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    • 专利摘要:
    Absorbent polymers and methods and systems for producing same and uses thereof The present invention relates to absorbent polymers made from beta-propiolactone and methods and systems for producing such polymers. betapropiolactone may be derived from ethylene oxide and carbon monoxide. The absorbent polymer may be biobased and / or biodegradable. absorbent polymers can be used for disposable diapers, adult incontinence products and feminine hygiene products, as well as for agricultural applications.
    公开号:BR102017023554A2
    申请号:R102017023554-8
    申请日:2017-10-31
    公开日:2019-02-19
    发明作者:Han Lee；John B. Ruhl；Robert E. LaPointe；Kyle SHERRY；Alexander Tseitlin；Sadesh H. Sookraj
    申请人:Novomer, Inc.；
    IPC主号:
    专利说明:

    ABSORBENT POLYMERS AND PRODUCTION METHODS AND SYSTEMS OF THE SAME AND USES OF THE SAME
    CROSS REFERENCE TO RELATED APPLICATION [0001] This application claims priority for US provisional application No. 62 / 416,611, filed on November 2, 2016, which is hereby incorporated by reference in its entirety.
    FIELD [0002] The present description generally refers to polymeric materials and, more specifically, to polymeric materials suitable for use as adsorbent materials and methods of production thereof.
    BACKGROUND [0003] Superabsorbent polymers are polymeric materials that can absorb and retain large amounts of water or aqueous solutions. Such polymeric materials are used extensively for the manufacture of disposable diapers, adult incontinence products and feminine hygiene products, as well as in agricultural applications.
    [0004] Superabsorbent polymers are commonly produced from polymerization of acrylic acid. However, due to the volatile price of acrylic acid and a shortage of supply, there is a desire in the art to produce polymeric materials with adsorbent properties from alternative sources. In particular, there is a need in the art to produce with bio-based, biodegradable polymeric materials with adsorbent properties, obtained from renewable sources.
    BRIEF SUMMARY
    Petition 870170103436, of 12/29/2017, p. 6/36
    2/30 [0005] Provided here are polymeric materials with adsorbent properties and production methods that focus on the need in the art. Such polymeric materials can be obtained from beta-propiolactone, which can be derived from renewable sources, such as ethylene oxide and bio-based carbon monoxide.
    [0006] In some respects, a method of producing a polymer is provided, comprising: combining betapropiolactone with a metal compound to produce acrylic acid, a salt thereof or a combination thereof; and polymerizing the acrylic acid, a salt thereof or a combination thereof, with a polymerization initiator and, optionally, a crosslinker to produce the polymer. In some variations of the above, polymerization is carried out pure or in a non-aqueous medium.
    In some variations, the metal compound is M, M2O, MOH or
    M + (CH2 = CHCOO - ) or a combination thereof.
    [0007]
    In other respects, provided is a method of producing a polymer, comprising:
    polymerization of beta-propiolactone with an ionic initiator in a reactor to produce a polymer intermediate, wherein the polymer intermediate has a polyacrylic acid backbone and a plurality of polypropiolactone side chains;
    b) increasing the temperature of the reactor to produce acrylic acid from at least part of the side chains in the polymer intermediate and to produce polymer acrylate from at least a part of the polymeric main structure of the polymer intermediate by thermolysis of the intermediate of polymer;
    Petition 870170103436, of 12/29/2017, p. 7/36
    3/30
    c) addition of a metal compound of the formula M, M2O, MOH or M+(CH2 = CHCOO-) or a combination thereof, to the reactor to at least partially neutralize the acrylic acid in the reactor to produce a mixture, wherein the mixture in the reactor comprises acrylic acid and M+(CH2 = CHCOO ), where M is a Group I metal; and
    d) polymerization of at least a part of the mixture in the reactor to produce the polymer, where the polymer comprises the repeating units
    of or ‘‘ f ’or a combination of them.CTOH Ο ^ Ο'Μ * was said [0008] In some variations of what previously, the steps (c) and (d) are carried out pure or in a medium no aqueous. [0009] In others aspects provided it is a method in production of a polymer, comprising:combination of beta- propiolactone with a compound in metal in a main reactor, where the compound in metal polymerization starts at least an part gives beta-
    propiolactone to produce polypropiolactone in the main reactor;
    thermolysis of at least a part of the polypropiolactone in the main reactor to produce acrylic acid;
    volatilization of at least part of the acrylic acid in the main reactor;
    passage of the volatilized acrylic acid through a distillation column;
    combination of acrylic acid obtained from the distillation column with a radical initiator, optional crosslinker and additional metal compound in a kneader reactor to produce a polyacrylic acid
    Petition 870170103436, of 12/29/2017, p. 8/36
    Partially neutralized 4/30; and feeding the partially neutralized polyacrylic acid from the kneader reactor to the main reactor, in which the final carboxylate groups of the partially neutralized polyacrylic acid initiate the polymerization of at least part of the beta-propiolactone in the main reactor to produce a polymer with branches of polypropiolactone.
    [0010] In some variations of the above, polymerization is carried out pure or in a non-aqueous medium.
    [0011] In other respects, provided is a polymer produced according to any of the methods described here. In some embodiments, the polymer is cross-linked. In some variations of the above, the polymer is biologically and / or biodegradable.
    [0012] The polymers described here or produced according to the methods described here may be suitable for use as an absorbent article (for example, for disposable diapers, adult incontinence products, or feminine hygiene products) or as products agricultural (eg for agricultural materials, and seed coatings).
    [0013] In yet other aspects, systems are provided to carry out the methods described here. In one embodiment, a system is provided, comprising: a main reactor; a distillation column connected to the main reactor; and a kneader reactor connected to the top of the main reactor through the distillation column. In another modality, a system is provided, comprising: a reactor
    Petition 870170103436, of 12/29/2017, p. 9/36
    Main 5/30; and a vessel, comprising a distillation column and a kneader reactor, in which the distillation column is connected to the top of the main reactor.
    [0014] In some variations of the previous embodiments, the main reactor is configured to: receive an inlet flow comprising beta-propiolactone, polymerize at least a part of the beta-propiolactone in the inlet to produce polypropiolactone, thermolyze at least a part of polypropiolactone to produce acrylic acid and volatilize at least part of the acrylic acid. In another variation, the main reactor is configured to: receive an inlet flow comprising beta-propiolactone, receive a mixture of a metal compound and heat transfer fluid minus a part of the beta-propiolactone in the polymerize by the inlet flow in the presence of the metal compound to produce polypropiolactone, thermolyze at least part of the polypropiolactone to produce acrylic acid volatilize at least part of the acrylic acid.
