FR2872166A1 - COMPOSITION BASED ON PLASTICIZED VINYL POLYMER AND USE THEREOF - Google Patents

Abstract

The present invention relates to a polymer composition comprising at least one vinyl polymer (PVC) and at least one polylactone (poly-ε-caprolactone), in particular for the preparation of films or flexible coatings, obtained by the method comprising the following steps: the vinyl polymer and at least one lactone monomer are mixed in order to obtain a paste, b) a polymerization initiator of the lactone monomers is introduced into the dough obtained above, and the mixture is mixed, c) the dough obtained above is subjected to a higher temperature. at 80 ° C., for a duration of at least 30 seconds, to cause the in situ polymerization of the lactone monomers into polylactones. The invention also relates to a premix for the preparation of such a polymer composition, as well as to a process for coating the surface of a support, in particular textile.

Description

COMPOSITION BASED ON POLYMER

  PLASTICIZED VINYL AND USE THEREOF

  The field of the present invention is that of coated fabrics and flexible films, and more particularly polymer compositions useful for producing such coatings and flexible films. In particular, it is compositions based on vinyl polymers plasticized with a polymer of the family of polylactones.

  Coated fabrics are nowadays part of our environment, for example those made of polyester-based fabric (usually polyethylene terephthalate) and a plasticized polyvinylchloride (PVC) coating.

  These fabrics have found many applications such as the realization of covers of blankets for transport, roofs of public or industrial buildings, sunscreen screens, print media for billboards or canvas for the furniture of garden.

  That said, these fabrics are now the object of criticism from environmental protection associations, as they are suspected of being a vector for the dissemination of phthalates, used as plasticizer for PVC, in the environment. environment. Indeed, these molecules tend to migrate within the PVC matrix of the coating to the surface and to escape by volatilization.

  Even if the harmfulness of phthalates could not be proven, reducing the losses by volatile emissions of these phthalates and more generally plasticizers associated with PVC appeared as a new constraint. In addition to the effects of accumulation in the environment, the loss of phthalates by the coating causes for the coated fabric itself disadvantages such as a stiffening of the fabric, a greasy feel and premature and pronounced fouling, and term, a narrowing. There is therefore a clear interest in limiting or even canceling this loss of plasticizer.

  To answer this problem, it is known to use polymeric plasticizers. The latter are mainly based on polyesters but other structures such as polyacrylics, nitrile rubbers and generally polymers compatible with PVC can be used. These polymeric plasticisers if they have a certain interest because of their low migratory character are in fact hardly used in the field of coating because they generate high viscosities that are not very compatible with the tools and the productivity required by the manufacture of these materials. tissue.

  One possibility to lower the viscosity of the coatings is to use a mixture comprising a polymeric plasticizer and a diluent. A diluent will lower the viscosity of the coating. However, since the diluent is not permanent, it will be removed by evaporation during gelation of the PVC.

  This solution, although technically attractive, is not desirable for two reasons. On the one hand, it requires the use of explosion-proof coating lines, which always imposes an additional investment cost. In addition these lines must be equipped with a flue gas treatment system, for example an incinerator, which further increases the investment cost On the other hand the use of these diluents being only transient, it is quickly expensive because it leads to unnecessary consumption of raw materials that do not remain in the coated fabric.

  It can be added that these diluents, because of their necessary affinity with PVC have a high propensity to remain in the coated fabric which requires a longer heat treatment without any guarantee not to keep traces of diluents likely to be released in air throughout the life of the coated fabric. The problem of the emission of the coated fabrics is therefore imperfectly solved by this means.

  It has also been proposed to use coatings obtained from a polymerizable plasticizer. This solution has already been envisaged using, for example, a diallyl phthalate whose double bonds are polymerized by a radical-type reaction. However, the amount of plasticizer which polymerizes does not exceed 50% for reasons of steric hindrance. There remains therefore in the coating a large part of uncured plasticizer likely to cause the disadvantages listed above. Moreover, the presence of residual double bonds in the coating is in itself a disadvantage because it induces a lower resistance to aging.

  In addition, the homopolymer of diallyl phthalate has a thermoset character which subsequently hinders its recycling.

  The use of polycaprolactone as PVC plasticizer is known, the mixture of the two polymers is miscible. On the market, it is therefore possible to find homopolymers or oligomers with a degree of polymerization generally greater than 4 used as plasticizer for PVC. These oligomers are waxy solids or pastes which do not make it possible to produce mixtures that are easily enducible at room temperature. In fact, these mixtures of PVC and polylactone, because of their high viscosity, are used for the manufacture of articles by extrusion or molding in particular.

