EP2274364A2 - Verfahren zur herstellung einer mischung aus einem halogenierten polymer und einem copolymer mit assoziativen gruppen - Google Patents

Verfahren zur herstellung einer mischung aus einem halogenierten polymer und einem copolymer mit assoziativen gruppen

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Publication number
EP2274364A2
EP2274364A2 EP09750041A EP09750041A EP2274364A2 EP 2274364 A2 EP2274364 A2 EP 2274364A2 EP 09750041 A EP09750041 A EP 09750041A EP 09750041 A EP09750041 A EP 09750041A EP 2274364 A2 EP2274364 A2 EP 2274364A2
Authority
EP
European Patent Office
Prior art keywords
copolymer
vinyl polymer
latex
halogenated vinyl
copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09750041A
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English (en)
French (fr)
Inventor
Manuel Hidalgo
Thierry Pascal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
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Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2274364A2 publication Critical patent/EP2274364A2/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

Definitions

  • 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.
  • WO 2006/016041 thus discloses polymers grafted with associative groups allowing to give them a higher elastic modulus and better resistance to solvents.
  • 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).
  • 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.
  • 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.
  • a halogenated vinyl polymer such as PVC
  • 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.
  • the present invention specifically relates to a process for preparing a polymer resin comprising the successive steps consisting of:
  • 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,
  • the present invention also relates to the resin obtainable by this method.
  • 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.
  • ком ⁇ онент it is meant that the halogenated vinyl polymer and the copolymer exhibit partial or complete miscibility.
  • 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.
  • SEM scanning electron microscopy
  • TEM transmission
  • AFM atomic force microscopy
  • Tg glass transition temperature measurements
  • the total miscibility results in the existence of a single Tg for the mixture
  • 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).
  • 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.
  • monomers (A) include (meth) acrylic monomers such as methyl methacrylate, polyethylene glycol methacrylate, methoxy polyethylene glycol methacrylate and acrylonitrile, or maleic anhydride.
  • 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.
  • PMMA-type copolymers carrying these associative groups
  • copolymers of polyethylene glycol side-chain monomers so-called PEG side-chain copolymers carrying these associative groups
  • associative groups 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.
  • 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,
  • 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.
  • ethylimidazolidone methacrylate or MEIO
  • ethylimidazolidone methacrylamide or WAM II
  • 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 sty
  • 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).
  • water-soluble radical polymerization initiators 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.
  • hydroperoxides such as tert-butyl hydroperoxide
  • water-soluble azo compounds such as 2,2'-azobis (2-amidinopropane) dihydrochloride
  • 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.
  • inorganic or organic reducing agents such as sodium or potassium bisulfite or metabisulphite, vitamin C (ascorbic acid), sodium or potassium hypophosphites.
  • 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.
  • chain transfer agents which make it possible to reduce the molecular masses.
  • 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.
  • 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.
  • additives such as antioxidants, such as butylhydroxytoluene (BHT), biocides and / or activators of polymerization initiators.
  • BHT butylhydroxytoluene
  • additives are generally used in proportions of between 0.01% and 5% by weight relative to the total weight of the monomers.
  • 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:
  • 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
  • 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;
  • 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.
  • 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.
  • 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
  • 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
  • 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.
  • 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.
  • the halogenated vinyl polymer may in particular be a fluorinated and / or chlorinated homo- or copolymer. It is usually a thermoplastic polymer.
  • 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.
  • 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.
  • fluoropolymers examples include:
  • PVDF polyvinylidene fluoride
  • HFP hexafluoropropylene
  • CFE chlorotrifluoroethylene
  • HFP hexafluoropropylene
  • VF3 trifluoroethylene
  • TFE tetrafluoroethylene
  • VF3 trifluoroethylene
  • 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; ⁇ m 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 ⁇ m,
  • an anionic emulsifier a soluble metal salt, in particular a copper salt,
  • a reducing agent such as ascorbic acid
  • 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.
  • the halogenated vinyl polymer is prepared by aqueous emulsion polymerization.
  • the halogenated vinyl polymer latexes, on the one hand, and the associative group-bearing copolymer according to the invention 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.
  • each of the latexes is diluted by adding water to a dry extract ranging from 10 to 40%, preferably from 15 to
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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).
  • a pulverulent resin containing an intimate mixture of the halogenated vinyl polymer and the associative group-carrying copolymer is obtained.
  • 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.
  • composition may be in particular in solid form or in the form of emulsions, suspensions or solutions.
  • composition according to the invention may contain various additives including one or more plasticizers.
  • polymeric plasticizers such as polyphthalates and polyadipates
  • monomeric plasticizers such as azelates, trimellitates (TOTM, TEHTM 7), 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.
  • 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),
  • - 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,
  • 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,
  • - 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,
  • additives may for example represent from 0.1 to 50% of the total weight of the composition.
  • 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.
  • 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.
  • 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.
  • 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 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 ⁇ m 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.
  • 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.
  • 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%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
EP09750041A 2008-05-07 2009-05-05 Verfahren zur herstellung einer mischung aus einem halogenierten polymer und einem copolymer mit assoziativen gruppen Withdrawn EP2274364A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0853030A FR2930945B1 (fr) 2008-05-07 2008-05-07 Procede de preparation d'un melange de polymere halogene et de copolymere porteur de groupes associatifs
PCT/FR2009/050827 WO2009141560A2 (fr) 2008-05-07 2009-05-05 Procédé de préparation d'un mélange de polymère halogéné et de copolymère porteur de groupes associatifs

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EP2274364A2 true EP2274364A2 (de) 2011-01-19

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EP (1) EP2274364A2 (de)
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WO2013043711A1 (en) 2011-09-19 2013-03-28 Fenwal, Inc. Red blood cell products and the storage of red blood cells in containers free of phthalate plasticizer
KR102554521B1 (ko) 2014-02-20 2023-07-11 프레제니우스 카비 도이치란트 게엠베하 적혈구 제품, 혈장 및 혈소판의 보관을 위한 비-ｄｅｈｐ 가소제를 갖는 의료용 컨테이너 및 시스템 구성요소
FR3067715B1 (fr) 2017-06-15 2019-07-05 Arkema France Encre a base de polymere fluore presentant une adhesion amelioree
CN113861459B (zh) * 2021-11-25 2023-07-21 四川轻化工大学 一种螺旋纳米碳纤维增强橡胶复合材料及其制备方法

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US2980652A (en) * 1958-09-19 1961-04-18 Rohm & Haas Unsaturated derivatives of n-(omega-aminoalkyl)-1, 3-cyclodiazolidin-2-ones and copolymers thereof
WO2005028557A1 (en) * 2003-09-23 2005-03-31 Solvay (Société Anonyme) Polymer composition
FR2891548B1 (fr) * 2005-10-05 2010-08-27 Solvay Dispersion aqueuse comprenant au moins un polymere du chlorure de vinylidene et au moins un copolymere

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FR2930945A1 (fr) 2009-11-13
US20110065860A1 (en) 2011-03-17
WO2009141560A3 (fr) 2010-01-28
WO2009141560A2 (fr) 2009-11-26

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