EP2630194A1

EP2630194A1 - Composition including a mixture of a thermoplastic condensation polymer and a supramolecular polymer, and manufacturing method

Info

Publication number: EP2630194A1
Application number: EP11787713.4A
Authority: EP
Inventors: Yves Deyrail; Anthony Dufrenne; Samuel Devisme; Nicolas Dufaure; Jean-Luc Couturier; Bruno Van Hemelryck; Manuel Hidalgo
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2010-10-21
Filing date: 2011-10-18
Publication date: 2013-08-28
Also published as: FR2966465B1; WO2012052673A1; CN103168079A; JP2013540193A; FR2966465A1; US20130261255A1

Abstract

The present invention relates to a composition, including: (i) 0.1 to 49 parts by weight of at least one thermoplastic condensation polymer; and (ii) 51 to 99.9 parts by weight of at least one supramolecular polymer obtainable by means of the reaction of at least one at least trifunctional compound (A) having first and second functions, wherein: at least one compound (B) has at least one reactive group capable of reacting with the first functions of (A), as well as at least one associative group; and at least one at least bifunctional group (C), the functions of which are capable of reacting with the second functions of the compound (A) so as to form ester, thioester, and amide bridges.

Description

Composition comprising a mixture of thermoplastic polycondensate and supramolecular polymer, and method of manufacture.

The present invention relates to compositions based on thermoplastic polycondensates and supramolecular polymers, their method of manufacture and their use in many fields of industry where injection molding is used.

Injection molding is a technique for manufacturing parts in large or very large series.

Injection-molded components are found in many fields such as automobiles, household appliances, computer equipment, and furniture. In these fields of industry, the dimensions of the molds may vary from a few millimeters to several meters, for parts of automobile bodies, or garden tables, for example.

Molds, installed on a press, are usually made of two shells that are strongly pressed against each other at the time of molding and spaced apart to allow the ejection of the molded part. In addition to these shells, the mold may comprise one or more cores intended to form the hollow parts of the part and punches for reserving openings in its walls. It often happens that we place in the mold "inserts" that will eventually be included in the room: it is most often threaded elements that locally overcome the insufficient resistance of the material constituting the body of the room. Unlike other processes where the mold is lost, the injection molding makes it possible to reuse the molds which is very advantageous. Injection molding also makes it possible to obtain very precise, well-finished parts that very often do not require any subsequent machining. Injection molding can therefore be used in particular for the manufacture of parts constituting visible parts of household appliances, televisions, and automotive dashboards, for example.

Materials used in injection molding processes must have a low shrinkage rate. This property is particularly important when materials are injected into molds with cores. In fact, the parts with a strong shrinkage contract during cooling and sometimes very strongly surround the cores around which they were cast, which causes a difficult extraction of the workpiece.

So-called supramolecular polymers are materials comprising compounds associated by non-covalent bonds, such as hydrogen, ionic and / or hydrophobic bonds. An advantage of these materials is that these physical bonds are reversible, especially under the influence of temperature or by the action of a selective solvent.

Some of them also have properties of elastomers. Unlike conventional elastomers, these materials have the advantage of being able to be fluidized above a certain temperature, which facilitates their implementation, in particular the good filling of the molds, as well as their recycling. Some of these supramolecular polymers are, moreover, constituted of molecules linked in networks exclusively by reversible physical bonds. Despite the relatively modest physical bonding forces of the molecules of such a supra-molecular network, these materials are, like conventional or conventional elastomers, capable of exhibiting dimensional stability over very long times and recovering their initial shape after large deformations. . They can be used to manufacture, for example, seals, thermal or acoustic insulators, tires, cables, sheaths, shoe soles, packaging, patches (cosmetics or dermo-pharmaceuticals), dressings, elastic clamps, vacuum tubes, or tubes and hoses for transporting fluids.

Supramolecular materials have already been described by the Applicant. In particular, the

Applicant has already described supramolecular materials having the behavior of elastomers.

An elastomeric material supramolecular self ^¬ healing is, furthermore, disclosed in WO 2006/087475. It comprises molecules containing at least three associative functional groups, such as imidazolidone groups, capable of forming several physical bonds and which can be obtained by reacting urea on the product of the reaction of a polyamine with triacids. The materials obtained according to the teachings of the documents WO 03/059964 and WO 2006/087475 contain triacids covalently linked via amide functions to intermediate junctions and / or termini consisting of the reaction product of the polyamine. with urea and who therefore contain numerous associative groups, that is to say containing NH and C = 0 functions capable of associating with each other by hydrogen bonds. Specifically, the publication of P. CORDIER, L. LEIBLER, F. TOURNILHAC and C. SOULIE-ZIAKOVIC in Nature, 451, 977 (2008) mentions that a polymer synthesized according to the procedure described in WO 2006/087475 has amidoethylimidazolidone terminations and di (amidoethyl) urea and diamidotetraethyl triurea junctions. It is understood that because of the synthesis process of these materials, the chemical nature of the aforementioned junctions and terminations are interdependent, in that it is not possible to vary the nature of the amidoethylimidazolidone termination without affecting the of the two junctions.

The document entitled "Versatile One-Pot Synthesis of Supramolecular Plastics, and Self-Healing Rubbers" by Damien MONTARNAL, François TOURNILHAC, Manuel HIDALGO, Jean-Luc COUTURIER, and Ludwik LEIBLER appeared in "Journal of the American Chemical Society," 131 ( 23): 7966; June 17, 2009 discloses an alternative method for obtaining supramolecular polymers, including those having elastomeric properties of the type of those published by P. CORDIER et al. This method makes it possible, among other things, to break the interdependence of the chemical natures between the junctions and the terminations of the supramolecular network. It thus becomes possible to control the chemical nature of the terminations independently of that of the junctions.

These new self-healing polymers have huge benefits like those of being easily processables, to be issued mainly from renewable raw materials, to be self-repairing.

However, it is difficult to implement supramolecular polymers in industrial processes using injection. In particular, the supramolecular polymers can be transported in screws of injection presses, then cast in a mold, but once out of the mold they exhibit a strong shrinkage, ie a decrease in the dimensions of the part that may occur immediately after, several hours after, even several days after the injection. In quantitative terms, the shrinkage can be characterized from at least one of the dimensions of the part such as its length. It is thus said, in one piece that it has undergone a shrinkage of x% with respect to the initial length of said piece measured at the time of injection into the mold, when its length has decreased by X% relative to the initial length of said piece measured at the time of injection into the mold.

Since injection is a method of transformation widely used in industry for many applications, there is a need for new compositions having the advantages of supramolecular polymers described above, while being injectable.

The Applicant has now found a way to improve the properties of these new supramolecular polymers by developing a composition comprising these polymers in combination with specific thermoplastic polycondensates, among which mention may be made of polyamides. Such a composition may comprise fillers, plasticizers and other additives. More specifically, the subject of the present invention is a composition comprising:

(i) from 0.1 to 49 parts by weight of at least one thermoplastic polycondensate; and

(ii) from 51 to 99.9 parts by weight of at least one supramolecular polymer obtainable by the reaction of at least one at least trifunctional compound (A) bearing first and second functions with:

at least one compound (B) bearing, on the one hand, at least one reactive group capable of reacting with the first functions of (A) and, on the other hand, at least one associative group; and

- At least one at least bifunctional compound (C) whose functions are likely to react with the second functions of the compound (A) to form ester, thioester, amide bridges.

The inventors have shown that the compositions which are the subject of the invention, comprising a thermoplastic polycondensate and a supramolecular polymer exhibit excellent property compromises. In particular, the compositions which are the subject of the invention make it possible to significantly improve the capacity of the supramolecular polymers to be used in industrial processes comprising a mold injection step while overcoming their main defect already mentioned above in know their important withdrawal.

In addition, the self-healing properties of the self-healing supramolecular polymers can be preserved in these compositions.

Thus, compositions according to the invention have both self-repairing properties but also a significantly reduced shrinkage rate. compared to that of supramolecular polymers used alone.

The inventors have shown in Example 4 that these compositions exhibit a shrinkage rate of 20% or less while retaining the properties of supramolecular polymers such as self-healing, whereas compositions which do not comprise polyamide-containing thermoplastic polycondensates exhibit a high degree of shrinkage. shrinkage greater than about 25%,

Surprisingly, the inventors have also shown that only thermoplastic polycondensates can maintain self-repair properties while having a significantly reduced shrinkage rate. Thus, certain thermoplastic polymers, not according to the invention does not provide an acceptable withdrawal rate (SBS), others have a very negative influence to the ability of self healing ^¬ (see in particular in Example 4, the compositions comprising Lotryl 24MA07 and Evatane 3345 PV)

As a preamble, it will be noted that the expression "included between" must be interpreted, in the present description, as including the boundaries cited.