  It is theoretically possible to heat the mixture beyond the melting point of the caprolactone homopolymer, to obtain a fluid product. However, the temperatures that must be reached are generally greater than 40 C, or even close to 80 C, and are sufficient to initiate the gelling of PVC. The paste obtained quickly becomes difficult to coat because of its viscosity. This method of preparation is not at all transposable industrially to the coating of substrates, coating or the manufacture of flexible films.

  Caprolactone monomer is also used as plasticizer for PVC. This monomer is however relatively mobile and gives PVCs which have a strong tendency to exude. Moreover its implementation is delicate because its high solvating power leads to rapid swelling of the PVC grain and the setting of mass of the mixture.

  For this reason monomeric caprolactone is not used as a plasticizer and its homopolymers or oligomers are preferred.

  All these remarks show that, to date, a satisfactory technical solution, both in terms of industrialization of the manufacture of coatings based on vinyl polymers, aging of coated fabrics, environmental protection and consumers, remains to be developed.

  Thus, an object of the invention is to develop a polymer composition comprising at least one vinyl polymer and at least one polylactone, especially for the preparation of films or flexible coatings, which meets all the requirements listed.

  In particular, an object of the invention is to provide a coating composition (in particular coating) and / or for the manufacture of a film, stable over time, that is to say, in particular, which does not release or few volatile constituents.

  Another object of the invention is to provide a composition which solves the problems related to the aging of the coating: stiffening, greasiness, fouling, shrinkage ...

  Yet another object of the invention is to provide a composition for the coating of a support or for the production of flexible films which is compatible with industrialization, in particular compositions whose viscosity is sufficiently low.

  A further object of the invention is to provide a recycling solution for vinyl polymers, in particular PVC, plasticized using phthalate type compounds.

  An object of the invention is also to provide a method of coating the surface of a support with such a polymer composition, in particular for textile backing, or for the production of flexible films.

  Thus, it is the merit of the inventor to have developed a polymer composition that solves all the aforementioned problems, without the disadvantages of previously proposed solutions. In particular, it has been shown that it is possible to obtain enducible formulations by combining at least one lactone monomer with at least one vinyl polymer, and then, by means of an in situ polymerization technique, lactone monomers into polylactone, to fix it in the mixture.

  This technique also makes it possible to fix the lactone monomers on coatings containing phthalates, which makes it possible to significantly increase the molecular weight of the phthalates and reduce their ability to migrate within the coating.

  According to a first aspect, the present invention relates to a polymer composition comprising at least one vinyl polymer and at least one polylactone, in particular for the preparation of films or flexible coatings, obtained by the process comprising the following steps: a) the vinyl polymer is mixed and at least one lactone monomer, in order to obtain a paste, b) introducing a polymerization initiator for the lactone monomers into the dough obtained above, and mixing, c) subjecting the dough obtained above to a temperature of greater than 80 ° C., for a duration of at least 30 seconds, to cause the in situ polymerization of the lactone monomers into polylactones.

  The term "vinyl polymer" means a vinyl compound prepared from vinyl-containing monomers CH2 = CH- or vinylidene CH2 = C <as well as from a mixture of such monomers, to produce homopolymers or copolymers. The vinyl group is attached to a group, and the vinylidene group is linked to one or two groups, which are or contain an aryl (for example styrene), oxygen (for example (meth) acrylic acid and its derivatives, especially methyl or ethyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, vinyl esters such as vinyl acetate, vinyl ketones), sulfur (for example, vinylsulfones, thioethers, sulfoxides, sulfonates), nitrogen (for example vinyl nitriles, amides, pyridines, pyrollidones, carbazoles), halogen (for example vinyl chloride or vinylidene fluoride) .

  Preferably, the vinyl polymer is a halogenated vinyl polymer which comprises at least 50 mol% of halogenated vinyl monomers, preferably selected from the group consisting of vinyl chloride, vinylidene chloride, vinyl fluoride, fluoride, vinyl fluoride and the like. vinylidene, optionally substituted, and mixtures thereof.

  More preferably still, the vinyl polymer is polyvinyl chloride (PVC), which is defined as a polymer or a copolymer obtained by (co) polymerization of at least 50 mol% of vinyl chloride with another olefin, such as vinyl acetate.

