FI96618B - Alfamono-olefin-based branched copolymer, process for preparing the same, its application in the production of thermoplastic mixtures and obtained thermoplastic mixtures - Google Patents

Description

• 96618

The present invention relates to an alpha-mono-olefin-based grafted copolymer, to a process for its preparation and to its use in particular as a substance for obtaining at least two incompatible thermoplastic polymers.

In some specific blends, the two incompatible polymers may be made compatible by incorporating a third polymer that is partially compatible with both polymers.

For example, it has been proposed to add various third polymers to the blend of polypropylene polyamides.

JP Patent Publication No. 70-030943 describes a composition comprising polypropylene, polyamide and polypropylene grafted with a maleic anhydride.

JP Patent Publication No. 59-149940 discloses a composition comprising polypropylene, polyamide and an ethylene / propylene copolymer grafted with maleic anhydride.

FR Patent Publication No. 2,107,538 describes a composition of polypropylene and glass fiber reinforced polyamide made compatible by the addition of a propylene copolymer and an alpha-olefin grafted with polyamide chains. The grafted copolymer is obtained from the polycondensation of an amino acid with maleic anhydride in the presence of a pre-grafted propylene copolymer.

JP Patent 60-233131 describes the preparation of a grafted copolymer by which a mixture of polypropylene and polyvinyl chloride is made compatible. This -.96618 2 grafted copolymer is obtained by reacting 2-20% by weight of maleic anhydride with modified polypropylene with a hydroxy-terminated polymethyl methacrylate.

The invention primarily relates to novel grafted copolymers consisting of at least one monoaminated polyamide oligomer and an alpha-monoolefin polymer (or copolymer) grafted with a monomer capable of reacting with the amine function of the monoaminated polyamide oligomer.

The invention also relates to a process for the preparation of this grafted copolymer. It is prepared by performing radical grafting on a polymer chain having groups derived from alpha-monoolefins and a monomer that can react with an amine function, and then adding a monoaminated polyamide oligomer to the grafted copolymer.

It is a further object of the invention to use this grafted copolymer to combine at least two incompatible thermoplastic polymers, however, at least one of which is compatible with the polyamide oligomer and the other with the alpha-monoolefin polymer or copolymer.

The copolymer according to the invention is a grafted copolymer represented by the formula AaMbXcPci, in which: - AaMb is a backbone (co) polymer, - XcPd denotes polymers grafted to a backbone (co) polymer, and is preferably a propylene derivative group, - M is selected from the group consisting of: - groups derived from an alpha-famonoolefin having 2 to 8 carbon atoms, preferably ethylene derivatives, and - more than one. groups derived from an alpha-monoolefin as described above which can be simply mixed together or copolymerized randomly or sequentially, preferably one of the alpha-mono-olefins being ethylene, - the groups A and M forming said (co) polymer backbone are randomly copolymerized or sequentially or simply mixed, - X is a group derived from a monomer selected from the group consisting of from compounds of the following formulas:

Rl 0 R1 R2 R3 H O

\ / \ / \ // I N ,. / l / / \ \ \ ^ C_cf R3O 0 OH C_ / \ Λ \ R2 0 R4 H 0 in which - R1 and R2 may be hydrogen or a straight or branched alkyl chain containing up to 8 carbon atoms, and at least one of them is hydrogen, - R3 is hydrogen or a straight or branched alkyl group having up to 10 carbon atoms, and - R 4 is a straight or branched alkenyl group having up to 12 carbon atoms, - P is derived from a polyamide oligomer: 0 r ° -r R 5

Il II /

H2N - (CH2) f - C - NH - (CH2) f -C - g - N

J \

Re - 96618 4 wherein: - f is a number from 3 to 11, - g is a number from 5 to 80, preferably from 15 to 55, - R 5 is hydrogen or a straight or branched alkyl group which may contain up to 20 carbon atoms, and - Rg is a straight or branched alkyl or alkenyl group containing up to 20 carbon atoms, a saturated or unsaturated cycloaliphatic group, an aromatic group or a combination of the foregoing, and - a, b, c and d are numbers defined as: - a is 0- 5000, preferably 350-2000, - the sum a + b is 350-45000, preferably 500-10000, - c is selected such that the weight ratio of the monomer X grafted to the backbone (co) polymer to the copolymer grafted with X is 500 ppm to 10% , preferably less than 2%, more preferably 5000 ppm to 1.5%, and - d is not zero, it is less than or equal to c and preferably at least equal to 0.3 c.