Polycondensates

By polycondensate is meant in the sense of the present invention a thermoplastic polymer or copolymer obtained by a step polymerization reaction, often called polycondensation. Staged or polycondensation polymerization is characterized by a reaction mechanism leading to the relatively slow progressive growth of the molecular weight chains according to the conversion rate of the monomers; obtaining high molecular weights is possible only at high conversions. Staged polymerization or polycondensation is a polymerization involving reaction between functions of the monomer or oligomer molecules. Moreover, although this is not always the case, it is common that in the stepwise polymerization (or by polycondensation), there is elimination of a by-product (small molecule) such as water, ammonia, etc. at each reaction step. In contrast to the stepwise polymerization or polycondensation, the addition polymerization or chain polymerization very rapidly generates, that is to say conversions to weak monomers, high molecular weight polymer chains. In the addition or chain polymerization, the monomers do not react with each other; rather, they tend to be added rapidly to active centers (initiator or growing polymer molecules carrying the propagation pattern, in most cases an ion or a free radical).

By way of example, the polycondensate is a polymer comprising a polyamide, polyester, polyether, polyethersester, polyurethane or polyurea block.

Advantageously, the polycondensate according to the invention comprises at least one polyester block. Advantageously, said polyester comprises a copolymer.

Advantageously, said polycondensate according to the invention comprising at least one polyester block is obtained from at least one of the following monomeric molecules: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,10-decanediol, acid reduced dimerized fat to obtain the corresponding diol, 2.5- furanedicarboxylic acid, succinic acid, azelaic acid, sebacic acid, dodecanedioic acid, myristic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and / or dimerized fatty acids.

Advantageously, said polycondensate according to the invention is a polyetherester.

Advantageously, the polycondensate comprises at least one polyurethane block. Advantageously, said polyurethane comprises a copolymer. Advantageously, said polycondensate comprising at least one polyurethane block is manufactured from at least one polyol, for example chosen from the following polyols: polyols derived from starch; erythritol; sorbitol; maltitol; mannitol; polyols derived from sugars, sucrose; isomalt; xylitol; polyols derived from maize, soya, cotton, rapeseed, sunflower or groundnuts; glycerol; propylene glycol ; ethylene glycol; biodiesel production reaction co-products; polyethylene glycol

(PEG), poly (1,2-propylene glycol) (PPG), poly (1,3-propylene glycol) (PO 3 G), polytetramethylene glycol

(PTMG).

Advantageously, said polycondensate comprising at least one polyurethane block is a polyetherurethane.

Advantageously, said polycondensate comprising at least one polyether block further comprises polyethers such as PTMG, PEG, PPG, PO 3 G, and poly (3-methyltetrahydrofuran.

Advantageously, said polycondensate is a polymer comprising polyamide blocks. The polyamide sequences may be present on the main chain of the polycondensate, or if it has one, on the side chain or chains. In the rest of the description, the polyamide sequences are also called block or polyamide pattern. In particular, the polycondensate may be chosen from homopolyamides and copolyamides.

Three types of polyamide units may constitute or be part of the polycondensate used in the invention.

According to a first type, the polyamide units come from the condensation of at least one carboxylic or anhydride diacid (aliphatic, cycloaliphatic or aromatic), in particular those having from 4 to 36 carbon atoms, preferably those having from 6 to 18 carbon atoms. carbon and at least one diamine (aliphatic, cycloaliphatic or aromatic) chosen in particular from those having from 2 to 20 carbon atoms, preferably those having from 6 to 15 carbon atoms.

As examples of aliphatic diacids, mention may be made of butanedioic, adipic, suberic, azelaic, sebacic, dodecanedicarboxylic, myristic, tetradecanedicarboxylic, hexadecanedicarboxylic, octadecanedicarboxylic and dimerized fatty acids.

As examples of cycloaliphatic diacids, mention may be made of 1,4-cyclohexyldicarboxylic acid.

As examples of aromatic diacids, mention may be made of terephthalic (T) and isophthalic (I) acids.

By way of examples of diacids, one can also cite, as a function of the number x of carbons of the molecule (Cx):

C4: succinic acid from glucose, for example;

C6: adipic acid from glucose for example;

C7: heptanedioic acid from castor oil; - C9: azelaic acid from oleic acid (ozonolysis) for example;

- CIO: sebacic acid from castor oil for example;

- Cil: undecanedioic acid from castor oil;

C12: dodecanedioic acid from biofermentation of dodecanoic acid = lauric acid (rich oil: palm kernel oil and coconut oil) for example;

- C13: brassylic acid from erucic acid (ozonolysis) found in rapeseed, for example;

- C14: tetradecanedioic acid by biofermentation of myristic acid (rich oil: palm kernel oil and coconut) for example;

C16: hexadecanedioic acid by biofermentation of palmitic acid (mainly palm oil) for example;

- C18: octadecanedioic acid obtained by biofermentation of stearic acid (a little in all vegetable oils but predominant in animal fats) for example;

C20: eicosanedioic acid obtained by biofermentation of arachidic acid (predominant in rapeseed oil) for example;

C22: docosanedioic acid obtained by metathesis of undecylenic acid (castor oil) for example

- C36: Fatty acid dimer derived mainly from oleic and linoleic acids.

By way of examples of anhydrides, mention may be made of succinic, maleic, glutaric and terephthalic anhydrides. Examples of aliphatic diamines that may be mentioned include tetramethylene diamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, 14 amino tetradecylamine, 16 amino hexadecylamine, 18 amino octadecyl amine, trimethylhexamethylene diamine.

By way of example of cycloaliphatic diamines, mention may be made of the isomers of bis (4-aminocyclohexyl) methane (BACM or PACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM or MACM), and 2 -2-bis (3-methyl-4-aminocyclohexyl) propane (BMACP),

Isophoronediamine (IPDA), 2,6-bis (aminomethyl) norbornane (BAMN) and piperazine (Pip).

By way of examples of diamines, mention may also be made, as a function of the number x of carbons of the molecule (Cx):

C4: butanediamine obtained by amination of succinic acid, by biofermentation;

C5: pentamethylene diamine (from lysine). Advantageously, the polycondensate according to the invention comprises at least one PA block based on PA 4.4, PA 4.6, PA 4.9, PA 4.10, PA 4.12, PA 4.14, PA 4.16, PA 4.18, PA 4.36, PA 6.4, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.13, PA 6.14, PA 6.16, PA 6.18, PA 6.36, PA 9.4, PA 9.6, PA 9.10, PA 9.12, PA 9.14, PA 9.18, PA 9.36, PA 10.4, PA

10.6, PA 10.9, PA 10.10, PA 10.12, PA 10.13, PA 10.14, PA 10.16, PA 10.18, PA 10.36, PA 10., PA BMACM.4, PA BMACM.6, PA BMACM.9, PA BMACM.10, PA BMACM.12, PA BMACM.14, PA BMACM16, PA BMACM18, PA BMACM36, PA PACM.4, PA PACM.6, PA PACM.9, PA PACM.10, PA PACM.12, PA

PACM.14, PA PACM.16, PA PACM.18, PA PACM.36, PA Pip.4, PA Pip.6, PA Pip.9, PA Pip.10, PA Pip.12, PA Pip.14, PA Pip.16, PA Pip.18 and / or PA Pip.36, and mixtures thereof. According to a second type, the polyamide units result from the condensation of one or more alpha omega-aminocarboxylic acids and / or one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 to 12 carbon atoms or a diamine.

By way of examples of lactams, mention may be made of caprolactam, oenantholactam and lauryllactam.

As examples of alpha omega amino carboxylic acid, there may be mentioned aminocaproic acid, amino-7-heptanoic acid, amino-11-undecanoic acid and amino-12-dodecanoic acid.

Advantageously, the polyamide blocks of the second type are made of polyamide 11, polyamide 12 or polyamide 6.

According to a third type, the polyamide blocks result from the condensation of at least one monomer of the first type with at least one monomer of the second type. In other words, the polyamide blocks result from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), with at least one diamine and one dicarboxylic acid.

In this case, the units or blocks PA are prepared by polycondensation:

aliphatic, cycloaliphatic or aromatic diamine (s) having X carbon atoms;

one or more dicarboxylic acids having Y carbon atoms; and

{Z} comonomer (s) chosen from lactams and alpha-omega aminocarboxylic acids having Z carbon atoms; in the presence of a chain limiter chosen from dicarboxylic or diamine diacids or an excess of diacid or diamine used as a structural unit;

Advantageously, the dicarboxylic acid having Y carbon atoms, which is introduced in excess with respect to the stoichiometry of the diamine or diamines, is used as chain limiter.

According to another variant (in the case of copolymers, that is to say copolyamides), the polyamide units result from the condensation of at least two different alpha omega aminocarboxylic acids or of at least two different lactams having from 6 to 12 carbon atoms or of a lactam and an aminocarboxylic acid having not the same number of carbon atoms in the possible presence of a chain limiter.