  PVC can be produced by emulsion, suspension, microsuspension or even by mass, according to techniques widely known to those skilled in the art. Preferably, its viscosity number or K-Wert is between 50 and 100 and more particularly between 60 and 80. A particularly preferred PVC is a suspension homopolymer of K-Wert 66.

  Advantageously, the weight percentage of vinyl polymer in the composition ranges from 35 to 70%.

  The polylactone is obtained by polymerization of lactone monomers, according to a coordination-insertion reaction. Lactones are cyclic esters comprising from 3 to 15 carbon atoms in the lactone ring. The carbon atoms of the lactone ring may be substituted by linear, C1-C5 or branched alkyl, alkoxy or alkoxyalkyl groups. Preferably, the lactone monomers are selected from ybutyrolactone, 8-valerolactone, ε-caprolactone, X, -lauryl lactone or mixtures thereof. In particular, ε-caprolactone is particularly preferred.

  The lactone monomers are polymerized via an insertion coordination reaction initiated by a metal alkoxide. The reaction is not disturbed by the presence of the usual components of the vinylic polymer coatings, such as the polymer itself, the thermal stabilizers, the fillers, the pigments and the monomeric plasticizers possibly present or other usual additives. In the case of the presence of a phthalate, the initiator simultaneously allows the phthalate to be attached by trans-esterification of the polylactone formed. The reaction can be conducted at temperatures between 80 and 220 C compatible with the usual conditions of production of vinyl polymer coatings, particularly PVC.

  Advantageously, the weight percentage of lactone monomers in the composition, before polymerization, is between 30 and 62%. The higher the proportion of lactone monomers, the more the composition obtained at the end of the preparation process, that is to say after polymerization of the lactone monomers, will be plasticized and flexible. Thus, the amount of lactone monomers introduced into the composition will depend essentially on the intended application.

  In order to initiate the coordination-insertion reaction, a metal alkoxide is used. The metal alkoxides may be compounds based on tin, titanium, zirconium or aluminum, known to those skilled in the art. Thus, preferably, the polymerization initiator of the lactone monomers is selected from the group consisting of tin, titanium, zirconium or aluminum alkoxides. Alkyltitanates are preferred and more particularly titanium tetrapropoxide.

  The percentage by weight of initiator is between 0.1 and 4% inclusive, depending on the degree of polymerization which is to be achieved with the lactone. High content will result in shorter chains and require shorter reaction times to achieve full conversion. A more particularly preferred content is between 1 and 2% inclusive.

  In particular, the polylactone has a number-average molar mass of between 1500 and 6000 g / mol, although this number-average molar mass can be much higher. The polydispersity index of the polylactone is between 1 and 2, preferably between 1.2 and 1.8. Such characteristics make it possible to produce compositions whose viscosity is compatible with coating techniques such as coating, or with the manufacture of flexible films, in particular by calendering.

  The initiator dose used makes it possible to obtain a rather rapid polymerization, compatible with the requirements of the industrial processes.

  Polymerization of the polylactone takes place under the effect of heat, at a temperature above 80 ° C., of between 80 and 260 ° C., preferably between 100 ° and 220 ° C. and more preferably between 160 ° and 190 ° C.. polymerization is selected to be compatible with the (s) vinyl polymer (s) used. For example, if the vinyl polymer is PVC, a polymerization temperature of less than 220 ° C. is preferred. If the vinyl polymer is more heat-resistant than PVC, which is for example the case of polyvinylidene fluoride, it will be possible to select a temperature greater than 220 ° C. and advantageously less than 260 ° C.

  The choice of the polymerization temperature can therefore be performed after routine tests by a person skilled in the art.

  The temperature applied to the vinyl polymer and lactone monomer composition affects the rate of polymerization. The amount of initiator introduced into the mixture plays on the number average molar mass of polylactones obtained. Thus, for a given amount of initiator, the higher the polymerization temperature, the greater the in situ polymerization rate of the lactone monomers to polylactones.

  The polymerization time is advantageously greater than 30 seconds, preferably between 1 and 3 minutes. However, the heat treatment could last longer, especially when the polymerization temperature is low or when the amount of initiator introduced into the composition is reduced.

  The polymerization time chosen should make it possible to approach a polymerization rate of the lactone monomers close to 100%, at least greater than 95%, while remaining compatible with an industrial implementation.

