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    • 专利摘要:
    The invention therefore proposes a new process for the continuous preparation of anionic polymers by radical polymerization. The polymers prepared by this process have a controlled molecular weight
    公开号:FR3030527A1
    申请号:FR1462899
    申请日:2014-12-19
    公开日:2016-06-24
    发明作者:Jean-Marc Suau；Yves Matter；Dominique Peycelon
    申请人:Coatex SAS；
    IPC主号:
    专利说明:

    [0001] The invention relates to a process for the continuous preparation of anionic polymers by radical route, as well as the polymers obtained by this method. BACKGROUND ART The continuous polymerization of free radical anionic polymers has already been described in application US 2014/0088280. In this application, the inventors have sought to develop a process for the preparation of anionic polymers in solution with a defined molar distribution, very narrow mass, energy efficient, that is to say without preheating, with a risk of clogging in the micromixer and or the reduced reactor and / or to the extent possible to avoid corrosion problems in the case of the use of monomers containing acidic groups. The inventors have thus proposed the use of micro-reactors having an internal diameter of less than 30 mm. Their process requires several mixtures upstream of the microreactor and a microreactor per zone of polymerization. However, it is still in search of methods for continuously polymerizing radically polymerizable anionic monomers, whose polymerization reaction is particularly exothermic and fast, which generates many technical and safety problems. In particular, acrylic acid, which is an extremely reactive monomer, will be mentioned. This is why, from an industrial point of view, today, it is still preferable to use semibatch processes which, however, generate relatively long cycle times.
    [0002] In addition, to the knowledge of the inventors, in the continuous reactors proposed to date, there are problems of formation of plugs blocking the reactors, due to the formation of gels during the polymerization. In addition, transformation rates are often low and may require additional treatments.
    [0003] DESCRIPTION OF THE INVENTION The invention thus proposes a new process for the continuous preparation of anionic polymers by radical polymerization. The polymers prepared by this process have a controlled molecular weight and a low polydispersity index.
    [0004] The subject of the invention is a process for the continuous preparation of an anionic polymer, with a molecular weight Mw of less than 10 000 g / mol, of dry extract (ES) of between 20% and 60% by weight, relative to total weight of the formula, by radical polymerization, comprising the following steps: a) at least one monomer chosen from acrylic acid, methacrylic acid and mixtures thereof, said monomer being able to be partially neutralized, b) has water, possibly hot, c) There is at least one initiator, d) Possibly at least one chain transfer agent, e) The components of steps a), b), c are introduced ) and d) in a tubular reactor having a length LR of at least 5 m and comprising at least one tubular section of length Ls and internal diameter D with Ls >> D, in which each tubular section comprises over its entire length a plurality of stationary baffles, opposed to the flow, under the fo rme of washers with a diameter identical to the internal diameter of the tubular section, thus forming a fluid in the tubular reactor, f) the tubular section is connected to a device for subjecting said fluid to an oscillatory movement, g) polymerization reaction in said reactor, optionally with a heating means for initiating the polymerization reaction, with a residence time in the reactor greater than 1 min, the residence time, the size of the holes in the baffles, their spacing , the movements of the device are chosen so as to ensure at all points in the reactor a good homogeneity of the mixture, h) is obtained at the outlet of the reactor said anionic polymer dissolved in water. The polymers are generally characterized by two indices / magnitudes / values: the polydispersity index PDI (also known as IP polymolecularity equivalent) and the molecular weight Mw (also referred to as an equivalent molar mass or molecular weight), expressed in terms of g / mol.
    [0005] The polydispersibility index PDI of the polymer is calculated as follows: it is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn.
    [0006] The polydispersity index reflects the molar mass distribution of the different macromolecules within the polymer solution. If all the macromolecules have the same degree of polymerization (thus the same molecular weight), this index is close to 1. If on the other hand, the macromolecules have different degrees of polymerization (and therefore different molecular weights), the PDI index is greater than 1. The molecular weight Mw and the PDI index are determined by gas chromatography (GPC) according to the method described before the examples.
    [0007] The molecular weight Mw of the anionic polymer obtained by the process according to the invention is advantageously between 1500 and 10 000 g / mol, more advantageously between 3500 and 7000 g / mol. The polydispersity index of the anionic polymer obtained by the process according to the invention is advantageously less than 4, more preferably less than 3.5, still more advantageously less than 3, and even more advantageously less than 2.5. The polydispersity index of the anionic polymer obtained by the process according to the invention is advantageously between 1.5 and 4, more advantageously between 1.5 and 3.5, more advantageously between 1.5 and 3, even more more preferably between 1.5 and 2.5. The solids content (ES) of the anionic polymer obtained by the process according to the invention is advantageously between 30% and 60% by weight or between 40% and 60% by weight, relative to the total weight of the formula.
