EP2274364A2

EP2274364A2 - Method for preparing a blend of halogenated polymer and of copolymer bearing associative groups

Info

Publication number: EP2274364A2
Application number: EP09750041A
Authority: EP
Inventors: Manuel Hidalgo; Thierry Pascal
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2008-05-07
Filing date: 2009-05-05
Publication date: 2011-01-19
Also published as: WO2009141560A2; FR2930945B1; US20110065860A1; FR2930945A1; WO2009141560A3

Abstract

The present invention relates to a method of preparing a polymer resin based on a halogenated vinyl polymer and a copolymer bearing associative groups, comprising the steps that consist in forming a latex of each of these polymers, blending said latices, then isolating and drying the polymers contained in said latices in order to form a pulverulent resin. The present invention also relates to said resin, to a pulverulent composition containing said resin, and also to the use of this composition for manufacturing rigid or plasticized materials.

Description

Process for preparing a mixture of halogenated polymer and associative group-bearing copolymer

The present invention relates to a process for preparing a pulverulent resin based on a halogenated vinyl polymer and an associative group-bearing copolymer. It also relates to said resin, a composition containing said resin, and the use of this composition for the manufacture of rigid or plasticized materials.

The so-called supramolecular materials are materials consisting of compounds associated by non-covalent bonds, such as hydrogen, ionic and / or hydrophobic bonds. It may be in particular polymers on which are grafted associative groups, likely to unite by cooperative hydrogen 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. The ease of use and / or the properties of the polymers, such as the mechanical, rheological, thermal, optical, chemical and physicochemical properties, can therefore be improved by the grafting of these associative groups. The latter can also impart the properties of high-mass polymers to low-mass polymers that are easier to prepare in a controlled manner.

The document WO 2006/016041 thus discloses polymers grafted with associative groups allowing to give them a higher elastic modulus and better resistance to solvents.

For its part, US Pat. No. 2,980,652 discloses copolymers containing associative groups of imidazolidone type, having a good ability to adhere to substrates, in particular metal substrates, and which are particularly useful for producing water-based paints.

Example 9 more particularly discloses the product of the reaction of UDETA on a copolymer of maleic anhydride and methyl methacrylate. This product is formulated into a lacquer that can be sprayed onto steel panels (Examples 14 and 15).

In this context, the Applicant has investigated the means for modifying halogenated vinyl polymers such as PVC to make them supramolecular materials and thus improve their properties. Various attempts have therefore been made to graft imidazolidone associative groups on PVC by reacting the latter with N-aminoethyl-2-imidazolidone (UDETA).

It has however appeared to the Applicants that the nucleophilic attack of the UDETA on PVC caused degradation of the latter by dehydrochlorination, with concomitant formation of hydrochloric acid, which made it impossible to directly graft UDETA en masse.

(without solvent) on PVC in PVC processing equipment such as calenders, extruders or presses. To circumvent this problem, other ways have been envisaged, all of which have major drawbacks.

This is the case for solvent grafting which, although allowing an adjustment of the operating conditions (concentration of PVC and UDETA, choice of solvent, temperature) to promote the substitution of PVC by UDETA at the expense of its degradation, requires the use of large amounts of solvent.

In addition, although it represents an interesting alternative, the copolymerization of vinyl chloride monomer with methacrylic monomers bearing associative groups of imidazolidone type would encounter the difficulty of obtaining copolymers of homogeneous composition, given the significant difference of the reactivity ratios of the methacrylic and acrylic monomers in general, with the vinyl chloride monomer (VCM) (see J. Bandrup et al., Polymer Handbook, ^3rd Edition, John Wiley).

Finally, the grafting of associative groups on a PVC via functions other than the amine function of UDETA, such as the mercaptan function, does not offer a satisfactory solution either, insofar as the synthesis of molecules bearing both associative functions of the imidazolidone type and non-amine grafting units, such as these mercaptan functions, add steps to the process for obtaining the grafted PVCs.

It is the merit of the Applicant to have developed a method for driving to a material of supramolecular type based on PVC, having improved properties while overcoming the aforementioned drawbacks. To achieve this goal, the Applicant has devised an "indirect modification" of a halogenated vinyl polymer such as PVC, by mixing, at the nanoscale, with a copolymer rich in monomers which, after polymerization, give mixtures compatible with PVC and also bearing given associative groups. It is thus possible to obtain a highly compatible homogeneous mixture of polymers and to indirectly convey certain associative groups in PVC in order to confer different properties.

More specifically, it has been demonstrated that the polymer bearing the associative groups according to the invention makes it possible to confer properties of strong adhesion to metals and improved creep resistance to the halogenated vinyl polymer such as PVC and could possibly provide it with in addition to improved rheological, mechanical or thermal properties, in particular greater elongation at break, better thermal stability, higher softening temperature and better resistance to low shear rate melting.