  The inventors have found that performing an in situ polymerization of the lactone monomers in the presence of the vinyl polymer improves the plasticizing effect of the polylactones. Without wishing to be bound by the theory, they interpret this observation as follows: during the mixing of the vinyl polymer and the lactone monomers, the latter are distributed along the vinyl polymer chains. Then, during the polymerization of the lactone monomers, the resulting polylactones are formed directly in contact with the vinyl polymer chains, which improves the plasticization (by lowering the glass transition temperature of the mixture) compared to a direct blend of vinyl polymer and polylactone.

  Moreover, the fact of starting by making a mixture of vinyl polymers and lactone monomers and then polymerizing in situ the lactone monomers makes it possible to overcome the difficulty of gelling the vinyl polymer from temperatures close to 40 to 80 ° C. In fact, the gelling of the vinyl polymer and the polymerization of the lactone monomers take place simultaneously, and after having applied the composition to a support. This results in a coating (or a film) based on vinyl polymer plasticized with polylactones, unlikely to escape the polymer, from a sufficiently fluid composition and compatible in particular with industrial coating techniques.

  Advantageously, the composition comprises at least one thermal stabilizer such as organometallic barium and zinc, tin, calcium and zinc soaps possibly associated with costabilizers such as epoxidized soybean oil. A particularly preferred thermal stabilizer is a mixture of mono- and di-octyl thioglycolate tin.

  Preferably, the weight percent of stabilizer is between 0.5 and 3% inclusive.

  In an optional manner, the mixture to be coated may also contain plasticizers and more particularly phthalates. In the latter case branched or unbranched alkyl phthalates such as diethylhexylphthalate (DEHP), diisononylphthalate, phthalates of C7 to C11 linear alcohols or their mixtures, diisodecyl phthalate are more particularly preferred.

  Advantageously, the percentage of optional phthalates relative to the weight of lactones is between 0 and 25%.

  Optionally the mixture to be coated may also contain compounds well known to the formulator of the art, such as heat stabilizers, fillers, flame retardants, pigments, dyes, UV stabilizers, antifungal agents, antioxidants.

  More preferably, a composition according to the invention has the following weight formula: E vinyl polymer, preferably halogenated: 35 to 70% by weight, monomeric lactones, preferably--caprolactone: 30 to 62% by weight, initiator. 0.1 to 4% by weight, optional additives: 0 to 15% by weight.

  A particularly preferred composition is that in which the vinyl polymer is polyvinyl chloride and the lactone monomers are ε-caprolactone.

  The composition according to the invention can be used in a wide variety of applications where a polylactone vinyl polymer / plasticizer composition is useful: in the coating of textile supports to produce coated fabrics having their application in the tarpaulins, waterproofing, protective or containment membranes, sun shades, or media for digital printing, clothing or the like; É in the coating of nonwoven supports, for making floor coverings, wall coverings, geotextiles; É for the coating of non-permanent supports for making flexible films ("cast films" in English); É to make beds on paper.

  The textile supports referred to are of variable nature: woven or non-woven, of natural or synthetic origin, that is to say comprising fibers of natural, synthetic or semi-synthetic origin, possibly in admixture, without limitation. It may also be a metal support, consisting for example of metal son. Thus, a composition according to the invention can advantageously be used for coating such textile substrates, according to techniques known to those skilled in the art.

  A composition according to the invention can also be used for the manufacture of flexible films, in particular by calendering, according to techniques known elsewhere.

  The invention also relates to a premix for the manufacture of a composition as described above, the premix comprising at least one vinyl polymer, preferably halogenated, at least one lactone monomer and optionally at least one optional additive selected from plasticizers, thermal stabilizers, fillers, flame retardants, pigments, dyes, UV stabilizers, antifungal agents and antioxidants.

  Furthermore, the invention relates to a method of coating the surface of a support with a polymer composition comprising at least one vinyl polymer and at least one polylactone, this process comprising the following steps: a) provision is made for a coating paste comprising at least one vinyl polymer, at least one lactone monomer and at least one lactone monomer polymerization initiator, b) applying the coating paste to the surface of the support, c) subjecting the coated support to a temperature of greater than 80, for a period of at least 30 seconds, to cause the gelling of the vinyl polymer and the in situ polymerization of the lactone monomers to polylactone.

  Of course, the temperature selected depends, as we have seen previously, the components of the polymer composition, but also characteristics of the coated support.

  According to different variants of the method, the support is a woven or non-woven permanent support, or a non-permanent support. For example, in the case of textile supports referred to are of variable nature: woven or non-woven, of natural or synthetic origin, that is to say comprising fibers of natural, synthetic or semi-synthetic origin, possibly in a mixture, without limitation. It may also be a metal support, consisting for example of a fabric made of metal son.

