SK89694A3 - Modified elastomer polypropylenes - Google Patents

Abstract

Elastomeric polypropylene (ELPP) and mixts. thereof with isotactic polypropylene (IPP), which are modified with unsatd. graft monomers, are claimed (I). Also claimed is a process for modifying ELPP and ELPP/IPP mixts. by grafting with ethylenically unsatd. graft monomers (II). Further claimed are blends of polyolefins and non-olefinic thermoplastics, contg. (I) as compatibility promoter.

Description

Technical field

The invention relates to modified elastomeric polypropylenes, mixtures thereof with isotactic polypropylenes, modified inoculations, as well as their use as additives for improving compatibility or adhesion.

BACKGROUND OF THE INVENTION

For example, EP-A-280,454, EP-A-317,358, WO 91/5008, US

No. 3,868,433, US 4,260,690, DE-A-41 31 908, it is known that isotactic polypropylenes (IPPs) can be chemically modified with seed monomers such as styrene, maleic anhydride (MSA), acrylic acid and derivatives thereof. These inoculation reactions produce inoculation copolymers of PP, which have a higher polarity compared to the starting PP. These products find use, for example, as additives to improve adhesion when coating with polyolefins, such as polyethylene, PP and PP copolymers, or as additives to improve compatibility in polyolefin-miscible polyolefin / polymer blends such as polyamides, polyesters, polycarbonates, polystyrenes, polyacrylates and polyurethanes. In both fields of application, the additive to improve adhesion or compatibility is located in the interlayer between the polyolefin and the metal or the mixed partner, and causes the adhesion of the materials through chemical and / or physical coupling (e.g. co-crystallization). In the case of mixtures of PP with other thermoplastics, for example polyamide 6 (PA6), the phase boundary layer structure significantly determines mechanical properties such as impact strength, strength and stiffness (modulus of elasticity). For example, the PP / PA6 mixture, which contains an additive to improve compatibility based on sterol-ethylene / butylene-styrene (SEBS), grafted with MSA, exhibits a relatively high toughness (impact toughness, Fallbolzentest). Similar properties have PP and PA6 blends using ethylene propylene rubber (EPR) inoculated with MSA as an additive to improve compatibility. However, said additives for improving compatibility, such as those of the SEBS type, have the disadvantage of a complex and expensive synthesis, since the copolymerization takes place in solution and subsequent seeding with functional monomers is required.

The grafted ethylene propylene rubber has the disadvantage of poor pourability, since the grafting in EPR is accompanied by a partial crosslinking of the ethylene moiety. The same applies to vaccinated EPDM.

In particular, additives for improving compatibility or adhesion based on isotactic polypropylenes have the disadvantage that in many fields of application of thermoplastics, such as in the manufacture of cars, tools and instruments, the mechanical properties of the mixtures used, in particular toughness, are insufficient.

For these reasons, it has been necessary to find substances which act as additives for improving the compatibility or adhesion for polyolefins and which cause improved mechanical properties, in particular higher toughness or lower brittleness, especially in mixtures of polyolefins with neolefin thermoplastics.

SUMMARY OF THE INVENTION

According to the invention, the problem is solved by using grafted copolymers of elastomeric PP (ELPP) or mixtures thereof with grafted polymers of isotactic polypropylenes (IPP) as additives for improving compatibility or adhesion.

Accordingly, the present invention provides elastomeric polypropylenes (ELPPs) modified with ethylenically unsaturated seed monomers, and mixtures thereof with isotactic polypropylenes (IPPs) modified with ethylenically unsaturated seed monomers.

The elastic polypropylenes used for the inoculation reactions are in particular those described in US 47335,225, US 4,522,982 and US 5,188,768. This includes both homopolymers and copolymers. They have a substantially stereospecific block arrangement of the structural chain and consist, for example, of blocks of isotactic and atactic propylene sequences that are alternately arranged on the polymer chain. It is also possible to insert additional comonomers into the polymer chain. The copolymers may contain other olefin units, such as ethylene, butene, pentene or hexene units, in addition to the propylene units in the molecule. They are prepared, for example, according to US 4,335,225 by polymerization with special catalysts which are prepared by reacting or mixing organic compounds Ti, Zr or Hf with a metal oxide, such as TiCl 2, SiO ₂ or MgO. In addition, elastic polyropylenes used for degradation can also be prepared analogously to US 4,522,982 using metallocene catalysts in combination with aluminoxanes or analogously US 5,118,768 to catalysts based on magnesium alkoxides and titanium tetrachloride in special electron donor environments.