    [0015] In certain variations of the systems described here, the distillation column is configured to receive the volatilized acrylic acid from the main reactor. In certain variations, the distillation column is configured to receive the volatilized acrylic acid from the main reactor, and feed the distilled acrylic acid to the kneading reactor.
    [0016] In certain variations of the systems described here, the kneader reactor is configured to: receive at least part of the distilled acrylic acid from the distillation column, receive a primer
    Petition 870170103436, of 12/29/2017, p. 10/36
    6/30 radical, optionally a crosslinker and a metal or metal salt, produce a partially neutralized polyacrylic acid from at least part of the acrylic acid in the kneader reactor and feed at least a part of the partially neutralized polyacrylic acid back in. main reactor. In other variations, the main reactor is further configured to: receive partially neutralized polyacrylic acid from the kneader reactor, and polymerize beta-propiolactone to produce a polymer with branches of polypropiolactone; and the main reactor further comprises an outlet configured to emit a flow of products comprising betapropiolactone, the polymer and heat transfer fluid.
    DESCRIPTION OF THE FIGURES [0017] The present application can be better understood by reference to the following description taken in conjunction with the attached figures, in which similar parts can be referred to by similar numerals.
    [0018] Figure 1 describes an exemplary system for carrying out the methods described here to produce an absorbent polymer of beta-propiolactone.
    DETAILED DESCRIPTION [0019] The following description presents exemplary methods, parameters and the like. It should be recognized, however, that such a description is not intended as a limitation on the scope of the present description, but is instead provided as a description of exemplary modalities.
    [0020] Provided here are polymers that have absorbent properties. In some ways, such
    Petition 870170103436, of 12/29/2017, p. 11/36
    7/30 polymers are produced from beta-propiolactone. Betapropiolactone can be produced from ethylene oxide carbonylation. When ethylene oxide and carbon monoxide are obtained from renewable sources, the polymers described here can be biologically based polymers. In addition, the polymers described here can be biodegradable. Such superabsorbent polymers can be used for disposable diapers, adult incontinence products and feminine hygiene products, maintaining or improving the performance of such products.
    [0021] The methods of producing such absorbent polymers and the structure and properties of such absorbent polymers are described in more detail below.
    Production methods for absorbent polymers [0022]
    In some respects, provided here are methods of producing a polymer having a polyacrylic acid backbone and a plurality of polypropiolactone side chains, and decomposing at least a part of the polypropiolactone side chains to produce polyacrylic acid.
    [0023]
    In certain aspects, provided is a method of producing a polymer, comprising:
    combining beta-propiolactone to produce acrylic acid, with a metal compound, a salt thereof or a combination thereof; and polymerizing the acrylic acid, a salt thereof or a combination thereof, with a polymerization initiator and optionally a crosslinker to produce the polymer. In some variations, the metal compound is a compound of the formula M, M2O, MOH or
    Petition 870170103436, of 12/29/2017, p. 12/36
    8/30
    M + (CH2 = CHCOO - ) or a combination thereof.
    [0024]
    In certain aspects, provided is a method of producing a polymer, comprising:
    ionic polymerization initiator in polymer intermediate has one and a plurality
    b) augmentation of a polymer, beta-propiolactone with reactor in which the main structure of side chains of the acrylic acid temperature from at least one side polymer structure to produce an intermediate of a polyacrylic acid polypropiolactone;
    reactor for producing a part of the chains in the polymer intermediate, and for producing acrylate from at least a part of the main polymer of the polymer intermediate by thermolysis of the polymer intermediate;
    c) addition of a metal compound of the formula M, M2O,
    MOH or M + (CH2 = CHCOO - ) or a combination thereof to the reactor to at least partially neutralize the acrylic acid in the reactor to produce a mixture, wherein the mixture in the reactor comprises acrylic acid and M + (CH2 = CHCOO - ) , where M is a Group I metal; and
    d) polymerization of at least part of the mixture in the reactor to produce the polymer, where 1 or
    CTOH [0025] the polymer comprises hCyX units
    Á or a combination thereof. crO ~ M + v
    In one variation, provided is a repeat method of producing a polymer, comprising:
    polymerization of beta-propiolactone with an ionic initiator in a reactor to produce a polymer intermediate, where the polymer intermediate has a main structure of polyacrylic acid
    Petition 870170103436, of 12/29/2017, p. 13/36
    9/30 and a plurality of polypropiolactone side chains;
    b) production of acrylic acid from at least part of the side chains in the polymer intermediate at an elevated temperature and production of acrylate polymer from at least part of the polymeric main structure of the polymer intermediate by thermolysis of the polymer intermediate ;
    c) adding a metal compound of the formula M, M2O, MOH or M + (CH2 = CHCOO - ) or a combination of them to the reactor to neutralize at least partially the acrylic acid in the reactor to produce a mixture, wherein the mixture in the reactor it comprises acrylic acid and M + (CH2 = CHCOO - ), where M is a Group I metal; and
    d) polymerization of at least a part of the mixture in the reactor to produce the polymer, where the polymer comprises the repeating units of
    or OH [0026]
    or a combination of them.
    The “M +
    In some variations of the above, the methods further comprise the isolation of at least a part of the polymer produced in step (d). In yet other variations, the methods further comprise: combining the isolated polymer with additional beta-propiolactone to produce polymer intermediate
    additional.[0027] In some variations of that was said previously, O method is performed continuously. [0028] In others variations of that was said previously, O method is performed to balance the
    exotherm from beta-propiolactone polymerization to produce the polymer intermediate with thermolysis
    Petition 870170103436, of 12/29/2017, p. 14/36
    10/30 of the polymer intermediate. For example, the heat of polymerization can be absorbed by thermolysis of the polypropiolactone side chains or evaporation of heat transfer fluid, or the reaction system can be designed to allow proper temperature control.
    [0029] In some variations, the method involves the
    combination in or separation of some of the steps (a) - (d). For example, in certain variations of previous, at steps (c) and (d) are performed together in one stage.[0030]Still in other variations of previous, at steps (c) and (d) are carried out pure or in a way no aqueous. [0031]In another aspect, provided is a method in production of one polymer, comprising: combination beta-propiolactone with one compound in
    metal in a main reactor, where the metal compound initiates the polymerization of at least part of the betapropiolactone to produce polypropiolactone in the main reactor;
    thermolysis of at least a part of the polypropiolactone in the main reactor to produce acrylic acid;
    volatilization of at least part of the acrylic acid in the main reactor;
    passage of the volatilized acrylic acid through a distillation column;
    combining acrylic acid obtained from a distillation column with a radical initiator, optional crosslinker and additional metal compound in a kneader reactor to produce a partially neutralized polyacrylic acid; and
    Petition 870170103436, of 12/29/2017, p. 15/36
    11/30 feeding of partially neutralized polyacrylic acid from the kneading reactor to the main reactor, where the final partially neutralized polyacrylic acid carboxylate groups initiate the polymerization of at least part of the beta-propiolactone in the main reactor to produce a polymer with branches of polypropiolactone.