  A support is considered as non-permanent if, over time, the coating and the support are intended to be separated from one another, which is for example the case when manufacturing flexible polymer films.

  The coating may advantageously be made by coating the support.

Examples

  Preparation of coating compositions Examples 1 to 3: Preparation of a plasticized PVC film Example 4: Comparative Example One introduces successively into a 250 ml container of s-caprolactone, the PVC powder and a thermal stabilizer, in the proportions by weight ( parts by weight) indicated in Table 1. Mixed for 2 minutes at room temperature (20 C) to obtain a homogeneous and fluid paste.

  The initiator is introduced into the paste obtained above, at the last moment to avoid hydrolysis of the initiator, and the initiator and the paste are rapidly mixed. Then, coated with a doctor blade, to obtain a film of thickness between 100 and 250 m.

  In Examples 1 to 4, the support is a silicone paper. The support thus coated is introduced into an oven heated to 185 ° C to be steamed for 1 to 3 minutes. The films are evaluated after cooling and detaching their support.

  After cooling, the transparency of the films obtained is evaluated and touched immediately after manufacture and after one month (sticky / oily or dry). The average number-average molecular weight of the poly-scaprolactone obtained after polymerization is measured by steric exclusion chromatography. The polydispersity index of the poly-ε-caprolactone is also measured. The conversion of the ε-caprolactone monomers into polymers is also measured.

  The acetone resistance of the obtained films is also evaluated by immersing them for 10 minutes in acetone.

  In the case of a vinyl polymer containing phthalates (in this case diethylhexylphthalate DEHP), the phthalate content is measured at the end of the polymerization of the lactone monomers.

  The results of these tests are reported in Table 2.

Table 1

  Ex. 1 Ex. 2 Ex. 3 Ex. 4 (Comp.) C-caprolactone 25 Diethylhexyl-5-phthalate (DEHP) PVC Suspension 25 25 25 K-wert 66 IRGASTAB 1,2 _ 1,2 1, 2 TK 262 GV Baerostat BZ561 - 1,2 - - Tetrapropoxide 2 2 0,5 titanium Oven at 185 ° C 3 min 3 min 2 min 1,5 min Thickness of film 150 120 165 150 (glue) IRGASTAB TK 262 GV : thermal stabilizer based on tin carboxylate, sold by the company CROMPTON Baerostat BZ 561: thermal stabilizer based on barium salts and zinc, sold by the company BAERLOCHER

Table 2

  Ex. 1 Ex. 2 Ex. 3 Ex. 4 (comp.) Transparency yes yes yes Yes Touch "initial" dry dry dry Fat Touch "1 month" dry dry dry Fat Resistance to OK OK OK embrittlement acetone M poly- E-capro- 1861 2470 5028 - lactone (g / mol) Index of 1.73 1,4 1,25 - polydispersity Conversion rate 100 100 100 0 E-caprolactone DEHP content 1.7% - - P / PM poly-E-caprolactone: number average molar mass of polycaprolactone Resistance to acetone: test of acetone resistance by immersion of the film in acetone for 10 minutes. Comparative Example 4, in which a lactone monomer polymerization initiator was not introduced, resulted in fatty-touch films, which it is desired to avoid.

  The composition is also analyzed by steric exclusion chromatography: no polycaprolactone peak is identified and a high proportion of residual monomer is observed. In the absence of titanate, polymerization of caprolactone did not occur.

  On the other hand, the PVC film of Example 4 is sensitive to acetone, which causes embrittlement of the film after only 10 minutes of immersion.

  On the contrary, the results of Examples 1 to 3 are particularly interesting. In fact, the plasticized PVC films obtained are transparent, have a dry feel as soon as they are manufactured and retain it over time. This is explained in particular by the fact that the conversion rate of ε-caprolactone is 100% (no residual monomer is observed), which means that the monomers are integrally fixed in caprolactone polymers. There are no mobile monomers within the polymer matrix. This is particularly interesting in the case of Example 3, where

  the ungrafted DEHP content is lowered from 9.7% (value in the initial mixture) to 1.7% (value in the film). Thus, the process according to the invention can be used to recycle plasticized PVC using phthalates, by fixing the free phthalates using the polylactone type plasticizer.

  Examples 1 and 2 make it possible to compare the effect of two different thermal stabilizers: the number-average molar mass of the polylactones is slightly greater in Example 2.

  Examples 1 and 3 make it possible to compare the influence of the proportion by weight of polymerization initiator in the composition. Decreasing the amount of initiator results in an increase in the number average molecular weight of the polylactones.

