpm for 14 hours. The concentrate thus obtained is Example 52. Examples 53 and 54 carry out a similar synthesis except that the feed time and the root flux are as shown in Example IV. Table 1 is modified. The effect of each of the three concentrates (52, 53, and 54) on improving the sag strength was also shown in Table IV. Table 4, mixed with Melt Flow 4 polypropylene.

ARC. spreadsheet

Example Conc. in the mixture (%) Descent directional tangent (min ^-1 ) Mass fraction of acrylate in the concentrate initiator Solid material (%) Temperature of polymerization CC) feed time (Min) Gyökfluxus Ref. 0 0.19 - 52 2.5 0.11 0.6 DTBP 47 150 122 0.000065 3.5 0:10 53 3.5 0.11 0.6 DTBP 45 150 90 0.00007 5.0 0:10 54 3.5 0.15 0.6 DTBP 49 150 78 0.00008 5.0 0:09

Example 55

This example and Table V show the unexpected advantage of the concentrate of Example 4 in improving the tensile strength of both high density polyethylene (HDPE) and linear low density polyethylene (LLDPE). HDPE data for two different MFR values (4 and 8) refer to 150 ° C. LLDPE values are measured on a single polymer having a density of 0.917 g / cm ³ , but at two different temperatures. Also, the luminance of the exemplified extruded polyethylene samples is significantly increased compared to unmodified control samples.

Table V.

polyethylene Additive (crowd%) Temperature CC) Descent time (min) 508 mm 762 mm HDPE, MFR = 8 0 150 8.7 9.3 2 10.2 11.9 3.5 15.8 30.0 5 31.4 -

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polyethylene Additive (crowd%) Temperature (° C) Descent time (min) 508 mm 762 mm HDPE, MFR = 4 0 150 8.0 9.0 3.5 10.5 12.0 5 26.0 - LLDPE, MFR = 2 0 170 5.3 6.0 5 17.7 21.4 LLDPE, MFR = 2 0 180 4.6 5.2 5 8.5 10.0

Example 56

Methacrylate-grafted polyethylene copolymer concentrate is synthesized in a manner similar to that described above for acrylate-grafted polypropylene. The acrylate-grafted polyethylene concentrate is prepared by polymerizing 100% methyl methacrylate monomer in the presence of polyethylene (polyethylene / monomer weight ratio 0.5: 1). The radicals are supplied by di (tert-butyl) peroxide at a rate of 0.00010 mol / dnE / min (radical flux). The monomer and initiator are fed over 60 minutes and 55% of the theoretical (100% conversion) solid is formed at the end of the reaction.

Equipped with dual spiral mixer (115 rpm) 6.6dm ^? 1760 g of hydrocarbon solvent and 725 g of polyethylene (MFR = 4 density = 0.95) were charged. The mixture was stirred at 150 ° C for 3 hours. Two solutions are added in minutes. The first consists of 1.63 g of di-tert-butyl peroxide and 48 g of methyl methacrylate.

A mixture of 1.73 g of di (tert-butyl) peroxide and 1401 g of methyl methacrylate was added over the next 58 minutes at the same rate as the second solution. This feed program provides a root flux of 0.00010 mol / dm ³ / min throughout the duration. After complete addition, stir for a further 15 minutes at 150 ° C. The reaction mixture is then concentrated at 200-250 ° C in a 30mm Wemer-Pfleiderer extruder with a vacuum outlet. Elemental analysis showed that the concentrate contained 64% (meth) acrylate.

Example 57

This example demonstrates that both acrylate-grafted polyethylene and acrylate-grafted polypropylene copolymer concentrate effectively reduce the tendency of HDPE to sag. A mixture of concentrate and melt flow number 4 with a density of 0.95 of HDPE is prepared by rolling at 220 ° C, and the material discharged from the roll is pressed at 210 ° C. The sag is measured in the same way as for polypropylene sheets, except that the thermostat is set at 150 ° C.

VI. spreadsheet

Concentrate preparation example number Concentration mixing ratio (%) ' Descent directional tangent (min ^-1 ) Descent time (min) 25.4 mm 76.2 mm control 0 0.57 7.4 9.4 56 5 0:27 9.0 13.0 56 10 0.11 10.0 19.8 4 5 <0.015 15.0 30 minutes Up to 31.7 mm

Example 58

This example demonstrates that grafted polyethylene and polypropylene concentrates effectively improve the tendency of HDPE to sag, whereas unmatched acrylate polymer having a similar M _w value does not. Even 5% commercial poly (methyl methacrylate) press powder (labeled "A", M _w = 105,000) does not result in a decrease in sag rate, but the presence of 3% poly (methyl methacrylate) in the graft copolymer already greatly reduces the rate of sag. .

The specific concentrate in this example was synthesized as follows: To prepare an acrylate-grafted polypropylene copolymer, a mixture of 5% ethyl acrylate (EA) and 95% methyl methacrylate (MMA) was polymerized in the presence of 0.4 melting point polypropylene m / m 0.67: 1). The radicals are supplied by di (tert-butyl) peroxide (DTBPO) at a rate of 0.00007 mol / dm ³ / min (radical flux). The monomer and initiator were added over 120 minutes. and 55% of the theoretical (100% conversion) solid is formed at the end of the reaction.

Equipped with stepping agitator impeller turbine mixers (375 rpm). A 6.6 dm ³ reactor was charged with 1780 g of hydrocarbon solvent and 880 g of polypropylene (MFR = 0.4). The mixture was stirred at 160 ° C for 2 hours14

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Vili. The temperature was lowered to 150 ° C for one hour. Add two solutions over two minutes. The first consists of 1.22 g of di (tert-butyl) peroxide and 20 g of hydrocarbon solvent. The second contains 0.0002 mg of hydroquinone monomethyl ether (MEHQ) and 0.05 g of di (tert-butyl) peroxide in a mixture of 1.1 g of ethyl acrylate and 21 g of methyl methacrylate. A mixture of 13 mg of MEHQ, 2.70 g of di-tert-butyl peroxide, 66 g of ethyl acrylate and 1253 g of methyl methacrylate was added in the same 118 minutes as the second solution. This feed program provides a root flux of 0.00007 mol / dm ³ / min over the entire duration. After complete addition, the reaction mixture was kept at 150 ° C for another 15 minutes and then concentrated at 200-250 ° C through a 30 mm Werner-Pfleiderer extruder with two vacuum outlets. Elemental analysis indicates that the concentrate contains 53% (meth) acrylate.

The HDPE (MFR = 7, density = 0.95) and graft copolymer concentrate were mixed by rolling at 200 'C, and the spinning material leaving the roller was pressed into a plate at 170' C. The sag is measured in the same way as for the polypropylene plate except that the thermostat is set at 150 ° C.

VII. spreadsheet

1 1 Example Concentration mixing ratio (Wt%) Descent Direction Angens (min ^-1 ) Descent time (min) 25.4 mm 50.8 mm control 0 0.59 7.4 8.7 THE 3.0 0.58 7.1 8.3 THE 5.0 0.54 7.6 9.0 56 5.0 0.27 - 10.3 4 2.0 0:28 8.2 10.2 4 3.5 0,056 9.4 15.8 4 5.0 0,038 10.4 31.4 58 3.5 0.37 7.4 9.2 58 5.0 0.30 8.1 10.0

Example 59

The concentrate of Example 4 was mixed with LLDPE. The results of the improvement in sag strength are shown in Table VIII. Table. The mixture of modifier and LLDPE is rolled at 170 ° C and the hot material leaving the roller is further rolled at 150 ° C. The sag is measured in the same way as for the polypropylene sheets at the temperatures indicated in the table.

“LLDPE, MFR = 2.3, with a density of 0.92 is recommended for casting and extrusion.

LLDPE recommended for blow molding and extrusion "B", MFR = 1, density 0.92.

LLDPE con- centralization tum Temperature (° C) sag directional agent (min ^-1 ) time (25.4 mm (Min) time (101.6 mm) (Min) THE no 180 0.58 3.4 5.6 THE 5% Example 4 180 0.24 5.2 10.6 THE no 170 0.54 3.9 6.4 THE 5% Example 4 170 0,096 9.5 23.0 B no 150 - 7.8 15.6 B 5% Example 4 150 - 33.7 minute 19 mmig

Example 60

This example illustrates the increased sagging strength and higher nucleation temperature of polybutylene as a result of mixing the concentrate. Injection-grade polybutylene (MFR = 4) is rolled with 2.44% by weight of the concentrate of Example 20 at 190 ° C and then

Press into 1.7 mm sheets. We measure the time to various bends at 145 'C and record the DSC curves at 20' C heating and cooling rates. Higher crystallization temperatures are associated with higher nucleation rates and faster solidification of the heated polymer.

IX. spreadsheet

Weight of concentrate Descent time (min: s) DSC temperatures ('C) 25.4 mm 50.8 mm 101.6 mm thaw crystallisation, tályoso Das Control (O) 5:20 7:50 10:23 128 45 2.44 7:24 15:53 > 30 129 55

Example 61

This example describes the preparation of an acrylate-grafted polypropylene copolymer concentrate. A mixture of 5% ethyl acrylate (EA) and 95% methyl methacrylate (MMA) monomer is polymerized in the presence of an equal amount of polypropylene. The radicals are supplied by di (tert-butyl) peroxide (DTBPO) at a rate of 0.00017 mol / dm ³ / min (radical flux). The monomer and initiator were added over 30 minutes and 50% of the theoretical (100% conversion) solid was formed at the end of the reaction.