    [0032] In some variations of the previous aspect, the polymerization is carried out pure or in a non-aqueous medium. In other variations of the foregoing, the method further comprises isolating a product stream from the main reactor, wherein the product stream comprises the polymer with polypropiolactone branches. In yet other variations, the product flow further comprises unreacted beta-propiolactone. In a variation that can be combined with the previous one, the method further comprises separating a stream of polymers comprising the polymer with branches of polypropiolactone from a recycle stream comprising the unreacted beta-propiolactone. In yet another variation that can be combined with the previous one, the method also comprises feeding the recycle stream inside the main reactor. In the above aspect and variations thereof, the radical initiator is used to polymerize acrylic acid and there is no need to feed the additional ionic initiator because the partially neutralized polyacrylic acid initiates the polymerization of betapropiolactone.
    [0033] Beta-propiolactone, initiators and other variations of the methods are described in more detail
    Petition 870170103436, of 12/29/2017, p. 16/36
    12/30 below.
    Beta-propiolactone [0034] Beta-propiolactone can be produced by any suitable methods or techniques known in the art. For example, in some variations, betapropiolactone is produced from ethylene oxide and carbon monoxide. Ethylene oxide undergoes carbonylation in the presence of a carbonylation catalyst and optionally a solvent.
    [0035] Thus, in some variations, the methods described here further include: carbonylation of ethylene oxide to produce beta-propiolactone. In certain variations, the methods described here further comprise: combination of ethylene oxide, carbon monoxide, a carbonylation catalyst and optionally a solvent to produce beta-propiolactone. In a variation, the methods described here further comprise: a combination of ethylene oxide, carbon monoxide, a carbonylation catalyst and a solvent to produce betapropiolactone.
    [0036] Beta-propiolactone can be isolated prior to polymerization to produce the polymers described here. Thus, in some variations, the methods described here further comprise: carbonylation of ethylene oxide to produce beta-propiolactone; and isolating at least a portion of the produced beta-propiolactone. In certain variations, the methods described here further comprise: combination of ethylene oxide, carbon monoxide, a carbonylation catalyst and optionally a solvent to produce beta-propiolactone; and hair insulation
    Petition 870170103436, of 12/29/2017, p. 17/36
    13/30 minus a portion of the beta-propiolactone produced. In a variation, the methods described here further comprise: combination of ethylene oxide, carbon monoxide, a carbonylation catalyst and a solvent to produce beta-propiolactone; and isolating at least a portion of the produced beta-propiolactone.
    [0037] In some variations of what was said earlier, ethylene oxide is provided in gaseous form. In certain variations, the ethylene oxide gas is converted into a liquid form and combined with a solvent, a carbonylation catalyst and carbon monoxide gas in the reactor. In some variations of the above, carbon monoxide is provided in a gaseous form.
    [0038] Any suitable carbonylation catalysts can be used to produce betapropiolactone. For example, in some variations, the carbonylation catalyst comprises a metallic carbonyl compound. In certain variations, the carbonylation catalyst is a metallic carbonyl compound with a solid support. Suitable carbonylation catalysts are described in, for example, WO 2010/118128. In some variations, the carbonylation catalyst comprises [(TPP) Al] [Co (CO) 4], [(ClTPP) Al] [Co (CO) 4], [(TPP) Cr] [Co (CO) 4] , [(ClTPP) Cr] [Co (CO) 4], [(salcy) Cr] [Co (CO) 4], [(salph) Cr] [Co (CO) 4] or [(salph) Al] [ Co (CO) 4]. It should be generally understood that 'tpp refers to tetrafenilporphyrin; ClTPP refers to meso-tetra (4chlorophenyl) porphyrin); salcy refers to (N, N'-bis (3.5
    Petition 870170103436, of 12/29/2017, p. 18/36
    14/30 di-tert-butylsalicylidene) -1,2-diaminocyclohexane); and salph refers to (N, N'-bis (salicylidene) -phenylenediamine).
    [0039] Any suitable solvents can be used to produce beta-propiolactone. In some variations, the solvent comprises an ether solvent. In one variation, the solvent comprises tetrahydrofuran.
    Ionic initiators [0040] In some variations, the ionic initiator comprises an alkali metal salt or an alkaline earth metal salt. In certain variations, the ionic initiator comprises an alkali metal carboxylate salt or an alkaline earth metal salt. In one variation, where the ionic initiator is an alkali metal salt.
    [0041] In other variations, the ionic initiator has a structure of the formula CH2 = CH2CO2-Z+, where Z+ it is an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium cation. In certain variations, the ionic initiator has a structure of the formula CH2 = CH2CO2 Z+, where Z+ is a quaternary ammonium cation. In one variation, the quaternary ammonium cation is a lower alkyl quaternary ammonium cation.
    [0042] In other variations, the ionic initiator is sodium acrylate or potassium acrylate. In certain variations, the ionic initiator is a methacrylate. In one variation, the ionic initiator is sodium methacrylate or potassium methacrylate.
    [0043] In some variations, any combinations of the ionic initiators described here can also be
    Petition 870170103436, of 12/29/2017, p. 19/36
    15/30 used.
    Metal compound [0044] In some variations, the metal compound is
    M, M2O, MOH, or M + (CH2 = CHCOO - ). In certain variations, the metal compound is M, M2O or MOH. In some variations, M is a Group I metal. In certain variations, M is sodium. For example, sodium metal, sodium oxide or sodium hydroxide can be used. Any combinations of the above can also be used.