As examples of polyamide units of the third type, mention may be made of those formed by the following polyamides (copolyamides):

PA 6 / 6.6 wherein 6 is caprolactam and 6.6 is a monomer resulting from the condensation of hexamethylenediamine with adipic acid.

PA 6.6 / Pip.10 / 12 wherein 6.6 denotes a monomer resulting from the condensation of hexamethylenediamine with adipic acid. Pip.10 denotes a monomer resulting from the condensation of piperazine with sebacic acid. 12 denotes lauryllactam.

PA 6.6 / 6.10 / 11/12 wherein 6.6 denotes a monomer resulting from the condensation of hexamethylenediamine with adipic acid. 6.10 denotes a monomer resulting from the condensation of hexamethylenediamine with sebacic acid. 11 designates amino-11-undecanoic acid. 12 denotes lauryllactam.

By way of examples, mention may also be made of PA 10.10 / 11, PA 6.10 / 11, PA10.12 / 11, PA 10.10 / 11/12, PA 6.10 / 10.10 / 11, PA 6.10 / 6.12 / 11, PA 6.10 /6.12/10.10.

Advantageously, the polycondensate used in the invention is a block copolymer in the form of polyether amide block, PEBA abbreviated.

The PEBAs therefore include any thermoplastic elastomer comprising at least one polyether block, the latter preferably being at least partially derived from THF, such as polytetramethylene glycol or PTMG, and at least one PA block (homopolyamide or copolyamide) as defined above. above.

Thus, preferably, the PEBA is a block copolymer comprising:

from 1 to 99% of at least one flexible polyether block derived at least partially from tetrahydrofuran, and

from 1 to 99% of at least one rigid block which is a polyamide block

Advantageously, said block copolymer comprising at least one flexible polyether block comprises at least one block based on polytetramethylene glycol (PTMG).

Advantageously, said PEBA is based on PA11-PTMG, PA10.10-PTMG, PA10.12-PTMG, PA10.14-PTMG, PA6.10-PTMG, PA6.12-PTMG, and / or PA6.18-PTMG preferably based on PAU-PTMG.

Advantageously, said block copolymer comprising at least one polyether block further comprises polyethers other than PTMG, such as PEG, PPG, PO 3 G, poly (3-methyltetrahydrofuran). Advantageously, the copolymer according to the invention is a block-segmented copolymer comprising three different types of blocks (hereafter called triblock), said triblock being chosen from copolyetheresteramides, copolyetheramideurethanes, copolyetheresterurethanes, in which (s) ):

the mass percentage of flexible polyether block is greater than 20%

the polyamide rigid block mass percentage is greater than 10%;

on the total mass of triblock.

Methods for synthesizing such a copolymer are known to those skilled in the art.

Advantageously, the PEBA copolymers comprise PA blocks comprising at least one of the following polyamides PA 11, PA 10.10, PA 10.12, PA 10.14, PA 10.18, PA 6.10, PA 6.12, PA 6.14, PA 6.18 as majority components (mass percentage). greater than 50% of the total mass of PA) and PE blocks comprising PTMG as the major component (mass percentage greater than 50% of the total mass of PE), and possibly P03G as other components of PE PE PE blocks. 'invention.

Particularly preferred block copolymers of the invention are PA11-PTMG, PA10.10-PTMG,

PA10.12-PTMG, PA10.14-PTMG, PA6.10-PTMG, PA6.12-PTMG, PA6.18-PTMG, and / or PA11-P03G

Advantageously, the polycondensate used in the invention is a polyamide block graft copolymer obtained by reacting an amine-terminated polyamide with the remains of an unsaturated monomer X fixed by grafting or copolymerization on a polyolefin trunk. This monomer X can be, for example, an unsaturated epoxide or an unsaturated carboxylic acid anhydride. The unsaturated carboxylic acid anhydride may be chosen for example from maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methylenecyclohex-4-ene-1,2-dicarboxylic anhydrides, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid and x-methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic acid. Maleic anhydride is advantageously used. It would not be outside the scope of the invention to replace all or part of the anhydride with an unsaturated carboxylic acid such as, for example, (meth) acrylic acid.

With regard to the polyolefin trunk, a polyolefin is defined as a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene. By way of example, mention may be made of:

Homopolymers and copolymers of polyethylene, in particular LDPE, HDPE, LLDPE (linear low density polyethylene or linear low density polyethylene), VLDPE (very low density polyethylene or very low density polyethylene) and metallocene polyethylene.

homopolymers or copolymers of propylene.

ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).

- Styrene / ethylene-butene / styrene block copolymers (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS).

copolymers of ethylene with at least one product chosen from salts or esters of acids unsaturated carboxylic compounds such as alkyl (meth) acrylate (for example methyl acrylate), or vinyl esters of saturated carboxylic acids such as vinyl acetate, the comonomer proportion being up to 40% by weight.

Advantageously, the polyolefin trunks to which the X residues are attached are X-grafted polyethylenes or copolymers of ethylene and X which are obtained, for example, by radical polymerization.

As regards the polyethylenes on which X is grafted, polyethylene is understood to mean homo- or copolymers.

As comonomers, we can mention:

alpha-olefins, advantageously those having from 3 to 30 carbon atoms. Examples have been cited above. These alpha-olefins may be used alone or in a mixture of two or more than two,

esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, alkyls having up to 24 carbon atoms, examples of alkyl acrylate or methacrylate are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate,

vinyl esters of saturated carboxylic acids such as, for example, acetate or vinyl propionate.

dienes such as, for example, 1,4-hexadiene. the polyethylene may comprise several of the foregoing comonomers.

Advantageously, the polyethylene which may be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density may be between 0.86 and 0.98 g / cm3. The MFI (viscosity number at 190 ° C., 2.16 kg) is advantageously between 20 and 1000 g / 10 min.

By way of example of polyethylenes, mention may be made of:

- low density polyethylene (LDPE)

- high density polyethylene (HDPE)

- linear low density polyethylene (LLDPE)

- very low density polyethylene (VLDPE)

polyethylene obtained by metallocene catalysis, EPR (ethylene-propylene rubber) elastomers

EPDM elastomers (ethylene-propylene diene)

- polyethylene blends with an EPR or

EPDM

ethylene-alkyl (meth) acrylate copolymers may contain up to 60% by weight of (meth) acrylate and preferably 2 to 40%.

Grafting is an operation known per se.

With regard to copolymers of ethylene and X, that is to say those in which X is not grafted, these are copolymers of ethylene, X and optionally another monomer which can be used. selected from the comonomers mentioned above for copolymers of ethylene for grafting.

The copolymers ethylene-maleic anhydride and ethylene-alkyl (meth) acrylate-maleic anhydride are advantageously used. These copolymers comprise from 0.2 to 10% by weight of maleic anhydride, from 0 to 40% and preferably from 5 to 40% by weight of alkyl (meth) acrylate. Their MFI is between 5 and 100 (190 ° C - 2.16 kg). The alkyl (meth) acrylates have already been described more high. The melting temperature is between 80 and 120 ° C.

Advantageously there is on average at least two moles of X per chain attached to the polyolefin trunk and preferably from 2 to 5. Those skilled in the art can easily determine the number of these X moles by FTIR analysis. is maleic anhydride and Mw = 95,000 g / mol of the polyolefin was found to correspond to an anhydride proportion of at least 1.5% by weight of the entire X-containing polyolefin trunk and preferably 2.5 to 4%. These mass-associated values of the amine terminated polyamides determine the proportion of polyamide and trunk in the polyamide block graft copolymer.

As regards the polyamide with amine end, polyamide is understood to mean the products mentioned above in a).

Supramolecular Polymers

The reagents used for the manufacture of the supramolecular polymers used in the composition according to the invention will now be described in more detail.

As indicated above, the supramolecular polymer is capable of being obtained by the reaction of at least one at least trifunctional compound (A) carrying first and second functions with:

at least one at least bifunctional compound (C) whose functions are capable of reacting with the second functions of the compound (A) to form ester or thioester bridges, or amide.

By "associative groups" is meant groups capable of associating with each other by hydrogen bonds, advantageously by 1 to 6 hydrogen bonds. Examples of usable associative groups are imidazolidinyl, triazolyl, triazinyl, bis-ureyl, ureido-pyrimidyl. It is preferred that the average number of terminal associative groups per molecule of the supramolecular polymer is at least 3. It is advantageously at most 6. These are covalently linked to the molecule. By "covalently" is meant that the associative groups are connected to the terminal functions of the molecule either via a direct bond or, preferably, via a chain, especially alkylene.

