WO2014124358A1 - Résine en microgranulés, sa fabrication et son utilisation - Google Patents

Résine en microgranulés, sa fabrication et son utilisation Download PDF

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Publication number
WO2014124358A1
WO2014124358A1 PCT/US2014/015541 US2014015541W WO2014124358A1 WO 2014124358 A1 WO2014124358 A1 WO 2014124358A1 US 2014015541 W US2014015541 W US 2014015541W WO 2014124358 A1 WO2014124358 A1 WO 2014124358A1
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WIPO (PCT)
Prior art keywords
resin composition
pellets
diameter
pelletized resin
pelletized
Prior art date
Application number
PCT/US2014/015541
Other languages
English (en)
Inventor
Gabriel O. SHONAIKE
Michael Q. Tran
Original Assignee
Invista Technologies S.A.R.L.
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Publication date
Application filed by Invista Technologies S.A.R.L. filed Critical Invista Technologies S.A.R.L.
Priority to CN201480020444.XA priority Critical patent/CN105121110B/zh
Publication of WO2014124358A1 publication Critical patent/WO2014124358A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/20—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/20—Tetrahydrofuran
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2669—Non-metals or compounds thereof
    • C08G65/2678—Sulfur or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2669—Non-metals or compounds thereof
    • C08G65/2684—Halogens or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B2009/125—Micropellets, microgranules, microparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to a novel micropelletized resin composition.
  • the pellets of the micropelletized resin composition have a diameter of less than about 1 mm, for example, 0.75 + 0.24 mm, and a length/diameter (L/D) ratio of from 0.5 to 2.0.
  • the micropelletized resin composition may comprise perfluorosulfonic acid ion exchange resin.
  • the invention further relates to an effective method for manufacturing the micropelletized resin composition, and use of the micropelletized resin composition as catalyst for conversion of organic compounds, for example, polymerizing at least one tetrahydrofuran or at least one tetrahydrofuran and at least one other cyclic ether to manufacture polyether glycol or copolyether glycol.
  • 5,403,912 discloses use of a perfluorinated resin sulfonic acid consisting of a backbone of fluoropolymer.
  • U.S. Pat. Pub. 2008/0071118 discloses use of a resin i having a perfluoroalkyl sulfonic acid group as a side chain in a list of possible catalysts.
  • U.S. Pat Pub. 2003/176630 discloses use of polymers comprising alpha- fluorosulfonic acids. Commercially standard fluorosulfonic acid resin pellets are extrudates of about 3.0 to 3.5 mm in diameter.
  • Copolymers of THF and cyclic ether are well known in the art. Their preparation is disclosed, for example, by Pruckmayr in U.S. Pat. No. 4,139,567 and U.S. Pat. No. 4,153,786. Such copolymers can be prepared by any of the known methods of cyclic ether polymerization, described for instance in
  • Polytetrahydrofuran by P. Dreyfuss (Gordon & Breach, N.Y. 1982). Such polymerization methods include catalysis by strong proton or Lewis acids, by heteropoly acids, as well as by perfluorosulfonic acids or acid resins. In some instances it may be advantageous to use a polymerization promoter, such as a carboxylic acid anhydride, as disclosed in U.S. Pat. No. 4,163, 115.
  • U.S. Pat. Nos. 4,120,903 and 4,139,567 disclose preparation of copolyether glycols by copolymerizing THF and an alkylene oxide or cyclic acetal over catalyst comprising a polymer containing fluorosulfonic acid groups and with water or an alkanediol as a chain terminator.
  • pelletized resin composition comprising at least about 90 % of the pellets being less than about 1 mm, for example, 0.75 + 0.24 mm, in diameter and having a length/diameter (L/D) ratio of 0.5 to 2.0, the pellets having an essentially smooth surface. None of the above publications teach a method for manufacturing such micropelletized resin composition, or a process for conversion of organic compounds at conversion effective conditions in the presence of a catalytically effective amount of such pelletized resin composition.
  • micropelletized resin composition in acidic form as catalyst for conversion of organic compounds, for example, polymerizing at least one tetrahydrofuran or at least one tetrahydrofuran and at least one other cyclic ether to manufacture polyether glycol or copolyether glycol.
  • the present invention provides an embodiment comprising a micropelletized resin composition comprising at least about 90 % of the pellets being less than about 1 mm in diameter and having a length/diameter (L/D) ratio of from 0.5 to 2.0, the pellets having an essentially smooth surface.