The frame (co) polymer:

Aa Mb where a, b, A and M are the same as defined above, tar-. any copolymer obtained by combining groups A and B derived from randomly or sequentially polymerized monomers, or optionally any mixture of polymers obtained by separately polymerizing the monomers from which A and M are derived, is tested.

This copolymerization or this mixture can be carried out by known methods.

Examples include copolymerization of propylene and alpha-olefin in the presence of a Ziegler catalyst, or coordination.

Il '1H: t liltt I I -i Μ I' 1 5 96618

The grafted copolymer of the invention can be obtained by radically grafting a monomer that can react with an amine function into the backbone (co) polymer and then adding the oligomer to the pre-grafted (co) polymer.

Monomer X is radically grafted onto the backbone (co) polymer and has a function that can react with the amine function.

The most preferred monomers X are citraconic anhydride, fumaric acid, mesaconic acid, 3-allyl succinic anhydride and especially maleic anhydride.

Grafting of monomer X to the backbone (co) polymer using a radical method is performed in the presence of a radical initiator such as dicumyl peroxide, benzyl peroxide or 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane.

Usually the initiator is used 2.5. 10 "4 to 4. 10" 2 relative to the weight of the (co) polymer.

The radical grafting of the monomer X into the backbone (co) polymer can be carried out in the molten state or as a solution in a backbone (co) polymer solvent. Suitable solvents include toluene, xylene and chlorobenzene.

Grafting in solution is especially recommended when the grafting percentage is desired to be greater than 1.5% (weight ratio of monomer X grafted to the backbone (co) polymer to the backbone (co) polymer grafted with X).

The backbone (co) polymer, monomer X and the radical polymerization initiator are placed in a (co) polymer solvent. The composition is heated to a temperature at which the thermal decomposition of the radical initiator begins and the grafting reaction takes place. In general, the reaction takes 0.5 to 10 times, preferably 1 to 4 times, the half-life of the radical initiator at the reaction temperature.

j 96618

In general, the decomposition temperature of the radical initiator is 90-200 ° C, preferably 110-140 ° C.

Radical grafting of monomer X in the molten state to the backbone (co) polymer is particularly suitable when the degree of grafting is desired to be between 500 ppm and 1.5%.

In radical grafting in the molten state, the backbone (co) polymer and the selected amounts of monomer X and the radical initiator are mixed, for example in an extruder. The mixture is heated to a selected temperature, generally 170-250 ° C, preferably 180-200 ° C.

The molten material is allowed to remain in the extruder for generally 15 seconds to 3 minutes, preferably 40 to 80 seconds.

The degree of grafting of monomer X to the backbone (co) polymer can be measured by administering anhydride functions using infrared spectrophotometry.

The monoaminated polyamide oligomer P is then added to the grafted (co) polymer: ϊ r n / * =

H2N (CH2) f C - NH- (CH2) c C g-N

; * L J \ e wherein f, g, R 5 and R 6 are as defined above.

This monoaminated polyamide oligomer can be obtained by polycondensation of an amino acid:

HaN- (CH2) f- or polyaddition using lactation: 1 · aa-i 14u i i 44a,.

7 96618 f (CHa) 1 \

M ~ T

H 0 wherein f and a are as defined above, present a monofunctional polymerization limiting agent; R »

^ NH

Re ^ where Rb and Rs are as defined above.

The most preferred amino acid monomers, i.e. lactams, for the preparation of the monoaminated oligomer according to the invention are caprolactam, 11-aminoundecanoic acid or dodecalactam.

The most preferred monofunctional polymerization limiters are laurylamine and oleylamine.

The above-mentioned polycondensation takes place by generally known methods, for example at 200-300 ° C, in a vacuum or in an inert atmosphere with stirring of the reaction mixture.

The average length of the oligomer chain is determined by the initial molar ratio between the polycondensable monomer, the lactam, and the monofunctional polymerization limiter.

When calculating the average chain length, one chain-limiting molecule per oligomer chain is generally calculated.

The addition of the monoaminated polyamide oligomer to the X-grafted backbone (co) polymer is accomplished by reaction with one amine function of the oligomer and at least one anhydride or acid function of the grafted (co) polymer. This creates amide or imide bonds.