    [0008] Monomers The monomer is selected from acrylic acid, methacrylic acid and mixtures thereof. Thus, the anionic polymer obtained may be a homopolymer or a copolymer.
    [0009] "Homopolymer or copolymer of (meth) acrylic acid" means either a polymer consisting exclusively of acrylic acid (homopolymer of acrylic acid) or a polymer consisting exclusively of methacrylic acid (homopolymer of methacrylic acid) or alternatively a polymer consisting of a mixture of acrylic acid and methacrylic acid (acrylic acid-methacrylic acid copolymer). In the latter case, according to one aspect of the invention, the molar ratio between acrylic acid monomers and methacrylic acid monomers can vary between 1: 100 and 100: 1, for example between 1: 1 and 100: 1 or between 1: 1 and 50: 1.
    [0010] Said monomer may be partially neutralized. Thus, in an alternative embodiment, 2% to 50% by weight of the (meth) acrylic acid monomer, relative to the total weight of the introduced (meth) acrylic acid monomer, is neutralized. It can be by means of a single neutralization agent or several neutralization agents. The monomer may for example be partially neutralized with an alkaline or alkaline earth hydroxide, an alkaline earth oxide, and / or with an amine. By way of example, mention may be made of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, calcium oxide and potassium oxide.
    [0011] Furthermore, the copolymer according to the invention may also comprise, in addition, one or more other ethylenically unsaturated monomer (s) chosen from the group consisting of 2-acrylamido-2- acid. methylpropanesulphonic acid (AMPS), maleic acid, fumaric acid, crotonic acid, itaconic acid, unsaturated telomers of acrylic acid, the monomers of formula (I): in which: - Ra, Rb and 12 represent, independently of one another, H or CH3, n is an integer ranging from 0 to 2 (i.e., 0, 1 or 2). In particular, the monomer may be allyl alcohol (n = 1), methallyl alcohol (n = 1), isoprenol (n = 2). Advantageously, isoprenol is used. By "unsaturated telomers of acrylic acid" is meant oligomers of acrylic acid or acryloxypropionic acid, of formula (II): ## STR2 ## where n is a variant integer from 1 to 10. These different oligomers can be mixed. When n = 1, the oligomer is a dimer of acrylic acid. In the presence of other unsaturated monomer (s), according to one aspect of the invention, the molar ratio between monomers of (meth) acrylic acid and other unsaturated monomer (s) can vary between 1: 1 and 100: 1, for example between 1: 1 and 75: 1 or between 1: 1 and 50: 1. The monomer is advantageously acrylic acid. At least one initiator and optionally at least one chain transfer agent are introduced into the reactor with these monomers. It is also possible to introduce at least one catalyst based on water-soluble metal salts. By "initiator" is meant, according to the present invention, a priming system comprising an oxidizer and optionally a reducing agent.
    [0012] In particular, the following systems are used: - hydrogen peroxide (H 2 O 2), a catalyst based on water-soluble metal salts, dipropyl dipropionic acid trithiocarbonate (DPTTC, CAS No. 6332-91-8) or its salts, for example its salt disodium (sodium dipropionate trithiocarbonate OR disodium salt of 2,2 '- [carbonothioylbis (thio) [bis-propanoic acid, CAS No. 86470-33-2), as represented by formula (III) below : S NaO ONa SS 0 H2O2, water-soluble metal salt catalyst, H2O2, water-soluble metal salt catalyst, sodium hypophosphite, H2O2, sodium hypophosphite, H2O2, water-soluble metal salt catalyst, sodium betabisulfite or sodium metabisulphite, Persulfate, water-soluble metal salt catalyst, Persulfate, sodium betabisulphite or sodium metabisulphite, Persulfate, sodium hypophosphite, with or without a water-soluble metal salt catalyst, Persu lfate, H 2 O 2, sodium hypophosphite, with or without a water-soluble metal salt catalyst, H 2 O 2, dipropyl trithiocarbonate, sodium hypophosphite, with or without a catalyst based on water-soluble metal salts.
    [0013] The persulfate is advantageously a sodium persulfate. The water-soluble metal salt catalyst is preferably selected from the group consisting of copper carbonates, copper sulfate, iron sulfate and a mixture of these compounds. When the system comprises hydrogen peroxide and a catalyst based on water-soluble metal salts, it is also possible to add hydroxylamine sulfate, which in particular makes it possible to lower the initiation temperature and to reduce the induction time.