By "reactive groups" or "functions" is meant chemical functions capable of reacting with other chemical functions to form covalent bonds, leading in particular to the formation of ester, thioester, amide, urea or urethane bridges and in particular ester and amide bridges. A "bifunctional" compound refers to a compound having two identical or different reactive functions. An "at least trifunctional" compound refers to a compound carrying at least three identical or different reactive functions.

By "fragment" is meant in the sense of the invention a unit of a molecule located between two or three bridges as defined above. A "bifunctional" moiety is obtainable from a bifunctional compound and a "trifunctional" moiety is obtainable from a trifunctional compound. The molecules of the polymer supramolecular include at least bifunctional fragments, preferably bifunctional, and at least trifunctional fragments, advantageously trifunctional.

Preferably, the compound (A) represents more than 50% by weight relative to the total weight of the supramolecular polymer.

The compound (A) used in the first step of the synthesis process of the supramolecular polymer may in particular carry at least three identical or different functions chosen from acid, ester or acyl chloride functions. It advantageously comprises from 5 to 100, preferably from 12 to 100 and more preferably from 24 to 90 carbon atoms.

Compound (A) may, when reacted with compound (B) and / or compound (C), be in admixture with mono- and difunctional compounds, such as mono- and diacids, particularly mono- and dimers of fatty acids.

It is preferred to use according to the invention as compound (A) mixtures of dimers (oligomers of 2 identical or different monomers) and trimers of fatty acids of vegetable origin. The compound (A) may thus be a trimer of at least one of the following acids, undecylenic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, eicosenoic acid and docosenoic acid, which are commonly found in tall oil fatty acids, rapeseed, corn, sunflower, soybean, grapeseed, linseed, jojoba, eicosapentaenoic acid and docosahexaenoic acid found in fish oils. The compound (A) may be a mixture of fatty acid trimer and diacids chosen from a linear alkyl dicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid and azelaic acid. , sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, thapsic acid, octadecanedioic acid or branched acid such as 3,3- glutaric dimethyl.

Examples of fatty acid trimers which may be mentioned are the compounds of the following formulas which illustrate the cyclic trimers derived from fatty acids with 18 carbon atoms, given that the compounds available commercially are mixtures of steric isomers and isomers of position of these structures, possibly partially or totally hydrogenated.

H ₃ C- (CH ₂ ) 4-CH ₂ - () - CH ₂ - (CH ₂ ) 5 -CH ₂ -COOH H ₃ C- (CH ₂ ) 4 -CH ₂ - (VcH ₂ - (CH ₂ ) ₅ -CH ₂ -COOH - (CH ₂₎ ₃ -CH ₂ -CH = CH-CH ₂ CH ₂ - (CH ₂₎ ₅ -CH ₂ -COOH

C18 acid trimer

It is thus possible to use a mixture of fatty acid oligomers containing dimers, trimers and monomers of linear or cyclic Cis fatty acids, said mixture being predominant in dimers and trimers and containing a small percentage (usually less than 5% ) of monomers. Preferably, said mixture comprises: 0 to 40% by weight, preferably 0.1 to 5% by weight of the same or different fatty acid monomers,

0.1 to 99% by weight, preferably 18 to 85% by weight of identical or different fatty acid dimers, and

0.1 to 90% by weight, preferably 5 to 85% by weight, of identical or different fatty acid trimers.

Even more preferably, said mixture of molecules derived from fatty acids has an average molecular weight greater than 400 g / mol.

Examples of dimeric / trimeric mixtures of fatty acids (% by weight) are:

Croda's Pripol® 1017 [MH: Uniqema has become Croda], a mixture of 75-80% of dimers and 18-22% of trimers with on the order of 1-3% of monomeric fatty acids,

• Croda's Pripol® 1048, a mixture of 50/50% dimer / trimers,

• Pripol® 1013 from Croda, a mixture of 95-98% dimers and 2-4% trimers with 0.2 to 6 maximum fatty acid monomers,

• Croda Pripol® 1006, a blend of 92-98% dimers and up to 4% trimers with a maximum of 0.4% of monomeric fatty acids,

• Croda Pripol® 1040, a mixture of dimers and trimers of fatty acid with at least 75% trimers and less than 1% of fatty acid monomers,

• Arizona Chemicals Unidyme® 60, a blend of 33% dimers and 67% trimers with less than 1% monomeric fatty acids, • Unidyme® 40 from Arizona Chemicals, a blend of 65% dimers and 35% trimers with less than 1% monomeric fatty acids,

Arizona Chemical Unidyme® 14, a mixture of 94% of dimers and less than 5% of trimers and other higher oligomers with about 1% of monomeric fatty acids,

Empol® 1008 from Cognis, a mixture of 92% of dimers and 3% of higher oligomers, essentially trimers, with about 5% of monomeric fatty acids,

Empol® 1018 from Cognis, a mixture of 81% of dimers and 14% of higher oligomers, essentially of which trimers, with about 5% of monomeric fatty acids,

• Oleon's Radiacid® 0980, a mixture of dimers and trimers with at least 70% trimers.

• Radiacid® 0950 from Oleon, a mixture of 79-85% dimers and 13-19% fatty acid trimers with 1-3% monomeric fatty acids.

Pripol®, Unidyme®, Empol®, and Radiacid® products include Cis fatty acid monomers and oligomers of fatty acids corresponding to multiple amino acids.

Cl8 ·

According to one particular embodiment, the mixture of diacid and triacid carboxylic acid may be partially or completely replaced by a diacid (s) and triacid (s) derivative, this derivative being chosen from an acid salt, an acid ester and an acid chloride.

As an example of an ester, mention may be made of a methyl, ethyl or isopropyl ester of a fatty acid as defined above. A preferred fatty acid ester is a fatty acid methyl ester, and particularly a fatty acid dimer methyl ester or a mixture of fatty acid oligomers as defined above.

As an example of a fatty acid chloride, mention may be made of sebacoyl chloride.

For its part, the compound (B) carries at least one reactive group which may in particular be selected from primary or secondary amine groups or alcohol. Alternatively, the compound (B) can carry at least two such identical or different groups. It is preferred according to the invention that the compound (B) carries at least one primary amine function.

In the particular case where the reactive group of the compound (B) is capable of reacting with both the first and second functions of the compound (A), it is preferred that, in the first step of the process, the ratio of the number of the reactive groups from the compound (B) to the sum of the functions of the compound (A) ranges from 0.05 to 0.8 and preferably from 0.15 to 0.7.

The compound (B) can thus satisfy any one of the formulas B1) to (B5):

bl)

(B2)

(B3)

NOT

(B4)

(B5)

or :

R denotes a unit containing at least one reactive function,

R 'denotes a hydrogen atom,

R ", R1 and R2 denote any group,

A denotes an oxygen or sulfur atom or an -NH group, preferably an oxygen atom.

Preferred examples of compounds (B) are 2-aminoethylimidazolidone (UDETA), 1- (2 - [(2-aminoethyl) amino] ethyl) imidazolidone (UTETA), l- (2- {2- [2 -aminoethylamino] ethyl} amino) ethyl] imidazolidone

(UTEPA), N- (6-aminohexyl) -N '- (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea (UPy), 3-amino-1,2,4 triazole and 4-amino-1,2,4-triazole. UDETA is preferred for use in the present invention.

Some of these compounds can be obtained by reacting urea with a polyamine. For example, UDETA, UTETA and UTEPA may be respectively prepared by reacting urea with diethylene triamine (DETA), triethylene tetramine (TETA) and tetraethylene pentamine (TEPA). The reaction of the compound (B) with the compound (A) may for example be carried out at a temperature of between 20 and 200 ° C., preferably between 130 and 170 ° C., for a period ranging from 1 to 15 hours, for example from 3 to 9 h, advantageously with stirring and under an inert atmosphere.

This compound is then reacted with at least one bifunctional compound (C) in such a way that the functions of (C) react with the second functions, i.e. the remaining reactive functions, of the compound (A). ). It will be avoided in this step to be placed under catalytic conditions likely to lead to homopolymerization of the compound (C).

The compound (C) carries at least two functions, identical or different, chosen in particular from the epoxy, alcohol and amine functions.

The compound (C) can be a diepoxide. It can thus be chosen from: bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromo bisphenol A diglycidyl ether, or hydroquinone diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether , 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether bisphenol A polypropylene glycol diglycidyl ether, diglycidyl ester of terephthalic acid, epoxidized polyunsaturated fatty acids, and epoxidized limonene; and their mixtures. Alternatively, the compound (C) may be a polyepoxide containing at least three epoxide functions, chosen for example from: castor oil triglycidyl ether, 1,1,1-tris (hydroxymethyl) propane triglycidyl ether, trisphenol triglycidyl ether, glycerol tridlycidyl ether, glycerol propoxylate triglycidyl ether, glycerol ethoxylate triglycidyl ether, trimethylol propane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritolpolyglycidyl ether, poly (glycidyl acrylate), polyglycidyl methacrylate epoxidized polyunsaturated fatty acids, epoxidized vegetable oils, epoxidized fish oils and epoxidized limonene.