According to the invention, the elastic polypropylenes (ELPPs) can be inoculated alone or in admixture with other, particularly isotactic polymers (IPPs). All other known polypropylene homopolymers or copolymers with other olefins can be used as other polypropylenes. However, it is also possible to separately inoculate ELPP and IPP and mix the modified polypropylenes. The mixtures preferably consist of elastic polypropylenes with a content of 0 to 80% by weight. %, particularly preferably 0.5 to 50% by weight. , in particular of isotactic polypropylenes.

The grafted polypropylenes of the invention are polypropylenes which have one or more chemically bonded (grafted) functional groups and / or polymer chains of monomodules having one or more functional groups along the polymer chain. ELPPs and / or IPPs can therefore be vaccinated with unsaturated mono- and / or dicarboxylic acids, their anhydrides, their esters with aliphatic alcohols and dialcohols containing 1 to 10 carbon atoms, and the glycidethers, vinyl alcohol esters as well as the vinyl aromatics or mixtures of these monomers, as well as mixtures of these monomers and olefins containing from 2 to 10 carbon atoms.

Particularly preferred in this connection are the grafting monomers of the ethylenically unsaturated aliphatic or aromatic carboxylic acid group or derivatives thereof, the maleic, acrylic or methacrylic acid group or derivatives thereof, and the vinyl aromatic groups. Possible derivatives are, for example, esters, anhydrides, acid halides, amides, imides or oxazolines.

Thus, for example, ELPP, IPP or mixtures of ELPP and IPP in solution or melt can be reacted by a process of free radical graft copolymerization with acrylic acid or its derivatives, such as methyl methacrylate, butyl acrylate, tert, butyl acrylate, glycidylacrylate, glycidyl methacrylate,

2-hydroxyethyl ester of acrylic acid or maleic acid and its derivatives, such as maleic anhydride (MSA), mono- and diesters of maleic acid with methanol, = ethanol, butanol and hexanol to form ELPP, optionally

IPP, modified with acid, acid ester, hydroxyester and glycidyl ether. Preparation of graft copolymers of ELPP and IPP and derivatives of vinyl alcohols, especially esters with aliphatic carboxylic acids, such as vinyl acetate, is likewise possible. Another group consists of inoculated products with vinylaromates, such as styrene. Furthermore, the reaction of ELPP or IPP with mixtures of seed monomers of any composition, such as mixtures of various acrylic acid derivatives, mixtures of acrylic acid and maleic acid derivatives, mixtures of acrylic acid derivatives with vinyl alcohol derivatives, mixtures of both acrylic acid and maleic acid derivatives, and / or vinylalcohol derivatives as well as vinylaromates such as styrene, and / or alpha-olefins containing 2 to 10 carbon atoms, to form grafted ELPP copolymers. optionally mixtures of grafted ELPP / IPP copolymers.

the content of seed monomers at about 0.1 to aboutwt., and the most preferred inoculation stage, i.e., graft polypropylenes, is preferably about 30wt%, more preferably at about 0.5 to about 10wt% at about 0.5 to about 5wt%.

according to the invention proceed according to

Λ,

ELPP, radical methods, for example, for IPP US 3,868,433, US or mixtures of ELPP polymers. Suitably in the aroma from 50 to 200 ° C, preferably in extrusion, preferably from 200 advantageously from 200 to initiate the formation of polymers such as peroxides or a radiation such as gamma

Preparation of graft copolymers or ELPP / IPP, can be graft copolymerized as described in EP-A-280.454, EP-A-317.358, WO 91/5008, 4,260,690, DE-A-41 31 908, inoculation with ELPP and IPP with ethylenically unsaturated inoculation The reaction is carried out, for example, in a solution, a hydrocarbon at a temperature range preferably from 80 to 150 ° C, or in a melt, at a temperature range from 170 to 300 to 250 ° C. Here, the dical initiators, the compounds and / or the high-energy radiation are electron radiation.