It is certainly already known from FR 2 891 548 that the adhesion of polyvinylidene chloride or PVDC to metal or polymer surfaces can be improved by mixing it with a copolymer containing monomers, in particular acrylic monomers, which carry groups. phosphonates and other monomers, especially acrylics. However, it is not suggested in this document that the use of a copolymer bearing associative groups of nitrogenous heterocycle type could make it possible to improve several properties of halogenated vinyl polymers such as PVDF.

The present invention specifically relates to a process for preparing a polymer resin comprising the successive steps consisting of:

And forming a first latex from at least one halogenated vinyl polymer and a second latex from at least one copolymer containing, on the one hand, units derived from a first monomer (A) rendering said copolymer compatible with said halogenated vinyl polymer and, on the other hand, units derived from a second monomer (B) bearing at least one associative group selected from imidazolidonyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups, preferably an imidazolidonyl group,

2- mixing said latexes, and 3 isolating and drying the polymers contained in said latex to form a powdery resin.

The present invention also relates to the resin obtainable by this method.

The different steps of the process according to the invention will now be described in more detail. It is understood that this process may comprise other steps than those mentioned above, in particular one or more preliminary, subsequent and / or intermediate steps, provided that the succession of steps mentioned above is respected. Latex formation

The first step of the process according to the invention comprises the formation of latex, on the one hand, a copolymer carrying given associative groups and, on the other hand, a halogenated vinyl polymer.

The copolymer bearing associative groups contains precisely, on the one hand, units of a first monomer (A) rendering said copolymer compatible with said halogenated vinyl polymer and, on the other hand, units of a second monomer (B) distinct from the pattern (A) and carrying one or more associative groups according to the invention. The monomer (A) preferably represents at least 20 mol% and advantageously at most 80 mol% of the copolymer.

By "compatible" it is meant that the halogenated vinyl polymer and the copolymer exhibit partial or complete miscibility. Depending on the nature of the copolymer and in particular of the monomer (A) used for its synthesis, compatibility within the meaning of the invention with the halogenated vinyl polymer can be obtained in proportions of the mixture of the two variable polymers. This compatibility can be demonstrated by physical miscibility measurements.

This total or partial miscibility can be identified by various analytical methods known to those skilled in the art such as scanning electron microscopy (SEM) or transmission (TEM) or atomic force microscopy (AFM), which can often identify inhomogeneities of mixtures in the form domains with a characteristic size greater than 1 micron (immiscibility), as well as glass transition temperature measurements, Tg, of the mixture of the two polymers. The total miscibility results in the existence of a single Tg for the mixture, and the partial miscibility results in the existence of two Tg, at least one of which is different from the Tg of the halogenated vinyl polymer and the Tg of the copolymer. Methods for measuring the Tg of polymers and polymer blends are known to those skilled in the art and include differential scanning calorimetry (DSC), volumetry or dynamic mechanical analysis (DMA).

Thus, any copolymer bearing associative groups according to the invention and compatible, in the sense explained above, with the halogenated vinyl polymer may be used according to the invention, in particular any copolymer based on a monomer (A). ) whose corresponding homopolymer is known to be miscible with the halogenated vinyl polymer or whose presence of units from the monomer (A) causes compatibility with the halogenated vinyl polymer. Non-exclusive examples of monomers (A) include (meth) acrylic monomers such as methyl methacrylate, polyethylene glycol methacrylate, methoxy polyethylene glycol methacrylate and acrylonitrile, or maleic anhydride. Examples of copolymers bearing associative groups which can be mixed, in proportions varying according to their nature and that of the halogenated vinyl polymer, with the halogenated vinyl polymer to obtain the compatibility and the effects of "indirect modification" by reversible physical bonds according to US Pat. invention, there may be mentioned copolymers of methyl methacrylate (so-called PMMA-type copolymers) carrying these associative groups, copolymers of polyethylene glycol side-chain monomers (so-called PEG side-chain copolymers) carrying these associative groups, copolymers of maleic anhydride bearing these associative groups or copolymers of acrylonitrile carrying these associative groups.

By "associative groups" is meant groups capable of associating with each other by hydrogen bonds, advantageously by 1 to 6 hydrogen bonds. The associative groups which can be used according to the invention are more specifically the imidazolidonyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups, the imidazolidonyl groups being preferred.

According to a preferred embodiment of the invention, the associative groups are introduced during the formation of the copolymer. The copolymer is thus capable of being obtained by copolymerization of the monomer (A) with a monomer (B) which carries the associative groups and optionally one or more other monomers, preferably from: - on the one hand, a monomer (A) which is a (meth) acrylic monomer selected from: methyl methacrylate, (methoxy) polyethylene glycol (meth) acrylate and acrylonitrile; or maleic anhydride,

- On the other hand, a monomer (B) bearing associative groups, preferably imidazolidonyl groups, which is advantageously chosen from: ethylimidazolidone methacrylate (or MEIO) and ethylimidazolidone methacrylamide (or WAM II) and optionally, one or more other monomers chosen from acrylic or methacrylic acids, their esters, their amides or their salts, itaconic acid, its esters, its amides or its salts, and styrene and its derivatives such as styrene sulfonate.