    Polymerization Initiators [0045]
    In some embodiments, the polymerization of step (d) of the methods described here is carried out in the presence of a polymerization initiator. Thus, in some variations, a method of producing a polymer is provided, comprising:
    polymerization of beta-propiolactone with an ionic initiator in a reactor to produce a polymer intermediate, wherein the polymer intermediate has a polyacrylic acid backbone and a plurality of polypropiolactone side chains;
    b) increasing the reactor temperature to produce acrylic acid from at least part of the polymer structure side chains in the polymer intermediate, and to produce acrylate from at least a part of the main polymer of the polymer intermediate by thermolysis of the intermediate polymer;
    c) addition of a metal compound of the formula M, M2O,
    MOH, or M + (CH2 = CHCOO - ) or a combination of these to the reactor to at least partially neutralize the acrylic acid in the reactor to produce a mixture, where the
    Petition 870170103436, of 12/29/2017, p. 20/36
    16/30 mixture in the reactor comprises acrylic acid and M+(CH2 = CHCOO ), where M is a Group I metal; and
    d) polymerization of at least a part of the mixture in the reactor in the presence of a polymerization initiator to produce the polymer, wherein the polymer comprises the repeating units
    ΧΧΛ of J or
    CTOH [0046] or a combination of
    In a variation, it is the same.
    A method of producing a polymer is provided, comprising:
    polymerization of beta-propiolactone with an ionic initiator in a reactor to produce a polymer intermediate, wherein the polymer intermediate has a polyacrylic acid backbone and a plurality of polypropiolactone side chains;
    b) production of acrylic acid from at least part of the side chains in the polymer intermediate at an elevated temperature and production of acrylate polymer from at least part of the polymeric main structure of the polymer intermediate by thermolysis of the polymer intermediate ;
    c) addition of a metal compound of the formula M, M2O, MOH, or M+(CH2 = CHCOO-) or a combination thereof to the reactor to at least partially neutralize the acrylic acid in the reactor to produce a mixture, wherein the mixture in the reactor comprises acrylic acid and M+(CH2 = CHCOO ), where M is a Group I metal; and
    d) polymerization of at least part of the mixture in the presence of a polymerization initiator in the reactor to produce the polymer, wherein the polymer comprises the repeating units
    Petition 870170103436, of 12/29/2017, p. 21/36
    17/30 of X Ο'ΌΗ [0047] or
    Tee or a combination thereof. o ^ otr
    In some embodiments, the polymerization initiator is a radical initiator. In some variations, the radical initiator comprises a peroxide, a persulfate or an azo compound. In other variations, the radical initiator is a redox initiator. In certain variations, the radical initiator comprises a hydroperoxide. In one variation, the radical initiator comprises hydrogen peroxide.
    [0048] In others modalities, O initiator in polymerization it is a thermal initiator or a photoinitiator or a combination From themselves. [0049] In some variations, O initiator in polymerization it is a peroxide or an acid. In a variation, O initiator of polymerization it's peroxide in hydrogen or
    Ascorbic acid.
    [0050]
    In other variations, any combinations of polymerization initiators described here can also be used.
    Crosslinkers [0051]
    In some embodiments, the methods described herein further comprise adding a crosslinker to the reactor in step (d) to polymerize at least part of the mixture in the reactor to produce the polymer, in which crosslinked polymer.
    Thus, in some variations, a method of producing a polymer is provided, comprising:
    polymerization of beta-propiolactone with an ionic initiator in a reactor to produce a polymer intermediate, in which the intermediate of
    Petition 870170103436, of 12/29/2017, p. 22/36
    The polymer has a polyacrylic acid backbone and a plurality of polypropiolactone side chains;
    b) increasing the reactor temperature to produce acrylic acid from at least part of the side chains in the polymer intermediate, and to produce acrylate polymer from at least a part of the polymeric main structure of the polymer intermediate by thermolysis of the intermediate polymer;
    c) adding a metal compound of the formula M, M2O, MOH, or M + (CH2 = CHCOO - ) or a combination of them to the reactor to neutralize at least partially the acrylic acid in the reactor to produce mixture in the reactor comprises acid one mixture, where acrylic and M + (CH2 = CHCOO - ), where
    M is a Group I metal;
    d) polymerization of at least a part of the mixture in the reactor in the presence of crosslinkers and optionally a polymerization initiator to produce the polymer, wherein the polymer comprises those of
    O
    J or a repeating units combination o:
    or
    The polymer is cross-linked.
    of them and where the [0052]
    In a variation, a method of producing a polymer is provided, comprising:
    polymerization of beta-propiolactone with an ionic initiator in a reactor to produce a polymer intermediate, wherein the polymer intermediate has a polyacrylic acid backbone and a plurality of polypropiolactone side chains;
    b) production of acrylic acid from at least part of the side chains in the polymer intermediate at an elevated temperature, and production of acrylate polymer
    Petition 870170103436, of 12/29/2017, p. 23/36
    19/30 from at least a part of the polymeric main structure of the polymer intermediate by thermolysis of the polymer intermediate;
    c) addition of a metal compound of the formula M, M2O,
    MOH, or M+(CH2 = CHCOO-) or a combination thereof to the reactor to at least partially neutralize the acrylic acid in the reactor to produce a mixture, wherein the mixture in the reactor comprises acrylic acid and M+(CH2 = CHCOO ), where M is a Group I metal; and
    d) polymerization of at least a part of the mixture in the presence of crosslinkers and optionally a polymerization initiator, in the reactor to produce the polymer, in which
    -Xví of 1 or I
    Ct OH rF ^ rpolymer is the polymer comprising the repeating units or a combination thereof and where the
    The O'M + reticulate.
    [0053]
    In some variations, the crosslinker is an organic compound comprising one or more
    In certain variations, the compound plus vinyl groups.
    organic comprises multiple vinyl groups. Crosslinkers comprising vinyl groups can radically copolymerize with acrylic acids to form a network of crosslinks. Suitable crosslinkers may include, for example, N, N'methylene-bisacrylamide, N, N'-ethylene-bis-methacrylamide, hexamethylene-bis-acrylamide, trialyl amine, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate and trimethylacrylate and trimethylacrylate. In other variations, any combinations of crosslinkers described here can also be used.
    Production systems for absorbent polymers [0054] Systems are also provided to carry out
    Petition 870170103436, of 12/29/2017, p. 24/36
    20/30 the methods described here. For example, with reference to figure 1, system 100 is an exemplary system for producing the polymers described here. System 100 includes reactor 110. The top of reactor 110 is connected to the distillation column part of vessel 120, which connects reactor 110 to the kneader reactor portion of vessel 120. Several inputs are fed into vessel 120, including optional radical initiator and crosslinker 104, metal or metal salt 106, and heat transfer fluid 108. Reactor 110 has an inlet for receiving flow of betapropiolactone 102 and an outlet for emitting product flow 150 comprising the polymers described herein.