«8 96618

The addition of oligomer P to the grafted backbone (co) polymer is preferably carried out in the molten state. Thus, the oligomer and the (co) polymer can be mixed in the extruder at 230-250 ° C. The molten material remains in the extruder for an average of 15 seconds to 5 minutes, preferably 1 to 3 minutes.

The addition of oligomer to the grafted backbone (co) polymer is evaluated using selective extraction of free polyamide oligomers, i.e., those that have not reacted to form the final grafted copolymer.

The grafted alpha-monoolefin copolymers according to the invention have the following advantages over other third polymers found in the literature: The degree of grafting of the polyamide oligomer into the grafted (co) polymer can be controlled and thus the structure of the grafted copolymer can also be better controlled.

- The average Mole alkyl mass of the polyamide monoaminated oligomer can be adjusted and controlled. The average molecular weight of a polyamide oligomer is therefore a decisive factor for the function and efficiency of the copolymer according to the invention as a substance which makes incompatible polymer blends compatible.

.. - The grafted copolymers according to the invention do not have chain ends which react in the polycondensation, when the components of the mixture are mixed with the graft copolymer according to the invention, said chain ends do not react uncontrollably. 1> 1 IM t Milli I I I M.

In particular, using the grafted copolymer according to the invention, at least two incompatible thermoplastic polymers can be homogeneously combined, one of which, however, is compatible with the polyamide oligomer forming said copolymer and the other with the backbone (co) polymer.

96618 9

The grafted copolymer can be incorporated into thermoplastic resins in the usual manner in a molten state in a mixing device. The copolymer may be added in an amount of 0.1 to 30, preferably 5 to 15% by weight relative to the weight of the mixture of thermoplastic resins.

Examples of polymers, thermoplastic resins which are compatible with the polyamide dioligomers coming into the graft copolymer are in particular: - aliphatic polyamides, such as polyamide-6, -11 or -12, semi-aromatic polyamides, in particular those defined in FR patent 1,588,130, 2,324,672 and 2,575,756, EP patents 53876 and JP patents 60,217,237 and 59,015. 447 - sequential polyetheresteramides, i.e. polyether segment amides and products described in U.S. Patents 4,332,920 and 4,331,786 - hydrolysed vinyl acetate - ethylene copolymers - resins containing phenol groups similar to polyparavinylphenols.

The term polymer also refers to copolymers in which the content of compatible groups contained in the copolymer is sufficient to maintain compatibility.

Polymers can also include mixtures of polymers (or copolymers) with various additives (impact modifiers, mineral fillers, glass fibers, pigments, etc.).

Examples of thermoplastic polymers compatible with the backbone (co) polymer are, in particular, polypropylene, polyethylene and ethylene / propylene copolymers.

By using the compatible agent according to the invention, improved mixtures can be realized, for example: polyamide-6 - polypropylene polyamide-6 - polyethylene polyamide-6 - ethylene / propylene copolymer polyamide-11 or -12 - polypropylene or polyethylene or ethylene / propylene copolymer ethylene copolymer or polyethylene or hydrolysed vinyl ethylene / propylene copolymer acetate polyparavinylphenol - polypropylene or polyethylene or ethylene / propylene copolymer polyether segment - polypropylene or polyethylene or amide ethylene / propylene copolymer semi-aromatic - polypropylene or polyethylene or polyamide ethylene

The compatibility provided by the grafted copolymer according to the invention can be determined by electron microscopy, as well as by the mechanical properties of products made from blends of incompatible thermoplastic polymers.

When the composition of a mixture of thermoplastic polymers not grafted according to the invention is examined by electron microscopy, large polymer nodules are generally seen in a matrix consisting of another polymer, the bond between the matrix and the nodules being generally almost non-existent. When the grafted copolymer according to the invention is added, the size of the nodules is considerably reduced. Phases: The binding is strong, it is seen in the fact that the matrix covers the nodules. Under these conditions, a plastic alloy is formed, which, as in metallurgy, does not mean mere alloys.

The mechanical properties of such thermoplastic mixtures are at least the same as those of the components, weighted by the volume fraction of each component, in some cases better <· a »1 1: 111 1,1» - «I.

11 96618 than with the two ingredients, I saw, for example, in terms of impact toughness.

In contrast to the blends of the invention, the mechanical properties of the same blends of the same incompatible polymers without the graft copolymer of the invention are generally closest to the component with inferior properties.

