Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/18—Stationary reactors having moving elements inside
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
  • B01J3/008—Processes carried out under supercritical conditions
• • 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
  • C08F14/00—Homopolymers and 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
  • C08F14/18—Monomers containing fluorine
  • C08F14/22—Vinylidene fluoride
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00004—Scale aspects
  • B01J2219/00006—Large-scale industrial plants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00027—Process aspects
  • B01J2219/00033—Continuous processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00027—Process aspects
  • B01J2219/0004—Processes in series
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
  • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
  • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
  • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
  • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
  • B01J2219/00094—Jackets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00164—Controlling or regulating processes controlling the flow
  • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

• the present invention relates to a process for the preparation of halogenated polymers and the halogenated polymers obtained.
• the objective of the present invention is therefore to overcome these limitations by proposing a continuous process for the preparation of halogenated polymers in a medium comprising liquid or supercritical carbon dioxide.
• a process for the continuous preparation of halogenated polymers comprising the radical polymerization of halogenated monomers in a medium comprising liquid or supercritical carbon dioxide in at least two reactors mixed under pressure in series.
• the process for the continuous preparation of halogenated polymers according to the invention comprises the radical polymerization of halogenated monomers in two reactors mixed under pressure in series.
• monomers and polymers are understood to be in the singular as in the plural.
• the term continuous process is intended to denote, for the purposes of the present invention, a process in which the supply of carbon dioxide, of monomers, of initiators and additives and the withdrawal of the content of each of the reactors are carried out continuously.
• the continuous process according to the invention is such as the control of supplies, racking and other conditions of polymerization ensures stationary operating conditions for each of the reactors.
• the process of the invention is carried out in a medium comprising carbon dioxide in the liquid or supercritical state.
• the process according to the invention is carried out in a medium comprising carbon dioxide in the supercritical state.
• the polymerization conditions of the process in accordance with the present invention are independently controlled and adapted in each reactor.
• the temperature in each of the reactors is at least -
• the temperature is at most 200 ° C, preferably at most 175 ° C, particularly preferably at most
• the pressure in each of the reactors is at least 5 bar, preferably at least 35 bar, particularly preferably at least 40 bar. Usually, the pressure is at most 3000 bar, preferably at most 700 bar, particularly preferably at most 500 bar.
• the density of the medium in each of the reactors is at least 500 kg / m, preferably at least 600 kg / m. Usually, the density of the medium in each of the reactors is at most 1200 kg / m 3 , preferably at most 1000 kg / m 3 .
• a particular aspect of the process according to the invention is that the adjustment of the density of the medium makes it possible to control the mutual solubilities of carbon dioxide, of the monomers, of the initiators and of the additives on the one hand, and of the halogenated polymers obtained from somewhere else.
• the polymerization conditions in the last reactor are adapted to make the halogenated polymers obtained insoluble in the medium.
• Another aspect of the process according to the present invention provides, at least downstream of the last reactor, for a step of purifying the halogenated polymer.
• the purification of the halogenated polymer can be carried out by means of pure carbon dioxide or by means of a mixture of carbon dioxide and of monomers either pure or recycled.
• the purification is carried out by means of a mixture of carbon dioxide and monomers either pure or recycled.
• the purification is carried out by means of a mixture of carbon dioxide and recycled monomers.
• Another preferred aspect of the process according to the present invention further provides, at least downstream of the last reactor, a step of recycling carbon dioxide and unconverted monomers.
• This step of recycling carbon dioxide and unconverted monomers can optionally be accompanied by a step of purifying carbon dioxide and unconverted monomers.
• This step of recycling carbon dioxide and unconverted monomers can also optionally be accompanied by a step of separating one or more of the constituents of the mixture of carbon dioxide / unconverted monomers so as to be able to recycle separately.
• Another particularly preferred aspect of the process according to the present invention provides that the step of purifying the halogenated polymer and / or the step of recycling carbon dioxide and unconverted monomers is preceded by a step of concentrating the suspension containing the halogenated polymer.
• This concentration can be carried out in any device suitable for this purpose, for example, by means of filters, cyclones or any other device with a filtration, centrifugation or gravitation effect.
• a very particularly preferred aspect contemplates that, in the process according to the invention, at least one of the steps of purifying the halogenated polymer, recycling carbon dioxide and unconverted monomers, concentrating the suspension containing the halogenated polymer is carried out at a pressure sufficiently close to that of the reactors to carry out these operations with a moderate energy cost of recompression.