    [0014] Mercaptans, as sole transfer agent or with the above-mentioned transfer agents, can be used to limit molecular weights. The polymerization is conducted substantially in water.
    [0015] Process Each of the components of steps a), b), c), d) is introduced into the reactor. Advantageously, at least one catalyst based on water-soluble metal salts is also available. The water can be hot. "Hot" means that the water is at a temperature above 20 ° C, up to its boiling point. In a variant, the water is heated to a temperature greater than 60 ° C., for example greater than 80 ° C.
    [0016] The method according to the invention makes it possible to envisage a large number of possibilities in the introduction of the components, depending on the nature of the components and the final application properties of the desired polymers. Thus, each of the components can be introduced at the same point in the reactor or at different points. In addition, for each of the components, the introduction can be total or sequenced in different parts of the reactor, with a constant or variable flow rate. According to one embodiment, the initiator is introduced at the inlet and / or downstream of the reactor, in one or more times. When the initiator comprises an oxidant and a reducing agent, their administration can be separated.
    [0017] According to another embodiment, the transfer agent is introduced at the inlet and / or downstream of the reactor, in one or more times. According to another embodiment, the monomer is introduced at the inlet and / or downstream of the reactor, in one or more times. According to one embodiment, the catalyst based on water-soluble metal salts is introduced at the inlet and / or downstream of the reactor, in one or more times.
    [0018] Each of these compounds can be introduced alone, or in admixture with any or all of the other compounds, in suitable proportions. For the purposes of the present invention, the term "downstream" means an introduction point which is closer to the outlet of the reactor than is the point of entry of the reactor. When the monomer is mixed with water before introduction into the reactor, the mixture is homogenized, advantageously in a static mixer (for example of the Sulzer SMX® type). In this homogeneous mixture, it is also possible to add: at least one initiator, optionally at least one transfer agent, optionally at least one catalyst based on water-soluble metal salts. The method according to the invention is characterized in that a device for subjecting the fluid to oscillatory movement is employed.
    [0019] The amplitude of the oscillatory movement advantageously varies from 0.3xd2 to 4xd2, more preferably from 0.7xd2 to 3xd2, still more preferably from 1xd2 to 2xd2. d2 is the external diameter of the baffles, as defined after.
    [0020] The frequency of the oscillatory movement advantageously varies from 0.1 to 100 Hz, more advantageously from 0.1 to 10 Hz, for example from 0.1 to 5 Hz, from 0.5 to 5 Hz or from 3 to 10 Hz. one embodiment, the amplitude of the oscillatory movement varies from 0.3xd2 to 4xd2, and the frequency of the oscillatory movement varies from 0.1 to 100 Hz. In the process according to the invention, the reactor is filled with liquid. Some reactions can generate gases but ideally one remains under conditions such that the fluid filling rate of the reactor, namely the volume occupied by the liquid in the reactor relative to the total volume of the reactor, is greater than 90%. In startup, the reactor is advantageously filled with water, which can be hot.
    [0021] The device is any means for imposing oscillatory directional motion on the fluid. This device may for example be a hydraulic piston, one or more membranes, a mechanical piston. This device may be external to the tubular reactor.
    [0022] The reactor / device assembly forms a COBR for "Continuous Baffled Reactor". The term "tubular" means a reactor whose length is much greater than the section.
    [0023] In one embodiment of the present invention, this section is circular. In this case, we speak of a cylindrical tubular reactor. In the present invention, the embodiment in which the section is circular is described in detail. This description will be adapted by those skilled in the art when the section is not circular. The tubular reactor comprises at least one tubular section of length Ls and of internal diameter D with Ls >> D. By far superior, ">>" means that the length Ls is at least 20 times greater than the internal diameter D. Ls may be identical to LR. To save space on the ground, the tubular reactor may comprise at least two tubular sections, each tubular section has an identical internal diameter, mounted substantially in parallel and connected by a bend. The elbow preferably has the shape of a U. The elbow also includes baffles advantageously. Advantageously, each tubular section has a constant internal diameter, which is identical from one section to another. D is advantageously less than 20 cm, more preferably less than 15 cm, still more preferably less than or equal to 10 cm. D is advantageously greater than 3 cm. In the zones where the polymerization can take place, each tubular section of the reactor comprises along its length a plurality of stationary baffles, opposite the flow.
    [0024] By "flow-opposed" is meant, according to the present invention, that the angle of the baffles, with respect to the flow, varies from 80 ° to 100 °. 11 is for example perpendicular or substantially perpendicular.
    [0025] The baffles are in the form of washers with a diameter identical to the internal diameter D of the tubular section. The baffles can be arranged on a rail thus facilitating their placement. This rail can be easily removed and then reintroduced into the tubular section, thus facilitating cleaning and maintenance of the reactor.