Such a copolymer may be prepared in latex form by radical polymerization methods in dispersed medium, for example in aqueous emulsion. These methods are well known to those skilled in the art and described in general and specialized works, as, for example, in Chapter 7 of the book "Synthetic Latexes: Elaboration, Properties, Applications", coordinated by C. Pichot and JC. Daniel (TEC & DOC editions of Lavoisier, France, 2006).

These methods use water-soluble radical polymerization initiators. Different radical generation mechanisms can be implemented such as, for example, thermal decomposition, oxidation-reduction reactions, decomposition caused by electromagnetic radiation and, in particular, radiation in the ultraviolet. Non-exclusive examples of water-soluble initiators include hydroperoxides such as tert-butyl hydroperoxide, water-soluble azo compounds such as 2,2'-azobis (2-amidinopropane) dihydrochloride, and organic or inorganic salts of 4,4'-Azobis (4-cyano valeric acid), inorganic oxidants such as sodium, potassium or ammonium persulfates, hydrogen peroxide, perchlorates, percarbonates and ferric salts. These oxidants can be used alone or in combination with inorganic or organic reducing agents such as sodium or potassium bisulfite or metabisulphite, vitamin C (ascorbic acid), sodium or potassium hypophosphites. These organic or inorganic reducing agents can also be used alone, that is to say in the absence of inorganic oxidants. The initiators soluble in the aqueous phase are used, in the case of emulsion polymerizations, in proportions ranging from 0.01 to 10% by weight relative to the total weight of the monomers.

In addition to the polymerization initiators, it may be useful to dissolve other additives in the monomers to be copolymerized, among which mention may be made of chain transfer agents which make it possible to reduce the molecular masses. By way of examples of chain transfer agents, mention may be made of alkyl mercaptans, such as methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan and tert-butyl. mercaptan, cyclohexyl mercaptan, benzyl mercaptan, n-octyl mercaptan, tert-nonyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, alkyl thioglycolates such as methyl thioglycolate, ethyl thioglycolate, 2- ethylhexyl thioglycolate or iso-octyl thioglycolate. The chain transfer agents are generally used in proportions of between 0.01 and 10%, and preferably between 0.5 and 2% by weight relative to the total weight of the monomers.

It is also possible to dissolve in the monomers to be copolymerized other additives such as antioxidants, such as butylhydroxytoluene (BHT), biocides and / or activators of polymerization initiators. These additives are generally used in proportions of between 0.01% and 5% by weight relative to the total weight of the monomers.

In addition, surfactants or stabilizers for constituting the starting emulsions and stabilizing the final latex obtained can be used. Three families of surfactants or stabilizers can be considered, namely:

1) surfactant molecules of natural or synthetic origin having a dispersing and stabilizing effect by electrostatic repulsion and comprising the positively or negatively charged amphiphilic molecules, or forming (amphoteric) zwitterions, in the aqueous phase, among which may be mentioned, for example non-exclusive examples: sodium or potassium alkyl sulphates or sulphonates, in particular sodium dodecyl sulphate, sodium or potassium alkyl aryl sulphates or sulphonates, in particular sodium dodecyl benzene sulphonate potassium, sodium or potassium salts, ammonium of fatty acids, in particular sodium stearate, alkylated and disulfonated diphenyl oxides, in particular commercial surfactants from the Dowfax ^® range, such as Dowfax ^® 2Al, sulphosuccinates and, in particular, commercial surfactants from the Aerosol range ^® such as Aerosol ^® MA 80 which is sodium dihexyl suifosuccinate or Aerosol ^® OT-75 which is the sodium dioctyl sulphosuccinate, phosphoric esters, fatty amines, polyamines and their salts, quaternary ammonium salts, such as alkyl trimethyl chlorides or ammonium bromides, betaines such as N-alkyl betaines or sulphobetaines, imidazolines carboxylates, as well as the ethoxylated derivatives of all these compounds;

2) surfactant molecules having a dispersing and stabilizing effect by steric repulsion, uncharged or nonionic, among which may be mentioned, by way of non-exclusive examples: ethoxylated alkyl phenols, ethoxylated fatty alcohols, block copolymers polyethylene oxide and polypropylene oxide, such as those of the Pluronic range, fatty acid esters, alkyl polyglycosides;

3) amphiphilic or completely hydrophilic polymeric molecules, which may or may not be charged, among which may be mentioned, by way of non-exclusive examples: polymers of natural or synthetic origin soluble in water, such as polymers and copolymers of (meth) acrylic acid and their salts, polymers and copolymers of acrylamide and its derivatives, polymers based on vinyl alcohol and vinyl acetate, hydroxyethyl cellulose and hydrophobic modified hydroxyethyl cellulose, polyvinyl caprolactam, and polyvinyl pyrrolidone.