• radical polymerization of halogenated monomers is intended to denote, for the purposes of the present invention, both the homopolymerization of halogenated monomers and their copolymerization with other ethylenically unsaturated monomers which can be polymerized by the radical route, with a view to obtaining halogenated polymers.
• halogenated polymers is meant for the purposes of the present invention, both homopolymers and copolymers of halogenated monomers.
• halogenated monomers such as fluorolefins, for example vinylidene fluoride, vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene; fluoroacrylates; ethers fluorinated vinyls, for example perfluorinated vinyl ethers bearing perfluoroalkyl groups containing from 1 to 6 carbon atoms; vinyl chloride and vinylidene chloride.
• fluorolefins for example vinylidene fluoride, vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene
• fluoroacrylates such as fluorolefins, for example vinylidene fluoride, vinyl fluoride, trifluoroethylene,
• the process for the polymerization of halogenated monomers according to the invention applies to the polymerization of monomers containing fluorine with a view to obtaining polymers containing fluorine.
• fluorine-containing polymers is meant for the purposes of the present invention, both homopolymers and copolymers of fluorine-containing monomers.
• fluorine-containing monomers such as fluorolefins, for example vinylidene fluoride, vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene; fluoroacrylates and fluorinated vinyl ethers, for example perfluorinated vinyl ethers carrying perfluoroalkyl groups containing from 1 to 6 carbon atoms.
• copolymers formed by these fluorine-containing monomers with one another such as for example the copolymers of vinylidene fluoride with another fluorinated monomer as defined above and the copolymers of one of the fluorine-containing monomers mentioned above.
• another ethylenically unsaturated monomer such as olefins, for example ethylene, propylene, styrene derivatives and styrene; halogenated olefins; vinyl ethers; vinyl esters such as for example vinyl acetate; acrylic acids, esters, nitriles and amides and methacrylic acids, esters, nitriles and amides.
• the process for the polymerization of halogenated monomers according to the invention applies to the polymerization of vinylidene fluoride with a view to obtaining polymers of vinylidene fluoride.
• vinylidene fluoride polymers is intended to denote, for the purposes of the present invention, both homopolymers of vinylidene fluoride and its copolymers with other ethylenically unsaturated monomers, which they are fluorinated (fluorolefins, for example vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene; fluoroacrylates; fluorinated vinyl ethers such as perfluorinated vinyl ethers carrying perfluoroalkyl groups containing from 1 to 6 carbon atoms) or not (olefins as for example ethylene, propylene, styrene derivatives and styrene; halogen
• Homopolymers of vinylidene fluoride and copolymers of vinylidene fluoride with a fluorinated comonomer are preferred. Homopolymers of vinylidene fluoride and copolymers of vinylidene fluoride and chlorotrifluoroethylene and copolymers of vinylidene fluoride and hexafluoropropylene are particularly preferred.
• the copolymers obtained preferably contain at least about 75% by weight of monomeric units derived from vinylidene fluoride.
• the total concentration of monomers in each of the reactors is usually at least 0.5 mole / liter, preferably at least 1 mole / liter.
• the total concentration of monomers in each of the reactors is usually at most 10 mole / liter, preferably at most 6 mole / liter.
• the polymerization process according to the invention is carried out by radical route and usually provides for the use of one or more initiators, the nature, number and concentration of which can also be chosen independently in each reactor, according to requirements.
• any suitable radical initiator can be used, in particular an organic radical initiator chosen for example from peroxides, such as diethyl peroxydicarbonate, diketyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxyisopropylcarbonate, t-butyl peroxy-n-decanoate, t-butyl peroxyacetate, di-t-butyl peroxide, dibenzoyl peroxide, dibenzoyl peroxide dioctanoyl, dilauroyl peroxide, dicumyl peroxide, di-t-amyl peroxide, t-but
• the concentration of initiators in each of the reactors is usually between 5 ⁇ 10 ⁇ 5 mole / liter and 0.1 mole / liter.
• the polymerization of the process of the present invention can optionally be carried out in the presence of one or more surfactants or one or more dispersing agents Any surfactant or any suitable dispersing agent known to those skilled in the art can be used.
• the process according to the invention can optionally be carried out in the presence of other additives than the additives mentioned above (initiators, surfactants, dispersing agents) making it possible to improve the implementation of the process and / or the characteristics of the resulting polymer.
• additives examples include chain transfer agents, anti-crusting agents, anti-static agents and co-solvents.
• the polymerization step according to the present invention is carried out in reactors mixed under high pressure. These mixed reactors can be of any type known to those skilled in the art, provided that they withstand the temperatures and high pressures necessary for carrying out the process.