    [0055] Referring again to figure 1, flow 102 comprising beta-propiolactone is fed into reactor 110 containing a mixture of metal or metal salt and heat transfer fluid. The metal or metal salt initiates the polymerization of beta-propiolactone to form polypropiolactone in the reactor. Reactor 110 can be operated under suitable conditions (for example, at a temperature of 180 ° C or higher) to thermolyze at least part of the polypropiolactone to form acrylic acid. The acrylic acid produced is volatilized under conditions in reactor 110 and distilled as it passes upward through the distillation column and into the kneading reaction part of vessel 120.
    [0056] A continuous feed of the radical initiator, crosslinker and metal or metal salt can be added within the reactor part of the vessel kneader 120 containing acrylic acid from the distillation column to produce partially polyacrylic acid
    Petition 870170103436, of 12/29/2017, p. 25/36
    21/30 neutralized reticulate. The polymer produced in the kneader reactor can be fed continuously into reactor 110 through the distillation column. The final carboxylate groups in the polymer initiate the polymerization of beta-propiolactone to produce a polymer with branches of polypropiolactone. The polypropiolactone chains in the polymer are thermolyzed to form acrylic acid in reactor 110.
    [0057] A part of the reaction mixture comprising beta-propiolactone, the polymer and heat transfer fluid is drained out of reactor 110 to form product flow 150. In other variations, product flow 150 can be separated into a polymer stream and a recycle stream comprising beta-propiolactone and the heat transfer fluid. The recycle stream can be fed back into the mixer reactor. The separation method for the polymer may include, for example, filtration of the product stream 150.
    [0058] It should be understood that, in other variations, the system 100 to perform the methods described here may have different configurations, including smaller or additional operating units to the system. In addition, entries within system 100 may vary according to the methods described here.
    [0059] In some respects, a system is provided, comprising:
    a main reactor; and a vessel, comprising a distillation column and a kneader reactor, in which the distillation column is connected to the top of the main reactor,
    Petition 870170103436, of 12/29/2017, p. 26/36
    22/30 where:
    the main reactor is configured to:
    receiving an inlet stream comprising betapropiolactone, receiving a mixture of a metal compound and heat transfer fluid, polymerizing at least part of the beta-propiolactone in the inlet stream in the presence of the metal compound to produce polypropiolactone, thermolysing at least one part of the polypropiolactone to produce acrylic acid, and to volatilize at least part of the acrylic acid;
    the distillation column is configured to receive the volatile acrylic acid from the main reactor, and feed the acrylic acid to the kneading reactor;
    the kneader reactor is configured to:
    receiving at least a part of the acrylic acid from the distillation column, receiving a radical initiator, optionally a crosslinker and a metal compound, producing a partially neutralized polyacrylic acid from at least a part of the acrylic acid in the reactor of the kneader, and feed at least part of the partially neutralized polyacrylic acid back into the main reactor, the main reactor is further configured to:
    receive partially neutralized polyacrylic acid from the kneading reactor, and polymerize beta-propiolactone to produce a
    Petition 870170103436, of 12/29/2017, p. 27/36
    23/30 polymer with branches of polypropiolactone, and the main reactor further comprises an outlet configured to emit a flow of products comprising beta-propiolactone, the polymer and heat transfer fluid.
    [0060] In a variation, a system is provided, comprising:
    a main reactor;
    a distillation column connected to the main reactor; and a kneader reactor connected to the top of the main reactor through the distillation column, where:
    the main reactor is configured to:
    receiving an inlet stream comprising betapropiolactone, polymerizing at least a part of the beta-propiolactone in the inlet stream to produce polypropiolactone, thermolysing at least a part of the polypropiolactone to produce acrylic acid, and volatilizing at least a part of the acrylic acid;
    the distillation column is configured to receive the volatilized acrylic acid from the main reactor;
    the kneader reactor is configured to:
    receiving at least part of the distilled acrylic acid from the distillation column, receiving a radical initiator, optionally a crosslinker and a metal compound, producing a partially neutralized polyacrylic acid from at least part of the acid
    Petition 870170103436, of 12/29/2017, p. 28/36
    24/30 acrylic in the kneading reactor, and feeding at least part of the partially neutralized polyacrylic acid back into the main reactor, the main reactor is further configured to:
    receive partially neutralized polyacrylic acid from the kneader reactor, and polymerize beta-propiolactone to produce a polymer with branches of polypropiolactone, and the main reactor further comprises an outlet configured to emit a flow of products comprising beta-propiolactone, the polymer and heat transfer fluid.
    [0061] The systems described here can be configured to receive beta-propiolactone provided or produced according to any of the methods described here. For example, in some embodiments, the inlet stream comprising beta-propiolactone is produced by carbonylating ethylene oxide. Thus, in some embodiments, the system further comprises a carbonylation reactor configured to carbonyl ethylene oxide to produce the inlet flow.
    [0062] In other variations, the system also comprises the separation unit to isolate the polymer in the product flow. In other variations, the separation unit separates the product stream into a polymer stream and a recycle stream comprising betapropiolactone and the heat transfer fluid. In yet other variations, the recycle stream can be fed back into the main reactor.
    Petition 870170103436, of 12/29/2017, p. 29/36
    25/30 [0063] The systems described here can also be configured to receive any of the initiators, crosslinkers and metal compounds described here. For example, in some variations, the metal compound is M, M2O, MOH, or M + (CH2 = CHCOO - ). In certain variations, M is a Group I metal. In one variation, the metal compound is sodium metal. In other variations, the metal compound is, sodium oxide, sodium hydroxide or sodium acrylate. A combination of such metal compounds can also be used. In yet other variations of the above, a crosslinker is used and the partially neutralized polyacrylic acid produced is crosslinked. Any of the crosslinkers described here can be used in the systems.
    [0064] In other variations, the heat transfer fluid can be any aprotic organic solvent with a boiling point greater than the boiling point of acrylic acid. In one variation, the heat transfer fluid is a high boiler.
    Absorbent Polymers [0065] In some respects, polymers produced according to any of the methods described here are provided.
    Bioteor [0066] In some variations of what was said earlier, the polymer has a bioteor greater than 0% and less than 100%. In certain variations from the previous, the
    polymer has a bioteor of at least 10%, fur any less 20%, fur any less 30%, fur any less 40%, fur any less 50%, fur any less 60%, fur any less 70%, fur any less 80%, fur any less 90%, fur any less 95%, fur any less 96%, fur any less 97%, fur any less 98%,
    Petition 870170103436, of 12/29/2017, p. 30/36
    26/30 at least 99%, at least 99.5%, at least 99.9%, at least 99.99% or 100%.