These dispersants or stabilizers are generally present in an amount of 0.1 to 10% by weight relative to the total weight of the monomers. It is also possible to carry out the emulsion polymerization in the absence of surfactants or stabilizing or dispersing agents; in this particular case, the final proportions of polymer, expressed as final solids content or final dry extract, that is to say, after evaporation of the volatiles and, in particular water, are less than 30% by weight , relative to the total weight of the latex resulting from the emulsion polymerization.

The aqueous emulsion polymerization can be carried out at atmospheric pressure or under pressure and at polymerization temperatures of between 5 ^° C. and

18O ⁰ C. Preferably, the copolymer is obtained at atmospheric pressure and at polymerization temperatures between 50 and 95 ⁰ C. The final concentrations or after polymerization of the copolymer and other non-volatile components are comprised between 1 and 75 % and preferably between

15 and 50% by weight, expressed as dry extract or final solids content, relative to the total weight of the emulsion (latex).

The process for synthesizing the copolymer may be continuous or in batches ("batch") or else semi-continuous type, that is to say with added additions of components, such as, for example, metered additions of monomers, either on their own or pre-emulsified additions of additives such as dispersants or stabilizers, initiators, or other additives.

The average diameter of the copolymer particles bearing associative groups obtained by radical polymerization in aqueous emulsion is generally less than 300 nm measured by particle size distribution. diffraction and diffusion using for example a MASTERSIZER2000 ^® device from the company MALVERN or using a sedimentometer.

For its part, the halogenated vinyl polymer may in particular be a fluorinated and / or chlorinated homo- or copolymer. It is usually a thermoplastic polymer.

A preferred example of chlorinated polymer is polyvinyl chloride or PVC. Such a polymer is sold especially by the company Arkema under the trade name Lacovyl ^®. Other chlorinated polymers useful in this invention are vinyl chloride copolymers with monomers such as acrylonitrile, ethylene, propylene, vinyl acetate, and polyvinylidene chloride or derivatives thereof. acrylic. It is also possible that the chlorinated polymer according to the invention is a mixture including at least two of the chlorinated polymers or copolymers above. In the case of vinyl chloride copolymers, it is preferable that the proportion of vinyl chloride units is greater than 25% and advantageously not more than 99% of the total weight of the copolymer.

As fluoropolymers, there may be mentioned those comprising one or more monomers of formula (D:

CFX = CHX '(I) where X and X 'independently denote a hydrogen or halogen atom (in particular fluorine or chlorine) or a perhalogenated alkyl radical (in particular perfluorinated). In particular, it is preferred that X = F and X '= H.

Examples of fluoropolymers that may be mentioned include:

polyvinylidene fluoride (PVDF),

copolymers of vinylidene fluoride with, for example, hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) or tetrafluoroethylene (TFE),

homo- and copolymers of trifluoroethylene (VF3),

the fluoroethylene / propylene copolymers (FEP),

copolymers of ethylene with fluoroethylene / propylene (FEP), tetrafluoroethylene (TFE), perfluoromethylvinyl ether (PFMVE), chlorotrifluoroethylene (CTFE) or hexafluoropropylene (HFP), and

- mixtures, some of these polymers being in particular sold by the company Arkema under the trade name Kynar ^®.

PVDF and PVC are preferred for use in the present invention.

The halogenated vinyl polymer can be obtained by aqueous microsuspension or aqueous emulsion polymerization processes, which are well known to those skilled in the art. The aqueous emulsion polymerization can thus be carried out using a water-soluble polymerization initiator such as a persulfate, in particular potassium, combined with an emulsifying agent such as sodium lauryl sulphate or sodium dodecyl benzene sulphonate and / or stabilizing polymers, and optionally to inorganic or organic reducing agents such as sodium formaldehyde sulfoxylate. Examples of such compounds have been described previously. The average diameter of the vinyl polymer particles halogen thus obtained is generally less than 500 nm, as measured by particle size by diffraction and scattering, using for example an apparatus MASTERSIZER2000 ^® from MALVERN or with the aid of a sedimentometer.

The polymerization in aqueous micro-suspension may be of inoculated type and carried out as described in particular in application FR 2 752 844, that is to say according to a process for the polymerization of vinyl chloride in the presence of:

a first vinyl chloride-based seeding polymer (P1) prepared as described, for example, in Application FR 2 309 569, the particles of which may have an average diameter of between 0.6 and 0.9; μm and contain at least one organosoluble initiator such as an organic peroxide,

a second vinyl chloride-based seeding polymer (P2), which may also be prepared as described in application FR 2 309 569 and whose particles have a mean diameter less than that of the particles of the first seed polymer (P1) and for example between 0.1 and 0.14 μm,

- water,

an anionic emulsifier, a soluble metal salt, in particular a copper salt,

a reducing agent such as ascorbic acid,

optionally, a water-soluble initiator such as ammonium persulfate.