In another variant, the compound (C) may be a diol. In this case, the compound (C) can be chosen from: ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol,

Octanediol, nonanediol, decanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyesters with hydroxy ends, polybutadienes with hydroxy ends, polydimethylsiloxanes with hydroxy ends, polyisobutylenes with hydroxy ends, polybutadiene-co-acrylonitrile copolymers with hydroxy ends, diol dimers derived from fatty acids and mixtures thereof.

According to another possibility, the compound (C) may be a polyol containing at least three alcohol functions. Examples of such compounds include: sugars such as sorbitol, pentaerythritol, trimethylolpropane, as well as glycerol and its ethoxylated and propoxylated derivatives, castor oil, and diol dimers derived from fatty acids such as Pripol 2033 Croda.

Alternatively, the compound (C) may be a polyamine. The polyamine may be any compound carrying at least two amine functions, preferably primary amine, and preferably a compound of formula (I):

H ₂ N- (CHRi) _m - (CHR 2) n- [NH- (CH 2) x] y -NH- (CHR ₃ ) p- (CHR ₄ ) _q -NH ₂

(i) in which:

R1, R2, R3 and R4 independently denote a hydrogen atom or a C1-C6 alkyl group such as a methyl group,

m, n, p and q independently denote an integer ranging from 1 to 3,

x denotes an integer ranging from 1 to 6,

y denotes an integer ranging from 0 to 2.

In formula (I) above, at least one, and preferably all, of the following conditions are satisfied:

• R1, R2, R3 and R4 denote a hydrogen atom,

M + n is 2, 3 or 6, preferably 2,

P + q is 2, 3 or 6, preferably 2,

X denotes an integer ranging from 2 to 4,

• y is 0 or 1, preferably 0.

Preferred examples of polyamines of formula (I) are DETA (diethylene triamine), TETA (triethylene tetramine), TEPA (tetraethylene pentamine) and dihexylene triamine.

Alternatively, the polyamine may be a linear alkylene diamine containing 3 to 40 carbon atoms such cadaverine, putrescine, hexamethylenediamine or 1,12-diaminododecane or a cyclic alkylene diamine such as isophorone diamine.

The reaction of the polyamine (compound (C)) with the mixture of diacid / triacid carboxylic acid or their derivatives salt, ester or acid chloride used (compound (A)), may, for example, be carried out at a temperature between 20 and 200 ° C, preferably between 140 and 180 ° C, for a period ranging from 1 to 24 hours, for example from 6 to 8 hours, advantageously with stirring and under an inert atmosphere.

In a preferred embodiment, the compound (A) is a mixture of polycarboxylic acids or its salt, ester or acid chloride derivative reacted with at least one compound (C) which is a polyamine in a molar ratio. amino functions to the acid functions of the dicarboxylic acid of between 0.95 and 0.0.2 and preferably between 0.85 and 0.3.

The supramolecular polymer used in the compositions which are the subject of the invention is derived from the reaction of the compound (A) with the compound (B) and with the compound (C). These reactions can be carried out simultaneously or successively. In the case where these reactions are conducted successively, the reaction of the compound (A) with the compound (B) will preferably be carried out first but the reverse order is also possible. They may also be carried out either in separate reactors or in the same reactor, without it being necessary to provide a washing or purification step after the first of these reactions.

It is preferred that the supramolecular polymer also contains intermolecular hydrophobic bonds, advantageously due to interactions between alkyl groups carried by each of the trifunctional molecules described above. By "alkyl" is meant in the sense of the invention side groups (CnH2n + 1) and not alkylene chains (CnH2n), for example. In a particularly preferred manner, each of these molecules comprises C6-C24 alkyl chains, advantageously in greater number than said terminal associative groups. They may in particular be provided by the compounds (A), in particular when they are trimers of fatty acids.

In a particular embodiment, the supramolecular polymer defined above is reacted with urea.

Thus, preferably, the product resulting from the reaction of at least one compound (A) with at least one compound (B) and at least one compound (C) is reacted with urea to form junctions di (Amidoethyl) urea, diamidotetraethyl triurea and / or urea.

The reaction can for example be carried out at a temperature of 110 to 180 ° C, preferably 120 to 160 ° C by carrying out a temperature ramp, for a period ranging from 30 minutes to 24 hours, preferably for a period of 1 hour. at 6 hours, under an inert atmosphere and, advantageously, with stirring. Again, this reaction can be carried out in a reactor separate from that or those used in the preceding step or steps, or in the same reactor. It is therefore clear that all the steps of the process for obtaining the supramolecular polymer can be carried out in the same reactor, by successive addition of the reagents, which makes the process particularly simple and economical. The urea has the function, in this step, to create additional associative groups, for example according to the following reaction schemes:

N (R _A ) (H) - (CH ₂ -N (R _B ) (H) + NH ₂ -CO-NH ₂ ->

R _C -N (H) (R _D ) + NH ₂ -CO-NH ₂ ->

The compounds (A), (B) and (C) described above can be introduced, in the molten state, in the solid state powdery or non-pulverulent, or liquid, for example in solution or aqueous dispersion. However, it is preferred that they be introduced in the solid state powder or in the molten state to avoid the use of solvents that need to be subsequently removed.

When the process for obtaining the supramolecular polymer has a final reaction step with urea, therefore, in addition to the reactions of (A) with (B) and (C), it is preferred that the compound (C) is a polyamine as described above, and it is particularly preferred that the compound (C) is diethylene triamine or DETA.

The proportions of (A), (B) and (C) used in the method of synthesis of the supramolecular polymer, as well as their nature, and the choice of whether or not to carry out an additional reaction step with urea, determine the mechanical characteristics of said polymer. Thus, it is possible to obtain mechanical properties ranging from those of an elastomer to those of a plastomer. These parameters also determine the solubility properties of said polymer. Thus, it is possible that the supramolecular polymer is completely or partially soluble in polar solvents such as alcohols.

According to one embodiment of the invention, the average number of associative groups per molecule is at least 1.2, preferably at least 2 or even at least 2.2.

The supramolecular polymers used in the compositions which are the subject of the invention advantageously have elastomeric properties, such as that of rubber elasticity or hyperelasticity, that is to say the property of being able to undergo uniaxial deformation at its temperature of use, for example at ambient temperature, of at least 20 ~ 6, for example for 15 minutes, and to recover, once this stress is relaxed, most of its initial dimension, for example, with deformation remanent less than 5% of its original size.

These supramolecular polymers may, moreover, be capable of self-healing after cutting and, after contacting the edges of the cut, have still elastomeric properties enabling them to undergo, for example, tensile deformation of at least 20%, or even at least 100% before breaking and recover most of their initial dimensions once the stress is relaxed, with, for example, a remanent deformation less than 10% of their initial dimension. The supramolecular polymers defined above are materials in the form of soft solids, which it is necessary to extract from the reactor used for their synthesis. According to one preferred variant, the product can be extracted from the reactor in the liquid state and "finished" by a heat treatment in an oven, oven, heating strips or any other suitable equipment until it is converted into a soft solid. The supramolecular polymer may be cut or ground, in particular cold, for example in a hammer mill, ball mill, balls, grinders or knives and then washed, for example with water, and optionally shaped, in particular by hot pressing, calendering, thermoforming or any other method.

Preferably, the supramolecular polymer, optionally washed with water, is roughly cut into strips or pieces

additives

The composition which is the subject of the invention can be used as such or in single or multiphase mixtures with one or more compounds such as petroleum cuts, solvents, mineral and organic fillers, plasticizers, tackifying resins, process aid "or aids implementation, lubricants, anti ^¬ oxidants, anti-radiation additives (anti-UV), pigments and / or dyes.

In particular, additives that can be added to the composition according to the invention are in particular: lubricants, such as stearic acid and its esters, waxy esters, polyethylene waxes, paraffin or acrylic lubricants

- the dyes

inorganic or organic pigments, such as those described in the document "Plastics Additives and Modifiers Handbook, Section VIII, Dyes", J. Edenbaum, Ed., Van Nostrand, pages 884-954. By way of examples of pigments which can be used, mention may be made of carbon black, titanium dioxide, clay, metal particles or treated mica particles of the IRIODIN® brand marketed by MERCK.

plasticizers such as esters, such as phthalates or adipates, ethers, such as di-methyl iso-sorbide, amides

thermal stabilizers and / or UV stabilizers, such as stearates of tin, lead, zinc, cadmium, barium or sodium, including the Thermolite from ARKEMA,

co-stabilizers such as epoxidized natural oils,

antioxidants, for example phenolic, sulfuric or phosphitic,

fillers or reinforcements, in particular cellulosic fillers, talc, calcium carbonate, mica or wollastonite, glass or metal oxides or hydrates, carbon black, silica,

antistatic agents,

- fungicides and biocides,

blowing agents for the production of expanded parts, such as azodicarbonamides, azobisobutyronitrile, diethyl azobisobutyrate, flameproofing agents, including antimony trioxide, zinc borate and brominated or chlorinated phosphate esters,

solvents, and

- their mixtures.