Into a 6.6dm ³ reactor equipped with a double helix stirrer (115 rpm), 1980 g of hydrocarbon solvent was introduced and heated to 170 ° C. 1000 g of polypropylene (MFR = 5) is added with a melt extruder set at 200 ° C at a rate of about 10 g / min. 45

After 21 minutes at 170 ° C, the monomer and initiator solutions are added. Two solutions were added over two minutes. The first consists of 0.44 g of di (tert-butyl) peroxide and 21 g of hydrocarbon solvent. A second mixture of 0.11 g of di-tert-butyl peroxide, 1.3 g of ethyl acrylate and 65 g of methyl methacrylate. A further mixture of 1.59 g of di-tert-butyl peroxide, 19 g of ethyl acrylate and 914 g of methyl methacrylate is added in the same manner as the second solution for a further 28 minutes. This feed program provides a root flux of 0.00017 mol / dm ³ / min over time. After complete addition, the reaction mixture was heated at 170 ° C for another 15 minutes and then concentrated by passing through a 30 mm Wemer-Pfleiderer extruder with vacuum outlets. According to elemental analysis (carbon content), the concentrate contains 35% (meth) acrylate.

The polypropylene plate (MFR = 4), with or without the concentrate of the example, is heated in an air thermostat to 190 ° C, then, immediately thereafter, strained over the female mold and vacuum-molded. To determine the thickness of the upper and lower corners, an average of 8 measurements was taken in mm on each of the four sides of the box. These measurements are summarized in Table X, which shows that there is less variation in wall thickness in the presence of the concentrate.

Table X.

Changes in wall thickness in vacuum-formed samples

polypropylene flax Wall thickness (mm) In the middle above Upstairs Down in the middle Down the corner Módosítat- lan 1.14 0.88 0.75 0,025 5% Example 61 0.97 0.97 0.35 0.21

Example 62

This example demonstrates a surprisingly high nucleation temperature and short crystallization time due to mixing the polymer concentrates of Examples 1 and 52 with melt flow rate 4 polypropylene. The nucleation temperature is measured at a cooling rate of 10 ° C / min, the melting temperature at a heating rate of 0 ° C / min, and the crystallization time is measured at 127 or 130 ° C under isothermal conditions. The degree of crystallinity is given for both the cooler and the heater. Comparison was performed with unmatched PMMA25 of similar M _w .

XI. spreadsheet

Crystallization temperature ('C) 127 127 130 130 130 130 130 Concentrate in mixture (%) 0 5 0 1.1 2.2 3.9 7.8 Example number of concentrate - 52 - 52 52 PMMA PMMA Crystallization time (min) 16.3 3.6 24.5 3.7 3.0 8.1 10.6 Nuclear temperature ('C) 105 112 107 118 118 112 110 Degree of crystallinity (%) 39 40 41 46 42 42 41 Melting temperature CC) 165 166 169 170 168 170 168 Degree of crystallinity l -. . 41 44 44 44 46 46 44

Example 63

This example demonstrates reduced equilibrium torque and improved flow time when the concentrate of Example 1 is mixed with melt flow rate 4 polypropylene. Measurements were made on a Haake Rheocord instrument under the test conditions described above. The maximum torque measured at the beginning of the flow is also reduced.

XII. spreadsheet

Weight of concentrate in polypropylene Time to Flow (s) Equilibrium torque (m g at 215 ° C) 0 109 695 3 50 690 5 50 670

Example 64

This example shows that the acrylate-grafted polypropylene copolymer concentrate is capable of improving the sagging strength of an acrylic sheet. Grafted polymer and 100 parts by weight of M _w value of 105,000 commercial acrylate core powder of 20 parts of Example 1 is rolled up, and then extruding. Tensile tests show that the concentrate plate can be heated to 5-10 ° C higher without flow than the unmodified plate.

65-66. examples

52-54. Prepared graft copolymer concentrates according to Examples XIII. under the conditions shown in Table.

HU 211 069 Β

XIII. spreadsheet

concentrate Acrylate% in concentrate initiator Solid material Monomer feed temperature (° C) time (Min) gyökfluxus THE 55 DTBP 50% 150 120 0.00010 B 55 DTBP 50% 150 120 0.00007

Concentrates A and B are mixed with polypropylene in a weight ratio of 2.8: 1 in 10 and mixed to form C concentrate. As with XTV. extruded with di (t-dodecyl) disulfide (DTDDS). As shown in this table, the descent data for 4% batches of concentrate C is shown in Table XIV. are shown in the table.

Table XIV

Example concentrate-% DTDDS% Descent directional tangent (min ^-1 ) 65 4 no 0.07 66 / a 4 0.03 0.05 66 / b 4 0.3 0.03

During processing, stabilization of the concentrate using DTDDS appears to further improve the melt strength.

Example 67

This example demonstrates that the graft copolymer has little effect on the high shear viscosity of the polypropylene but has a significant effect on the low shear viscosity.

The grafted copolymer of Example 1 was admixed in an amount of 5% by weight to a melt-flow-grade polypropylene homopolymer 25 as in Example 63. Capillary and disc viscometer measurements are made at various temperatures, both low and high shear, under the conditions described above. In the XV. The results shown in Table 1A show an increase in low shear viscosity, especially at temperatures below 210 ° C, while the high shear viscosity is practically unchanged.

Table XV

test Conditions:% Concentrate Temperature (° C) Little clipping High shear 0 5 0 5 Capillary Itch. ³ 180 94,000 133,000 1900 2000 Capillary Itch. ^the 190 80,000 110,000 1900 1600 Capillary Itch. ^the 210 57,000 75,000 1200 1100 Disc Viscosity ^b 190 63,000 99,000 2100 2100 Viscosity Disc ¹¹ 210 54,000 58,000 1800 1800 Viscosity Disc ¹¹ 230 37,000 39,000 1500 1400

Shear conditions:

a: low shear = 1.0 s ^-1 ; high shear = 1000 s ^-1 b: low shear = 0.1 s ^-1 ; high shear = 500 s ^-1

Example 68

This example demonstrates increased snow resistance, that is, reduced snow loss due to the use of disulfide or substituted triazine stabilizer. An acrylate-grafted polypropylene copolymer, similar to that of Example 4, is blended with roll stabilizers. 98 g of graft copolymer were melted on a rolling mill at 195 ° C, then 2 g of a stabilizer were added and rolled for another 2 minutes. The material is removed from the rolling mill, cut into pieces and granulated. One or more stabilizer concentrates thus prepared are mixed with a further grafted copolymer in a similar manner to obtain a grafted copolymer containing 100-5000 ppm of stabilizer. The results of stabilization by TGA measurements are shown in Table XVI. Table. The weight loss temperature is the temperature at which a given percentage weight loss occurs at a heating rate of 20 C / min under nitrogen as measured on a DuPont ThermoGravimetric Analy60. Although neither stabilizer is harmful

EN 211 069 Β for heat resistance, only items 2 and 7 in the list below show significant increases in stability.

The stabilizers tested are:

1. DLTDP (dilauryl thiodipropionate)

2. TNPP [tris (nonylphenyl) phosphite] 5

3. Irganox 1010 <tetrakis {methylene [3,5-di (tert-butyl) -4-hydroxyhydrocinnamate]} methane>

4. DTDDS [di (tert.-dodecyl) disulfide]

5. Irgafos 168 (tris [2,4-di (tert-butyl) phenyl] phosphite}

6. Weston 618 (distearyl pentaerythritol diphosphite)

7. Cyanox 1790 [tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione]

8. Irganox 1076 [octadecyl-3,5-di (tert-butyl) -4-hydroxyhydrocinnamate]

9. Topanol CA (3: 1 condensate of 3-methyl-6-tert-butylphenol and crotonaldehyde).

XVI. spreadsheet

Stabilizer (ppm) Temperature loss CC) 1 4+ 3 4 5 6 7 8 9 1% 10% 279 325 600 274 318 2000 281 328 600 280 327 2000 271 317 2000 275 320 300 286 345 1000 297 368 272 317 600 2000 279 323 2000 2000 278 322 600 2000 280 323 2000 2000 278 321 2000 300 291 358 600 2000 S600 280 324 273 319 600 273 318 2000 271 318 600 272 319 2000 272 319 600 2000 273 320 2000 2000 274 321 600 2000 285 328 2000 2000 279 322 600 2000 296 333 2000 2000 298 338 600 2000 286 328 2000 2000 285 325 2000 285 325 2000 600 278 321 2000 2000 277 321 2000 600 276 32! - 2000 2000 277 319 1000 280 319

HU 211 069 Β

Stabilizer (ppm) Loss of temperature ('C) 1 2 3 4 5 6 7 8 9 1% 10% 2000 285 323 4000 291 329 100 1000 285 329 300 1000 289 331 100 2000 289 327 300 2000 292 335 600 2000 282 325 1000 2000 288 325 1000 4000 291 331 2000 4000 291 331 2000 278 318 2000 278 322 1000 2000 277 316 300 2000 285 326 1000 2000 280 321 600 2000 286 327

Example 69

This example illustrates the preparation of larger amounts of graft copolymer. They are used for many of the tests below. The procedure and composition are the same as in Example 52, with some modifications. We combine several types of production. In all but one of the preparations, the radicals are formed at a rate of 0.000070 mol / dm ³ / min (root flux). The monomer and initiator are added over 120 minutes and 50% of the theoretical (100% conversion) solid is formed at the end of the reaction.

Equipped with intermittent turbine mixer blades. 86.4 kg of hydrocarbon solvent and 34.5 kg of polypropylene homopolymer (MFR = 4) were charged to a 380 dm ³ reactor. After degassing over three cycles (vacuum degassing and then filling with nitrogen to atmospheric pressure), the reactor was pressurized with nitrogen at 103 kPa and heated at 150 ° C for 2 hours. The pressure is then adjusted to 241 kPa and the reaction mixture is kept at 150 for a further 3 hours. Two solutions were added over 15 minutes. The first 59 g of DTBPO in 841 g of hydrocarbon solvent. A second mixture of 0.32 kg ethyl acrylate and 6.14 kg methyl methacrylate. The first solution was added at a lower rate, with an additional 103 g of DTBPO and 1479 g of hydrocarbon solvent being added over 105 minutes. Meanwhile, 2.26 kg of ethyl acrylate and 43.0 kg of methyl methacrylate monomer were also introduced over a period of 105 minutes. The exothermic reaction raises the temperature to about 160 ° C. After the addition was complete, 5 kg of hydrocarbon solvent was added to the reaction mixture.