    [0067] In some variations, the bioteor (also referred to as biologically based content ”) can be determined based on the following:
    % Bioteor or Biologically Based Content = [Biocarbon (Organic)] / [Carbon (Organic) Total] * 100%, as determined by ASTM D6866 (Standard test methods for determining the biobased content of solid, liquid samples and gaseous using radiocarbon analysis).
    [0068] The bioteor of the polymers may depend on the bioteor of the beta-propiolactone used. For example, in some variations of the methods described here, the betapropiolactone used to produce the polymers described here may have a bioteor greater than 0% and less than 100%. In certain variations of the methods described here, the beta-propiolactone used to produce the polymers described here may have a bioteor of at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least least 60%, at least 70%, at least 80%, at least
    90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, at least 99.9%, at least 99.99%, or 100%. In certain variations, beta-propiolactone derived from renewable sources is used. In other variations, at least a part of the beta-propiolactone used is derived from renewable sources and at least a part of the beta-propiolactone is derived from non-renewable sources.
    [0069] The beta-propiolactone bioteor can
    Petition 870170103436, of 12/29/2017, p. 31/36
    27/30 depend, for example, on the bioteor of ethylene oxide and carbon monoxide used. In some variations, both ethylene oxide and carbon monoxide are derived from renewable sources.
    Biodegradable
    [0070] In some variations of what was said previously, the pol dimer has an biodegradability of fur any less 10%, fur any less 20%, fur any less 30%, fur any less 40%, fur any less 50%, fur any less 60%, fur any less 70%, fur minus 80%, fur any less 90%, fur any less 95%, fur any less 96%, fur any less 97%, fur any less 98%, fur any less 99%, fur any less
    99.5%, at least 99.9%, at least 99.99% or 100%.
    [0071] In some variations of the above, biodegradable is as defined and determined based on ASTM D5338-15 (Standard test method for the determination of aerobic biodegradation of plastic materials under controlled composting conditions, incorporating thermophilic temperatures).
    Use of absorbent polymers [0072] In other respects, absorbent articles comprising the polymers described here or produced according to the methods described here are also provided here.
    [0073] In some variations, the adsorbent article also includes at least one organic or inorganic additive. Suitable inorganic additives can include, for example, metals (such as aluminum or tin), as well as clays. The incorporation of such solids can enhance the absorbent properties of the polymer or polymer compositions. Examples of organic additives may include, for example, plasticizers such as polybutene, polypropene,
    Petition 870170103436, of 12/29/2017, p. 32/36
    28/30 polybutadiene, polyisobutene and / or polyisoprene.
    [0074] In some modalities, the absorbent article is a disposable diaper, a product for adult incontinence or a product for feminine hygiene. In some variations of what was said earlier, the absorbent article is biologically and / or biodegradable.
    [0075] In certain respects, a biodegradable fabric is provided, comprising any of the polymers described here or produced according to the methods described here. In some variations of the above, the biodegradable fabric further comprises at least one organic or inorganic additive.
    Agricultural Uses [0076] The polymers described here or produced according to the methods described here may also be suitable for agricultural use. In other respects, an agricultural product is provided comprising the polymers described herein or produced according to the methods described here. Such an agricultural product can be a material used in planting and / or growing plants or a seed or a crop.
    [0077] For example, the polymers described here or produced according to the methods described here can be used as agricultural materials to retain water for crops. Thus, in some variations, an agricultural material is provided comprising the polymers described herein or produced according to the methods described here. In certain variations, agricultural material also includes at least one organic or inorganic additive.
    [0078] In other variations, a seed is provided
    Petition 870170103436, of 12/29/2017, p. 33/36
    29/30 coated with the polymers described here or produced according to the methods described here. In other embodiments, a seed mixture comprising seeds is provided, in which at least part of the seeds are coated with the polymers described herein or produced according to the methods described here. When the polymer or polymer compositions biodegrade, water can be released.
    [0079] In still other aspects, a method is provided, comprising planting seeds, in which at least part of the seeds are coated with the polymers described here or produced according to the methods described here. In some variations, the method further comprises the growth of plants from at least part of the seeds planted under conditions in which the polymers biodegrade to release water for the seeds and / or plants.
    EXAMPLES [0080] The following example is illustrative only and is not intended to limit any aspect of the present description in any way.
    Example 1
    Synthesis of Absorbent Polymers [0081] This Example demonstrates the synthesis of a polymer from beta-propiolactone (bPL).
    [0082] Polymerization of bPL initiated by poly (sodium acrylate): 2 g of bPL were added to a flask containing 260 mg of poly (sodium acrylate). The reaction hurts at 50 ° C for 16 hours. 1 H NMR of the resulting product showed complete consumption of bPL.
    Petition 870170103436, of 12/29/2017, p. 34/36
    30/30 [0083] Branched PPL poly (sodium acrylate) thermolysis: the resulting product from the above step was then thermolysed at 160 ° C-180 ° C and acrylic acid generated from the thermolysis was isolated by vacuum distillation . The remaining residue from the thermolysis was poly (sodium acrylate) as determined by 1 H NMR and the liquid collected from the vacuum distillation was confirmed to be acrylic acid by 1 H NMR.
    [ooi] Synthesis of acrylic acid polymer in pure condition: to a 40 mL scintillation flask equipped with a stir bar and an explosion disc, 1.80 g of acrylic acid (Sigma Aldrich, 99%) and 0, 20 g of 80% sodium oxide (Sigma Aldrich) was added at room temperature with stirring. Then, 0.024 g of N, N'methylenobis (acrylamide) (99%, Sigma Aldrich) was added with stirring. The resulting mixture was then heated in a reaction block to 100 ° C for 30 minutes. The solution was then purged with nitrogen by means of a needle through the blast disc. After approximately 5 minutes of N2 spraying, an exotherm at 72 ° C was observed with gaseous effluent. Heat to the flask was discontinued. The resulting solid material was ground to a fine powder with a mortar and pestle, then added to a medium medium sized 100 mL fried filter. The material was rinsed three times with deionized water (DI), 50 mL of each aliquot. The gel-like material was dried overnight in a vacuum oven at 105 ° C, yielding 0.285 g of white solid.
    权利要求:
    Claims (12)
    [1]
    Method of production of a polymer, characterized by the fact of understanding:
    combination of beta-propiolactone with a metal compound of the formula M, M 2 0,
    MOH or M + (CH 2 = CHCOO-) or a combination thereof to produce acrylic acid, a salt thereof or a combination thereof; and polymerization of acrylic acid, a salt thereof or a combination thereof with a polymerization initiator and optionally a crosslinker to produce the polymer.