• mixed reactor is intended to denote, for the purposes of the present invention, a reactor provided with a mixing device serving for the homogenization of the reaction medium, such as for example paddle, screw or turbine agitators.
• a mixing device serving for the homogenization of the reaction medium, such as for example paddle, screw or turbine agitators.
• Each of the reactors can be of a different type.
• reactors can also be individually equipped with a heating system and / or a cooling system used to control the temperature in each of the reactors.
• the reactor temperature will usually be controlled by a heat exchange system consisting, for example, of a jacket or a heat exchanger inside the reactor, conveying a heat transfer fluid.
• the heat released can be used to bring the reactants and (co) solvents up to temperature downstream and / or upstream of the reactor in question.
• the process of the invention also allows the pressure, density and other polymerization conditions to be adapted independently in each reactor, on the one hand, by regulating the flow rate and / or of the pressure at the outlet of each reactor for example by taking a part of the production of said reactor, and, on the other hand, by feeding each reactor with monomers, initiators, additives and / or carbon dioxide.
• the present invention further relates to halogenated polymers, which can in particular be obtained by the process according to the invention, with bi- or plurimodal distribution of molecular weights.
• the bi- or plurimodal distribution of the molecular masses of the polymers according to the invention is preferably characterized by a first mode situated between 10 kg / mole and 100 kg / mole and by a second mode 3 to 30 times greater than the first.
• the bi- or plurimodal distribution of the molecular weights of the polymers according to the invention is particularly preferably characterized by a first mode situated between 20 kg / mole and 70 kg / mole and by a second mode 5 to 20 times greater than the first.
• the bi- or plurimodal distribution of the molecular weights of the polymers according to the invention is preferably such that the weight fraction of the first sub-distribution is between 0.2 and 20% by weight and in a particularly preferred manner such that the weight fraction of the first sub-distribution is between 1 and 10% by weight.
• the halogenated polymers according to the invention are characterized by a bimodal distribution of molecular weights which can have the abovementioned characteristics as regards the first and second modes and as regards the weight fraction of the first sub-distribution.
• the halogenated polymers according to the invention are characterized by a ratio between the dynamic viscosity measured at a frequency of 0.1 rad / s and that measured at a frequency of 100 rad / s, greater than or equal to 10.
• Halogenated polymers characterized by a ratio between the dynamic viscosity measured at a frequency of 0.1 rad / s and that measured at a frequency of 100 rad / s, greater than or equal to 20 are particularly desired and those characterized by a such a ratio greater than or equal to 40 are very particularly desired.
• the halogenated polymers according to the invention are characterized by a bi- or plurimodal distribution of the degree of incorporation of the monomers.
• the present invention further relates to halogenated polymers, which can in particular be obtained by the process according to the invention, with bi- or plurimodal distribution of the degree of incorporation of the monomers.
• halogenated polymers can be characterized by a monomodal distribution or by a bi- or plurimodal distribution of molecular masses.
• these halogenated polymers are characterized by a bi- or plurimodal distribution of molecular weights.
• the bi- or plurimodal distribution of the molecular masses of the polymers according to the invention is preferably characterized by a first mode situated between 10 kg / mole and 100 kg / mole and by a second mode 3 to 30 times greater than the first.
• the bi- or plurimodal distribution of the molecular weights of the polymers according to the invention is particularly preferably characterized by a first mode situated between 20 kg / mole and 70 kg / mole and by a second mode 5 to 20 times greater than the first.
• the bi- or plurimodal distribution of the molecular weights of the polymers according to the invention is preferably such that the weight fraction of the first sub-distribution is between 0.2 and 20% by weight and in a particularly preferred manner such that the weight fraction of the first sub-distribution is between 1 and 10% by weight.
• these halogenated polymers are characterized by a bimodal distribution of the molecular masses which can have the abovementioned characteristics as regards the first and second modes and as regards the weight fraction of the first sub-distribution.
• the halogenated polymers according to the invention are characterized by a ratio between the dynamic viscosity measured at a frequency of 0.1 rad / s and that measured at a frequency of 100 rad / s, greater than or equal to 10
• Halogenated polymers characterized by a ratio between the dynamic viscosity measured at a frequency of 0.1 rad / s and that measured at a frequency of 100 rad / s, greater than or equal to 20 are particularly desired and those characterized by such a ratio greater than or equal to 40 is very particularly desired.
• molecular weight distribution is meant for the purposes of the present invention, that measured by steric exclusion chromatography.