The following examples illustrate the invention without, however, limiting it in any way.

Example 1 A. Preparation of Graft Copolymer

A mixture of 100 parts by weight of ethylene / propylene 11a sequenced copolymer (12% by weight of ethylene, melt index = 5, melting point = 163 ° C) and 1.6 parts of maleic anhydride and 1.7 parts by weight are placed in a Werner-type extruder. 2,5-Dimethyl-2,5- (ditertiobutylperoxy) -hexane dissolved in one part of chlorobenzene.

The composition is heated to 200 ° C, the screw rotation speed is 100 rpm.

The mixture is subjected to an anti-volatility treatment before passing into the die to remove chlorobenzene and unreacted maleic anhydride.

A test batch of grafted polymer is taken from the mouth of the die, which is dissolved in xylene and blended in acetone to purify the batch.

Using infrared spectrophotometry to determine the anhydride functions of the dosing beam, the amount of grafted anhydride is determined to be 1.16% by weight.

Gel permeability chromatography determines that the average molecular weight is 32,000.

12 96618 B. Preparation of polyamide oligomer (P)

31 kg of caprolactam, 0.91 kg of laurylamine and 3.5 liters of water are placed in a stainless steel 100 liter reactor vessel.

The reactor is kept closed at 250 ° C for 2 hours after being purged with nitrogen and stirred at 35 rpm. The atmospheric pressure in the reactor is reduced for 1 hour.

After purging the reactor with nitrogen for 15 minutes, the oligomer is poured into water, dried, washed with water at 80 ° C and then dried for 16 hours at 80 ° C in an oven vacuum.

A polyamide oligomer with an average molecular weight of 5700 is determined by potentiometric dosage measurement of terminal amine functions.

C. Preparation of Graft Copolymer

In a Werner ZSK30 type extruder, a mixture containing 59.8 parts by weight of the grafted backbone copolymer described in A and 40.2 parts of the oligomer described in B is mixed. Heat to 240 ° C.

The mixture remains in the extruder for an average of about 3 minutes.

A test batch is taken from the mouth of the nozzle and placed in a Kumagawa-type traction device.

Selectively separate with formic acid polyamide oligomers that have not reacted with the anhydride functions of the maleic acid-treated copolymer. By this method, the percentage of condensation of the polyamide oligomer in the grafted (co) polymer is 65%.

The grafted copolymer thus obtained can be represented by: il · 114 III H - 13 96618 Αβ63 Ml 36 Xa, 78 P2 f 45 where A is a group derived from propylene M is a group derived from ethylene X is a group derived from maleic anhydride and P is a caprolactam oligomer Mn = 5700

Example 2

A mixture of 33 parts by weight of polypropylene, 57 parts by weight of polyamide-6 and 10 parts by weight of the maleic acid-treated backbone copolymer prepared in Example 1 (A) is introduced into the Werner-type extruder by continuous feed (test batch 1).

The temperature of the substance in the tube is 255-270 ° C. The screw rotation speed is 150 rpm and the material flow rate is 20 kg / h.

Under similar conditions, a mixture of 33 parts by weight of polypropylene, 57 parts of polyamide-6 and 10 parts of the grafted copolymer prepared in Example 1 (C) is extruded (test batch 2).

Prepare, similarly under similar conditions, a reference mixture containing (by weight) 36.7 parts of polypropylene and 63.3 parts of polyamide-6 (experimental batch 3).

The polypropylene used in Experiments 1, 2 and 3 is a propylene homopolymer having a melt index of 3 and a melting point of 166 ° C, and the polyamide-6 used is a caprolactam homopolymer having a melting point of 218 ° C.

: Test batches 1, 2 and 3 are sprayed into 100 x 100 x 3 mm sheets from which test pieces ISO 1/2 according to NFT 51034 are cut.

Some of the test pieces are cut in the direction of the spray flow (test pieces A), while some are cut perpendicular to the direction of the spray flow (test pieces B).

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Test pieces according to the standard defined by the Institut Francais du Caoutchouc (test pieces C) are also cast.

Test pieces A, B and C are evaluated by tensile stretching according to NFT 51034.

The test pieces of test batch 3 (comparative) are very brittle: they break at 5-6% elongation. The composition is thus coarse and inhomogeneous and shows poor adhesion between the two components of the comparative test batch 3.