    Method, according to claim 1, characterized by the fact that the polymerization is carried out pure or in a non-aqueous medium.
    Method of production of a polymer, characterized by the fact of understanding:
    polymerization of beta-propiolactone with an ionic initiator in a reactor to produce a polymer intermediate, wherein the polymer intermediate has a polyacrylic acid backbone and a plurality of polypropiolactone side chains;
    b) increasing the temperature of the reactor to produce acrylic acid from at least part of the side chains in the polymer intermediate and to produce polymer acrylate from at least a part of the polymeric main structure of the polymer intermediate by thermolysis of the intermediate of polymer;
    c) addition of a metal compound of the formula M, M 2 0,
    MOH or M + (CH 2 = CHCOO “) or a combination of these to the reactor to at least partially neutralize the acrylic acid in the reactor to produce a mixture, where the mixture in
    [2]
    2/12 reactor comprises acrylic acid and M + (CH2 = CHCOO _ ), where
    M is a Group I metal; and
    d) polymerization of at least a part of the mixture in the reactor to produce the polymer, wherein the polymer comprises the repetition units of O <X OH or oAtm * or a combination thereof.
    4. Method according to claim 3, characterized by the fact that steps (c) and (d) are carried out pure or in a non-aqueous medium.
    Method according to claim 3 or 4, characterized in that the ionic initiator comprises an alkali metal salt, an alkaline earth metal salt or a combination thereof.
    6. Method according to claim 3 or 4, characterized in that the ionic initiator comprises an alkali metal carboxylate salt, an alkaline earth metal salt or a combination thereof.
    7. Method according to claim 3 or 4, characterized by the fact that the ionic initiator is an alkali metal salt.
    8. Method according to claim 3 or 4, characterized by the fact that the ionic initiator has a structure of formula CH2 = CH2CO2Z + , wherein Z + is an alkali metal, an alkaline earth metal ammonium, an ammonium cation quaternary or phosphonium.
    9.
    Method, according to characterized by the fact that quaternary ammonium cation is a lower alkyl quaternary ammonium cation.
    10.
    Method according to claim
    [3]
    3 or 4, vjoil r | a · 'π
    3/12 characterized by the fact that the initiator sodium acrylate or potassium acrylate or a combination of them.
    Method according to claim 3 or 4, characterized by the fact that the ionic initiator is a methacrylate.
    12. Method, in wake up with any an of claims 1 The 11, featured by the fact that M is a metal of the Group I • 13. Method,in wake up with any an of claims 1 The 11, featured by the fact that M is sodium. 14. Method,in wake up with any an of claims 1 The 13, featured by the fact that
    polymerization is carried out in the presence of a polymerization initiator.
    15. Method according to claim 14, characterized in that the polymerization initiator is a radical initiator.
    16. Method, according to claim
    15, characterized by the fact that the radical initiator comprises a peroxide, a persulfate or an azo compound or a combination thereof.
    17. Method, according with The claim 15, characterized by fact that the radical initiator it is a redox initiator. 18. Method, according with The claim 15, characterized by fact that the in radical maker comprises a hydroperoxide. 19. Method, according with The claim 15,
    [4]
    4/12 characterized by the fact that the initiator comprises hydrogen peroxide.
    radical
    20. Method according to claim 14, characterized by the fact that the polymerization initiator is a thermal initiator or a photoinitiator or a combination thereof.
    21. Method according to claim 14, characterized in that the polymerization initiator is a peroxide or an acid.
    22. Method according to any one of claims 3 to 21, characterized in that it further comprises the addition of a crosslinker to the reactor in step (d) to polymerize at least part of the mixture in the reactor to produce the polymer, wherein the polymer is cross-linked.
    23. Method according to any one of claims 3 to 22, characterized in that it further comprises:
    isolating at least a part of the polymer produced in step (d); and combining the isolated polymer with additional beta-propiolactone to produce additional polymer intermediate.
    24. Method of production of a polymer, characterized by the fact of understanding:
    combining beta-propiolactone with a metal compound in a main reactor, where the metal compound initiates the polymerization of at least part of the betapropiolactone to produce polypropiolactone in the main reactor;
    [5]
    5/12 thermolysis of at least one in the main reactor to produce acrylic acid; volatilization of at least part of the acrylic acid in the main reactor;
    passage of the volatilized acrylic acid through a distillation column;
    combining acrylic acid obtained from a distillation column with a radical initiator, optional crosslinker and additional metal compound in a kneading reactor to produce a partially neutralized polyacrylic acid; and feeding the partially neutralized polyacrylic acid from the kneading reactor to the main reactor, where the final partially neutralized polyacrylic acid carboxylate groups initiate the polymerization of at least part of the beta-propiolactone in the main reactor to produce a branching polymer polypropiolactone.
    25. Method according to claim 24, characterized in that it further comprises the isolation of a product stream from the main reactor, in which the product stream comprises the polymer with branches of polypropiolactone.
    26. Method according to claim 25, characterized in that the product stream further comprises unreacted beta-propiolactone.
    27. Method according to any one of claims 24 to 26, characterized in that it further comprises the separation of a flow of polymers comprising the polymer with branches of
    [6]
    6/12 polypropiolactone from a stream comprising unreacted beta-propiolactone.
    28. Method, according to claim 27, characterized by the fact that it also comprises the supply of the recycle stream inside the main reactor.
    29. Method according to any one of claims 24 to 28, characterized in that the metal compound is a compound of the formula Μ, M2O, MOH or M + (CH2 = CHCOO ~) or a combination thereof.
    30. Method, in wake up with claim 29, character ized by fact that is a Group I metal. 31. Method, in wake up with claim 29, character ized by fact that M is sodium. 32. Method, in wake up with any one of
    claims 24 to 31, characterized in that the radical initiator comprises a peroxide, a persulfate or an azo compound or a combination thereof.
    33. Method, of a deal with any an of claims 24 to 31 , characterized fur fact in that 0 radical initiator is a redox initiator. 34. Method, of a deal with any an of claims 24 to 31 , characterized fur fact in that 0
    radical initiator comprises a hydroperoxide.
    35. Method, in a deal with any an of claims 24 to 31, featured by the fact in that 0 initiator radical comprises hydrogen peroxide. 36. Method, in a deal with any an of claims 1 to 35, featured by the fact in that 0 method is continuous. 37. Method, in a deal with any an of
    [7]
    7/12 claims 1 to 36, characterized in that it also comprises the carbonylation of ethylene oxide to produce beta-propiolactone.