  • a micropelletized resin composition comprising at least about 90 % of the pellets being less than about 1 mm in diameter and having a length/diameter (L/D) ratio of from 0.5 to 2.0, the pellets having an essentially smooth surface.
  • Another embodiment comprises the pelletized resin composition wherein the diameter of at least about 90 %, for example from about 95 to about 100 %, of the pellets is about 0.75 + 0.24 mm.
  • Another embodiment of the present invention comprises the pelletized resin composition comprising
  • Another embodiment of the invention comprises a method for manufacturing a micropelletized resin composition product comprising melt extruding an extrudable resin composition having a viscosity greater than about 1 x 10 4 Pascal (Pa.s) through a suitable die to form an extrudate strand, cooling the extrudate strand to form a cooled extrudate strand, passing the cooled extrudate strand into a pelletizer system including a rotor with more than 12 teeth, such as from 14 to 28 teeth, for example 24 teeth, at least one ionized air jet, and vacuum extraction at the exit of the pelletizer system to form pelletized resin product, whereby the pelletized resin product is at least about 90 % less than about 1 mm, for example, about 0.75 + 0.24 mm, in diameter and has an L/D ratio of from 0.5 to 2.0, the pellets of the pelletized resin product having an essentially smooth surface.
  • a pelletizer system including a rotor with more than 12 teeth, such as from 14 to 28 teeth, for example 24 teeth,
  • Another embodiment of the invention provides a micropelletized resin composition comprising at least about 50 % of the pellets being less than about 1 mm in diameter and having a length/diameter (L/D) ratio of from 0.5 to 2.0, the pellets having an essentially smooth surface.
  • Another embodiment comprises the pelletized resin composition wherein the diameter of at least about 60 %, for example from about 75 or 80 %, of the pellets is about 0.75 + 0.24 mm.
  • a majority of the pellets of the pellets being less than about 1 mm in diameter and having a length/diameter (L/D) ratio of from 0.5 to 2.0.
  • Another embodiment of the invention comprises a process for converting organic compounds to conversion product over a catalytically effective amount of the uniformly sized micropelletized resin composition in acidic form, such as, for example, manufacturing polyether glycol or copolyether glycol having a mean molecular weight of from about 200 dalton to about 30,000 dalton which comprises the step of polymerizing a reaction mixture comprising at least one tetrahydrofuran or at least one tetrahydrofuran and at least one other cyclic ether at polymerization effective conditions in the presence of a catalytically effective amount of the micropelletized resin composition comprising perfluorosulfonic ion exchange resin, and optionally in the presence of an acylium ion precursor, carboxylic acid, and/or a chain terminator.
  • manufacturing polyether glycol or copolyether glycol having a mean molecular weight of from about 200 dalton to about 30,000 dalton which comprises the step of polymerizing a reaction mixture comprising at least one te
  • the present invention is directed to a specific novel micropelletized resin composition, an effective method for manufacturing the micropelletized resin composition, and use thereof in acidic form as catalyst for conversion of organic compounds, for example, in manufacturing polyether glycol or copolyether glycol.
  • micropellets of the present invention are extruded and pelletized resin having controlled geometrical dimensions. They may be cylindrical, spherical or another physical form as may be dictated by their end use.
  • the pellets of the micropelletized resin composition of the invention uniformly have a diameter of less than about 1 mm, for example, 0.75 + 0.24 mm, and a length/diameter (L/D) ratio of from 0.5 to 2.0, preferably from 0.75 to 1.25.
  • the micropelletized resin composition may comprise perfluorosulfonic acid ion exchange resin such as disclosed in U.S. Pat. No. 4,433,082, incorporated herein by reference.
  • the pellets of the micropelletized resin composition are uniformly at least about 90 %, such as at least about 95 %, for example from about 95 to 100 %, less than about 1 mm, for example, 0.75 + 0.24 mm, in diameter and have a length/diameter (L/D) ratio of from 0.5 to 2.0, preferably from 0.75 to 1.25.
  • the pellets have an essentially smooth surface, indicated by visual evaluation of microphotographs at magnification of approximately 50X.
  • the diameter and L/D ratio of the micropelletized resin composition is indicated by measurement evaluation of microphotographs at magnification of approximately 50X.