The test pieces A, B and C of test batch 1 are different: test pieces A and B are weaker than test piece C. This is due to inhomogeneity and orientation sensitivity.

All three specimen types in Test Lot 2 are homogeneous and highly resistant to stretching. Thus, they are not sensitive to transformation or orientation.

Experimental batches 1 and 2 were also subjected to an impact test by the Char-py method at room temperature after being sprayed with rods.

The failure rate of test batch 1 is 60. None of the rods tested in test batch 2 failed.

* ·

Example 3

A mixture of 100 parts by weight of ethylene / propylene sequenced copolymer (12% by weight of ethylene, melt index = 5, melting point = 163 ° C) of 1.5 parts of maleic anhydride and 1.7 parts of 2.5- dimethyl-2,5-di (tert-butylperoxy) hexane dissolved in one part of chlorobenzene.

The pressing and cleaning conditions are the same as in Example 1, point A.

il; MtiiUR lii a *:: 15 96618

Infrared spectrophotometric dosing of the anhydride functions of the test batch of the grafted copolymer shows that 1.02% of the anhydride is grafted.

The average molecular weight number Mn measured using gel permeation chromatography is 19700.

B. Prepare the monoaminated polyamide oligomer under the same conditions as in Example 1B, the weight ratio of caprolactam to laurylamine is 15.7. The average molecular weight number Mn of the oligomer is 2800.

C. In a Werner ZSK30 type extruder, a mixture of 77 parts by weight of a grafted copolymer as previously described and 23 parts by weight of a polyamide oligomer as previously described is mixed in the molten state under the same conditions as in Example 1 (C).

After extrusion, the condensation of the oligomer in the grafted backbone copolymer is measured under the same conditions as in Example 1, point C: 65.8%.

The grafted copolymer thus obtained can be represented by: A «0» Μθ4 Χϊ, ΟΪ P1, 35: * where A is a group derived from propylene «M is a group derived from ethylene X is a group derived from maleic anhydride and P is a group derived from a caprolactam oligomer Mn = 2800

Example 4: A mixture of 50 parts by weight of polypropylene and 50 parts by weight of hydrolyzed ethyl vinyl alcohol copolymer (EVOH) is heated to 220 ° C and mixed in a Brabender-type plastography vessel for 30 minutes, stirring speed 50 rpm (test batch 4).

16 96618

A mixture of 49 parts by weight of polypropylene, 49 parts by weight of EVOH and 2 parts by weight of a maleic acid-treated ethylene / propylene backbone copolymer as described in Example 3 (A) (experimental batch 5) is mixed under the same conditions as above.

Under the same conditions, a mixture of 49 parts by weight of polypropylene, 49 parts by weight of EVOH and 2 parts by weight of the graft copolymer prepared in Example 3 (C) is also prepared (test batch 6).

The polypropylene used in experimental batches 4, 5 and 6 has a melt index of 5, a melting point of 166 ° C and an ethylene content of 38 mol% of EVOH used.

Experimental lots 4, 5, and 6 are examined with a scanning electron microscope (magnification 2500-fold).

Looking at experimental batch 4, it can be seen that its two polymers are poorly compatible: EVOH nodules, diameter 11-27 μπι, are clearly visible in the polypropylene matrix.

In addition, it can be seen that the adhesion between the EVOH nodules and the polypropylene matrix is very poor.

Looking at experimental batch 5, the structure is found to be quite rough: the diameter of the EVOH nodules is 5.7-7 μπι, the adhesion to the polypropylene matrix is poor.

«I

Looking at the test batch 6, the composition turns out to be very fine, the nodules have a diameter of 1.7-2.8 μm and the adhesion to the polypropylene matrix is very good.

Example 5

A mixture of 50 parts by weight of polypropylene and 50 parts by weight of polyparavinylphenol (PPVP) is heated to 200 ° C and stirred in a Brabender-type plastography vessel for 15 minutes, stirring speed 50 rpm (test batch 7).

Il t »4« III I I I Λ: 17 96618

A mixture of 49 parts by weight of propylene, 49 parts of PPVP and 2 parts by weight of a maleic acid-treated ethylene / propylene copolymer as described in Example 3 (A) is mixed under the same conditions as above (experimental batch 8).