The reaction mixture was left in the reactor for an additional 30 minutes and transferred to another vessel also under pressure at 150 ° C. During the transfer, 80 g of (di (tert.-dodecyl) disulphide dissolved in 320 g of hydrocarbon solvent) are introduced into the second vessel. es, a Welding Engineers twin screw extruder where it is evaporated.

During evaporation, the next batch can be prepared in the reaction vessel. Moreover, it can be transferred to the second vessel while the extrusion is in progress. In this way, multiple batches can be made in a "semi-batch" mode, i.e. batchwise in the reactor and continuously fed to the extruder.

For the final preparation of the mixture, the radical flux is 0.000050 (42 g of DTBPO and 858 g of hydrocarbon solvent at first addition, 73 g of DTBPO and 1502 g of hydrocarbon solvent at second).

The final mixture of Example 69 was prepared by mixing 13 portions of the above preparation and a portion of the final variant in pasteurized form. A sample of each portion, when mixed with polypropylene, exhibits acceptable sag strength.

Example 70

This example illustrates that the graft copolymers of the present invention result in increased stability when copolymerized with an alkylthioalkyl monomer, in particular ethylthioethyl methacrylate.

The stability of the graft copolymers of alternating monomer composition is evaluated. Each was prepared according to Example 4, only the monomer composition was changed and the product was swallowed by evaporation of the solvent rather than by extrusion. Monomer compositions and TGA results are reported in Section XVII. is summarized in Table. The rö19

The following reductions are: EA = ethyl acrylate, MMA = methyl methacrylate, ETEMA = ethyl thioethyl methacrylate, MA = methyl acrylate. The% weight loss temperature is the temperature at which that percentage weight loss is achieved at a heating rate of 20 ° C / min under nitrogen as measured on a DuPont ThermoGravimetrix Analyzer.

XVII. spreadsheet

Composition of graft acrylate polymer Weight Loss Temperature ('C) 1% 2% 5% 10% 95% MMA + 5% EA 221 274 307 333 95% MMA + 5% EA + 0.05% ETEMA 260 289 314 346 95% MMA + 5% EA + 0.25% ETEMA 281 305 335 360 95% MMA + 5% MA 254 290 317 325

Example 71

This example illustrates that another method for preparing methacrylate ester-grafted polyolefin copolymers does not provide a polymer that effectively improves the shrinkage property of polypropylene. No. 2,987,501. Following Example 2 of U.S. Patent No. 4, a linear low density polyethylene homopolymer (MFR = 2.3) was immersed in fuming nitric acid at 70 ° C for 30 minutes. After recovery, it is washed with water and dried. The polyethylene thus treated was refluxed over boiled methyl methacrylate for 4 hours. The un grafted poly (methyl methacrylate) is removed from the polymer by extraction with methyl ethyl ketone as described. Ojtatlan The polymer molecular weight determined by GPC: M _w = 430,000, M _n = 170 000 XVIII. The graft copolymer containing 43% by weight of PMMA and 57% by weight of PE is formed according to the data of Table II. Prior to extraction, the whole sample contained 67% PMMA and 33% PE, thus having a PMMA grafting efficiency of 63.1%.

XVIII. spreadsheet

Weight of polyethylene (g) Mass before reaction (after nitration) (g) Mass after reaction and extraction (g) Weight of polymer extracted (g) 3.397 3.48 5.964 4.40

The resulting grafted polymer from which the un grafted polymer is not removed is mixed with 4% by volume of melt flow polypropylene. The latter is used as a measurement standard for descent. The grafted copolymer of this example is poorly dispersed and conspicuous coarse non-dispersed fragments remain. The shrinkage value (0.31) is worse than that of the unmodified polymer (0.18) and the same amount of the modified graft copolymer of Example 69 (0.02).

The graft copolymer of the example is also rolled into linear low density polyethylene (MFR = 2.3) as described in Example 59. Again, a poor dispersion is obtained, with large, visible pieces of the undispersed modifier. The tensile strength is measured at 150 'Con as in Example 59. The directional tangent of the unmodified control was 0.39, and that of the exemplary grafted copolymer was 0.23. When compared to the grafted copolymer of Example 4, it is found to be much lower (0.10).

72-77. examples

These examples illustrate the preparation of a mixture of graft copolymer and polypropylene homopolymer in the form of granules, which can be further processed into extruded or extruded molds.

The grafted copolymer of Example 69 is not separated from the un grafted polypropylene and the acrylate polymer. It is thus used in the form of granules 3.2 mm long which are cut from an extruded cord.

The following polypropylenes were used: Aristech T1-4020F (Aristech Chemical Corporation, Pittsburgh, PA, USA), Himont 6523 (Himont Corporation, Wilmington, Delaware, USA) and Rexene 14S4A (Rexene Corporation, Dallas, Texas, USA). Their properties can be found in XIII. Table 1 shows; "Copolymer" in the table refers to a copolymer of ethylene.

The grafted copolymer is mixed with 5% polypropylene in a planetary mixer. The line is extruded using an Egan 60mm twin screw extruder having a length to diameter ratio of 32: 1. After cooling, the string is cut into granules. Various feed rates and worm speeds are used. The conditions for large scale sample production for unmodified and modified polymers are described in Table XX. is summarized in Table. The shrinkage tests of Example 1 were also performed on a number of other modified polymer samples after processing under other conditions. The results are comparable to those of the XIX. Table.

XIX. spreadsheet

Polypropylenes and their controls, mixed with a methyl methacrylate-grafted copolymer

Example Example 69 graft polymer phr * Polypropylene base polymer MEG ereszke- Dej name MFR composition of full 72 - Aristech TI 4020F 2 Copolymer mer 0.23 73 5 0.02 74 - Himont 6523 4 homo- polymer 0.36 75 5 m 0.11 ** 76 - Rexene 14S4A 4 Copolymer mer 0.35 77 5 0.14

* 100 parts by weight of base polymerTe relative to the ink ** The sample breaks during the test; sagging of mixtures processed under slightly different conditions 0.06-0.09.

HU 211 069 Β

XX. spreadsheet

XIX. Processing conditions for premixtures in Table

Example: 72 73 74 75 76 77 Amended: - 5% 5% - 5% Input set! speed (kg / h) 90.7 181.4 90.7 181.4 181.4 181.4 Actual feed! speed (kg / h) 90.2 185 89.8 181.4 178.7 182.3 snail Speed (Rev / m) 101 200 100 200 200 200 Propulsion 103 121 97 111 112 112 Auger power (mkg / s) 1258 3033 1184 2811 2811 2811 Head pressure (kPa) 2137 2758 1448 2068 2275 2206 Cylinder temperatures (”C) 1.zóna 163 163 163 163 163 163 2-8. zones 204 204 204 204 204 204 Temperature Tool CC) 204 204 204 204 204 204 Ömledékhőfok CC) 213 222 208 216 217 217

78-83. Examples 30

These examples illustrate the preparation of graft copolymer and other polypropylene blends on various mixing devices in the form of granules which can be further processed into a film or profile. Amoco 6214 is a film-grade polypropylene transparency additive. Eastman 4E11 is an impact-resistant, extrusion grade propylene / ethylene copolymer used for profile extrusion. In the present case, 1 and 5% by weight of the grafted copolymer of Example 69 are used in the blends.

The two polymers are worked up using planetary mixers and the mixture is processed in an 83 mm Werner-Pfleiderer interpenetrating twin-screw twin screw extruder using a 24/1 length / diameter screw. The granules are continuously fed into the extruder with an Acrison "weight loss meter" dispenser. The mass that flows and mixes in the extruder is extruded into cords with a 33-hole die, cooled in a water tray, dried, cut into granules and packaged. The machine setting conditions for each thread are shown in ΧΧΙ-ΧΧΠ. Table.

XXI. spreadsheet

Composition of mixtures and basic polymers

Example Modifier% basic Polymer 78 - Eastman 4E11 Copolymer 79 1

Example Modifier% basic Polymer 80 5 81 - Amoco 6214 homopolymer 82 1 83 5

XXII. spreadsheet

Preparation conditions for the various mixtures of Table XXL

Example Zone Temperature CC) set / actual Conditions 79 Z l 229/229 Z-2 235/216 RPM: 125 Z-3 249/227 torque: 73-75% Z-4 213/302 set power: 65 Z-5 235/221 vacuum: 380 tons Z-6 (tool) 227/227 ömledékhőfok (cord): 227 ° C Z-7 (tool) 238/241 yield: 150 kg / h 80 Z l 229/229 RPM: 125

HU 211 069 Β

Example Zone Temperature ('C) set / actual Conditions Z-2 235/216 of torque. · 73-75% Z-3 249/235 set power: 65 Z-4 213/302 vacuum: 47,250.5 kPa Z-5 235/232 melting point: 205207 'C Z-6 241/241 yield: 218 kg / h Z-7 238/238 82 Z l 288/288 RPM: 90 Z-2 296/304 torque: 50-53% Z-3 299/260 set power supply: 50 Z-4 252/316 vacuum: 40,443.8 kPa Z-5 293/293 melting point: 223 'C Z-6 266/232 yield: 116 kg / h Z-7 268/266 83 Z l 288/285 RPM: 90 Z-2 293/272 torque: 50-56% Z-3 299/254 set power supply: 50 Z-4 224/310 vacuum: 27,033.7 kPa Z-5 266/249 melting point: 226 'C 6 Z 266/229 yield: 122 kg / h Z-7 268/272

84-87. examples

These examples illustrate the use of the grafted copolymer of the invention in the manufacture of polypropylene bottles.

The grafted polymer of Example 69 is mixed in varying amounts, up to 5%, into one of two commercial blown polypropylene blown bottles. The base polymer of Example 84 is a statistical ethylene / propylene copolymer with a probability of 2-4% ethylene, Fina 7231 (MFR = 2) from Fina Oil and Chemical Co., Dallas, Texas. The base polymer of Example 86 is a propylene homopolymer (MFR = 2) from Quantum Chemical, USI Division (Rolling Meadows, Illinois, USA), under the tradename Norchem 7200GF. The mixtures are prepared with planetary mixers.