Preferably, the composition which is the subject of the invention comprises at least one inorganic filler, such as silica, calcium carbonate, talc or titanium dioxide. The presence of a filler in the compositions which are the subject of the invention makes it possible to improve their capacity to be implemented in industrial processes comprising a step of injection into a mold by decreasing the shrinkage rate.

The composition that is the subject of the invention can in particular be used to manufacture in a general manner all the objects requiring an injection molding step. It can be for example, of:

- Toys: figurines, characters and dolls, assembly game pieces, models, rolling body and parts, floating, flying, decorative pieces, models and educational materials,

Amenity items: coat hangers, hangers, desk accessories, pen bodies and trimmings, key rings, suitcases, cosmetic wrappers, corner protectors for boxes and luggage, guitar picks, combs, garden tables, glasses ,

- Utility accessories: crates, crates, lockers, wastebaskets, toolboxes, tool handles, clips and collars, corner protectors, shoes, soles, stone guards, sport protection shells, helmet fittings, pedals bicycle, cups, bowls, buckets, containers, serving trays, ice scrapers, brushes, squeegees, stoppers, bottles. Pharmaceutical Accessories Joints, Septa, Diaphragms, Fittings, Valves, Flasks

Parts for 1 household appliances and electrical equipment: hulls, structures, equipment frames, gaskets and insulation (dust, water)

- Parts for electronics: shields for screens, telephones, keyboards, personal computers, mice, hulls and connector plugs, buttons, keypad keys, gromets (cable sealing rings), headphones, loudspeakers, ventilation grilles, extractors (hot air)

- Parts for electrical equipment: control panels, strips, junction boxes, plugs and regulating controls, electrical panels, racks of electrical components such as electromagnets, contactors, transformers, switches, isolators for electric fences, ducts cables, joints

- Automotive parts: interior door trim, dashboard hulls, center console, drawers, hatches and hatch hinges and boxes, storage boxes, sun visor mountings, mirror mountings, air vents and air-conditioning, propellers, grilles, parts used in de-oiling devices, air intakes, net fasteners, seat shelves, side and rear seat guards, fasteners, handles, commodos, lighting boxes, fuses, covers or compartments of electrical or electronic accessories in the engine compartment or passenger compartment (light, rain sensors), gromets (= cable trays), washers, valves, valves, fuel connections, power steering, air-conditioning oil, hoods and insulating plugs, clamps, lighting adjustment systems (headlights), clutch acoustic shutters. Wheels, rollers, gear, stops, pads. Mud guards for tractors, trailers and motorhomes. Fluid tanks

- Accessories for the building: clips for ducts, fixing or screwing bolts, clips for grilles, accessories for aluminum joinery, grommets and connection boxes

-Parts for industry: Rigid elements, pallet pallets, rollers

-Furniture parts: soft rolling belts for rollers, end caps, shutters, knobs, handles, skids, nut covers, cable passes, mounting inserts, wedges, wedges, stops, anatomical seat hulls, armrests.

The subject of the invention is also the use of the composition which is the subject of the invention for the abovementioned purposes.

Processes subject of the invention

The supramolecular polymers as defined above can be mixed and co-milled (ground together) with the selected polycondensates, or preferentially ground and mixed with the polycondensate (s). ) chosen (s) obtained in the form of granules or powder and optionally with fillers (such as silica) and other additives, so as to obtain a mixture in the form of granules or powder, containing the two types of polymers. Preferably, the grinding step is carried out at low temperature (cryo-grinding), that is to say, below room temperature (between -175 ° C and room temperature). According to another method of manufacture, the supramolecular polymer (s) is (are) mixed with the polycondensate (s) in any tool for implementing polymers, such as, for example, a mixer with cylinders (calender), an internal mixer, an extruder, a compression press ..., the mixture can be recovered, for example in the form of granules, plates, films, flaps, pieces, strips, rushes, balls, pancakes. The mixture thus obtained can then be cut or milled to obtain a physical form suitable for feeding an injection molding machine. The preferred physical forms are those of granules, powders, rushes or strips

According to a third method of manufacture, the polycondensate or polycondensates for mixing, alone or with other additives such as silica, may be introduced during any of the synthesis steps of the supramolecular polymers as described above. When this is the case, the preferred way is to introduce the polycondensate (s) into the synthesis reactor with the initial raw materials, i.e., even before the first chemical reaction step is complete. The synthesis of the supramolecular polymer is, in this case, in the presence of (or) polycondensate (s). The synthesis steps described above for the supramolecular polymers according to the invention are thus linked in the presence of the polycondensate and the final solid mixture is recovered in the form of plates, balls, balls, pieces, pancakes, etc. The mixture in this form can be subjected to grinding, homogenization, mixing with other additives, etc. provided that its final form is suitable for feeding a press injection. Thus, for example, the mixture resulting from the synthesis in the form of plates can be cut then cryocrushed to obtain a powder or granules for feeding conventional injection presses.

The subject of the invention is therefore a method for manufacturing a composition, said method comprising:

a step of reaction of at least one at least trifunctional compound (A) carrying first and second functions with at least one compound (B) bearing, on the one hand, at least one reactive group capable of reacting with the first functions of (A) and, on the other hand, at least one associative group;

a reaction step of at least one at least one bifunctional compound (C) whose functions are capable of reacting with the second functions of the compound (A) to form ester, thioester or amide bridges,

optionally a reaction step with urea, and

a step of adding a thermoplastic polycondensate as defined above, before, during or after any of the above steps.

Each reaction step mentioned above may be followed by a firing step at a temperature between 100 ° C and 250 ° C for a time ranging from 1 hour to 5 days at a pressure of between 300 mbar and 1 bar.

As indicated above, these reactions can be carried out simultaneously or successively. In the case where these reactions are carried out successively, the reaction of the compound (A) with the compound (B) will preferably be carried out first but the reverse order is also possible. They can also be carried out either in separate reactors or in the same reactor, or in reactors, then furnaces, autoclaves, or other equipment in which the reactions will lead to the physical transformation of the products into soft solids.

The invention will be better understood in the light of the following examples, given for purposes of illustration only, and which are not intended to limit the scope of the invention, defined by the appended claims.

EXAMPLES

Example 1 Preparation of a supramolecular polymer A

First stage:

Sub-step a: In a reactor with a diameter of 60 mm and a nominal volume of 500 ml equipped with a bottom valve, a thermal fluid temperature regulation, a mechanical stirrer, a dropping funnel, of a Dean-Stark and a gas inlet, preheated to 40 ° C., 76 g of Empol® 1016 [acid number 194, monomer level (4%), dimer (80%), trimer (16%)] and 6.7 g of purified UDETA (52 mmol) is a ratio [NH2] / [COOH] of 0.2. The bath temperature is raised to 150 ° C for 8 hours under a flow of nitrogen of 500 ml / minute and stirring of 280 rpm. During this step, the decrease of the δΝΗ2 signal (1505 cm-1), the increase of the signal vC = 0 (1648 cm-1) and the evolution of water vapor are observed by infrared spectroscopy. The judgment of the reaction is decided when the release of steam ceases (8 hours in the present example).

After this substep, the product of the reaction is stored at 50 ° C in the reactor.

- Sub-step b: We use the same assembly and the same conditions (nitrogen, stirring) as before. 10.7 g (104 mmol) of diethylene triamine (purity 98%) are placed in the dropping funnel.

The reactor body is heated to 160 ° C and the amine is slowly added dropwise intermittently over a total of 3 hours. The reaction is allowed to continue for another 4 hours at 160.degree. During this second step infrared spectroscopy shows the same type of evolution as before. The end of the release of water vapor, again noted, is used as a criterion for stopping the reaction.

After this step, the product is collected by the bottom valve (86 g are collected) and stored at room temperature. It is a highly adhesive viscoelastic liquid on many substrates including glass, metal and paper. The glass transition temperature measured by DSC (Differential Scanning Calorimetry) is -11 ° C. Rheological measurements made in plane parallel geometry with an imposed deformation of 1% provided, at the loading frequency of 1 rad / s, the following results:

T (° C) 25 35 50 70 90

G '(Pa) 33078 9812 1884 234 34

G "Pa) 49311 17568 4695 947 225 Second step:

In a wide reactor (diameter 100 mm) of nominal volume 500 ml equipped with a temperature control by heat transfer fluid, a mechanical stirrer and a gas inlet preheated to 80 ° C, is introduced 67 g of the above product and 6.1 g of urea. The stirring is set at 50 rpm and the temperature is raised to 135 ° C. After half an hour at this temperature and throughout the rest of the process, it is found using a pH indicator paper a consequent release of ammonia. Throughout this step, monitoring the reaction by infrared spectroscopy reveals the decrease of the urea signal vC = 0 1675 cm-1.