    [0026] The term "washers" discs with concentric annular holes which have the appearance of washers. The largest diameter of this washer is called external diameter d2. The term "of a diameter identical to the internal diameter of the tubular section" that the outer diameter d2 is substantially equal to the diameter D to force all the material to cross the baffle through its central opening, while being slightly lower for allow handling (insert / withdrawal) of the rail without friction, in particular during the cleaning / maintenance phases of the reactor.
    [0027] The baffles are spaced, regularly or not, a distance advantageously from 1D to 3D, but allowing the maintenance of homogeneity. In a variant, the spacing between the baffles is regular. In another variant, the spacing between the baffles is irregular. Advantageously, the baffles are spaced apart by a distance ranging from 1D to 2.5D, for example 2D.
    [0028] The spacing of the baffles can be adapted according to the progress of the polymerization reaction, and thus be different in the zones where the polymerization begins, in the zones where the polymerization is in progress, in the zones where the polymerization ends .
    [0029] The presence of baffles is necessary during the polymerization process. Thus, advantageously, as long as the conversion rate of the monomer is less than 90%, the tubular reactor comprises baffles.
    [0030] Advantageously, the baffles comprise concentric annular holes such that the ratio d 2 / d 1, where d 2 is the external diameter of the washer and the internal diameter of the washer, varies from 1.2 to 5, more advantageously from 1.5 to 2.5.
    [0031] The residence time in the reactor is advantageously between 1 min and 20 min, more advantageously between 1 min and 10 min. The flow rate in each tubular section can be raised to very high. It is advantageously greater than 20 kg / h, more preferably greater than 100 kg / h and can be up to 1 or several ton (s) / h, depending on the diameter. At different points in the reactor, it is possible to introduce reagents. It is also possible to insert measuring and / or control devices, probes or sensors, in particular for measuring online or continuously the temperature, the pressure, the conversion rate, the viscosity. Examples include infrared, near or medium IR measurements and RAMAN measurements. The heating means may be the introduction of hot water directly into the tubular reactor and / or the reactor may include one or more devices for providing calories, such as a jacket. In one embodiment, the reactor comprises at least one device for supplying or discharging calories, such as double jacket sections, allowing temperature control that may be different from one zone to another .
    [0032] Depending on the needs, the means may heat or cool some sections of the tubular reactor. An example of a reactor is shown in FIG. 1. In this figure, a tubular baffled reactor is generally shown at 1 and comprises tubular sections 2 connected by U-bends 3. Extending radially inwards from the side of the container, a number of annular baffles 4. The annular baffles are joined together by rails (not shown in Figure 1) in a substantially equidistant manner, and are arranged substantially in parallel. The annular baffles are present in each tubular section, including in the U-bends (even if they are not shown in Figure 1). The reactor comprises an inlet 5 and an outlet 6. The reactor 1 also comprises reagent introduction zones and measurement zones, represented by the I / O symbol in the figure. I / O means input / output, and thus shows that it is possible to introduce reagents or measuring devices into the reactor but that it is also possible to take samples for example. In input, the reactor is connected to an external device 9 for subjecting the fluid to an oscillatory movement. This figure also shows tubular sections not comprising baffles, in areas where the polymerization is complete (consumption of the monomer and / or radicals) and where the polymer formed can for example be neutralized. There is no representation here of a double envelope, or double envelope segment, which would make it possible to control and maintain a constant temperature or a uniform temperature profile gradient in the reactor 1 by means of a cooler. heater. In Figure 2, there is shown the internal diameters d1 and external d2 of the baffle. The process according to the invention makes it possible to effectively control the molecular weight of the polymer formed. It also makes it possible to obtain polymers having a low polydispersity index. By the process, the conversion rate of the monomer is high. It varies advantageously from 80% to 100%, for example from 90% to 100%. The polymers obtained by the process according to the invention or by using an apparatus according to the invention can be used as an anti-scale agent in the treatment of water or as an additive in detergent formulations. In an advantageous variant of the invention, a neutralization agent, such as an alkali metal or alkaline earth metal hydroxide, is also injected into the reactor in a zone where the conversion of the monomer is greater than 90%. . Such an injection will allow to conduct in the same reactor a neutralization reaction of the polymer formed. The polymer may be totally or partially neutralized by means of one or more neutralizing agents, for example monovalent (or monofunctional) or plurivalent (multifunctional or divalent) agents.