Injection molding of the samples was performed on a Jomar Model 40 (Jomar Corporation, Pleasentville, NJ). The polymer blend is injection-molded into a four-hole die (two cavities of which are sealed), centered on a mandrel with an air vent at the end. This provides an inflatable hose. The design of the heated tool is such that training is provided at the distal end to fasten the cap. The temperature of the tool is controlled at the neck, side wall and bottom of the bottle. From here, the hoses go to the second station, where they blow into a bottle shape, then cool down at the third station and get out of the machine. The thus prepared 103.5 cm ³ flask bottles were evaluated for surface luminosity, transparency, thickness uniformity, wall thickness and other properties as well as workability compared to unmodified controls.

Comparison of the bottle of Example 85 with the control of Example 84 shows a slight improvement in luminance, a significant increase in contact transparency, and a noticeable increase in stiffness. Similarly, Example 84 appolymer containing the 1% grafted polymer is also preferred to the control. The effect on transparency is not visible for the bottle of Example 87 compared to Example 86.

XXIII. spreadsheet

Processing conditions for the bottles

Example Basis- poly- mer - grafting Temperatures ('C) Example t% Ömle- DEK Bottom Wall Neck 84 84 - - 243 77.7 104 48.9 85 84 69 5 249 82.2 110 48.9 86 86 - - 243 77.7 104 48.9 87 86 69 5 249 82.2 110 48.9

For reasons not completely clarified, the same additive, at 5%, is detrimental to the formation of bottles made of homopolymers or copolymers with higher melt flow rates, even if the processing temperature is properly adjusted; most problems are related to poor distribution of the modifier. Such poor distribution is not obtained for other mixing, processing and testing operations. A slightly stiffer and improved gloss bottle can be inflatable by blending 0.5% by weight of graft polymer compared to the additive-free control.

From a premix containing t% of grafted copolymer and another impact resistant copolymer (MFR = 2) (Example 73), a bottle with severe material unevenness can be made. Dry blends (with the polymer of Example 72) containing 0.5% graft copolymer can be used to make bottles of improved luster and contact transparency.

88-94. examples

These examples illustrate the usefulness of the grafted polymer of the present invention in polypropylene foam and

EN 211 069 Β in the manufacture of expanded board. In the examples, the polypropylene homopolymer (MFR = 2) of Example 72, a premix of this polymer with a graft copolymer of methacrylate / polypropylene (Example 73) and a premix of Example 73 (Example 88) containing 1% talc are used. Each is granulated while blending with Ampacet 40104 blowing agent. Ampacet is a proprietary azodicarboxylic acid propellant, a proprietary chemical blowing agent with 10% dispersion in polyethylene. Manufactured by Ampacet Corporation, 250 South Terrace Avenue, Mt. Vernon, N. Y. 10550. Mixing 10 parts by weight of Ampacet means introducing 1 part by weight of proprietary propellant.

The polymer blend is processed with a 25.4mm single screw extruder manufactured by Killion Extruders Corporation, a 24: 1 length to diameter screw, a 4: 1 compression ratio, and a 1mm diameter die orifice. The extrusion conditions are described below. The tooling pressure of the unmodified polymer shows severe fluctuations (between 6900 and 12,400 kPa), while the mixture containing 5% by weight of graft copolymer can be extruded at constant die pressure. In both cases a good cell size distribution is observed. In the graft polymer modified mixture, larger, uniform cells are formed when the amount of active blowing agent is increased to 2%. The presence of 1% talc in the modified polyolefin results in the best cell structure and increased linear velocity.

The foam density of the rods was measured according to ALT method ASTM D-792. Although the unmodified base polymer provides the lowest density foam, the cellular structure of the modified polymer foams is generally regular.

The same three materials were processed with a similar technology using a 202 mm wide flat film tool. The foamed sheet is placed on a heated collection roll. There is no significant difference in processing properties between the three types of polymer blends. Preparation and results of each sample are shown in Table XXIV. are shown in the table.

XXIV. spreadsheet

Form: Wand Wand Wand Juice- honey Juice- honey Juice- honey Example: 89 90 91 92 93 94 Polymer Example: 72 73 88 21 73 73 Talc by weight 1 Propellant crowd% 1 1 1 1 1 1 extruder rev / min. 80 80 80 75 75 75 Ömledékhő- moderation (° C) 214 208 209 227 227 227 Hot melt pressure (kg / cm ² ) 127 127 140 56 42 42 Output (m / min) 13 15 23 Sample density (g / cm ³ ) 0.469 0.664 0.733

95-98. examples

These examples illustrate the use of methyl methacrylate grafted polypropylene copolymer in the production of blown polypropylene film. A blend of Example 74 control polypropylene homopolymer, 5 wt% graft copolymer of Example 69, and a dry blend of Example 74 polypropylene 1 g and 5% graft copolymer of Example 69 were blown.

The blown film is produced on a Killion (Killion Extruders Co., Cedar Grove, NJ) film blowing line operating a 25.4 mm single screw extruder at a melt temperature of about 216 ° C, with a 50 mm spiral mandrel blower, air blower and Killion Vertical Film Blowing Tower. Following the film blowing tower is a pair of clamping rollers for compressing the hose, and behind it is a pulling device which pulls the film across the pair of rollers. The speed of the tool and the puller are adjusted to produce a 5.6mm double film of either 108 or 165mm widths with blowing ratios of 2.125 and 3.25 respectively, while the maximum speed of the cylinder pair is 7.65 and 5, 94 m / min.

Table XXV

Example Material Thickness 95 Example 74 without additive 0.051 to 0.066 96 Example 75 with 5% by weight of additive .056 to .064 97 Example 74 5% by weight, dry blend 0.051 to 0.058 98 Example 74 1% by weight, dry blend 0.051 to 0.058

Himont polypropylene homopolymer 6523 (MFR = 4) is blown into a 0.025 mm film (single layer). This is Example 95 as a control. The hose has a slight inclination, so that the solidification line (onset of crystallization) is at an angle to the tool. The incline of the hose reduces the uniformity of film thickness.

When 5% by weight of the graft copolymer of Example 69 is present, as in Example 96, the hose is stabilized, extends at the level of the freezing line and gets closer to the tool. Both 108 mm and 165 mm expanded flat films are made. Although there is some fluctuation in tool pressure, the most stable hose is formed when the latter is formed.

An increase in hose stability was also observed in Examples 97 and 98 for dry blends containing 1 and 51% graft copolymer, respectively. There is no significant difference in the appearance of the film between the pre-mixed mass and the dry mix with 51% additive.

Modified film has a lower transparency transparency. Contact transparency is unchanged. The side view color of the modified and unmodified film rolls is also the same.

The "opening" of the control and modified films is also examined. Although this is a very qualitative test (we pinch the compressed foil hose and

EN 211 069 Β how easily it opens), we do not notice any difference between unmodified and modified polymers.

99-104. examples

These experiments demonstrate the use of the grafted polymer of the invention in the manufacture of cast polypropylene film. The single-screw extruder manufactured by Killion Co. is equipped with a 3.81 cm, 24: 1 length / diameter screw, 20.3 cm wide and 0.635 mm bobbin tool, cooling roller and torque-operated film winder. The melt temperature in the extruder is 226 ° C. The peeling speed of the die extruded film leaving the cooling roller is adjusted to produce different film thicknesses. The film thickness is measured by taking into account an undesirable width shrinkage called "necking". The stiffness of the film and the color of the side view of the film roll are qualitatively determined. The film thickness is adjusted by increasing the peripheral speed of the torque-driven winder and decreasing the extruder yield by reducing the screw speed.

XXVI. spreadsheet

Example film Starting material Form 99 Example 74 unmodified 100 Example 75 Premixture, 5% GCP 101 Examples 74 and 69 Dry mix, 5% gcp 102 Example 81 unmodified 103 Example 82 Premixture, 1% GCP 104 Example 83 Premix, 5% gcp

GCP = graft copolymer of Example 69.

The film of the composition of Example 99 had a uniform and reproducible thickness over 0.25 mm and below 2.5 mm. Example 100 affords an acceptable film with improved side-view color and less "fading". Example 101 also produces a smaller yellowing, but the side view color does not improve. Both modified products are stiffer than the control film for a given thickness, making it easier to roll. The addition of the grafted polymer increases the opacity of the film.

A 102-104. In Examples 1 to 4, no difference in grafting was observed by the addition of the grafted copolymer. The film containing both 1% and 5% graft polymer was stiffer than the unmodified control (Examples 103 and 104 compared to Example 102).

Example 105

This example illustrates that a bi-directional stretch film can be made from 5% polypropylene / methyl methacrylate grafted copolymer polypropylene. Under the limited conditions tested, which are optimal for the unmodified polymer, there is no particular benefit of the additive. Under the same extrusion and longitudinal stretching (MDO) conditions, the modified polymer does not achieve and maintain the peeling rate that is possible with the unmodified material during transverse stretching (TDO).

The control polymer is the high melt transparency commercial homopolymer of melting point 2.2 of Example 81 which is suitable for film production. The premixed compositions contain 1 and 5% of the grafted copolymer according to Examples 82 and 83 respectively, prepared according to Example 69 (under the respective extrusion conditions, 5% by weight of the grafted copolymer of Example 69 in the base polymer of Example 81). gives a very poor dispersion, many gels are formed in the foil and tears are frequent). The blends are processed with a 50.8 mm Davis-Standard single-screw extruder through a 0.48 m wide die and a 1.02 m stretch cylinder to form the extruded hose after cutting with compressed air. . The roller rotates in a water bath so the film cools completely. The longitudinal stretching of the film is performed using a apparatus supplied by Marshall and Williams Co. (Providence, RI, USA) consisting of a heated roll. Their speed is set to provide one-way stretching.