  • micropellets of the present invention which may comprise perfluorosulfonic acid ion exchange resin, such as for example any disclosed in U.S. Pat. No. 4,433,082, incorporated herein by reference, or in particular Solvay
  • Solexis ® is manufactured by melt extruding an extrudable polymer comprising same through the die of an extruder.
  • the resin for extruding is in the perfluorosulfonyl fluoride form. It is a thermoplastic that can be processed at elevated temperature.
  • the extruder is not especially critical so long as it effectively manufactures extrudate strand from high viscosity, i.e. greater than about 1 x 10 4 Pa.s, material. Feed rate and percentage of open area in the extrusion die, however, have been found to be significant.
  • the extruder may be, for example, a single or twin screw.
  • fluoropolymer such as perfluorosulfonic acid ion exchange resin has high viscosity of from 1 x 10 4 to 1 x 10 5 Pa.s
  • a twin screw extruder is preferred because it devolitizes better and, if the extrudable polymer feed material is in powder form, it surges better.
  • Feed rate in the die must be from 2.75 to 4.25 Ib/hr, for example about 3.2 Ib/hr. Open area in the die must be 0.8 + 0.1 mm.
  • the extrudate strand emerges from the extruder die, it is cooled either by dry or water cooling. The cooled strand then enters a pelletizer system where it is formed into the micropellets of the present invention.
  • the pelletizer system is extremely important for manufacture of the micropelletized resin composition of the invention.
  • at least one ionized air jet is provided directly into the cutting chamber of the pelletizer system.
  • a rotor with more than 12 teeth such as from 14 to 28 teeth, for example 24 teeth, instead of the conventional rotor with 12 teeth, is used inside the cutting chamber of the pelletizer system to minimize turbulence in the chamber.
  • vacuum extraction is used at the exit of the pelletizer system at from about 850 to about 1000 mbar.
  • the micropelletized resin composition may be used as catalyst for organic compound conversion reactions such as, for example, esterification, etherification and polymerization.
  • An embodiment of use of the micropelletized resin composition as catalyst for esterification comprises contacting an alcohol, e.g. methanol, and acid, e.g.
  • micropelletized resin composition as catalyst for etherification comprises contacting, for example, 1 ,4-butanediol with a catalytically effective amount of the catalyst at reaction conditions including, for example, a temperature of from 100 to 180 °C and pressure from 200 to 1500 mmHg, to produce THF.
  • Use of the micropelletized resin composition of the present invention as catalyst for polymerization is extremely important.
  • An embodiment of this use comprises manufacturing polyether glycol or copolyether glycol.
  • the process for manufacturing polyether glycol or copolyether glycol having a number average molecular weight of from about 200 dalton to about 30,000 dalton comprises the step of polymerizing at least one tetrahydrofuran or at least one tetrahydrofuran and at least one other cyclic ether, for example alkylene oxide, at polymerization effective conditions including, for example a temperature of from about 0 to about 80 °C, in the presence of catalyst comprising the
  • micropelletized resin composition of the present invention optionally in the presence of an acylium ion precursor, carboxylic acid, and/or a chain terminator.
  • An embodiment of this invention therefore, provides a process for manufacturing poly(tetramethylene ether) glycol (PTMEG), its copolymers and their esters by polymerization of a reaction mixture comprising tetrahydrofuran (THF) and optional comonomers which comprises the step of polymerizing at least one tetrahydrofuran at polymerization effective conditions including, for example a temperature of from about 0 to about 80 °C, in the presence of catalyst comprising the micropelletized resin composition of the present invention, optionally in the presence of an acylium ion precursor, carboxylic acid, and/or a chain terminator.
  • THF tetrahydrofuran
  • Another embodiment of this invention provides a process for manufacturing poly(tetramethylene-co-alkyleneether) glycol having a number average molecular weight of from about 650 dalton to about 4000 dalton, and a viscosity of from about 80 cP to about 4000 cP, which comprises the step of polymerizing at least one tetrahydrofuran and at least one alkylene oxide at polymerization effective conditions including, for example a temperature of from about 0 to about 80 °C, in the presence of catalyst comprising the micropelletized resin composition of the present invention, optionally in the presence of an acylium ion precursor, carboxylic acid, and/or a chain terminator.