  EXAMPLE 5 Preparation of a Fabric Coated with a Plasticized PVC Composition The procedure of Example 5 is carried out in the same manner as in Example 1, by preparing a coating composition from the following formulation: caprolactone: 15 parts by weight PVC suspension K-Wert: 25 parts by weight IRGASTAB TK 262 GV: 1 part by weight Titanium tetrapropoxide: 2 parts by weight In this example, the carrier is a high tenacity polyester terephthalate taffeta of mass density 182 g / m2. The coated support is parboiled for 3 minutes at 185 ° C.

  After cooling, a soft, surface-weight, 330 g / m2 dry-touch fabric is obtained to the touch.

  The coated fabric is immersed in a cup containing acetone for 10 minutes without being tampered with.

  The coating is also analyzed by size exclusion chromatography. A polycaprolactone peak having a number average molecular weight of 2880 g / mol and a polydispersity index of 1.35 is identified.

  The conversion of ε-caprolactone is 100% because no residual monomer is observed.

Claims (14)

  A polymer composition comprising at least one vinyl polymer and at least one polylactone, in particular for the preparation of films or flexible coatings, obtained by the process comprising the following steps: a) mixing the vinyl polymer and at least one lactone monomer, for to obtain a paste, b) introducing a polymerization initiator of the lactone monomers into the dough previously obtained, and mixing, c) submitting the dough obtained above a temperature above 80 C, for a period of at least 30 seconds, to cause polymerization in situ of the lactone monomers into polylactones.   2. Composition according to the preceding claim, wherein the vinyl polymer is a halogenated vinyl polymer which comprises at least 50 mol% of halogenated vinyl monomers, preferably selected from the group consisting of vinyl chloride, vinylidene chloride, vinyl chloride and the like. vinyl fluoride, vinylidene fluoride, optionally substituted, and mixtures thereof.   3. Composition according to any one of the preceding claims, in which the lactone monomers comprise from 3 to 15 carbon atoms in the lactone ring, said lactone monomers being preferably selected from the group consisting of γ-butyrolactone, valerolactone, α-caprolactone, 2-lauryl-lactone, optionally substituted, and mixtures thereof.   A composition according to any one of the preceding claims wherein the lactone monomers are ε-caprolactone and the vinyl polymer is polyvinyl chloride.   5. Composition according to any one of the preceding claims, in which the polylactone has a polydispersity index of between 1 and 2.   6. Composition according to any one of the preceding claims, in which the polymerization initiator of the lactone monomers is a metal alkoxide, preferably selected from the group consisting of tin, titanium, zirconium or aluminum alkoxides. .   The composition of any preceding claim, wherein the polymerization initiator is titanium tetrapropoxide.   8. Composition according to any one of the preceding claims, further comprising the following optional additives: additional plasticizer; thermal stabilizer; charge; flame retardant; pigment; dye; UV stabilizer; antifungal agent; antioxidant.   9. Composition according to any one of the preceding claims, in which the weight formula of the composition is the following: vinyl polymer, preferably halogenated: 35 to 70% by weight, lactone monomers, preferably ε-caprolactone: 30 to 62% by weight, o initiator. 0.1 to 4% by weight, o optional additives: 0 to 35% by weight.   10. Premix for the manufacture of a composition according to any one of the preceding claims, the premix comprising at least one vinyl polymer, preferably halogenated, at least one lactone monomer and optionally at least one optional additive selected from plasticizers, thermal stabilizers, fillers, flame retardants, pigments, dyes, UV stabilizers, antifungal agents and antioxidants.   11. A method of coating the surface of a support with a polymer composition comprising at least one vinyl polymer and at least one polylactone, said method comprising the following steps: a) a coating paste comprising at least one at least one vinyl polymer, at least one lactone monomer and at least one lactone monomer polymerization initiator, b) the coating paste is applied to the surface of the support, c) the coated support is subjected to a temperature above 80 ° C. for a period of at least 30 seconds, to cause the gelling of the vinyl polymer and the in situ polymerization of the lactone monomers to polylactone.   12. Method according to the preceding claim, wherein the support is a woven or non-woven permanent support, or a non-permanent support.   13. Use of a composition according to any one of claims 1 to 9 for coating a support, preferably a woven or non-woven fabric, of natural or synthetic origin.   14. Use of a composition according to any one of claims 1 to 9 for the manufacture of flexible films, in particular by calendering.