    38. Method, of a deal with any one of claims 1 to 37, characterized fur fact in further understand the combination of oxide in ethylene and carbon monoxide in the presence of a catalyst in carbonylation and optionally a solvent for to produce The beta-propiolactone. 39. Polymer, featured fur fact to be produced according with the method, as defined in
    of the previous claims.
    any
    40.
    Absorbent article, characterized by the fact that it comprises a polymer, as defined in the claim
    39.
    41. Absorbent article according to claim 40, characterized by the fact that it also comprises at least one organic or inorganic additive.
    42. Absorbent article according to claim 40 or 41, characterized in that the absorbent article is a disposable diaper, adult incontinence product or feminine hygiene product.
    43. Absorbent article according to any one of claims 40 to 42, characterized in that the absorbent article is biodegradable.
    44. Biodegradable tissue, characterized by the fact that it comprises:
    a polymer, as defined in claim 39; and at least one organic or inorganic additive.
    [8]
    12/12
    45.
    Agricultural product, characterized by the fact that it comprises a polymer, as defined in the claim
    39.
    46. Agricultural product according to claim 45, characterized by the fact that the agricultural product is a material for retaining water for crops.
    47. Agricultural product according to claim 45, characterized by the fact that the agricultural product is a seed or a crop.
    48. Seed, characterized by the fact that the seed is coated with a polymer, as defined in claim 39.
    49. Seed mixture, characterized by the fact that it comprises a plurality of seeds, in which at least part of the seeds is coated with a polymer, as defined in claim 39.
    50.
    Method, characterized by the fact of understanding the planting of seeds, as defined in the claim
    48, or a seed mixture as defined in claim 49.
    51. Method according to the claim
    50, characterized by the fact that it also comprises seed development in plants under conditions suitable for biodegradable polymer to release water for the seeds, plants or a combination thereof.
    52. System, characterized by the fact that it comprises:
    a main reactor;
    a distillation column connected to the main reactor;
    a kneading reactor connected to the top of the reactor
    [9]
    Main 9/12 through the distillation column, where:
    the main reactor is configured to:
    receiving an inlet stream comprising betapropiolactone;
    polymerize at least part of the betapropiolactone in the inlet stream to produce polypropiolactone;
    thermolysing at least a part of the polypropiolactone to produce acrylic acid; and volatilizing at least a part of the acrylic acid; the distillation column is configured to receive the volatilized acrylic acid from the main reactor;
    the kneading reactor is configured to:
    receiving at least part of the distilled acrylic acid from the distillation column;
    receiving a radical initiator, optionally a crosslinker and a metal or metal salt;
    producing a partially neutralized polyacrylic acid from at least part of the acrylic acid in the kneading reactor; and feeding at least a part of the partially neutralized polyacrylic acid back into the main reactor; and the main reactor is further configured to:
    receiving partially neutralized polyacrylic acid from the kneading reactor; and polymerizing beta-propiolactone to produce a polymer with branches of polypropiolactone; and
    [10]
    10/12 the main reactor further comprises one configured to emit a flow of products comprising beta-propiolactone, the polymer and heat transfer fluid.
    53. System, characterized by the fact to understand: one main reactor and; one vase comprising an column of distillation and a reactor kneader, in what the column distillation is connected to the top of the reactor main,
    on what:
    the main reactor is configured to:
    receiving an inlet stream comprising betapropiolactone;
    receiving a mixture of a metal compound and heat transfer fluid;
    polymerize at least part of the betapropiolactone in the inlet stream in the presence of the metal compound to produce polypropiolactone;
    thermolysing at least a part of the polypropiolactone to produce acrylic acid; and volatilizing at least a part of the acrylic acid; the distillation column is configured to receive the volatile acrylic acid from the main reactor and feed the acrylic acid to the kneading reactor;
    the kneader reactor is configured to:
    receiving at least part of the acrylic acid from the distillation column;
    receiving a radical initiator, optionally a crosslinker and a metal compound;
    produce a partially polyacrylic acid
    [11]
    11/12 neutralized from at least part of the acid '·;
    acrylic in the kneading reactor and;
    feeding at least part of the partially neutralized polyacrylic acid back into the main reactor;
    the main reactor is further configured to:
    receiving partially neutralized polyacrylic acid from the kneading reactor; and polymerizing beta-propiolactone to produce a polymer with branches of polypropiolactone; and the main reactor further comprises an outlet configured to emit a flow of products comprising beta-propiolactone, the polymer and heat transfer fluid.
    54. System according to claim 52 or 53, characterized by the fact that it further comprises a carbonylation reactor configured to carbonyl ethylene oxide to produce the inlet flow.
    55. System according to any one of claims 52 to 54, characterized in that it further comprises a separation unit, configured to isolate the polymer from the product stream.
    56. System according to any one of claims 52 to 54, characterized in that it further comprises a separation unit, configured to separate the product stream into a stream of polymers comprising the polymer, and a recycle stream comprising the beta-propiolactone and the heat transfer fluid.
    57. System according to claim 56,
    [12]
    12/12 characterized by the fact that the separation unit θ '' '-' · 'is still configured to feed the recycle flow back into the main reactor.
    58. The system of any one of claims 52 to 57, characterized in that the heat transfer fluid comprises an aprotic organic solvent with a boiling point greater than the boiling point of acrylic acid.
    59. System according to any one of claims 52 to 58, characterized in that the radical initiator comprises a peroxide, a persulfate or an azo compound or a combination thereof.
    60. System according to any one of claims 52
    58, characterized by the fact that the radical initiator is a redox initiator.
    61. System according to any one of claims 52 to
    58, characterized by the fact that the radical initiator comprises a hydroperoxide.
    62. System according to any one of claims 52 to
    58, characterized by the fact that the radical initiator comprises hydrogen peroxide.
    63. System according to any one of claims 52
    62, characterized by the fact that the metal compound is a compound of formula Μ, M2O, MOH, or a combination thereof.
    M + (CH2 = CHCOO _ ) or a
    64. System, in wake up with The claim 63, characterized by fact that My M Group I metal. 65. System, in wake up with The claim 63, characterized by fact that M is sodium
    1/1
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    法律状态:
    2019-02-19| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2021-02-17| B11A| Dismissal acc. art.33 of ipl - examination not requested within 36 months of filing|
    2021-05-04| B11Y| Definitive dismissal acc. article 33 of ipl - extension of time limit for request of examination expired|
    优先权:
    申请号 | 申请日 | 专利标题
    US201662416611P| true| 2016-11-02|2016-11-02|
    US62/416,611|2016-11-02|
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