    [0033] If the polymer is partially neutralized, it can be by means of a single neutralizing agent or several neutralizing agents. For example, it is possible to envisage the following methods of neutralization, alone or in combination: a molar percentage of neutralization of the active acid sites of the polymer with a neutralization agent containing the calcium ion of between 2% and 60%; for example between 25% and 55% or between 2% and 15%, a molar percentage of neutralization of the active acid sites of the polymer with one or more monofunctional neutralization agents containing sodium ion and / or lithium ion and or the potassium ion of between 7% and 97%, for example between 20% and 60% or between 60% and 97%, a molar percentage of neutralization of the active acid sites of the polymer with a neutralizing agent containing the magnesium, barium, zinc, aluminum or amine ion or mixtures thereof and in particular by a neutralization agent containing the magnesium ion of between 0% and 60%, for example between 10% and 55%. From the zone of introduction of these neutralizing agents, the tubular sections may or may not include the baffles.
    [0034] At the outlet, the reactor can be connected to a tubular reactor equipped or not with an oscillating device as defined above, with a stirred reactor, a flash distillation column. The tubular may make it possible to conduct a neutralization reaction of the polymer formed. The flash distillation column makes it possible to increase the dry extract of the polymer by the use of the calories resulting from the polymerization and the elimination of the water by expansion. The process according to the invention is particularly suitable for the synthesis of poly (acrylic acid). By the process according to the invention, it is possible to obtain a poly (acrylic acid) with a molecular weight Mw of between 1000 and 10,000 g / mol and a PDI polydispersity index of between 1.5 and 4. It is then possible to to easily neutralize it continuously, either in the tubular reactor itself, or in a tubular connected to the reactor, as described above.
    [0035] The molecular weight Mw of the poly (acrylic acid) obtained by the process according to the invention is for example between 1500 and 10 000 g / mol, or for example between 3500 and 7000 g / mol.
    [0036] The polydispersity index PDI is advantageously between 2 and 3, more advantageously between 2 and 2.6. The subject of the invention is therefore also a process according to the invention, in which the monomer is acrylic acid and the polymer obtained is poly (acrylic acid) with a molecular weight Mw of between 1,000 and 10,000 g / mol and with a polydispersity index between 1.5 and 4. The subject of the invention is also the anionic polymers obtained by the process according to the invention.
    [0037] Description of the Methods for Characterizing the Polymers Obtained Molecular Weight Mw of the Polymer Such a technique uses a WATERST ™ liquid chromatography apparatus equipped with a detector. This detector is a WATERS refractometric concentration detector. This liquid chromatography apparatus is provided with a steric exclusion column appropriately chosen by those skilled in the art in order to separate the different molecular weights of the polymers studied. The liquid elution phase is an aqueous phase adjusted to pH 9 with 1N sodium hydroxide containing 0.05M NaHCO 3, 0.1M NaNO 3, 0.02M trietanolamine and 0.03% NaN 3. In a detailed manner, according to a first step, the polymerization solution is diluted to 0.9% dry in the solubilization solvent of the CES, which corresponds to the liquid phase of elution of the CES to which 0.04% is added. of dimethylformamide which acts as a flow marker or internal standard. Then filtered at 0.2 μm. 100 μl are then injected into the chromatography apparatus (eluent: an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05M NaHCO 3, 0.1M NaNO 3, 0.02M trietanolamine and 0.03% NaN3). The liquid chromatography apparatus contains an isocratic pump (WATERSTM 515) with a flow rate of 0.8 ml / min. The chromatography apparatus also comprises an oven which itself comprises in series the following column system: a precolumn GUARD COLUMN type ULTRAHYDROGEL WATERSTm 6 cm long and 40 mm internal diameter, and a linear column type ULTRAHYDROGEL WATERSTm 30 cm long and 7.8 mm inside diameter. The detection system consists of a refractometric detector type RI WATERS Tm 410. The oven is heated to a temperature of 60 ° C, and the refractometer is heated to a temperature of 45 ° C. The chromatography apparatus is calibrated by standards of powdered polyacrylate of various molecular weights certified by the supplier: POLYMER STANDARD SERVICE or AMERICAN POLYMER STANDARDS CORPORATION. Amount of Residual Monomers The amount of residual monomers is measured according to standard techniques, known to those skilled in the art, for example by High Pressure Liquid Chromatography (HPLC) or in English "High Performance Liquid Chromatography" (HPLC). In this method, the constituent components of the mixture are separated on a stationary phase, and detected by a UV detector. After calibration of the detector, it is possible for example from the area of the peak corresponding to the acrylic compound to obtain the amount of residual (meth) acrylic acid.
    [0038] This method is described in particular in the "Experimental Organic Chemistry" manual, by M. Chavanne, A. Julien, G. J. Beaudoin, E. Flamand, second edition, Editions Modulo, chapter 18, pages 271-325.