Under the same conditions, a mixture of 49 parts by weight of polypropylene, 49 parts of PPVP and 2 parts by weight of the graft copolymer prepared in Example 3 (C) is also prepared (test batch 9).

The polypropylene used in Experiments 7, 8 and 9 has a melt index of 5, a melting point of 116 ° C and the PPVP used is an oligomer having an average molecular weight of 4000 and a melting point of 160-200 ° C.

Experimental lots 7, 8 and 9 are examined with a scanning electron microscope (magnification 2500 times).

Examining the experimental batch 7, it can be seen that the structure is rather rough, continuous phases or ovoid PPVP nodules can be seen in places, with a mean diameter of 30 μιη dispersed in the PP matrix. The complete incompatibility of the polymers is indicated by detectable fractures.

Looking at experimental batch 8, it is observed that PPVP is better dispersed in polypropylene. Dispersed in a PP matrix -: * these PPVP nodules have an average diameter of about 10 μπι. The adhesion between the phases is not better than in the experimental batch 7.

Looking at experimental batch 9, the composition turns out to be very fine, the PPVP nodules * dispersed in the PP matrix * have a mean diameter of 2 μπι and the adhesion to the matrix is significantly better than in experimental batches 7 and 8.

Example 6

A mixture of 50 parts by weight of polypropylene and 50 parts by weight of polyetheresteramide is heated to 220 ° C and mixed in a Brabender-type plastography vessel for 15 minutes, stirring speed 50 rpm (test batch 10).

A mixture of 49 parts by weight of propylene, 49 parts by weight of polyetheresteramide and 2 parts by weight of a maleic acid-treated ethylene / propylene backbone copolymer as described in Example 3 (A) (experimental batch 11).

Under the same conditions, a mixture of 49 parts by weight of polypropylene, 49 parts by weight of polyetheresteramide and 2 parts by weight of the grafted copolymer prepared in Example 3 (C) is also prepared (test batch 12).

The polypropylene used in experiments 10, 11 and 12 has a melt index of 5, a melting point of 166 ° C and the polyetheresteramide is obtained by copolycondensation of dicarboxylated polyamide-12-α, ω-sequences, Mn = 600 and dihydroxylated polytetramethylene glycol-α, 2000.

Experimental lots 10, 11 and 12 are examined with a scanning electron microscope (magnification 2500 times).

Looking at the test batch 10, it can be seen that it is particularly rough, marked by a three-dimensional network.

Considering the test batch 11, there is no noticeable improvement in adhesion or reduction of the three-dimensional network compared to the test batch 10.

Looking at experimental batch 12, the composition turns out to be less coarse than in experimental batches 10 and 11. The structure of experimental batch 12 is no longer characterized by a three-dimensional network, but by the dispersion of polyetheresteramide modules in the polypropylene matrix.

Example 7

A mixture of 50 parts by weight of polypropylene and 50 parts by weight of a semi-aromatic amorphous polyamide is heated to 220 ° C and mixed by Brabender-type plastography. lii t 1: 1 ii Uisi 19 96618 tia for 30 minutes, stirring speed 50 rpm (test batch 13).

A mixture of 49 parts by weight of propylene, 49 parts of a semi-aromatic amorphous polyamide and 2 parts of a maleic acid-treated ethylene / propylene backbone copolymer as described in Example 3 (A) (experimental batch 14) is mixed under the same conditions as above.

Under the same conditions, a mixture of 49 parts by weight of polypropylene, 49 parts by weight of a semi-aromatic amorphous polyamide and 2 parts by weight of a grafted copolymer prepared according to Example 3 (C) (test batch 15) is also prepared.

The polypropylene used in experiments 13, 14 and 15 has a melt index of 5, a melting point of 166 ° C and the semi-aromatic amorphous polyamide used is based on terephthalic acid and trimethyl (2,2,4- and 2,4,4-) diamino-1,6 -heksaaniin.

Experimental lots 13, 14 and 15 are examined with a scanning electron microscope (magnification 2500 times).

Considering Experimental Batch 13, a polymer incompatibility is observed: nodules of semi-aromatic amorphous polyamide with a diameter of 30 μm can be distinguished in the polypropylene matrix, and adhesion between the nodules of semi-aromatic amorphous .. polyamide and the PP matrix is # non-existent.

The experimental batch 14 is quite rough in structure: the average diameter of the semi-aromatic amorphous polyamide nodules dispersed in the polypropylene matrix is 5 μm, and the adhesion between the nodules and the matrix is mediocre.