• the distribution of molecular weights is called unimodal if it can be described, in the case of an asymmetric distribution by the relation (1), or in the case of a symmetrical distribution by the relation (2) ):
• the distribution of molecular masses is called bimodal, if it can only be described by the combination of two sub-distributions according to the relation (1) and / or (2), with a coefficient of determination d 'at least 0.99, the deconvolution of the bimodal distributions making it possible to quantify the mass proportions of each of two sub-distributions by the area of the peaks.
• the deconvolution is carried out by the combination of relations (1) and / or (2) specific to each of the sub-distributions.
• dynamic viscosity is meant, for the purposes of the present invention, the viscosity determined by means of an imposed deformation rheogoniometer, marketed by RHEOMETRICS under the name ARES (ADVANCED RHEOLOGICAL EXPANSION SYSTEM), on a sample, placed between 2 trays parallel and subjected to deformation, 25 mm in diameter and 2 mm thick cut from a pressed plate.
• ARES ADVANCED RHEOLOGICAL EXPANSION SYSTEM
• degree of incorporation of the monomers is meant, for the purposes of the present invention, the amounts expressed in percent of the different monomers which constitute the halogenated polymer.
• bi- or plurimodal distribution of the incorporation rate of each monomer is meant, for the purposes of the present invention, any mass distribution of this incorporation rate which has two or more modes.
• the process and the polymers according to the invention have multiple advantages.
• the mechanical and rheological properties of polymers usually depend not only on the molecular weight and incorporation rate of the various monomers in the polymer, but also on their complete distributions.
• the method according to the invention makes it possible to obtain halogenated polymers having bi- or plurimodal distributions of molecular weights and / or bi- or plurimodal distributions of the rate of incorporation of the various monomers in the polymer chain. Optimizing this type of distribution makes it possible to particularly improve the processability and the physical properties of the objects used.
• the process according to the invention is particularly advantageous in this respect, thanks to better control of the parameters and more targeted control of the conditions under which the polymerization takes place in each of the reactors in series.
• the different components of the bi- or plurimodal distributions are obtained directly as an intimate mixture on the molecular scale, which makes the polymers obtained more efficient compared to blends in the molten state of different polymers of monomodal distributions of molecular weights and incorporation rate of the different monomers.
• the method according to the invention also makes it possible to vary the arrangement of the monomers in the polymer chain of the polymers obtained.
• Figure 1 illustrates the present invention without limiting its scope. It represents a schematic view of an embodiment of the process of the present invention for two reactors connected in series.
• a first reactor is continuously supplied with carbon dioxide, initiators, monomers and additives; part of the carbon dioxide and unconverted monomers recovered downstream from the second reactor can also be recycled there.
• the control of the supplies of the first reactor makes it possible to control the residence time and the concentrations of the various constituents there.
• the state of mixing in the reactor is obtained by an appropriate device.
• the heat of polymerization is used to bring the contents of the reactor to the reaction temperature, any excess heat is removed by circulation of a cold fluid in a double jacket or in a heat exchange device located in the reactor. . This makes it possible to control the temperature of the first reactor.
• the content of the first reactor comprising the polymer produced is withdrawn to the second reactor.
• This controlled withdrawal makes it possible to regulate the pressure of the first reactor.
• the second reactor can also be supplied with carbon dioxide, the initiator, monomers and pure additives, as well as with the rest of the carbon dioxide and unconverted monomers recovered downstream from the second reactor and recycled.
• the control of the supplies of the second reactor makes it possible to control a residence time and concentrations of different compounds different from the residence time and the concentrations prevailing in the first reactor.
• the thermal control of the second reactor follows the same principles as the thermal control of the first reactor, and allows it to impose a temperature different from the temperature of the first reactor.
• the suspension of particles of the polymer is drawn off towards a sector for concentrating the suspension containing the halogenated polymer.
• This controlled withdrawal makes it possible to regulate a pressure in the second reactor different from the pressure of the first reactor.
• the fluid (continuous phase) separated from the polymer suspension in the concentration sector is recycled under high pressure to the reactors or also directed under high pressure, to a sector for purifying the polymer.
• the concentrated polymer suspension is then directed to a polymer purification sector, where carbon dioxide and / or pure monomers can be used to rid the polymer of residues of initiators, polymerization additives and sub- products.
• the carbon dioxide and / or the pure or recycled monomers added for the purification, as well as the carbon dioxide, the monomers and the unconverted monomers accompanying the polymer at the exit of the concentration sector of the suspension are then directed , depending on their pressure level, either directly to the high pressure recycling, ie towards a low pressure recycling sector.
• the purified polymer is finally conditioned and packaged, constituting the finished product.

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• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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