The temperature is maintained in total two hours at

135 ° C, then 1 hour at 140 ° C, then one hour at 145 ° C. At this stage, it is found that the initially turbid reaction mixture tends to become transparent. One gram of water is added and the solution becomes cloudy again. The mixture is heated to 150 ° C. for about 1 hour, during which time the evolution of ammonia is observed.

The stopping criterion is this time that the product is solid and clings to the axis of the agitator. As soon as this is the case, the product is collected on the stirring rod.

Formatting:

The pieces obtained are placed in a plastic bag and cold-milled with a hammer. Fragments of size 1 to 2 mm are washed by immersion in water for 72 hours. In the water, the washed fragments have tendency to stick to each other. The sample, previously drained, is redrawn into pieces of approximately 5 mm in size and placed in a mold made of a 1.6 mm thick brass plate pierced with a rectangular hole, placed between two sheets of paper. anti adhesive. After a first pressing at 120 ° C. for 10 minutes (applied pressure 10 MPa), the film obtained has thickness irregularities which are corrected by addition of material and repressing until a satisfactory appearance is obtained.

Example 2 Preparation of a supramolecular polymer B

In a Schott reactor of useful volume 4000 ml, placed on an electric balloon heater and equipped with a temperature probe, a mechanical stirring with a mobile anchor type poly tetrafluoroethylene, a dropping funnel, a condenser condenser, a Dean-Stark and a nitrogen inlet ending with a plunger rod poly tetra fluoroethylene, 1000 g of Pripol® 1040 Uniqema® (acid number 186), or 3 32 moles of carboxylic acid and 245 g of UDETA at 87.6% purity by weight (1.66 moles of amine). It is assumed that the impurities of the UDETA can provide the equivalent of 0.13 mol extra. The mixture is heated to 170 ° C to remove the condensation water. When the condensation water is removed and trapped in the Dean-stark, the medium is cooled to 80 ° C. At 80 ° C., 294 g of a DGEBA type epoxy resin, the Resolution® Epikote® 828 EL (epoxy level of 5.2 mol / kg), or 1.53 mol, are added and left under stirring at 80 ° C for 15 minutes. The product thus obtained is emptied from the reactor and may be stored without cooking in polypropylene jars. To obtain the final material, an oven baking at 120 ° C. for 24 hours can be carried out, preferably in a 5 mm thick layer in a non-adherent support, such as polytetrafluoroethylene-coated trays.

Example 3

Four compositions were used in Example 3. a) Pebax® 2533 supplied by ARKEMA, which is a polycondensate b) a supramolecular polymer (A) obtained according to Example 1 loaded with 10% by weight of amorphous silica Ultrasil® VN3 from Evonik and c) a mixture of supramolecular polymer A loaded with 10% by weight of silica, mixed with 10% by weight of Pebax® 2533, a mixture of 81% by weight of the supramolecular polymer (A) , 9% by weight of silica and 10% by weight of Pebax®, d) a mixture of supramolecular polymer A loaded with 10% by weight of silica, mixed with 20% by weight of Pebax® 2533, a mixture of 72% by weight of the supramolecular polymer (A), 8% by weight of silica and 20% by weight of Pebax®. The 4 compositions were mixed for 10 minutes in a DSM brand micro-extruder with a capacity of 15 cm ³ and provided with a recirculation channel, the material temperature is measured at 142-144 ° C. according to the tests, the screw speed is set at 100 RPM. The 3 compositions, recovered in the form of rods are then cut into granules and injected into a mold using a micro-injection injection DSM brand. The temperature of the piston is set at 160 ° C and that of the mold at 25 ° C. The injection cycle is: 5 bars for 1 second, raised to 10 bars in 3 seconds and hold at 10 bar for 5 seconds. The mold makes it possible to produce test pieces conforming to the ISO 527 1BA standard. Injection post-injection measurements are made by comparing the nominal length of the test specimen mold with the length of the injected product after an "equilibration" time of 3 days, during which the specimens are kept at room temperature.

Qualitative scarring measurements are performed by cutting a specimen in half, gluing it together and allowing it to heal for one hour to 24 hours; the healed test specimens are then pulled and their resistance compared

(qualitative estimate of the force required to recase them, qualitative or quantitative estimate of the deformation undergone at break) after an identical healing time for all the test pieces to be compared in the same series. A notation ranging from -

(no scarring) at +++ (very good scarring) is given to each specimen. The results of the removal and healing measures are shown in Table 1 below:

Table 1

Composition length removal scarring

Pebax® 2533 7.5 0% -

90% Polymer (A)

10% silica 5 33% +++

81% Polymer (A)

9% silica

10% Pebax® 2533 7 7% ++

72% Polymer (A)

8% silica

20% Pebax® 2533 7 7% + Example 4

Mixtures are made under the same conditions as in Example 3, using the following products:

- Pebax® 2533: polyether amide blocks marketed by Arkema.

Polymer B: supramolecular polymer of Example 2

Silica: amorphous silica sold under the name Ultrasil® VN3 by the company Evonik.

SBS: Styrene / Butadiene / Styrene Copolymer sold under the name Evoprene® by the company Alphagary

HX2656: polyamide sold under the name Platamid® by the company Arkema

Apolhya® graft copolymer with polyamide blocks sold under the name Apolhya® by the company Arkema

3345 PV: ethylene / vinyl acetate copolymer marketed under the name Evatane® by the company Arkema

24 MA 07: copolymer sold under the name Lotryl® by the company Arkema

the formulations and test results are shown in Table 2 below.

Table 2 Composition Length (cm) Removal Healing

Pebax® 2533 7.5 0% -

SBS 7.3 3% - Table 2 (continued) 0% Polymer B 5.3 29% +++ 0% silica

6.5% Polymer B

.5% silica 5.3 29% +++ 5% SBS

6.5% Polymer B 7 7% ++ 5% silica

5% HX2656

6.5% Polymer B

.5% silica

5% Apolhya® 6, 6 12% +++ 2% Polymer B 7.2 4% +++% silica

0% Apolhya®

6.5% Polymer B 6, 5 13%

.5% silica

5% 3345 HP

6.5% Polymer B 6, 4 15%

.5% silica

5% 24 MA 07

1% Polymer B 7.2 4% ++% silica

0% Pebax 2533

6.5% Polymer B 7.3% ++ 5% silica

5% Pebax 2533

2% Polymer B 7.3% +% silica

0% Pebax 2533 It is observed that some compositions do not allow to have an acceptable shrinkage (SBS), others have a lower shrinkage but more self-healing (Lotryl 24MA07 and Evatane 3345 PV), others on the other hand have a low removal and good self-healing (Platamid HX2656, Apolhya®, Pebax 2533). For Apolhya®, we see that 20% is preferable at 15%, and it is the best mixture (in terms of self-healing / shrinkage compromise)

EXAMPLE 5 Preparation of a composition comprising a supramolecular polymer B obtained in Example 2, silica, and a polycondensate which is a graft copolymer with polyamide blocks (Apolhya®) in powder form.

In a 3-liter Schott double-shell reactor equipped with an anchor-type mechanical stirrer, a Dean-Stark surmounted by a condenser, a dropping funnel and a temperature probe, 1000 g of Pripol

1040 (Croda, 3.32 mol of COOH function), 124 g of Ultrasil VN3 silica (Evonik) and 309 g of Apolhya® (Arkema) powder. The mixture is heated to 80 ° C. and 225 g of 95% UDETA (Arkema, 1.66 mol) are added via the dropping funnel and the mixture is then heated to 170 ° C. and allowed to react for 3 hours. We recover

36g of water in the Dean-Stark. The temperature of the reaction medium is allowed to return to 120 ° C., then 319 g of Epikote 828EL (Resolution, 1.66 mol of epoxide function) are added. The mixture is stirred for 15 minutes and then the reactor is drained via a 2 mm sieve. 1851 g of product are obtained, which is then baked in Teflon trays for 24 hours at 120 ° C. to give the injectable composition. The product resulting from cooking can be cut into strips or cryo-milled to obtain a powder or cryo-fractured to obtain granules. In these different forms, strips, granules, powder, the product can be fed into an injection press. In this example, the product resulting from the cooking was cryocrystalline. To do this, the product resulting from the cooking, in the form of plates 27 x 37 cm and 2-5 mm thick was cooled in a freezer at -15 ° C. The cold product was broken into pieces with the aid of a mallet and fed at the same time with a mass of at least equivalent dry ice, in a GERICKE brand crusher with a 5 mm gate. The crushed products were post-additivated with 1% Ultrasil silica

VN3 (Evonik) to avoid re-agglomeration and dry ice was allowed to evaporate when stored in a room at 21 ° C.