    [0039] Dry extract The polymer concentration is measured by desiccation, by methods known to those skilled in the art. Residence time It can be measured using a tracer such as saline. For this purpose, for a prescribed flow rate, a saline solution is injected at t = 0 and the conductivity and the conductivity variation as a function of time are measured at the outlet of the reactor. The following examples illustrate the invention.
    [0040] Example 1 This example illustrates the continuous polymerization of acrylic acid in a tubular reactor of length L = 20 m and internal diameter D = 15 mm equipped with a system that can oscillate at a frequency of 0 to 10 Hz with an amplitude of between 0 and 5 cm. The oscillations are mechanically transmitted to the fluid present inside said reactor using a sealed sliding piston. A Ni-Tech® reactor is used here.
    [0041] The acrylic acid is polymerized in the presence of a priming system composed of hydrogen peroxide, coupled with metal salts as well as with hydroxylamine sulfate. A transfer agent is used to limit the molecular weights of the manufactured polyacrylic acid. This is the DPTTC salt. The final dry extract of poly (acrylic acid) is about 35%.
    [0042] The reagents are separated in three separate preparation tanks and are mixed just prior to their introduction into the tubular reactor to ensure that the polymerization begins only inside said reactor. The reagents from the three tanks are mixed using a static mixer (type SMX®) using three separate pumps.
    [0043] The rates of introduction of the reagents into the static mixer and thus into the downstream reactor are adjusted so that the introduced masses are proportional to the values mentioned in the table below: Tank 1 Tank 2, thermostated at 80 ° C. Cell 3 AA Salt Sulfate Fe (Kg) Sulfate Water Peroxide Water 100% DPTTC dehydrated hydroxylamine (Kg) demineralized (Kg) demineralized hydrogen (Kg) 100% 35% prepared (Kg) (Kg) (Kg) 35 1 The flows of the three pumps connected to the three preparatory tanks are then proportionally modified to adjust the residence time in the tubular reactor. Said residence time is measured visually by adding a colored tracer or using a conductivity meter and a saline solution. The polymer produced by this way can be collected in order to evaluate the physico-chemical characteristics. The product sampled is a low viscosity aqueous polymer solution. In addition to the overall flow rate (resulting from the sum of the flows of the three pumps), the frequency as well as the amplitude printed by the oscillator can be modified. As soon as one of these parameters is modified, it is necessary to wait for a time at least equal to five times the residence time in the reactor before collecting a sample at the outlet of the reactor or at an intermediate collection point (and this in order to reach the steady state characteristic of a continuous process).
    [0044] For the recipe in Table 1, a residence time in the reactor of about four minutes provides an acceptable degree of conversion. The flow rate of the three pumps is then set so that the overall flow is close to 40 Kg per hour.
    [0045] Under these operating conditions, the amplitude and the frequency of the oscillations are modified. In all cases, an exotherm and a rise in pressure are observed in the reactor. The maximum temperature observed was 150 ° C and the maximum pressure was 10 bar.
    [0046] Characterization of the polymers obtained Frequency (Hz) Amplitude (mm) Conversion Mn (g / mol) Mw (g / mol) IP (%) 1.25 25 94.9 1 925 5 570 2.9 1.25 50 98 2150 5 980 2.8 2.5 12.5 95.2 1 870 5 405 2.9 2.5 25 94.8 1 960 5 485 2.8 2.5 50 92.1 1 790 5 650 3.2 5 25 96.3 1,750 5,040 2,9 5 50 94,8 1,710 5,320 3.1 25 95.6 1 800 5 460 3.0 10 50 97.3 1 880 5 190 2.8 Table 2 10 No did not observe gel formation. EXAMPLE 2 This example illustrates the continuous polymerization of acrylic acid in a tubular reactor of length L = 20 m and internal diameter D = 5 mm equipped with a system capable of oscillating at a frequency of 0 to 10 Hz with amplitude between 0 and 5 cm. The oscillations are mechanically transmitted to the fluid present inside said reactor using a sealed sliding piston. A Ni-Tech® reactor is used here.
    [0047] The recipe is similar to that used in Example 1. The final dry extract of polyacrylic acid is about 35%.
    [0048] The rates of introduction of the reagents into the static mixer and thus into the downstream reactor are adjusted so that the introduced masses are proportional to the values mentioned in Table 1, Example 1. The residence time in the reactor is fixed at about two minutes and the flow rate of the three pumps is then fixed so that the overall flow is close to 80 Kg per hour. Under these operating conditions, the amplitude and the frequency of the oscillations are modified. In all cases, an exotherm and a rise in pressure are observed in the reactor. The maximum temperature observed was 150 ° C and the maximum pressure was 10 bar.