  • Another embodiment of this invention provides a process for manufacturing poly(tetramethylene-co-ethyleneether) glycol a number average molecular weight of from about 650 dalton to about 4000 dalton, and a viscosity of from about 80 cP to about 4000 cP, which comprises the step of polymerizing at least one tetrahydrofuran and ethylene oxide at polymerization effective conditions including, for example a temperature of from about 0 to about 80 °C, in the presence of catalyst comprising the micropelletized resin composition of the present invention, optionally in the presence of an acylium ion precursor, carboxylic acid, and/or a chain terminator.
  • polyether and copolyether glycols having a number average molecular weight of from about 200 dalton to about 30,000 dalton, for example from about 650 dalton to about 4,000 dalton, and a viscosity of from about 80 cP to about 4000 cP are recovered.
  • a high percentage, such as for example from 50 to about 100 wt %, of the "other cyclic ether", for example alkylene oxide (e.g. EO), in the feedstock to the polymerization step is consumed in this reaction.
  • unreacted feedstock tetrahydrofuran, other cyclic ether, e.g. alkylene oxide, dimer of the alkylene oxide if present, and any lower boiling components present are removed.
  • PTMEG polytetramethylene ether glycol.
  • PTMEG is also known as polyoxybutylene glycol.
  • copolyether glycol as used herein in the singular, unless otherwise indicated, means copolymers of tetrahydrofuran and at least one other cyclic ether, e.g. alkylene oxide, which are also known as polyoxybutylene polyoxyalkylene glycols.
  • An example of a copolyether glycol is a copolymer of tetrahydrofuran and ethylene oxide. This copolyether glycol is also known as poly(tetramethylene-co- ethyleneether) glycol.
  • THF tetrahydrofuran and includes within its meaning alkyl substituted tetrahydrofuran capable of copolymerizing with THF, for example 2-methyltetrahydrofuran, 3- methyltetrahydrofuran, and 3-ethyltetrahydrofuran.
  • alkylene oxide as used herein, unless otherwise indicated, means a compound containing two, three or four carbon atoms in its alkylene oxide ring.
  • the alkylene oxide can be unsubstituted or substituted with, for example, linear or branched alkyl of 1 to 6 carbon atoms, or aryl which is unsubstituted or substituted by alkyl and/or alkoxy of 1 or 2 carbon atoms, or halogen atoms such as chlorine or fluorine.
  • Examples of such compounds include ethylene oxide (EO); 1 ,2-propylene oxide; 1 ,3-propylene oxide; 1 ,2-butylene oxide; 1 ,3-butylene oxide; 2,3-butylene oxide; styrene oxide; 2,2-bis-chloromethyl-1 ,3-propylene oxide; epichlorohydrin; perfluoroalkyl oxiranes, for example (1 H,1 H-perfluoropentyl) oxirane; and combinations thereof.
  • EO ethylene oxide
  • 1 ,2-propylene oxide 1 ,3-propylene oxide
  • 1 ,2-butylene oxide 1 ,3-butylene oxide
  • 2,3-butylene oxide 2,3-butylene oxide
  • styrene oxide 2,2-bis-chloromethyl-1 ,3-propylene oxide
  • epichlorohydrin perfluoroalkyl oxiranes, for example (1 H,1 H-perfluoropentyl) oxi
  • the THF used as a reactant in the process can be any of those commercially available. Typically, the THF has a water content of less than about 0.03% by weight and a peroxide content of less than about 0.005% by weight. If the THF contains unsaturated compounds, their concentration should be such that they do not have a detrimental effect on the polymerization process of the present invention or the polymerization product thereof. For example, for some applications it is preferred that the copolyether glycol product of the present invention having a high molar concentration of alkylene oxide has low APHA color, such as, for example less than about 100 APHA units.
  • the THF can contain an oxidation inhibitor such as butylated hydroxytoluene (BHT) to prevent formation of undesirable byproducts and color.
  • BHT butylated hydroxytoluene
  • one or more alkyl substituted THF's capable of copolymerizing with THF can be used as a co-reactant, in an amount from about 0.1 to about 70% by weight of the THF. Examples of such alkyl substituted THF's include 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, and 3- ethy Itetrahyd rof u ra n .
  • the alkylene oxide used as a reactant in the present process may be a compound containing two, three or four carbon atoms in its alkylene oxide ring.
  • the alkylene oxide can be unsubstituted or substituted with, for example, alkyl groups, aryl groups, or halogen atoms. It may be selected from, for example, the group consisting of ethylene oxide; ,2-propylene oxide; 1 ,3-propylene oxide; 1 ,2-butylene oxide; 2,3-butylene oxide; 1 ,3-butylene oxide; 2,2- bischloromethyl oxetane; epichlorohydrin and combinations thereof.