The granules thus obtained were fed into an injection press marketed by the company.

ARBURG under the name allrounder with a closing force of 35 tons. The diameter of the plasticizing screw is 30 mm for a length / diameter ratio of 15. The injection temperature used is 155 ° C. and the mold is regulated at 25 ° C. The part injected in less than one second (0.8s) is a dumbbell of the IFC type. The holding time is 18 s at a holding pressure of 50 bar hydraulic. The cooling time in the mold is 30s. Under these conditions, the final withdrawal of the coin is about 8%. Example 6 Preparation of a composition comprising a supramolecular polymer B obtained in Example 2, silica, and a polycondensate which is a graft copolymer with polyamide blocks (Apolhya®) in the form of microparticles

In a 3-liter Schott double-jacketed reactor equipped with an anchor-type mechanical stirrer, a Dean-Stark surmounted by a condenser, a dropping funnel and a temperature probe, 670 g of Pripol

1040 (Croda, 2.22 mol of COOH function), 83 g of Ultrasil VN3 silica (Evonik) and 207 g of Apolhya® (Arkema) in micro-granules. The mixture is heated to 80 ° C. and 151 g of 95% UDETA (Arkema, 1.11 mol) are added via the dropping funnel, and the mixture is heated to 170 ° C. and allowed to react for 3.5 hours.

We recover 22g of water in the Dean-Stark. The temperature of the reaction medium is allowed to return to 120 ° C., then 214 g of Epikote 828EL (Resolution, 1.11 mol of epoxide function) are added. The mixture is stirred for 15 minutes and the reactor is drained. 1281 g of product are obtained, which is then oven-baked in Teflon trays for 24 hours at 120 ° C. to give the injectible composition.

The product resulting from the cooking was cryo-fractured as indicated in Example 5.

The granules thus obtained were fed into an injection press marketed by ARBURG under the name Allrounder having a closing force of 35 tons. The diameter of the plasticizing screw is 30 mm for a ratio

Length / Diameter 15. The injection temperature used is 155 ° C and the mold is regulated at 20 ° C. The part injected in less than one second (0.8s) is a IFC dumbbell. The holding time is 10 s at a holding pressure of 35 bar hydraulic. The cooling time in the mold is 30s. Under these conditions, the final withdrawal of the coin is approximately 17%

Example 7 Preparation of a composition comprising a supramolecular polymer B obtained in Example 2, silica, and a polycondensate which is a PEBA

In a 3-liter Schott double-shell reactor equipped with an anchor-type mechanical stirrer, a Dean-Stark surmounted by a condenser, a dropping funnel and a temperature probe, 665 g of Pripol

1040 (Croda, 2.20 mol of COOH function), 82 g of Ultrasil VN3 silica (Evonik) and 205 g of Pebax 2533 (Arkema) in granules. The mixture is heated to 80 ° C. and 150 g of 95% UDETA (Arkema, 1.10 mol) are added via the dropping funnel, then the mixture is heated to 170 ° C. and allowed to react for 3 hours. We recover

26g of water in the Dean-Stark. The temperature of the reaction medium is allowed to return to 120 ° C., then 212 g of Epikote 828EL (Resolution, 1.10 mol of epoxide function) are added. The mixture is stirred for 15 minutes and the reactor is drained. 1257 g of product is obtained, which is then baked in Teflon trays for 24 hours at 120 ° C. to give the injectable composition.

The granules thus obtained were fed into an injection press marketed by ARBURG under the name Allrounder having a closing force of 35 tons. The diameter of the screw plasticization is 30 mm for a length / diameter ratio of 15. The injection temperature used is 175 ° C. and the mold is regulated at 30 ° C. The part injected in less than one second (0.8s) is a dumbbell of the IFC type. The holding time is 40 s at a holding pressure of 25 bar hydraulic. The cooling time in the mold is 30s. Under these conditions, the final withdrawal of the coin is about 7%

EXAMPLE 8 Grinding and Blending of Supramolecular Polymer B obtained in Example 2, of Silica, and of a Polycondensate Which Is a PEBA

300 g of supramolecular polymer obtained according to Example 2 were cryo-fractured as described in Example 5. The crushed product was sieved to isolate the 3-5 mm fraction, and additive of 6% silica Ultrasil VN3 (Evonik ). The granules thus obtained were mixed with granules of Apolhya® (ARKEMA) in dry mix 80% supramolecular polymer / 20% Apolhya®. This mixture was fed into an injection press marketed by ARBURG under the name allrounder having a closing force of 35 tons. The diameter of the plasticizing screw is 30 mm for a length / diameter ratio of 15. The injection temperature used is 160 ° C. and the mold is regulated at 30 ° C. The part injected in less than one second (0.8s) is a dumbbell of the IFC type. The holding time is 30 s at a holding pressure of 125 bar hydraulic. The cooling time in the mold is 30s. Under these conditions, the final removal of the coin is about 11%.

Claims

1. Composition comprising:

(ii) from 51 to 99.9 parts by weight of at least one supramolecular polymer obtainable by the reaction of at least one at least trifunctional compound

(A) carrying first and second functions with:

2. Composition according to claim 1, characterized in that the polycondensate is a polymer comprising a polyamide block, polyester, polyether, polyethersester, polyurethane, or polyurea.

3. Composition according to claim 1 or 2, characterized in that the polycondensate is chosen from homopolyamides and copolyamides.

4. Composition according to any one of claims 1 to 3, characterized in that the compound (A) is a trimer of at least one of the following acids: undecylenic acid, myristoleic acid, palmitoleic acid , oleic acid, linoleic acid, linolenic acid, ricinoleic acid, eicosenoic acid, docosenoic acid, eicosapentaenoic acid and docosahexaenoic acid.

5. Composition according to any one of claims 1 to 4, characterized in that the compound (A) is a mixture of fatty acid trimer and dicarboxylic acid selected from: a linear alkyl dicarboxylic acid including glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, thapsic acid, octadecanedioic or branched acid including 3,3-dimethyl glutaric acid.

6. Composition according to any one of claims 1 to 5, characterized in that the compound (B) corresponds to one of formulas (B1) to (B5):

(B5) where:

R denotes a unit containing at least one reactive function,

R 'denotes a hydrogen atom,

R ", Ri and R ₂ denote any group,

A denotes an oxygen or sulfur atom or an -NH group, preferably an oxygen atom.

7. Composition according to Claim 6, characterized in that the compound (B) is chosen from: 2-aminoethylimidazolidone, 1- (2- [(2-aminoethyl) amino] ethyl) imidazolidone, 1- (2- { 2 - [(2-aminoethylamino] ethyl] amino) ethyl] imidazolidone, N- (6-aminohexyl) - '- (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea, 3 -amino-1,2,4-triazole and 4-amino-1,2,4-triazole.

8. Composition according to any one of claims 1 to 7, characterized in that the compound (C) carries at least two functions, identical or different, selected from the epoxy functions, alcohol and amine.

9. Composition according to Claim 8, characterized in that the compound (C) corresponds to the formula (I): H ₂ N- (CHRi) _m - (CHR 2) n- [NH- (CH 2) x] y -NH- (CHR ₃ ) p- (CHR ₄ ) _q -NH ₂

(i) in which:

R 1, R ₂ , R ₃ and R ₄ independently denote a hydrogen atom or a C ₁ -C 6 alkyl group such as a methyl group,

m, n, p and q independently denote an integer ranging from 1 to 3,

x denotes an integer ranging from 1 to 6,

y denotes an integer ranging from 0 to 2.

10. Composition according to claim 9, characterized in that, in the formula (I), at least one, and preferably all, the conditions below are satisfied:

R 1, R ₂ , R ₃ and R ₄ denote a hydrogen atom,

M + n is equal to 2, 3 or 6, preferably 2,

P + q is equal to 2, 3 or 6, preferably 2,

X denotes an integer ranging from 2 to 4,

• y is 0 or 1, preferably 0.

11. Composition according to claim 10, characterized in that the compound (C) is chosen from: diethylene triamine, triethylene tetramine, tetraethylene pentamine, dihexylene triamine, cadaverine, putrescine, 1 hexamethylenediamine or 1 , 12-diaminododecane or a cyclic alkylene diamine such as isophorone diamine.

12. Composition according to any one of claims 1 to 11, characterized in that the polymer supramolecular as defined above in claims 1 to 11 is reacted with urea.

13. Composition according to any one of claims l to 12 characterized in that it further comprises a mineral filler.

The method of manufacturing a composition of any one of claims 1 to 13, said method comprising:

optionally a reaction step with urea, and

a step of adding a thermoplastic polycondensate as defined in claims 1 to 3 before, during, or after any of the above steps.