    [0049] Characterization of the polymers obtained Frequency (Hz) Amplitude (mm) Conversion (%) Mn Mw IP (g / mol) (g / mol) 1.25 25 93.1 2 050 6 200 3.0 1.875 25 91.2 1 950 6,450 3.3 2.5 25 93.2 1 840 5 930 3.2 5 25 95.3 1 910 6 030 3.2 10 25 90.7 2 020 6 740 3.3 Table 3 We do not have observed gel formation.
    [0050] Example 3 This example illustrates the continuous polymerization of acrylic acid in a tubular reactor of length L = 20 m and internal diameter D = 15 mm equipped with a system that can oscillate at a frequency of 0 to 10 Hz with an amplitude of between 0 and 5 cm. The oscillations are mechanically transmitted to the fluid present inside said reactor using a sealed sliding piston. A Ni-Tech® reactor is used here. The acrylic acid is polymerized in the presence of a priming system composed of sodium persulfate, coupled with metal salts as well as sodium hypophosphite. The latter plays both the role of reducing agent and transfer agent. The final dry extract of poly (acrylic acid) is about 35%.
    [0051] The reagents are separated in three separate preparation tanks and are mixed just prior to their introduction into the tubular reactor to ensure that the polymerization begins only inside said reactor. The reagents from the three tanks are mixed using a static mixer (type SMX) using three separate pumps. The rates of introduction of the reagents into the static mixer and thus into the downstream reactor are adjusted so that the masses introduced are proportional to the values mentioned in the table below: Tank 1 Tank 2, thermostatically controlled at 80 ° C. ° C Vat 3 AA 100% Sulfate Hypophosphite Water Persulfate Water (Kg) deionized sodium (Kg) deionized sodium iron (Kg) (Kg) (Kg) (Kg) 35 0.01 6.0 45 4 10 Table 4 The flow rates of the three pumps connected to the three preparatory tanks are then proportionally modified to adjust the residence time in the tubular reactor. Said residence time is measured visually by adding a colored tracer or using a conductivity meter and a saline solution. The polymer produced by this way can be collected in order to evaluate the physico-chemical characteristics. The withdrawn product is a low viscosity aqueous polymeric solution. In addition to the overall flow rate (resulting from the sum of the flows of the three pumps), the frequency as well as the amplitude printed by the oscillator can be modified. As soon as one of these parameters is modified, it is necessary to wait for a time at least equal to five times the residence time in the reactor before collecting a sample at the outlet of the reactor or at an intermediate collection point ( and this in order to reach the steady state characteristic of a continuous process). In all cases, an exotherm and a rise in pressure are observed in the reactor. The maximum temperature observed was 155 ° C and the maximum pressure was about 11 bar.
    [0052] For the recipe as described above, a residence time in the reactor of about three minutes provides a very good degree of conversion. The flow rate of the three pumps is then set so that the overall flow is close to 60 Kg per hour. Under these operating conditions, the amplitude and the frequency of the oscillations are modified. Characterization of polymers obtained Frequency Amplitude (mm) Conversion Mn (g / mol) Mw (g / mol) IP (Hz) (%) 0.625 50 99.1 1 540 4 565 3.0 1.25 25 99.99 1 535 6 040 3.9 1.25 50 99.99 1 445 5 785 4.0 2.5 25 99.6 2 210 8 960 4.1 2.5 50 99.99 1 750 6 780 3.9 5 25 98 , 9 1 830 6 540 3.6 5 50 99.7 2 150 7 300 3.4 10 5 99.99 2 130 7 650 3.6 10 25 99.99 1 970 6 600 3.4 10 50 97.6 Table 5 Gel formation was not observed.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. Process for the continuous preparation of an anionic polymer, dry extract (ES) of between 20% and 60% by weight, relative to the total weight of the formula, with a weight-average molecular weight Mw of less than 10,000 g / mol by radical polymerization, comprising the following steps: a) at least one monomer chosen from acrylic acid, methacrylic acid and mixtures thereof, said monomer being able to be partially neutralized, b) water is available optionally hot, c) At least one initiator is available, d) Possibly at least one chain transfer agent is provided, e) The components of steps a), b), c) and d) are introduced. in a tubular reactor having a length LR of at least 5 m and comprising at least one tubular section of length Ls and internal diameter D such that Ls is at least 20 times larger than D, in which each tubular section comprises throughout its length a plurality of stationary baffles, opposite The tubular section is connected to the flow in the form of washers of identical diameter to the internal diameter of the tubular section, thus forming a fluid in the tubular reactor. The tubular section is connected to a device for subjecting said fluid to oscillatory movement. g) a polymerization reaction is carried out in said reactor, optionally with a heating means for initiating the polymerization reaction, with a residence time in the reactor of greater than 1 min, the residence time, the size of the holes in the baffles, their spacing, the movements of the device are chosen so as to ensure at all points in the reactor good homogeneity of the mixture, h) is obtained at the reactor outlet said anionic polymer in solution in water. 30
    [0002]
    2. A method according to any one of the preceding claims, wherein D is less than 20 cm, preferably less than 15 cm, more preferably less than or equal to 10 cm.