It is a further object of the invention to use ELPPs modified according to the invention, or mixtures thereof with modified IPPs, as additives to improve compactness and adhesion for olefins, especially in mixtures with polyolefins with neolefin thermoplastics, or as additives to improve adhesion at polyolefin-metal joints. The grafted ELPP or ELPP / PP copolymers according to the invention can be used as additives to improve compatibility, in particular in mixtures which consist of both polyethylenes, IPP or its copolymers with ethylene and other alpha-olefins, as well as neolefin thermoplastics, for example from the group polyamides, polyesters, polycarbonates, polystyrenes, polyacrylates and polyurethanes.

A further object of the invention are mixtures of polyolefins and non-olefin thermoplastics, which contain grafted ELPP and / or ELPP / IPP copolymers as additives to improve compatibility. The compositions of the invention exhibit better mechanical properties, for example higher toughness values (Doppel-V impact resistance, Fallbolzentest) and lower toughness values than mixtures of the same composition with inoculated IPP as an additive to improve compatibility. The compositions of the invention may further comprise conventional additives such as technological and long-term stabilizers, nucleating agents, reinforcing agents and fillers such as talc, chalk or kaolin. Thus, for example, advantages are obtained when the compositions according to the invention contain 2 to 50% by weight, preferably 10 to 40% by weight. talc or 1-40 wt. reinforcing fibers such as glass fibers or carbon fibers.

The compositions of the invention contain about 0.1 to 30% by weight of an additive to improve compatibility. Preference is given to using 1 to 15% by weight, particularly preferably 2 to 10% by weight, of an additive to improve compatibility. The mixing ratio of the polyolefin to the non-olefin thermoplastics extends over the total possible mixing range and is about 5 to 95% by weight, preferably 30 to 80% by weight. % polyolefin and 5 to 95% by weight, preferably 20 to 70% hmox. a neolefin thermoplastic. The mixtures are used, for example, in extrusion or compression molding to produce films or moldings.

DETAILED DESCRIPTION OF THE INVENTION

In the following, particularly advantageous combinations of additives according to the invention for improving compatibility for special mixtures are given as examples:

(a) ELPP, inoculated with MSA, ELPP, inoculated with MSA-styrene, and ELPP, inoculated with acrylic acid, for mixtures of IPP and its copolymers with polyamides, for example PA 6, PA 6,6 and their copolymers with aromatic modules such as phthalic acid , terephthalic acid, isophthalic acid, p-, o- and m-phenylenediamine, aromatic carboxylic amino acids such as p-, o-, and m-aminobenzoic acid and other aromatic dicarboxylic acids, diamines and aminocarboxylic acids containing more than 1 aromatic ring .

b) ELPP, inoculated with MSA, for mixtures of IPP and its copolymers with polyesters, for example polyalkylene terephthalate, such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) and their copolymers with other comonomers such as p-hydroxybenzoic acid, isophthalic acid and / or other aliphatic diols and diphenols, as well as mixtures with fully aromatic esters,

(c) ELPP, inoculated with MSA for mixtures of IPP and its copolymers with thermoplastic polyurethanes;

(d) ELPP, inoculated with glycidyl methacrylate and glycidyl acrylate, for mixtures of IPP and its copolymers with polyesters, for example polyalkylene terephthalar (PET, PBT) and its copolymers with other comonomers, such as in point b, as well as mixtures with fully aromatic polyesters;

(e) other grafted ELPP copolymers with acrylic acid derivatives such as methyl methacrylate, butyl acrylate, hydroxyester of acrylic acid, acrylic acid, oxazoline or acrylic and methacrylic acid derivatives for mixtures of IPP and its copolymers with polyesters, for example polyalkylene terephthalates, (PET, PBT) and copolymers thereof with other comonomers, such as in point b, as well as mixtures with fully aromatic polyesters,

(f) ELPP, inoculated with vinyl acetate, for mixtures of IPP and its copolymers with polyesters, such as polyalkylene terephthalate (PET, PBT) and their copolymers with other comonomers, such as in point b, as well as mixtures with fully aromatic polyesters;

(g) ELPP, vaccinated with glycidyl methacrylate and glycidyl acrylate, for mixtures of IPP and its copolymers with polycarbonates;

(h) styrene-grafted ELPP for mixtures of IPP and its copolymers with polystyrene and its copolymers;

(I) styrene-grafted ELPP for mixtures of IPP and its copolymers with polycarbonates and its copolymers;

(j) ELPP, grafted with glycidyl methacrylate and glycidyl acrylate, and other grafted ELPP copolymers with acrylic acid derivatives such as methyl methacrylate, butyl acrylate, hydroxyester of acrylic acid, acrylic acid, for mixtures of IPP and its copolymers with polyacrylates and polymethyl methacrylate,

k) a mixture of 50 to 99.5% pot. ELPP, vaccinated MSA, and 0.5 to 50 wt%. vaccinated IPP, for mixtures of IPP and its copolymers with polyamides.