The average diameter of the vinyl polymer particles halogen thus obtained is generally less than 2000 nm, as measured by particle size by diffraction and scattering, using for example an apparatus MASTERSIZER2000 ^® from MALVERN or with the aid of a sedimentometer.

It is preferred according to the invention that the halogenated vinyl polymer is prepared by aqueous emulsion polymerization.

Blend of latex

In the second step of the process according to the invention, the halogenated vinyl polymer latexes, on the one hand, and the associative group-bearing copolymer according to the invention, on the other hand, can be mixed by any means known to the skilled in the art, for example in a tank equipped with a stirring means, or continuously in a static mixer.

It is preferred that before or after mixing each of the latexes is diluted by adding water to a dry extract ranging from 10 to 40%, preferably from 15 to

ZJ) o _•

In addition, the latices are preferably mixed in a ratio of the halogenated vinyl polymer to the copolymer carrying associative groups ranging from 1: 200 to 100: 1, more preferably from 1: 100 to 1: 1 (in dry matter).

Formation and drying of the powdery resin

In the third step of the process according to the invention, after mixing and optionally filtering, the latices obtained above are subjected to any method making it possible to isolate the polymers in the form of particles from this mixture. This process can either comprise or be followed by a drying step.

Examples of such methods include spray drying, coagulation and lyophilization.

Spray drying involves injecting the latex mixture, generally via spray nozzles, into a stream of hot air which has the effect of converting the latexes into polymer droplets and drying them. Specifically, the mixture is sprayed using conventional spray known to the skilled person, such as a camera PRODUCTION MINOR ^® the company Niro, generally choosing a range of air inlet temperature between 300 and 12O ⁰ C and a flow rate such that the exit temperatures of the air and of the atomized product are between 100 ^° C. and 50 ^° C. On the other hand, the coagulation of the polymer latices is generally carried out by mixing them under adequate agitation with a coagulation agent based on a bivalent or trivalent metal salt such as chlorides, sulphates, nitrates or calcium acetates, aluminum , iron, magnesium, strontium, barium, tin or zinc. Other types of coagulation agents may be used, such as ammonium carbonate, organic compounds of methyl isobutyl carbinol type (described for example in patent application GB659722) or dioctyl phthalate (described for example in the application JP 7268021), or cationic or anionic polymers (described for example in the patent application FR 2373564).

The amount of coagulation agent used is usually between 100 and 50,000 ppm and preferably between 500 and 6000 ppm. In addition to the coagulation agent, a coagulation additive such as a modified polyamine may be added to facilitate filtration and to increase the solids level in the coagulated product after filtration. Furthermore, the pH of the medium can be adjusted to a value of between 2 and 7 by introducing a dilute acid, such as hydrochloric acid or sulfuric acid, to obtain a coagulate in the form of friable agglomerates, which are easier to filter.

The coagulation of the latices can also be obtained by adding, under appropriate agitation, a strong mineral acid, such as hydrochloric acid or acid. sulfuric acid, with or without the addition of a coagulation agent as described above, the amounts of acid being fixed so as to obtain a pH close to 1. A process of the above type is described in patent application GB1233144 .

Other coagulation technologies may be used. These involve either a heating of the latex under strong stirring via steam injection, with or without the addition of coagulation agent, as described in patent application DE954920, that is to say specific stirring at very high mechanical shear, such as turbine coagulators requiring or not the use of a coagulation agent (as described in patent application JP4106106), or a thin-film latex freezing in a continuous process as described in patent application FR2531716).

In one or other of these processes, a pulverulent resin containing an intimate mixture of the halogenated vinyl polymer and the associative group-carrying copolymer is obtained.

When this mixture has been spray-dried, a powder is generally obtained whose particle size is between 10 and 150 μm. When this mixture has been dried by coagulation, a powder is generally obtained whose particle size is between 10 and 300 μm.

The particle size of the powder is measured by diffraction and scattering, using for example an apparatus MASTERSIZER2000 ^® from MALVERN or with the aid of a sedimentometer. The invention also relates to a composition containing the pulverulent resin described above, optionally in ground form.

This composition may be in particular in solid form or in the form of emulsions, suspensions or solutions.

Apart from the resin described above, the composition according to the invention may contain various additives including one or more plasticizers.

These may for example be chosen from: polymeric plasticizers such as polyphthalates and polyadipates; monomeric plasticizers such as azelates, trimellitates (TOTM, TEHTM ...), sebacates (DIOS, DINS, DIDS ...), adipates (DOA, DEHA, DINA, DIPA ...), phthalates ( DOP, DEHP, DIDP, DINP ...), citrates, benzoates, tallates, glutarates, fumarates, maleates, oleates, palmitates, acetates such as acetylated monoglycerides; and their mixtures. Phthalates such as di-octyl phthalate, dialkyl adipates such as ditridecyl adipate (DTDA), di-acetylated monoglycerides such as glycerol monolaurate di-acetate and dialkyl sebacates such as diisodecyl sebacate (DIDS) are preferred for use in the present invention. The amount of plasticizer may for example be from 60 to 100% by weight, based on the weight of the halogenated vinyl polymer.