    [0003]
    3. Method according to any one of the preceding claims, wherein the baffles are spaced, regularly or not, a distance ranging from 1D to 3D.
    [0004]
    4. A method according to any one of the preceding claims, wherein the baffles comprise concentric annular holes such that the ratio d2 / d1, where d2 is the outer diameter of the washer and dl the inner diameter of the washer, varies from 1 , 2 to
    [0005]
    5. A method according to any one of the preceding claims, wherein the amplitude of the oscillatory movement varies from 0.3xd2 to 4xd2, and the frequency of the oscillatory movement varies from 0.1 to 100 Hz.
    [0006]
    6. A method according to any one of the preceding claims, wherein the reactor comprises one or more devices for providing or removing calories, allowing a temperature control that can be different from one zone to another .
    [0007]
    7. Method according to any one of the preceding claims, wherein the initiator is introduced at the inlet and / or downstream of the reactor, in one or more times.
    [0008]
    8. Process according to any one of the preceding claims, in which the monomer is introduced at the inlet and / or downstream of the reactor, in one or more times.
    [0009]
    9. Process according to any one of the preceding claims, in which a catalyst based on water-soluble metal salts is also introduced, at the inlet and / or downstream of the reactor, in one or more times.
    [0010]
    The process according to any one of the preceding claims, wherein there is further available one or more other ethylenically unsaturated monomer (s) selected from the group consisting of acid 2. -acrylamido-2-methylpropanesulphonic acid (AMPS), maleic acid, fumaric acid, crotonic acid, itaconic acid, unsaturated telomers of acrylic acid, the monomers of formula (I): (CHF ) - OH "(I) in which: - Ra, Rb and Re represent, independently of each other, H or CH3, - n is an integer varying between 0 and 2.
    [0011]
    11. Process according to any one of the preceding claims, in which the monomer is acrylic acid and the polymer obtained following step d) is poly (acrylic acid) with a molecular weight Mw of between 1,000 and 10,000. g / mol and polydispersity index between 1.5 and 4.
    [0012]
    The process according to any of the preceding claims, wherein a neutralization agent is also injected into the reactor at a zone where the monomer conversion is greater than 90%.
    [0013]
    13. Process according to any one of the preceding claims, in which the reactor is connected at the outlet to a tubular reactor equipped or not with an oscillatory device as defined above, with a stirred reactor and / or a flash distillation column.
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    EP3233939B1|2020-03-25|
    WO2016097614A1|2016-06-23|
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    JP6721579B2|2020-07-15|
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    BR112017007712B1|2022-01-11|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1462899A|FR3030527B1|2014-12-19|2014-12-19|PROCESS FOR THE CONTINUOUS PREPARATION OF ANIONIC POLYMERS BY RADICAL METHOD|FR1462899A| FR3030527B1|2014-12-19|2014-12-19|PROCESS FOR THE CONTINUOUS PREPARATION OF ANIONIC POLYMERS BY RADICAL METHOD|
    EP15822983.1A| EP3233939B1|2014-12-19|2015-12-17|Method for the continuous production of anionic polymers using radicals|
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    US15/521,725| US10214599B2|2014-12-19|2015-12-17|Method for the continuous production of anionic polymers using radicals|
    CN201580059090.4A| CN107108794B|2014-12-19|2015-12-17|Method for continuous production of anionic polymers using free radicals|
    BR112017007712-4A| BR112017007712B1|2014-12-19|2015-12-17|METHOD FOR THE CONTINUOUS PRODUCTION OF ANIONIC POLYMERS USING RADICALS|
    JP2017519540A| JP6721579B2|2014-12-19|2015-12-17|Method for continuous production of anionic polymers using radicals|
    PCT/FR2015/053561| WO2016097614A1|2014-12-19|2015-12-17|Method for the continuous production of anionic polymers using radicals|
    ES15822983T| ES2802200T3|2014-12-19|2015-12-17|Procedure for the continuous production of anionic polymers using radicals|
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