Following MDO, the film is cut into strips of appropriate width and rolled. From these rollers, the foil is fed to the TDO, which consists of three heating zone furnaces, film transfer rollers and clamping clamps for lateral stretching.

The film of Example 81 (unmodified polymer) was stretched in MDO 4.75: 1 to 5.0: 1 and TDO in 9: 1. The unmodified polymer at a ratio of 4.75: 1 can maintain a transfer rate of 8.69 m / min to TDO, and the unmodified polymer film with a 5.0: 1 MDO ratio has a speed of 6.85 m / min.

The film of Example 82 (containing 1% grafted polymer) may have a MDO ratio of 4.75: 1 and a TDO ratio of 9: 1, thus maintaining a feed rate of 6.85 m / min. Frequent foil rupture occurs when the MDO ratio and transmission speed are higher. This bi-directional stretch film appears to be slightly more covered than the bi-directional stretch film of Example 80. There is no difference between the rolls of Examples 81 and 82 in the side view color detected when rolled up.

The films of Example 83 have an MDO ratio of 4.75: 1 or 5.0: 1 or 5.25: 1, and a TDO ratio of 9: 1. The best film is obtained at a peel speed of 6.85 m / min and the lowest MDO ratio; under more stress conditions, a rupture may occur. The films of Example 83 are noticeably more covered and have a freezing line closer to the tool than the control film of Example 81.

Example 106

This example demonstrates a profile extrusion experiment using graft copolymer modified polypropylene according to the invention. Single-screw extruder with suitable tool, cooler, puller and sizing device24

EN 211 069 and extrude a longitudinally ribbed, solid rod-shaped profile. The rod has a diameter of 4.83 cm with ribs of 2.67 cm (which extend beyond the rod). The ribs are 1.52 cm wide. With the unmodified polymer (Tenite 4E11 copolymer from Eastman Chemical, see Example 78), it was difficult to maintain symmetry of the profile due to sag and distortion. If the mixture of Examples 79 or 80 (containing 1% or 5% of the grafted copolymer) is used, the shape stability is improved.

Example 107

This example illustrates the use of the grafted copolymer mixture of the invention to modify polypropylene for the production of better quality plastic tubes. For this purpose, the unmodified polymer of Example 69 and a premixed mixture of 5% graft copolymer were used. as described in Examples.

A 25.4mm single screw Killion extruder (Killion Extruders Co., Cedar Grove, N.J.) with a 24: 1 length to diameter screw, 11.4mm outer diameter and variable inside diameter pipe tool, 0.25m long cooling water tray. equipped with air blower, scraper and cutting equipment. Processing conditions and observations are set out in Section XXVII. are shown in the table. Oval is the ratio of the smallest to the largest outer diameter, as measured by a caliper; when set to 1, the tube is perfectly circular.

XXVll. spreadsheet

Tubes made of polypropylene and modified polypropylene

Polymer Ömledék- temperature (° C) Melt pressure (kPa) (a) Adjusted inside diameter (mm) ovality Example 72 217 8270 8.1 0.75 Example 73 214 6890 8.1 0.88 (b) Example 74 185 9650 8.1 0.97 Example 75 197 6890 8.1 (c) 0.77 Example 76 184 6890 8.1 (d) 0.92 Example 77 180 8270 8.1 (d) 0.90 (b, e)

(a) The extrusion rate is equivalent for unmodified and modified polymers.

(b) The tube extruded from the modified material is more rigid.

(c) Higher melt temperatures are required to avoid the formation of a "shark boron" surface on the tube.

(d) For this polymer with a larger MFR core, lower melt temperature and higher peel speed result in a tube with a smaller outer diameter.

(e) The tube of modified material is more covered

When the unmodified polymer is made into a tube of favorable ovality, the main effect of the additive is to improve the stiffness of the tube. In the case of the polymer of Example 72, the ovality is difficult to control at an acceptable yield rate, but the modified polymer (Example 73) also has better oval and stiffness.

108th-109th examples

These examples illustrate the preparation of talc-containing premixes. The particle size of the white, soft-flaked talc used is 40 μιη-ηέΐ; Known as Cantal MM-45-90 (Canada Talc Industries Limited, Madoc, Ontario). The amount of admixture is 20%. Polypropylene is a homopolymer of Himont 6523 (MFR = 4). The grafted copolymer in 5% by weight is the product of Example 69. The samples were mixed and prepared in a 30 mm twin-screw twin screw extruder made by Wemer-Pfleiderer. The polymer blends are prepared in a planetary mixer prior to extrusion.

The conditions for the preparation of mixtures are described in the XXIX. Table. The extruder has a screw speed of 200 rpm, without application of vacuum, with a yield of 4.54.6 kg / h and torques of 85-86%.

XXV1I1. spreadsheet

Mix % talc Amended basic Polymer Example 108 (control) 20 Cantal - 801% Himont 6523 Example 109 20 Cantal Example 69 5t% 75t% Himont 6523

XXIX. spreadsheet

Zone Extruder Zone Temperatures ('C) Example 108 set / fact. Example 109 set / fact, Z l 125/148 125/151 Z-2 220/218 220/219 Z-3 230/228 230/229 7-4 230/242 230/241 Z-5 240/239 240/239 6 Z 240/239 240/239 Z-7 240/242 240/239 Z-8 (tool) 225/239 225/239 melt 239 243

110-112. examples

These examples show injection molding of polypropylenes of different compositions and melt flow rates containing the graft copolymer of the present invention. In two examples, 20% of the talc is also present in the polymer.

Polypropylene can be molded into useful molds by means of swivel injection molding machines, such as the Model 221-51-250 from Arburg Maschinen Fabrik (Lossburg, Germany). An extruder equipped with an ASTM tool for the preparation of various specimens is used to prepare the test samples. The processing conditions chosen are not changed for the various modified and unmodified polymers. There were no difficulties in processing. XXX. Table II shows injection molded mixtures; XXXI. table the processing conditions; XXXII. table the module values; XXXIII. Table of Dynatup

EN 211 069 Β impact work; XXXIV. Table 5 shows the heat storage temperatures for modified polymers and controls.

In each of these lists of injection-molded polymers and mixtures, each sample contains 1 or 5% by weight of the grafted copolymer of Example 69. The basic polypropylene polymers are the same as in the previous examples; HP means homopolymer, CP copolymer, numbers represent MFR values. Mixtures containing talc a

They correspond to Examples 108 and 109. All materials are in bulk pre-blends except dry blends which are directly injected from the powder. (C) indicates unmodified control, (CT) talc-filled but no graft copolymer.

Each test method is an ASTM standard procedure: bending modulus and strength are measured in accordance with ASTM D-790, thermal stability temperature is measured in ASTM D-648, and Dynatup impact work is measured in accordance with ASTM D-3763.

XXX. Table 2 shows the melt flow rate (MFR) of unmodified and premixed materials. In most cases, the melt flow rate remains unchanged or only slightly decreased due to the presence of the grafted copolymer, so that the melt viscosity does not increase too much under these medium shear conditions. No. ASTM D-1238. the melt flow rate measured according to the standard method under "L" conditions (230 ° C, 298.2 kPa) is expressed in g / 10 min.

XXX. spreadsheet

Example Alappo- copolymer graft (%) talc (%) Dry- mix? MFR 74 (0 HP.4 - - 4.40; 4.06 75 HP.4 5 - - 6.07 UO HP.4 5 - Yes 108 (CT) HP, 4 - 20 - 109 HP.4 5 20 - 76 (C) CP.4 - - - 4.47 77 CP 4 5 - - 3.75 111 CP 4 5 - Yes 72 (C) CP 2 - - - 2.37 73 CP 2 5 - - 2.02 112 CP 2 5 - Yes 78 (C) CP - - - 2.92 79 CP 1 - - 2.04 80 CP 5 - - 2.12 81 (C) CP - - - 2.33 82 CP 1 - - 3.81 83 CP 5 - - 2.16

XXXI. spreadsheet

Conditions for injection molding of polypropylene

Cylinder temperatures ('C) Set / measured Etetózóna 216/216 Compression zone 216/216 feeder Zone 216/216 nozzle 216/216 Fixed half-tool 49/49 Moving half-tool 49/49 Cycle times (s): Injection molding 14 consolidation 14 Closing tool 1.2 Opening tool 0.5 Full cycle 0.5 Machine operating parameters: Screw speed (rpm) 400 Tensile Pressure (kPa) 172 Initial Injection Pressure (kPa) 861

XXXII. spreadsheet

Example Bending modulus (MPa) Maximum bending stress (MPa) 74 (C) 1470.6 43.8 75 1744.4 47.5 110 1783.1 46.9 108 (CT) 2768.0 52.0 109 2867.0 54.5

XXXII. The values of the bending modulus in Table 3 show the stiffening effect of the graft copolymer.

XXXIII. Table 1 gives the Dynatup impact work in joules at different temperatures for the mixtures and controls tested. The doses generally indicate a slight improvement in the premixed materials, but the impact strength is impaired when the dry mixture of graft copolymer and base polymer is injected; however, it is improved if the talc-filled mixture also contains a grafted copolymer.

XXXIII. Table Dynatup Impact Work (joule)

- Example Temperature 23 'C 15 'C +5 'C -5 'C 74 (C) 4.9 ± 2.7 4.4 + 1.5 3.8 ± 0.3 2.6 ± 0.41 75 5.7 ± 3.4 4.6 ± 0.8 2.7 + 1.5 3.4 + 1.09 110 3.4 + 1.1 2.0 ± 0.5 1.9 ± 1.0 l, 5 ± 0.41 108 (CT) 3.0 ± 0.5 3.4 + 0.8 4.2 ± 1.6 5 ± 2.5 O 109 1.9 + 0.5 4.1 ± 2.3 4.8 ± 1.8 5 ± 2.5 O 76 (0 40.0 ± 0.5 77 43.9 ± 0.4

HU 211 069 Β

Example Temperature 23 'C 15'C +5 'C -5 'C 111 14.0 ± 6.4 72 (C) 37.9 ± 1.8 73 43, l ± l0,3 112 32.4 ± 9.5 78 (C) 36.7 ± 0.4 79 36.3 ± 1.1 80 37.1 ± 0.7 81 * (C) 13.3 ± 10.7 - O 3.3 ± 8 2.7 ± 0.2 82 4.9 ± 0.7 - 3.0 ± l, 4 3.0 ± 0.8 83 7.6 ± 3.7 - O 3.3 ± 8 3.5 ± 1.1

* The high standard deviation given at room temperature raises doubts.