I. A method for producing elastomeric polypropylene

Example A:

1.1. Catalyst Production • 44.22 g of tetraneolyl zirconium (TNZ; Tm = 66 C, Du Pont) of gray brown was dissolved in an atmosphere of pure nitrogen in 620 ml of oxygen-free n-hexane on a copper catalyst (BASF R 3-11 catalyst at 70 ° C) ) and free of water and polar impurities at 20 ^° C in a reaction vessel under a shielding gas atmosphere on molecular sieves 4A and 10A, respectively. The resulting suspension was filtered after 15 minutes after settling the bulk of the insoluble residue particles on a glass frit in a glass reaction vessel under an inert gas atmosphere equipped with a stirrer, cooled to -40 ° C (heated above 150 ° C and purged with pure nitrogen (containing O _2). maximum 2ppm)). The contents of the reaction vessel were further stirred after completion of the filtration (which lasted approximately 140 minutes) for a further 15 minutes at 40 ° C so that the TNZ would be as quantitative as possible. After settling the TNZ, the residual solution was filtered on a filter plug under nitrogen pressure to another cooled reaction vessel under an inert gas atmosphere. The remaining TNZ was dissolved in an additional volume of 350 mL of N-hexane at about 5-10 ° C for 15 minutes and re-precipitated after cooling to -34 ° C.

d. After sedimentation of the precipitate the TNZ solution was again filtered using positive nitrogen pressure through a glass filter candle into the ^M re - action of the container with protective gas atmosphere, with the first mother liquor. Subsequently, TNZ was dried using a vacuum pump (below 1 Pa) with cold precipitation by liquid nitrogen cooling. The purified TNZ had a melting point of 68 ° C and was white to cream. The combined mother liquors were concentrated to approximately 200 mL and TNZ still in solution precipitated in the cold at -40 ° C. After further pressure filtration through a filter plug, TNZ was redissolved in 100 mL hexane, reprecipitated at -40 ° C, filtered and dried under vacuum as described above. The overall yield of this purification process was 82.2%. All processes were performed under pure nitrogen.

A 6-liter four-necked reaction vessel was weighed with conditioned Al 2 O 3 (Alumina C, DEGUSSA product, conditioned at approximately 800 to 1000 ° C under a stream of nitrogen and after 16 hours storage at 50% relative humidity and 23 ° C air temperature) after repeated drying at 400 ° C under a stream of nitrogen to achieve an optimum surface hydroxyl concentration of approximately 1 mmol / g Alumina C) and supplemented with 5035 ml of n-hexane, purified on BASF R 3-11 catalyst and molecular sieves 4A and 10A, respectively. The suspension was stirred for about 1 hour at 400 rpm. Then 33.23 g of the above TNZ (without the mother liquor product) was dissolved at 46 ° C in 465 ml n-hexane (purified according to the above procedure) and this TNZ solution ¹ was added dropwise to the Al 2 O 3 slurry with stirring for 50 minutes. wherein there was a significant decrease in the viscosity of the suspension after the addition of a small amount of TNZ solution. After addition of the TNZ solution, the number of revolutions was reduced to approximately 120 rpm. and stirring was continued for 12.5 hours in the absence of light. To speed up the filtration, the solid catalyst obtained was allowed to settle for 1 hour and finally the solution was filtered by pressure filtration through a sintered glass (3 hours). Subsequently, the solid catalyst was dried under vacuum at a value below 1 Pa (a diffusion oil pump with two interconnected freezing chambers, cooled with liquid nitrogen) with stirring until a constant weight of 292 g. All operations were performed in a pure nitrogen atmosphere. The obtained TNZ / Al 2 O 3 catalyst was an easily filterable beige to light brown powder, which tended to form tiny spheres of approximately 1 mm diameter. The Zr content was 1.66% by weight.