The composition according to the invention may furthermore contain: - lubricants such as stearic acid and its esters (the Loxiol G12 ^® Cognis), wax esters (the Loxiol G70 S ^® Cognis), polyethylene waxes, paraffin wax or acrylic lubricants (including Plastistrength ^® , in particular LlOOO, from ARKEMA),

inorganic or organic pigments, such as carbon black or titanium dioxide,

- thermal stabilizers and / or UV, such as tin stearate, lead, zinc, cadmium, barium or sodium, the Thermolite ^® from Arkema,

- co-stabilizers such as epoxidized natural oils, especially soybean oils such as epoxidized Ecepox ^® PB3 from Arkema,

antioxidants, for example phenolic, sulfuric or phosphitic,

fillers or reinforcements, especially cellulosic fillers, talc, calcium carbonate, mica or wollastonite, glass or metal oxides or hydrates, antistatic agents,

- fungicides and biocides,

- anti-shock agents, such as copolymers of MBS, which Clearstrength ^® C303H from Arkema, and acrylic modifiers of core-shell type such as Durastrength ^® from Arkema,

blowing agents such as azodicarbonamides, azobisobutyronitrile, diethyl azobisisobutyrate,

flameproofing agents, including antimony trioxide, zinc borate and brominated or chlorinated phosphate esters,

solvents, and

- their mixtures. These additives may for example represent from 0.1 to 50% of the total weight of the composition.

The composition according to the invention can be used for the manufacture of materials that are rigid or plasticized. To do this, it can be implemented by any means, including calendering, extrusion, extrusion blow molding, injection molding, rotational molding, thermoforming, etc.

This composition can thus be used for the manufacture of coatings, in particular floor and wall coverings, furniture, mesh parts or parts of the passenger compartment of motor vehicles (such as skins for dashboards, steering wheels and door cladding); clothing ; joints, particularly in the building or automobile industry; self-adhesive film, food, agricultural, stationery; sheets and roof plates, as well as cladding boards; profiles, including shower and window; shutters, doors, skirting boards, angles; cables; and devices for transporting or storing fluids, in particular tubes, ducts, pumps, valves or fittings; electrical boxes; garden hoses; bottles and flasks, foil, especially for packaging; stretch films; blood or solute bags; transfusion tubes; microgroove records; of toys ; panels; helmets; shoes ; draperies, curtains or tablecloths; buoys; gloves; blinds; fiber; glues and adhesives; of membranes. The invention therefore also relates to the aforementioned uses.

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

EXAMPLES

Example 1 Preparation of a PVC Latex

Example 1a: Emulsion Synthesis of a PVC Latex (Particle Diameter = 200 nm)

In a 30 liter autoclave equipped with an anchor-type stirring device, 10 liters of deionized water are introduced. 2.2 g of sodium formaldehyde sulfoxylate, 2.2 g of disodium salt of ethylene diamine tetraacetic acid and 0.24 g of pentahydrate iron sulfate are added. The autoclave is closed, the stirring is started at 80 rpm and it is drawn under vacuum at a pressure of 0.04 bar for 30 minutes. 8 kg of vinyl chloride monomer (VCM) are charged. The temperature of the reaction medium is then brought to 66 ^° C. by heating the autoclave via its double jacket in a heating ramp at 2 ° C./min. When the temperature reaches 66 ^° C., a solution of potassium persulfate in water at 2 g / liter is injected at a rate of 270 ml / hour for 1 hour and then at 180 ml / hour for 4 hours. After a period of 30 minutes at a temperature of 66 ^° C., a solution of sodium lauryl sodium sulfate at 80 g / liter is injected at a flow rate of 250 ml / hour for 4 hours. The reaction is continued until a pressure drop of -1 bar relative to the initial CVM pressure. At this level of pressure drop, the autoclave is cooled to 50 ^° C. by injection of water at 18 ^° C. into the double jacket. The total reaction time since the end of the heating ramp to -1 bar is approximately 5 hours. At 50 ^° C. under reduced stirring at 50 rpm, the CVM is degassed and the autoclave is then placed under dynamic vacuum for 4 hours in order to remove residual VCM. 19.2 kg of 37.5% latex of dry extract are thus recovered. The diameter of the elementary particles, measured with the Brookhaven granulometer, is 226 nm.

Example Ib: Emulsion Synthesis of a PVC Latex (Particle Diameter = 100 nm)

In a 30-liter autoclave equipped with an anchor-type stirring device, 8.8 liters of de-ionized water, 32 g of lauric acid and 9 g of potassium hydroxide are introduced from a solution at 100 g / liter. 1.1 g of sodium formaldehyde sulfoxylate, 1 g of disodium salt of ethylene diamine tetraacetic acid and 0.11 g of iron sulfate penahydrate are added. The autoclave is closed, the stirring is started at 80 rpm and it is drawn under vacuum at a pressure of 0.04 bar for 30 minutes. 8 kg of vinyl chloride monomer (VCM) are charged. The temperature of the reaction medium is raised to 55 ^° C. by heating the autoclave by means of its double jacket on a ramp of heating of 2 ° C / min. When the temperature reaches 55 ^° C., a solution of ammonium persulfate in water at 4 g / liter is injected at a rate of 200 ml / hour for 5 hours.