XXXIV. Table 1 is a series of snow holding temperatures and hardness! values. The modified polymer appears to have slightly higher snow holding temperatures and higher hardness, although these results are not completely consistent. Rockwell hardnesses are determined separately for each of the two samples in each example.

XXXIV. spreadsheet

Example Bending temperature ('C) 2 'C / min with heating Rockwell hardness "C" SPECTRUM 411 kPa 1645 kPa 74 (C) 110.9 61.0 58.4 56.5 75 113.8 63.3 60.7 59.3 110 117.3 68.7 57.9 46.9 108 (CT) 128.2 76.8 57.3 64.7 109 124.7 81.9 65.4 63.7

Example 113

This example illustrates the effect of the molecular weight of the polypropylene as the stock polymer of the graft copolymer to alter the tendency of the polypropylene to vary in melting. The grafted polymer is made from polypropylenes of various melt flow rates. Each modifier was prepared as in Example 58. Himont PD-701 polypropylene with MFR 35 has 65% solids yield, Himont Pro-fax 6323 polypropylene (MFR = 12) 60%, Himont Pro-fax 6523 (MFR = 4) and Himont Profax Of 6723 (MFR = 0.8), 55%. Molecular weights of the base polypropylene polymers, if known, are disclosed in XXXV. are shown in the table.

It is estimated that some of these polypropylene have a melt strength of 4% by weight. Each blend is made using standard rolling and pressing conditions, except for blends of polypropylene with a melt flow rate of 0.8 and the same modifier, which are rolled at 215 ° C and pressed at 215 ° C. The rate of descent is measured by a standard procedure. The descent directional tangents at 190 'C are shown in FIG. Table.

XXXV. spreadsheet

Molecular weight and mfr data for polypropylene based blends

Móltömeg- source Average molecular weight (10 ⁵ molar) MFR = 12 MFR = 4 MFR = 0.8 (the) 3 4.3 7.1 (B) 2.45 3.05 2.5; 4.7 (0 0.27 * 0.45 * -

Sources of Molecular Weight Values: (a) Details of the shipping company. (b) Sheehan et al., J. Appl., Polym. Sci., 8, 2359 (1964). (c) Mays et al., J. Appl. Polym. Sci., 34, 2619 (1987).

* These values are numerical molar masses.

XXXVI. spreadsheet

Directional tangent of polypropylene-based polyolefin blends (min ~ ^} ) at 190 'C

Amended (4%) Polypropylene (96%) MFR = 35 MFR = 12 MFR = 4 MFR = 0.8 - 1.6 0.52 0.25 0.099 MFR = 35 based on PP 1.8 0.52 0.23 0.074 MFR = 12 based on PP 1.2 0.41 0,034 <0.02 MFR = 4 based on PP 1.0 0.16 0,022 <0.02 MFR = 0.8 based on PP 0.64 0.16 0.031 <0.02

In each case, a decrease in the rate of sag is observed, except in the case of a high melt flow base polymer modified with a high melt flow (low molecular weight) polypropylene graft. The molecular weight of melt flow polymer 35 is not known precisely; is believed to be made from a polymer of higher molecular weight by thermal / oxidation processing. Such a process not only reduces the molecular weight but also narrows the initially wide molecular weight distribution.

Example 114

This example illustrates the efficacy of the grafted copolymers of the present invention in making polymers that are otherwise poorly compatible. In this example, the graft copolymer of the present invention is mixed with a polyolefin and a polar polymer in a twisting twin screw extruder (Baker-Perkins MPC / V 30) with a 10: 1 length / diameter screw. The extruder is operated at 200 rpm and the temperatures are adjusted to facilitate mixing of the polymers and to obtain a good melt. The light27

EN 211,069 Β The melt temperatures measured in the Zone XXXVIII. are shown in the second column. The melt was added directly to a 38mm single screw, 8: 1 length to diameter granulation extruder. The melt temperatures in the zone between the mixer and the granulating extruder are set forth in Table XXXVIII. Table 3 shows column 3. The melt is extruded onto a string, cooled in a water bath and crushed into granules.

The polymers used in the mixtures of the present example are described in XXXVII. is summarized in Table. XXXIX. Table 6 shows that the graft copolymer has little effect on the tensile strength of the unmixed polymer, ie it does not significantly affect the toughness of the additive. The XL. and XLI. As shown in Table II, the improved tensile strength of the polymer blends indicates an improvement in the compatibility of the blend components with the graft copolymers of the present invention.

Under suitable mixing conditions, an improvement in compatibility may also result in a reduction in the size of the polymer domains present in the mixture. Scanning electron microscopy also confirms that in some sample dots the size of the domains is significantly reduced when graft copolymer is mixed. For example, the average size of the polypropylene domains is 2 micrometers in the PMMA / PP mixture 70:30 in Example 114. Add 5 t% compatibility enhancement to the domain size

0.43 gm. Although not all major males are reduced in size, a 5% additive often results in a 10-30% reduction. This also suggests that the compatibility enhancer acts at the interfaces of the polymer domains rather than the individual polymers themselves.

XLI. Table 4 summarizes the compatibility enhancement effect of graft copolymers on different polymer blends.

XXXVII. spreadsheet

The polymers used in the mixing examples

polymer Notation in the tables Name Manufacturer brand Name Density Other features SAN Styrene / acrylonitrile polymer Monsanto Lustro SAN 33 1.07 MFR = 14 ASTM D-1 238 (I). PA66 Nylon 6.6 DuPont Zytel 101 1.14 op. = 255 'C ASTMD-2117 Pet Polyethylene terephthalate) Eastman Kodak Kodapak PET7352 1.4 44 mol% E Mp = 164 'F MFR = 5.5 190'Con 2160 g ter. EVOH Ethylene / vinyl alcohol copolymer Eval Co. America Eval EP-E105 1.14 44 mol% E op. = 164 'C MFR = 5.5 190'Con 2160 g ter. PC Poly carbonate General Electric Plastics Lexan 121 1.20 MFR = 16.5 for ASTM D 1238 (O). PVC Poly vinyl chloride) Georgia Gulf Co. SP-7107 1.35 PMMA Poly (methyl methacrylate) Rohm and Haas Co. Pexiglas VM 1.18 MFR = 15 INTACT Ethylene / propylene copolymer Exxon Vistalon 719 0.89 54 Mooney ASTM D-l 646 HDPE High density polyethylene Phillips 66 Co. Marlex HMN 5060 0,950 MFR = 4 PP polypropylene Himont Pro-Fax 6523 0.903 MFR = 4 EVE Ethylene / vinyl acetate copolymer DuPont Elvas 650 0.933 12% VA MFR = 8 LLDPE Linear low density polyethylene Exxon Escorene LL-6202 0.926 MFR = 12 PS Polystyrene Huntsman Chemical PS-203 (Crystal) 1.06 MFR = 8 PBT Poly (butylene terephthalate) General Electric Valox 6120 PA 6 Nylon 6 Allied Signal Capron 8253 1.09 op. = 21 'C ABS Acrylonitrile / Butadiene / Styrene polymer Dow Chemical Magnum 341 1.05 MFR = 5 PC / PBT PC / PBT alloy General Electric Xenoy HOL 1.21

HU 211 069 B

XXXVIII. spreadsheet

Polymer Melt temperatures (° C) mixer When transferring PMMA 225-235 210-220 SAN 220-230 210-220 EVOH 205-225 200-215 PA66 260-275 255-270 Pet 245-275 245-255 PVC 205-230 190-215 PC 250-290 240-270

The granulate is dried and then injected on a rotary molding machine (New Britain Model 75).

XXXIX. spreadsheet

Compatibility enhancing effect on the tensile strength of the polymer

Polymer Tensile strength (MPa) Concentration of additive 0t% 5% 15% PMMA 65.44 64.79 61.27 SAN 71.91 62.74 55.89 EVOH 68.78 66.21 63.78 PA66 64.82 64.68 66.60 Pet 58.26 59.33 59.72 PVC 45.25 44.97 45.22 PC 62.63 63.05 63.70 HDPE 22.59 22.66 24.14 PP 33.02 34.03 33.95 INTACT 4.79 5.50 5.84 LLDPE 10.91 11.80 12.99 EVE 8.64 8.67 8.17

XL. spreadsheet

Tensile strength (MPa) of mixtures of polyolefins and polar polymers

Polar polymer 30% polar polymer 55% polar polymer 80% by weight polar polymer 0t% 5t% 15% 0t% 5% 15% 0t% 5% 15% HDPE ♦ PMMA 25.26 27.00 30,26 31,42 38.30 39.54 50.78 53.77 55.55 * SAN 25.77 28.09 30.57 34.71 41.51 38.33 51.88 55.08 51.23 * EVOH 26.57 26.80 27.74 33.18 38.00 39.58 49.24 51.32 50.79 PA66 26.94 28.85 29.72 38.34 38.11 38.33 61.22 65.62 69.23 Pet 25.97 28.61 30,98 37.70 37.93 40.09 50.23 51.72 50.91 PVC 20.89 22.92 24.86 19.91 23.67 27.34 26,18 30.72 34.87 PC 25.66 28.80 30.93 31.11 35.20 38.53 55.61 50.41 51.92 PP * PMMA 34.02 35,37 37.81 40.23 43.45 45.84 46.40 53.70 56.6 * SAN 33.67 38.76 41.05 37.67 47.65 46.08 41.11 54.12 51.81 * EVOH 32.85 37.40 38.56 35.01 44,65 45,60 42.73 53.38 52.57 PA66 32.06 40.29 40.38 42.72 52.17 51.10 64.71 67.84 66.15