(b) Polymerization:

A 20 liter double-shell reactor with a paddle stirrer with a polished surface, a thermostatic shell, a temperature, speed and torque measurement, heated at 160 ° C and 10 Pa after three vacuum rinses with propene were charged with 7.3 kg of propene at 25 ° C. ° C After increasing the number of revolutions to 400 rpm. 10.02 g of the catalyst prepared according to 1.1 were flushed with 300 ml of liquid propene (approximately 20 ° C) and after two minutes the speed was reduced to 260 rpm. Over the next 10 minutes, the temperature of the propene was raised up to 60 ° C and maintained at that temperature for 120 minutes. from the addition of the catalyst. Then the speed was reduced to 200 rpm. and 1880 g of acetone preheated to 50 ° C were introduced into the reactor over a 3 minute period of nitrogen overpressure. After increasing the number of revolutions to 400 rpm. to about 2 minutes and then reduced to 100 rpm. in 60 minutes, unused propene was withdrawn at 60-46 ° C. The remaining acetone slurry of the ELPP elastomeric polypropylene was miscible and could be drained through an opening at the bottom of the reactor.

After filtering the ELPP and drying in a stream of nitrogen at 50 ° C, 1.88 kg of a granular, non-sticky ELPP and a melting point (Tm) of 148.1 ° C (measured on a Du Porrt 910/20 differential calorimeter) were obtained. Analyst 2100)), according to the calculated Zr 89 ppm content and Al ₂ 0 ₃ 0.49 wt% content. The ELPP had an MFI (melt flow index according to ISO

1133 / DIN 53735 at 230 ° C / 2.16 kg) less than 0.01 g / 10 min.

Example B:

λ

The elastic polypropylene obtained according to Example A, ¹¹ is milled on a roll mill cooled below 0 DEG C. to a particle size of less than 3 mm. Then, 0.2% by weight, bis (2 (1,1-dimethylethyl) peroxoisopropyl) benzol (Perkadox)

14SFI, Fa. Akzo), calculated on the amount of polypropylene, the mixture was melted at 190 ° C on a 18 mm Brabender single screw extruder and extruded at a rate of 1kg / h through a round nozzle to a 3 mm diameter skein. The residence time in the extruder was about 1 minute. The skein was granulated after solidification in a water bath. The elastic polypropylene was degraded up to an MFI of 25 g / 10 min. The MFI was measured according to ISO 1133 / DIN 53735 at 230 ° C / 2.16 kg.

II. Method of making the additive to improve compatibility:

Example 1:

50 g of the elastomeric PP according to Example A (MFI: 25) was dissolved in 1250 ml of xylol (mixture of isomers) under a nitrogen atmosphere in a 2-liter, oil bath, reflux condenser, nitrogen inlet, hermetically sealed stirrer and dropping funnel. stirring at 120 ° C and then 60g of maleic anhydride (MSA) was added. 40 g of benzoyl peroxide dissolved in 100 ml of xylene was added dropwise at 130 DEG C. over 60 minutes. The solution was stirred for an additional 60 minutes and after cooling to 80 ° C was added to 2.5 L of acetone. The precipitated graft copolymer was aspirated, washed in 2.5 L of acetone, aspirated again and dried under vacuum at 80 ° C for 8 hours.

The MSA vaccination degree, as determined by infrared spectroscopy 12, was 1.2% by weight, calculated on the total.

Comparative Example VI:

Analogous to Example 1, an additive was prepared to improve compatibility, but instead of ELPP, 100 g isotactic PP (IPP, Daplen B-Pulver, reaction product, PCD polymers, MFI: small 0.001) in 1250 ml xylene with 60 g MSA were used for the reaction. and 40 g of benzoyl peroxide. The degree of seeding, determined by IR spectroscopy, was 1.3% by weight, calculated on the total.

Example 2:

In analogy to the procedure described in Example 1, 100 g of elastomeric polypropylene (ELPP) according to Example B with MFI: 25, dissolved in 650 ml of xylene, 40 g of MSA and 20 g of benzoyl peroxide were used for the reaction. The MSA vaccination rate was

2.9% by weight, calculated on the total quantity.