After a period of 30 minutes at a temperature of 55 ^° C., a solution of sodium dodecyl benzene sulphonate at 88 g / liter is injected at a flow rate of 250 ml / hour for 4 hours. The reaction is continued until a pressure drop of -1 bar relative to the initial CVM pressure. At this level of pressure drop, the autoclave is cooled to 40 ^° C. by injection of water at 18 ^° C. into the double jacket. The total reaction time since the end of the heating ramp to -1 bar is approximately 5 hours. At 40 ^° C. under reduced stirring at 50 rpm, the CVM is degassed and then the autoclave is placed under dynamic vacuum for 4 hours to remove the residual CVM. Thus, 18 kg of latex containing 39.3% of dry extract are recovered. The average particle size of the elementary particles, measured with the Brookhaven granulometer, is 115 nm.

Example 2; Preparation of a copolymer latex carrying associative groups

In a 30-liter autoclave equipped with an anchor-type stirring device, a system for condensing reflux vapors and taps for introducing the reagents, 10 liters of deionized water are introduced. 2.2 g of sodium formaldehyde sulfoxylate are added; 2.2 g of disodium salt of ethylene diamine tetraacetic acid and 0.24 g of iron sulfate pentahydrate. The autoclave is closed, stirring is started at 80 ° C. rpm and purge the medium by bubbling nitrogen for 30 minutes. 5.6 kg of methyl methacrylate are then successively charged; 0.48 kg of ethyl acrylate; 1.92 kg of Norsocryl ^® N102 Arkema (mixture of 25% by weight of ethyl imidazolidone methacrylate, EIOM, and 75% by weight methyl methacrylate); and 36.5 g of Arkema n-dodecyl mercaptan. The temperature of the reaction medium is then raised to 70 ^° C. by heating the autoclave via its double jacket in a heating ramp at 2 ° C./min. When the temperature reaches 70 ^° C., a solution of potassium persulfate in water at 2 g / liter is injected at a rate of 200 ml / hour for 1 hour and then at 150 ml / hour for 3 hours.

After 30 minutes at a temperature of 70 ^° C., a solution of sodium lauryl sulfate at 100 g / liter is injected at a flow rate of 250 ml / hour for 3.5 hours. After the addition of potassium persulfate and sodium lauryl sulfate, the reaction is completed by a treatment of one hour at 80 ^° C. with stirring. The autoclave is then cooled to 20 ^° C. by injection of water at 18 ^° C. into the double jacket. The total reaction time since the end of the heating ramp until the end of the treatment at 80 ^° C. is approximately 5 hours. 18.7 kg of 38.4% latex of dry extract are thus recovered. The diameter of the elementary particles, measured with the Brookhaven granulometer, is 235 nm.

Example 3 Mixing and Spraying Latex According to the Invention The latices of Example la (or Ib) and of Example 2 are diluted by adding deionized water to a solids content of 20%. 15 kg of each diluted latex are incorporated in a tank of 50 liters equipped with an anchor stirrer. The latex mixture is homogenized with stirring at 50 rpm for 1 hour at room temperature. After this homogenization step, the latex mixture is filtered on a 100 μm mesh wire mesh.

The latex mixture is then dried with a Niro Minor Production type atomizer equipped with a two-fluid bifluid nozzle having an internal diameter of 1 mm. The operating atomizing conditions are set as follows: inlet temperature = 15O ⁰ C, outlet temperature = 7O ⁰ C, atomization air pressure = 3 bar. Under these conditions, the drying rate stabilizes at 14 kg of latex / hour. The atomizer is kept in operation for 2 hours. 5.5 kg of mixing powder are thus obtained. The residual moisture content in the powder is less than 0.5%.

EXAMPLE 4 Mixing and coagulation / drying of the latices according to the invention

The latices of Example la (or Ib) and of Example 2 are diluted by adding deionized water to a solids content of 20%. 15 kg of each diluted latex are incorporated in a tank of 50 liters equipped with an anchor stirrer. The latex mixture is homogenized with stirring at 50 rpm for 1 hour at room temperature. After this step homogenization, the latex mixture is filtered on a wire mesh mesh 100 microns.