HU 211 069 Β

Polar polymer 30% polar polymer 55% polar polymer 80% polar polymer 0% 5t% 15% 0t% 5% 15% 0t% 5% 15% Pet 32.93 33.80 35.15 39.47 43.87 43.64 37.67 53.12 54.04 PVC 36.32 37.68 39.35 35.28 37.87 40.79 30.88 40.00 42.56 PC 33.82 36.68 39.09 36.69 40.13 44.64 42.38 46.24 51.64 INTACT PMMA 8.20 10.87 12.51 19.99 24.17 27.81 42.47 44.59 46.93 AAN 8.10 12.53 14.11 22.14 28.82 28.15 45.92 50.68 44.58 EVOH 12.19 12.04 11.69 24.92 24,66 23,17 41.29 42.39 42,70 PA66 13.04 13.04 12.36 27.62 27.98 26.33 40.87 48.77 43.48 Pet 7.94 8.40 11.13 20,22 20.43 22,27 33.72 37.00 38.87 PVC 6.17 9.05 12.88 12.93 18.28 19.22 25.50 28.41 30.60 PC 10,31 12.05 13.66 23,10 24.34 25.60 40.18 41.79 42.76 LLDPE PMMA 15.23 18.63 20.90 24.88 30.68 32.84 48.95 55.36 54.14 SAN 15.78 21:08 22.57 26,50 35.76 36.71 47,52 56.92 48.84 EVOH 16.83 17:26 18.26 30.02 31.74 31.87 51.83 50.71 52.29 PA66 17.93 17.99 19.98 29.67 28.49 25.23 64.65 67.55 67.26 Pet 15.33 18.09 20.35 25.53 28.23 30.78 45.02 46.16 42.87 PVC 14.72 14.12 15.73 12.45 18.09 20.50 25.99 30.54 33.69 PC 13.64 19:20 18.48 19.22 27.83 30.46 38.45 40.59 38.86

EVE

PMMA 10.57 11.28 14.38 23.06 21,10 28.31 45.99 47.02 50.87 SAN 12.40 13.62 15.22 27.97 27.29 29.35 48.94 52.01 46.14 EVOH 13.13 13.97 16.59 32.41 28.65 35.43 50.97 50.28 48.81 PA66 14.15 13:54 14.42 27.36 24.59 26.92 40.75 38.35 31.60 ! Pet 14.55 14.35 12.31 21.22 23.90 26.45 43.20 43.91 48.44 PVC 7.69 8.28 10.25 13.40 14.29 18.17 19.22 23.76 28.12 PC 14:05 14.54 13.52 19.78 21.79 24.85 39.26 40.55 41.46

* The ratio of polar polymer is 20.45 to 70% (instead of 30.55 or 80%)

XLI. spreadsheet

Compatibility enhancing effect on tensile strength of blends of polyolefins and polar polymers

Polar polymer Increase in tensile strength (MPa) of the additive 301% polar polymer 55% polar polymer 80% by weight polar polymer 5t% 15t% 5% 15% 5% 15% HDPE PMMA 1.74 5.01 7.38 8.12 2.99 4.77 SAN 2.32 4.80 6.80 3.63 3.21 -0.64 * EVOH 0.23 1.17 4.81 6.39 2.08 1.54 PA66 1.90 2.77 -0.2? -0.01 4.40 8.00 Pet 2.65 5:01 0.23 2.39 1.48 0.68 PVC 2.03 3.97 3.76 7:43 4.54 8.69 ^P E 3.14 5.27 4:10 7:42 -5.20 -3.69

HU 211 069 Β

Polar polymer Increase in tensile strength (MPa) of the additive 301% polar polymer 55% polar polymer 801% polar polymer 5t% 15% 5t% 15% 5t% 15t% PP * PMMA 1.35 3.79 3.22 5.61 7.29 10.22 SAN 5.09 7.38 9.98 8.41 13.02 10.70 * EVOH 4.56 5.72 9.64 10.59 10.65 9.83 PA66 8.23 8.32 9.45 8.38 3.13 1.44 Pet 0.86 2.22 4.34 4.17 15.44 16.37 PVC 1.36 3.03 2.59 5.51 9.11 11.68 PC 2.86 5.27 3.43 7.94 3.85 9.26 INTACT PMMA 2.66 4.30 4.18 7.82 2.12 4.46 SAN 4.43 6.01 6.68 6.01 4.76 -1.34 EVOH -0.15 -0.50 -0.27 -1.75 1.10 1.41 PA66 0.01 -0.68 0.36 -1.29 7.90 2.61 Pet 0:46 3.19 0.21 2.05 3.29 5.16 PVC 2.86 6.71 5.35 6.29 2.91 5.10 PC 1.74 3.35 1.24 2.50 1.61 2.59 LLDPE PMMA 3.40 5.67 5.80 7.96 6.42 5.19 SAN 5.31 6.80 9.26 10.21 9.40 1.32 EVOH 0.43 1.43 1.72 1.85 -1.12 0.45 PA66 0.06 2.05 -1.19 -4.44 2.90 2.61 Pet 2.76 5.01 2.70 5.25 1.14 -2.14 PVC -0.59 1.01 5.64 8:05 4.56 7.70 PC 5.56 4.85 8.61 11.24 2.14 0.41 EVE PMMA 0.71 3.81 -1.95 5.25 1.03 4.87 SAN 1.22 2.81 -0.68 1.38 3.07 -2.80 EVOH 0.83 3.45 -3.75 3.02 -0.68 -2.16 PA66 -0.61 0.27 -2.77 -0.44 -2.40 -9.15 Pet -0.20 -2.25 2.68 5.23 0.70 5.24 PVC 0.59 2.56 0.89 4.76 4.54 8.89 PC 0.49 -0.53 2.01 5.07 1.30 2.20

* The proportion of polar polymer is 20, 45, and 70% (30, 55, and 80%, respectively).

HU 211 069 B

XLII. Table II

HDPE PP INTACT LLDPE EVE PMMA +++ ₊₊₊ > +++ +++ +++ SAN +++ +++ +++ +++ 4- EVOH + +++ ¹ 0 0 + PA66 + +++> + + 0 Pet + ++ ' + + + PVC +++ +++ +++ ++ ¹ + PC + +++ ¹ + + +

+++ = Compatibility enhancer at all three polyolefin / polar polymer ratios (not necessarily at all additive concentrations).

++ = Two of the three polyolefin / polar polymer ratios are compatibility enhancers.

+ = One of the three polyolefin / polar polymer ratios is a compatibility enhancer.

= Does not improve compatibility at any polyolefin / polar polymer ratio. at any concentration of compatibility enhancer (1) = 10-80% domain size reduction as further evidence of compatibility enhancement

Example 775

In this example, the compatibility enhancement effects on selected polymer pairs are evaluated. The mixtures are combined to form a mass, pressed and tested for tensile strength as described above. XLIII. The results of Table 3 show again that the compatibility enhancement effect on polar polymers is minimal or negative, but on polar / apolar polymer blends. High tensile strength improvement in ABS / PP blend. Smaller but significant improvement in PP blends with PA6 and PC / PBT. The effect of PS blends is negligible.

XLIII. Table - Tensile strength (MPa)

Polar polymer Apolar polymer Polar polymer Polar polymer with 15% graft copolymer Mixes ¹ Mixture with ^{1 to} 15% graft copolymer PBT PP 43.02 45.11 36.96 38.96 PA6 PP 56.11 51.67 43.50 47.04 PS HDPE 45.26 40.45 36.48 33.76 PS PP 45.26 40.45 38.88 37.36 ABS PP 51.25 52.25 32.25 42,55 PC / PBT PP 51.77 51.79 38.99 41.88

(1) In each case, the mixture is defined as a mixture of 55 parts by weight of a polar polymer and 45 parts by weight of a polar polymer.

The effect of the grafted copolymer on the multi-component blends exemplified by blended polymer waste is described in XLIV. table. In each case, the tensile strength shows a significant increase when the compatibility enhancer is present.

XLIV. spreadsheet

Making multi-component blends compatible

Polar polymers Apolar polymers together- férhe- tőség- corrective tensile tószi- lárd- pany (MPa) PS Pet PVC HDPE LLDPE PP 12 7 5 33.5 33.5 9 no 16.27 12 7 5 33.5 33.5 9 5 17.67 12 7 5 33.5 33.5 9 15 21.77 12 8 - 35 35 10 no 18.62 12 8 - 35 35 10 5 19.98 12 8 - 35 35 10 15 22.16 12 - 6 36 36 10 no 17.06 12 - 6 36 36 10 5 19,21 12 - 6 36 36 10 15 21.91

Example 116

This example provides further data to improve the compatibility of the polymer blends with the graft copolymers of the present invention.

Mixtures of ethylene / vinyl alcohol copolymer (Kuraray EPF101A), polypropylene (Himont 6523) and graft copolymer were brought to a liquid state on a 7.62 x 17.78 cm electric roller at 204 ° C and rolled for a further 3 minutes. The mass is pressed at 204 ° C and 103 MPa for 3 minutes (Carver Press, 12.7 cm x 1.2.7 cm x 3.175 mm) and then pressed at 103 MPa for 3 minutes at room temperature. In this example, two graft copolymers are used. The first (copolymer A) is made from 100 parts by weight of a polypropylene homopolymer (MFR = 4) and 100 parts by weight of a mixture of methyl methacrylate / ethyl acrylate / methacrylic acid (93: 2: 5), conducted in Isopar E solvent at 160 ° C. hours with a 50% solids content at a root flux of 0.00012 mol / dm ³ / min provided by di (tert-butyl) peroxide. The isolated product contains 44% acrylate. The second graft copolymer (copolymer B) is made from 100 parts by weight of a polypropylene homopolymer (MFR = 4) and 150 parts by weight of a 95: 5 mixture of methyl methacrylate / ethyl acrylate, also in Isopar E solvent at 155 ° C with 60% solids. up to 0.00010 mol / dm ³ / min. The product has an acrylate content of 53%. The incorporation of graft copolymers increases tensile strength and tensile modulus.