Comparative example V2:

Analogously to Example 1, 100 g of isotactic polypropylene (Daplen RT 551, PCD polymers) with MFI: 28 dissolved in 650 ml of xylene, with 60 g of MSA and 40 g of benzoyl peroxide were used for the reaction. The MSA vaccination grade was 2.7% by weight, calculated on the total amount.

Example 3:

In analogy to the procedure described in Example 1, 100 g of the elastomeric polypropylene of Example B with MFI: 25 dissolved in 650 ml of xylene, 40 g of glycidyl methacrylate (GMA, Fluka Chemie) and 20 g of benzoyl peroxide were used. The inoculation degree of GMA, determined by IR spectroscopy, was 1.9% by weight, calculated on the total.

Comparative example V3:

In analogy to the procedure described in Example 1, 100 g of isotactic PP (IPP, Daplen RT 551, PCD polymers, MFI: 28) in 750 ml of xylene, with 40 g of GMA and 20 g of benzoyl peroxide were used for the reaction. The inoculation degree of GMA, determined by IR spectroscopy, was 2.0% by weight, calculated on the total.

Example 4:

In analogy to the procedure described in Example 1, 100 g of the elastomeric polypropylene of Example B with MFI: 25, dissolved in 650 ml of xylene, with 40 g of styrene and 20 g of benzoyl peroxide, were used for the reaction. The styrene grafting degree, determined gravimetrically, was 10.4% by weight, calculated on the total.

Comparative example V4:

Analogously to Example 1, 100 g isotactic polypropylene (Daplen RT 551, PCD polymers) with MFI: 28 dissolved in 650 ml xylene, 50 g styrene and 20 g benzoyl peroxide were used for the reaction. The styrene vaccination grade, determined gravimetrically, was 9.8% by weight, calculated on the total.

III. Preparation of mixtures:

Example 5:

Polypropylene / polyamide 6 blend together with inoculated ELPP copolymers according to Example 1 as an additive to improve compatibility (VM), IPP / PA6 / BM composition = 60/35/5% by weight.

Mixture of 3000 g IPP (Daplen BE 50, PCD polymers, MFI: 0.3),

1750 g of polyamide 6 (SH3, from Leuna Verke AG, viscosity according to DIN 53727: 140 cc / g in 96 percent sulfuric acid) and 250 g of grafted ELPP copolymer according to Example 1 were extruded at a mass temperature of 255 ° C in a Berstorff ZE 25 twin screw extruder. L / D = 49.5) at a mass flow rate of 5 kg / h, cured in a water bath and granulated. After drying under vacuum at 80 ° C (8 hours), the granulate of the mixture was injected at a meat temperature of 260 ° C and a compression temperature of 40 ° C onto 150x80x2 mm plates. The samples milled from these plates were then conditioned for 10 days at 70 ° C and 60% relative humidity. The following mechanical tests were performed: determination of the E modulus in bending according to DIN 53 457 (1987) on 50x10x2mm samples at 23 ° C; determination of Doppel-V impact strength according to DIN 53 753 (1981) on 50x6x2mm samples at 23 ° C; Determination of the Schadigungsarbeit (Vmax) and Durchstossarbeit (Vges.) in the breakdown test according to DIN 53 443/2. part (1984) on plates 150x80x2mm at 23 ° C. The mechanical properties are set out in Table 1.

Comparative example V5:

In analogy to the conditions and mixing ratios given in Example 5, an IPP / PA 6 mixture was prepared together with an IPP inoculated with MSA not according to the invention described in Comparative Example VI: 3000 g IPP (60 wt%), 1750 g PA 6 (35 wt%) and 250 g of IPP, inoculated with MSA (according to Comparative Example VI; 5 wt%). The mechanical test values are given in Table 1.

Example 6:

Analogous to the conditions of Example 5, a mixture of IPP / PA 6 in a mixing ratio (IPP / PA 6 / VM) of 75/20/5% by weight was prepared. together with an ELPP grafted with MSA as described in Example 1 as an additive to improve compatibility: 3750 g (75% wt.) IPP, 1000 g (20% wt.) polyamide 6, and 2050 g (5% wt.) graft copolymer ELPP. according to Example 1. The results of the mechanical tests of the mixture are given in Table 1.