Looking at the test batch 15, the composition turns out to be quite fine: the nodules of the semi-aromatic amorphous polyamide have an average diameter of 3.3 μm and good adhesion between them and the PP matrix.

20 96618

Example 8

A mixture of 50 parts by weight of polypropylene and 50 parts by weight of a semi-aromatic amorphous polyamide is heated to 280 DEG C. and stirred in a Haake-type plastography vessel for 20 minutes, stirring speed 50 rpm (test batch 16).

Under the same conditions as above, a mixture of 49 parts by weight of polypropylene, 49 parts by weight of a semi-aromatic amorphous polyamide and 2 parts by weight of a maleic acid-treated ethylene / propylene copolymer as described in Example 3 (A) (experimental batch 17) is mixed.

Under the same conditions, a mixture of 49 parts by weight of polypropylene, 49 parts by weight of a semi-aromatic amorphous polyamide and 2 parts by weight of a grafted copolymer prepared according to Example 3 (C) (test batch 18) is also prepared.

The polypropylene used in Experiments 16, 17 and 18 has a melt index of 5, a melting point of 166 ° C and the semi-aromatic amorphous polyamide used is based on isophthalic acid and 4,4'-diamine-3,3'-dimethyldicyclohexylmethane and lauryl lactam.

Experimental lots 16, 17 and 18 are examined with a scanning electron microscope (magnification 2500 times).

Examination of test batch 16 reveals an incompatibility of the polymers: nodules of a semi-aromatic amorphous polyamide with a diameter of 20 μπι can be distinguished in the polypropylene matrix. In addition, the adhesion between the nodules of the semi-aromatic amorphous polyamide and the PP matrix is non-existent.

Test batch 17 has a rather rough structure: the average diameter of the semi-aromatic amorphous polyamide modules dispersed in the polypropylene matrix is 10 μπι. Adhesion between nodules and matrix is mediocre.

1 tft-r il h I! ·> «T: 21 96618

Looking at the experimental batch 18, the composition turns out to be quite fine: the nodules of the semi-aromatic amorphous polyamide have an average diameter of 3.5 μιη and good adhesion between them and the polypropylene matrix.

Example 9

A mixture of 26 parts by weight of polypropylene, 67 parts by weight of polyamide-6 and 7 parts by weight of the maleic acid-treated ethylene / propylene copolymer prepared in Example 3 (A) is introduced into a Werner-type extruder by continuous feed (test batch 19).

The temperature of the substance in the tube is 260-290 ° C. The screw rotation speed is 150 rpm and the material flow rate is 20 kg / h.

Under similar conditions, a mixture of 26 parts by weight of polypropylene, 67 parts of polyamide-6 and 7 parts of the grafted copolymer prepared in Example 3 (C) is extruded (test batch 20).

A reference mixture containing 32.7% by weight of polypropylene and 67.3 parts of polyamide-6 (test batch 21) is also prepared under similar conditions.

The polypropylene used in Experiments 19, 20 and 21 is a polypropylene homopolymer having a melt index of 12 and a melting point of 166 ° C, the polyamide-6 used is a caprolactam homopolymer having a melting point of 218 ° C.

Test batches 19, 20 and 21 are injected into rods measuring 127 x 12.7 x 6.4 • mm and their ISO impact resistance IZOD is evaluated at 23 ° C and 40 ° C. Results in the following table.

22 96618

Test lot Impact resistance IZOD

23 ° C to 40 ° C

19 6 9 20 10,5 13 21 2 3 4 «I IS-t N» I I 1 «I; i

Claims (10)