The 30 kg of the latex mixture are then introduced into a glass reactor with a volume of 60 liters and an inside diameter of 300 mm, which is provided with a double jacket heated by a thermoregulated bath and a stirring mobile. three-blade propeller, also called "impeller" with a diameter of 205 mm. The stirring speed is increased to 600 rpm in successive increments of 100 rpm. 180 ml of 95% concentrated sulfuric acid are added in 5 minutes to lower the pH of the mixture to 1. The coagulation of the latex is thus obtained. The coagulated latex is heated at 90 ^° C. for 30 minutes after a heating ramp at 2 ° C./minutes. At the end of this heating step, the coagulated latex is neutralized by casting a soda solution at 100 g / liter and then hot filtered under a pressure of 5 bar on a polypropylene fabric having an average pore size of 6. .mu.m. The filtrate is washed by adding 10 liters of deionized water and then dried at 60 ^° C. in a ventilated oven to constant weight. 5.9 kg of mixing powder are thus obtained. The residual moisture content in the powder is less than 0.5%.

Claims

A process for preparing a polymeric resin comprising the following steps of: forming a first latex from at least one halogenated vinyl polymer and a second latex from at least one copolymer comprising a on the one hand, units derived from a first monomer (A) rendering said copolymer compatible with said halogenated vinyl polymer and, on the other hand, units derived from a second monomer (B) bearing at least one associative group chosen from the imidazolidonyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups, preferably an imidazolidonyl group, 2-mixing said latexes, and

3- isolate and dry the polymers contained in said latex to form a powdery resin.

2. Method according to claim 1, characterized in that the copolymer is capable of being obtained from:

on the one hand, a monomer (A) which is a (meth) acrylic monomer chosen from: methyl methacrylate, (methoxy) polyethylene glycol (meth) acrylate, acrylonitrile and maleic anhydride,

- On the other hand, a monomer (B) bearing associative groups, preferably imidazolidonyl groups, which is advantageously chosen from: ethylimidazolidone methacrylate (or MEIO) and ethylimidazolidone methacrylamide (or WAM II) , and

optionally, one or more other monomers chosen from acrylic or methacrylic acids, their esters, their amides or their salts, itaconic acid, its esters, its amides or its salts, and styrene and its derivatives such as 4-styrene sulphonate.

3. Method according to one of claims 1 and 2, characterized in that said copolymer is obtainable by radical polymerization in aqueous emulsion.

4. Method according to any one of the claims

1 to 3, characterized in that the halogenated vinyl polymer is chosen from: polyvinyl chloride (PVC); ; copolymers of vinyl chloride with monomers selected from acrylonitrile, ethylene, propylene, or vinyl acetate; polyvinylidene chloride; and their mixtures.

5. Method according to any one of claims 1 to 3, characterized in that the halogenated vinyl polymer is chosen from fluorinated polymers comprising one or more monomers of formula (I):

CFX = CHX '(I)

where X and X 'independently denote a hydrogen or halogen atom (in particular fluorine or chlorine) or a perhalogenated (in particular perfluorinated) alkyl radical, preferably with X = F and X' = H.

6. Process according to any one of claims 1 to 3, characterized in that the halogenated vinyl polymer is chosen from:

polyvinylidene fluoride (PVDF), copolymers of vinylidene fluoride with, for example, hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) or tetrafluoroethylene (TFE),

homo- and copolymers of trifluoroethylene (VF3),

the fluoroethylene / propylene copolymers (FEP),

copolymers of ethylene with fluoroethylene / propylene (FEP), tetrafluoroethylene

(TFE), perfluoromethylvinyl ether (PFMVE), chlorotrifluoroethylene (CTFE) or hexafluoropropylene (HFP), and

- their mixtures.

7. Process according to any one of Claims 1 to 6, characterized in that the halogenated vinyl polymer is capable of being obtained by means of an aqueous micro-suspension polymerization process, optionally of inoculated type, or in aqueous emulsion.

8. Process according to any one of claims 1 to 7, characterized in that, in the second stage of the process, the latices are mixed in a ratio of the halogenated vinyl polymer to the copolymer bearing associative groups ranging from 1: 200 to 100. : 1, more preferably from 1: 100 to 1: 1 (in dry matter).

9. Method according to any one of claims 1 to 8, characterized in that, in the third step of the process, the latex is subjected to a spray drying process, coagulation or lyophilization.

10. Resin obtainable by the process according to any one of claims 1 to 9.

11. Composition comprising the resin according to claim 10 and optionally plasticizers.

12. Use of the composition according to claim 11 for the manufacture of coatings, including floor and wall coverings, furniture, mesh parts or parts of the passenger compartment of motor vehicles (such as skins dashboard, steering wheels and door trim); clothing ; joints, particularly in the building or automobile industry; self-adhesive film, food, agricultural, stationery; sheets and roof plates, as well as cladding boards; profiles, including shower and window; shutters, doors, skirting boards, angles; cables; and devices for transporting or storing fluids, in particular tubes, ducts, pumps, valves or fittings; electrical boxes; garden hoses; bottles and flasks, foil, especially for packaging; stretch films; blood or solute bags; transfusion tubes; microgroove records; of toys ; panels; helmets; shoes ; draperies, curtains or tablecloths; buoys; gloves; blinds; fiber; glues and adhesives; of membranes.