Comparative example V6:

Analogously to the conditions set forth in Example 6, an IPP / PA 6 mixture was prepared according to a mixing ratio (IPP / PA 6 / VM) of 75/20/5% by weight, together with the IPP grafted with MSA described in Comparative Example VI as an additive. to improve compatibility: 3750 g (75% w / w) IPP, 1000 g (20% w / w) polyamide 6, and 250 g (5% w / w) graft IPP copolymer from ^β · Comparative Example VI.

The results of the mechanical tests of the mixture are shown in Table 1.

Example 7:

IPP / polyamide 6 blend together with the grafted ELPP copolymers of Example 2 as additives to improve compatibility, blend composition (IPP / PA 6 / VM) .45 / 50/5.

A mixture of 18 g (45 wt.%) IPP (Daplen BE 50, PCD polymers, MFI: 0.3), 20 g (50 wt.%) Polyamide 6 was charged to a Brabender-Plasticorder with an electrically heatable 50 ml plasticization chamber. (SH3, by Leuna-Verke, viscosity according to DIN 53 727: 150 cc / g in 96% sulfuric acid) and 2 g (5% by weight) of the graft copolymer ELPP of Example 2 at 260 ° C chamber temperature with plasticizers switched on ( 60 rpm), plasticized for 5 minutes and then removed from the plasticizing chamber. The mixture was processed at 260 ° C into a 200x80x2 mm plate from which 50x10x2 mm test specimens were milled to determine the modulus E in bending. Module E in bend is shown in Table 1.

Comparative example V7:

Analogously to the conditions of Example 7, an IPP / polyamide 6 blend was prepared together with the graft copolymer.

IPP from Comparative Example V2 as an additive to improve compatibility. Mixture composition (IPP / PA 6 / VN) 45/50/5: 18 g (45 wt%) IPP (MFI: 0.3), 20 g (50 wt%) polyamide and 2 g (5 wt%, of the grafted IPP copolymer of Comparative Example V2.

The modulus E in strength is shown in Table 1.

Example 8:

IPP / polyethylene terephthalate (PET) blend together with the grafted ELPP copolymer of Example 3 as an additive to improve compatibility.

Analogously to Example 7, a mixture of 18 g (45% by weight) of IPP, 20 g (50% by weight) of PET (Polyclear F, from Hoechst, MV: 60,000) and 2 g (5% by weight) of the graft copolymer was prepared. ELPP of Example 3. Module E in bend is shown in the table

First

Comparative example V8:

Analogously to the conditions of Example 8, an IPP / polyethylene terephthalate mixture was prepared together with the grafted IPP copolymer of Comparative Example V3 as an additive to improve compatibility.

Mixture composition (IPP / PET / VM) 45/50/5: 18 g (45% w / w) IPP (MFI: 0.3), 20 g (50% w / w) PET and 2 g (5% w / w) the grafted IPP copolymer of Comparative Example V3.

Module E in bend is shown in Table 1.

Example 9:

Process for preparing the IPP / polycarbonate (PC) mixture together with the grafted ELPP copolymer of Example 3 as an additive to improve compatibility.

Analogous to Example 7, a mixture of 18 g (45% by weight) IPP, 20 g (50% by weight) PC (Lexan PK 1340, from General Electric, MVR (melt volume flow rate according to ISO) was prepared.

1133, 300 ° C / 1.2 kg): 6 ml / 10 min) and 2 g (5% w / w) of the grafted ELPP copolymer of Example 3. The flexural modulus E is shown in Table 1.

Comparative example V9:

Analogously to the conditions of Example 9, an IPP / polycarbonate mixture was prepared together with the grafted IPP copolymer from Comparative Example V3 as an additive to improve compatibility.

Mixture composition (IPP / PC / VM) 45/50/5: 18 g (45% w / w) IPP (MFI: 0.3), 20 g (50% w / w) PC and 2 g (5% w / w) the grafted IPP copolymer of Comparative Example V3.

Module E in bend is shown in Table 1.

Example 10:

Process for the preparation of the IPP / Polystyrene (PS) mixture together with the grafted ELPP copolymer of Example 4 as an additive to improve compatibility.

Analogously to Example 7, a mixture of 18 g (45 wt.%) IPP, 20 g (50 wt.%) PS (PSH 165, BASF, viscosity according to ISO 1628/1 (1984) 119 ml / g) and 2 was prepared. g (5% w / w) of the grafted ELPP copolymer of Example 4.