1. Branched copolymer, characterized in that it is illustrated by Form In AaMbXcPci, in which: - AaMb is a strain (co) polymer, - XcP (ε refers to branched polymers of the strain (co) polymer in which - A is a group derived from alpha mono-olefin containing 2-8 carbon atoms and is preferably a propene derivative group, - M is selected from the group consisting of: - groups derived from alpha monolefin containing 2-8 carbon atoms and 96618 - groups derived from several alpha mono-olefins of the kind described above single or copolymerized randomly or sequentially, wherein one of the alpha monolefins is preferably ethylene, wherein - the groups A and M, which form said strain (co) polymer, are copolymerized statistically or sequentially or are mixed simply, - X is a group derived from a monomer selected from compounds of the following formulas: R1 9 R1 r2 r3 H o Xc_ / O \ / \ s \ / 7 \ c \ 'C_C RoO 0 OH C_C / \ A \ R2 0 R4 H X0 which: - R 1 and R 2 may be hydrogen or a straight or branched alkyl chain containing not more than 8 carbon atoms, and at least one of them is hydrogen, - R 3 is hydrogen or a straight or branched alkyl group containing not more than 10 carbon atoms, and - R 4 is a straight or branched alkenyl group containing not more than 12 carbon atoms, - P is derived from the polyamide oligomer: 0 Γ 0 Ί r5 II II / H2N - (CH2) f - C - NH (CH2) f -C - σ _ NTJ \ r6 • wherein: in Iti MH M4: in 96618 - f is a tai between 3-11, - g is a tai between 5-80, preferably between 15-55, - R5 is hydrogen or a straight or branched alkyl group which may contain at most Is a straight or branched alkyl or alkenyl group containing not more than 20 carbon atoms, a saturated or unsaturated cycloaliphatic group, an aromatic group or a combination of these, and - a, b, c and d is tai as defined: - a is 0-5000, preferably 350-2000, - the sum a + b is 350-45000, preferably preferably 500-10000, - c is selected so that the weight ratio of monomer X branched in the parent (co) polymer to the copolymer branched with X is 500 ppm - 10%, preferably 5000 ppm - 2%, and - d is not zero, it is less or the same as c and preferably at least as large as 0.3 c. Process for the preparation of a branched copolymer according to claim 1, characterized in that: - a radical branching in the strain (co) polymer is carried out by means of a monomer which reacts with an amine function and - a branched copolymer is added in advance with a polyamide oligomer. Process according to Claim 2, characterized in that the monomer which reacts with an amine function is selected from the group of citraconic anhydride, fumaric acid, mesaconic acid, 3-allyl succinic anhydride and preferably maleic anhydride. Method according to claim 2 or 3, characterized in that the polyamide oligomer O r O η R5 II II / H2N - (CH2) f _ C__NH _ (CH2) f _C__a _ N r T3 \ Re 96618 in which f, g, R5 and Rg are the same as defined above, obtained by polycondensing the amino acid: O H 2 N - (CH 2) f - OH or by means of polyaddition from lactam: A CH 2) N * C J II II H 0 in which f and a are the same as defined above, in the presence of monofunctional restriction agent for polymerization: R5 'SVSsNH ./ in which R5 and Rg are the same as defined above. 5. A process according to claim 4, characterized in that the monomer used for polysutide oligomer synthesis is selected in the group consisting of caprolactam, 11-aminone decanoic acid and dodecalactam. Process according to Claim 4 or 5, characterized in that among the advantageous monofunctional limiting agents for polymerization are laurylamine and oleylamine. A blend formed from at least two incompatible thermoplastic polymers made compatible by the addition of the compound of claim 1. «>: HtlMH I H1I: / <96618 A mixture according to claim 7, characterized in that it contains branched polymer according to claim 1 and any of the following thermoplastic polymer pairs: aliphatic (co) polyamide - propylene and / or ethylene (co) polymer, semi-aromatic (co) polymer - propylene and / or ethylene (co) polymer, segment amide polyether - propylene and / or ethylene (co) polymer, vinylphenol polymer - propylene and / or ethylene (co) polymer, hydrolyzed (ethylene vinyl acetate) copolymer - propylene and / or ethylene (co) polymer. A mixture according to claim 8, selected from the following pairs: polyamide-6 - polypropylene polyamide-6 - polyethylene polyamide-6 - ethylene / propylene copolymer polyamide-11 or -12 - polypropylene or polyethylene or ethylene / propylene copolymer ethylene copolymer-hydrolyzed - polypropylene or polyethylene or vinyl acetate ethylene / propylene copolymer segment polyetheramide - polypropylene or polyethylene or ethylene / propylene copolymer 4 4 polyparavinylphenol - polypropylene or polyethylene or ethylene / propylene copolymer semi-aromatic - polypropylene or polyethylene or polyamide ethylene / propylene copolymer 10. A composition according to claims 7-9, characterized in that it contains 0.1-30% by weight, preferably 5-15% by weight, of branched copolymer according to claim 1 in relation to the weight of the thermoplastic resin mixture.