HU 211 069 B

XLV. spreadsheet

Making EVOH compatible with polypropylene

EVOH (G) PP (g) Graft copolymer (g) Notched Izod tensile force (J / m) tensile solid- pany (MPa) pulling modulates lus (MPa) 90 30 0 21 29.85 2570 90 25 5 ' 21 48.06 3190 90 25 5 ² 22 46.75 3270 30 90 0 18 21.37 1930 30 75 15 ' 18 29,79 2140 30 75 15 ² 13 30.41 2030

(1) Copolymer A (see above).

(2) Copolymer B (see above).

Claims (24)

CLAIMS 1. A process for the preparation of a graft copolymer composition for improving the physical properties of polyolefins, optionally containing a graft polyolefin additive, characterized in that: a) introducing into the reactor vessel an inert solvent and an apolar polyolefin having a weight average molecular weight of between 50,000 and 1,000,000, comprising one or more monomer units, namely ethylene, propylene, butylene and / or 4-methylpentene monomer units; contain; b) dissolving the apolar polyolefin mentioned in a) in the solvent by heating to the extent necessary for dissolution; c) adding to the mixture obtained by stirring at least 80% by weight of a methacrylic acid ester of the formula CH ₂ = C (CH ₃ ) COOR, wherein R is a C 1 -C 8 alkyl group, and optionally up to 20% by weight of other copolymerizable acrylates; a monomer or a mixture of monomers containing a monomer; d) polymerizing the monomer or monomer mixture added in step c) to a strain having an average molecular weight of 20,000 to 200,000 by grafting an oil-soluble solution at a temperature in the range of 60 ° C to 200 ° C for 1 hour. a free radical initiator at a time of about 0.0001 to 0.0005 equivalents / liter / min is provided at the temperature of the reaction mixture, and this initiator addition and temperature is maintained until the graft polymerization is complete, and e) removing the solvent from the polymerization mixture and optionally mixing the un grafted polyolefin with the resulting copolymer to form a mixture comprising the copolymer and the un grafted polyolefin in a weight ratio of from 0.2: 99.8 to 10:90. (Priority: March 29, 1988) 2. A process according to claim 1, wherein the solvent is removed by a volatile extruder. (Priority: March 29, 1988) Process according to claim 1 or 2, characterized in that the solvent is a hydrocarbon solvent. (Priority: March 29, 1988) 4. A process according to any one of claims 1 to 3, wherein the polyolefin strain is a polyolefin containing methyl methacrylate as a polypropylene and / or methacrylate monomer. (Priority: March 29, 1988) 5. Process according to any one of claims 1 to 3, characterized in that the polyolefin strain is polypropylene, polyethylene, polybutylene and / or at least 80% by weight of a propylene copolymer made of ethylene. (Priority: March 29, 1988) 6. A process according to any one of claims 1 to 3, characterized in that the graft copolymer is physically mixed with the graft polyolefin. (Priority: March 29, 1988) A physical mixture comprising (A) a polyolefin and (B) a graft copolymer for improving the elastic modulus and resistance to sagging of polyolefins, wherein the graft copolymer component is a graft copolymer composition according to claim 1, wherein (A) and The weight ratio of component (B) is between 99.8: 0.2 and 0.2: 99.8. (Priority: March 29, 1988) 8. A mixture according to claim 7 wherein the weight ratio of component (A) to component (B) is between 99.8: 0.2 and 90:10. (Priority: March 29, 1988) 9. A mixture according to claim 7 or 8, characterized in that it comprises, in addition to components (A) and (B) according to claim 7, a component (C) of a graft-free methacrylate polymer having the same monomer composition as in claim 7. The monomer composition of claim 1 (b). (Priority: March 29, 1988) 10. A physical blend comprising polyolefin and a graft copolymer for improving the elongation modulus and resistance to sagging of polyolefins, characterized in that: (a) a concentrate comprising a graft copolymer composition according to claim 1 in an amount of from 5% to 50% by weight, based on the total weight of the mixture, of un grafted polymer, or b) a composition which, in addition to 0.2 to 5% by weight of graft copolymer composition and 99.8 to 95% by weight of polyolefin, optionally contains other known additives, such as stabilizers, plasticizers, flame retardants or blowing agents, preferably 0.001 to 0.5%. by weight of alkyl polysulfide, preferably di-tert-dodecyl disulfide or optionally 0.0010.1% by weight of tris (polyalkylhydroxybenzyl) -s-triazintrione, preferably tris (4-tert-butyl-3-hydroxy) -2,6-dimethylbenzyl) -s-triazine (1H, 3H, 5H) -trione and / or optionally a blowing agent, preferably in an amount of 1 to 2% by weight based on the total weight of the composition, preferably 200% blowing agent. At a temperature of between C and 230 ° C, nitrogen gas is released. (Priority: 03.03.1989) 11. A composition according to claim 10, wherein the unmetered methacrylate polymer is present in an amount of at least 80% by weight of the composition. (Priority: 03.03.1989) HU 211 069 Β 12. A process for the production of shaped articles, characterized in that the product is prepared according to the method of Figs. The polymer mixture of claim 1 is prepared by known molding operations. (Priority: March 29, 1988) The process according to claim 12, wherein the shaped product is produced by calendering, extrusion or milling, optionally by foaming or in the form of lozenges. (Priority: March 29, 1988) 14. A13. The process according to claim 1, wherein the product is made from a blend containing at least 80% by weight of the total polymeric material without grafting polypropylene. (Priority: March 29, 1988) 15. A process for producing a fiber, sheet, film, or solid profile body or hollow tube, wherein the product is as described in any of claims 7-9. The polymer blend of claim 1 is prepared by extrusion in a known manner. (Priority: March 1, 1989) The method of making a film or fiber according to claim 15. characterized in that the product is obtained by orienting the polymer chains in a known manner, namely monoaxially for fibers and biaxially for films. (Priority: 03.03.1989) 17. An improved compatibility mixture of one or more polar polymers and one or more non-polar polymers, wherein the compatibilizer is present in an amount of from 0.2 to 10% by weight based on the total weight of the mixture. A graft copolymer composition according to any one of claims 1 to 6. (Priority: 03.03.1989) 18. The improved compatibility mixture according to claim 17, wherein the apolar polymer is a polyolefin, preferably polypropylene and or polyethylene, in particular high density polyethylene and / or ethylene / vinyl acetate and / or ethylene / propylene / unconjugated diene terpolymer. and as polar polymer acrylic polymer, styrene / acrylonitrile polymer, ethylene / vinyl alcohol polymer, polyamide, polyester, especially polyethylene terephthalate, polycarbonate, polyvinyl chloride, acrylonitrile / butadiene / a styrene polymer, polyvinylidene chloride, a mixture of polyesters and polycarbonates and / or a mixture of polyvinyl chloride and a polyester; A graft copolymer composition as claimed in any one of claims 1 to 6, wherein the weight ratio of polar polymer (s) to apolar polymer (s) in the whole mixture is between 95: 5 and 5:95, and the graft polymer is present in polar, apolar and graft 0.210 parts by weight in 100 parts by weight of a total mixture of polymers. (Priority: 03.03.1989) The mixture of claim 18, wherein the weight ratio of the polar polymer (s) to the non-polar polymers is between 80:20 and 20:80. (Priority: 03.03.1989) 20. A mixture according to claim 18 or 19, wherein the grafted polymer is present in an amount of from 0.5 to 5 parts by weight per 100 parts by weight of the mixture of polar, apolar and grafted polymers. (Priority: 03/01/1989) 21. A method for improving the elastic modulus and / or sag resistance of polyolefins, comprising mixing the polyolefin with a graft polymer prepared according to claim 1 in an amount sufficient to achieve a weight ratio of graft polymer to un graft polyolefin of 0.2: 99.820: 80. which (a) a polyolefin strain of an apolar strain of one or more units of ethylene, propylene, butylene and / or 4-methylpentene having an average molecular weight of between 50 000 and 1 000 000, and b) at least one type of polyolefin chain having covalent bonds to said strain having an average molecular weight of from 20,000 to 200,000, wherein said chain is present in a weight ratio of from 1: 9 to 4: 1 by weight of the polyolefin strain, and containing at least 80% by weight of a methacrylic acid ester unit of the formula CH ₂ = C (CH ₃ ) -COOR where R is a C 1 -C 8 alkyl group and optionally up to 20% by weight of other acrylic monomer units; ) in a weight ratio of 0.2: 99.8 to 99.8: 0.2. (Priority: March 29, 1988) 22. A process according to claim 21, wherein the mixing is carried out at a temperature of at least 150 ° C and 0.0010.05% by weight of alkyl polysulfide, preferably di-tert-dodecyl, based on the total weight of the mixture prior to mixing. polysulfide is added. (Priority: March 29, 1988) The process according to claim 21 or 22, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polybutylene, and polyethylene / prolipropylene or polypropylene / polybutylene. (Priority: March 29, 1988) 24. A method for improving compatibility between polymers of different polarity levels, comprising blending 0.2 to 20% by weight, based on the total weight of the polymer blend, of the graft polymer produced by the process of claim 1, which comprises: (a) an apolar strain of polyolefin having one or more units of ethylene, propylene, butylene and / or 4-methylpentene, having an average molecular weight of between 50 000 and 1 000 000, and b) at least one type of polyolefin chain having covalent bonds to said strain having an average molecular weight of from 20,000 to 200,000, wherein said chain is present in a weight ratio of from 1: 9 to 4: 1 by weight of the polyolefin strain, and containing at least 80% by weight of a methacrylic acid ester unit of the formula CH ₂ = C (CH ₃ ) -COOR where R is a C 1 -C 8 alkyl group and optionally up to 20% by weight of other acrylic monomer units; ) in a ratio of from 0.2: 99.8 to 99.8: 0.2, such that the grafted polymer is present in a ratio of up to 20 parts and at least 80 parts by weight of the polyolefin.