Module E in bend is shown in Table 1.

Comparative example V10:

Analogously to the conditions of Example 10, an IPP / polystyrene mixture was prepared together with a graft IPP copolymer from Comparative Example V4 as an additive to improve compatibility.

Mixture composition (IPP / PS / VM) 45/50/5: 18 g (45% w / w) IPP (MFI: 0.3), 20 g (50% w / w) PS and 2 g (5% w / w) of the grafted IPP copolymer of Comparative Example V4.

Module E in bend is shown in Table 1.

From the measured values shown in Table 1, it can be seen that the compositions in which the additives used to improve the compatibility according to the invention were used have a much lower stiffness (lower modulus E) and a much better toughness (Fallbolzentest and Doppel V impact resistance). use of known additives to improve compatibility.

Table 1: Properties of mixtures

Ex. mixture VM of Ex. E modul (MPa) FB (J) Vmax. Vges. DV (kJ / m ^) i q 1 q 5 PP / PA 1 985 1010 6 9 44,6 9 V5 PP / PA VI 1405 1289 5.3 7.8 22.7 2.4 6 PP / PA 1 1134 1082 22 23 48.1 5.2 V6 · PP / PA VI 1298 1276 2,2 3,6 32.8 4.7 7 PP / PA 2 1552 V7 PP / PA V2 2061 8 PP / PET 3 1795 V8 PP / PET V3 2277 9 PP / PC 3 1442 V9 PP / PC V3 1580 10 PP / PS 4 1683 V10 PP / PS V4 1953

E modul flexural modulus according to DIN 53 457 (1987) FB Fallbolzentest according to DIN 53 443 2 (23 'C) (1984) part Vmax work at maximum strength Vges total work DV notch impact strength Doppel-V acc (1981) DIN 53753 (D test in the processing direction (Q) transversal test for processing direction PP polypropylene PA polyamide PET polyethylene terephthalate PC polycarbonate PS polystyrene IN M additive to improve compatibility

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Claims (10)

PATENT CLAIMS Modified elastomeric polypropylenes (ELPPs) and mixtures thereof with modified isotactic polypropylenes (IPPs), characterized in that the elastomeric polypropylenes (ELPPs) are modified with ethylenically unsaturated grafts. A monomers and mixtures thereof with isotactic polypropylenes w (IPP), which are modified with ethylenically unsaturated seed monomers. The modified ELPP and mixtures thereof according to claim 1, characterized in that the seeding monomers belong to the group of ethylenically unsaturated aliphatic or aromatic carboxylic acids or derivatives thereof. The modified ELPP and mixtures thereof according to claim 1 or 2, characterized in that the seeding monomers belong to the group of maleic acid or its derivatives, acrylic acid or its derivatives, methacrylic acid or its derivatives. Modified ELPPs and mixtures thereof according to claim 1, characterized in that the seeding monomers belong to the group of vinyl aromatics or vinyl alcohol esters. IN Modified ELPPs and mixtures thereof according to one of claims 1 to 4, characterized in that their content in the seed monomers (seed stage) is 0.1 to 30% by weight, preferably 0.5 to 10% by weight. %, particularly preferably 0.5 to% by weight. Modified ELPPs and mixtures thereof according to one of claims 1 to 5, characterized in that they contain 0 to 80% by weight, preferably 0.5 to 50% by weight, of the modified IPP. A method of modifying elastomeric polypropylenes (ELPPs) or mixtures thereof with isotactic polypropylenes (IPPs), characterized in that the ELPPs or mixtures of ELPPs and IPPs are grafted with ethylenically unsaturated seed monomers. Use of modified ELPPs and / or mixtures thereof with modified IPPs according to one of claims 1 to 7 as an additive to improve compatibility in mixtures of polyolefins with neolefin thermoplastics. Use of modified ELPPs and / or mixtures thereof with modified IPPs according to one of claims 1 to 7 as an additive for improving adhesion in polyolefin and metal laminates and / or laminates. A mixture of polyolefins and neolefin thermoplastics, characterized in that it contains modified ELPPs and / or mixtures thereof with modified IPPs according to one of claims 1 to 9 as an additive for improving compatibility.