  • the alkylene oxide has a water content of less than about 0.03% by weight, a total aldehyde content of less than about 0.01 % by weight, and an acidity (as acetic acid) of less than about 0.002% by weight.
  • the alkylene oxide should be low in color and non-volatile residue.
  • the optional acylium ion precursor for use in the process of the present invention can be any compound capable of generating the acetyl oxonium ion of THF under reaction conditions.
  • Representative of acylium ion precursors are acetyl halides and carboxylic acid anhydrides. Anhydrides of carboxylic acids whose carboxylic acid moieties contain from 1 to 16 carbon atoms are preferred, especially those of from 1 to 4 carbon atoms.
  • Non-limiting examples of such anhydrides are acetic anhydride, propionic anhydride and formic -acetic anhydride.
  • the anhydride preferred for use herein because of its efficiency is acetic anhydride.
  • the acylium ion precursor is ordinarily present in the reaction mixture, at least initially, at a concentration of from about 0.1 to about 15 wt %, preferably from about 0.7 to about 10 wt %.
  • the molecular weight of the polymer product can be limited by the optional addition to the reaction mixture of an aliphatic carboxylic acid of form 1 to 16 carbon atoms, preferably from 1 to 5 carbon atoms. Acetic acid is preferred for use herein due to its low cost and effectiveness.
  • the acylium ion precursor/ carboxylic acid weight ratio should be within the range of from about 20:1 to about 0.1 :1 , preferably from about 10:1 to about 0.5 to 1. Generally speaking, the more carboxylic acid used, the lower the molecular weight of the product.
  • the aliphatic carboxylic acid when it is used, is ordinarily added to the reaction mixture at a concentration of from about 0.1 to about 10%, by weight of the THF, preferably from about 0.5 to about 5 wt %.
  • acylium ion precursor acetic anhydride
  • THF trifluoroacetic acid
  • carboxylic acid be present in the reaction mixture at a combined concentration of from about 0.5 to about 20%, by weight of the reaction mass, preferably from about 1 to about 0 wt %.
  • the optional chain terminator for use in the process of the present invention is selected from the group consisting of water, alkanediol containing from 2 to about 10 carbon atoms and combinations thereof. Water and 1 ,4-butanediol are preferred for their low cost and availability. These compounds can be used in combination to regulate the molecular weight of the final product.
  • the catalyst is present in the polymerization step of the present invention in a catalytically effective amount, which in the usual case means a concentration of from about 0.01% to about 30% by weight of the reaction mixture, preferably from about 0.05% to about 15%, even more preferably from about 0.1 % to about 10%.
  • the polymerization step of the present invention is generally carried out at from about 0 to about 80 °C, such as from about 20 to about 70 °C, for example from about 30 to about 70 °C.
  • the process is ordinarily run at atmospheric pressure, but reduced or elevated pressure may be used to aid in controlling the temperature of the reaction mixture during the reaction.
  • the pressure employed may be from about 200 to about 800 mmHg, for example from about 300 to about 500 mmHg.
  • the polymerization step of the process may be conducted under an inert gas atmosphere.
  • suitable inert gases for use herein include nitrogen, carbon dioxide, or the noble gases.
  • the polymerization step of the process can also be carried out in the presence of hydrogen at hydrogen pressure from about 0.1 to about 10 bars.
  • the micropelletized ion exchanged resin composition catalyst can be separated from the reaction mixture by filtration, decantation or centrifugation, and reused. If the process is run in a continuous fashion, the catalyst can simply be allowed to remain in the reactor while fresh reactants are fed in and product is removed.
  • a sample of commercially manufactured perfluorosulfonic acid ion exchange resin pellets (Solvay Solexis ® ) having an average size of between 3 and 3.5 mm is secured and a portion thereof set aside. The remaining portion is placed in the hopper of an 18 mm co-rotating twin-screw extruder constructed of corrosion resistant high nickel alloy and extruded through an annular die having an 8 mm die hole. Screw rpm is maintained at 33 and motor torque/amperage at 23 %.
  • the twin-screw barrel is segmented into 8 zones at die temperatures ranging from 150 °C at the feed inlet to 355 °C at the exit, with melt pressure measured at 620 psi.
  • Feed rate in the die is maintained at approximately 3.2 Ib/hr. Open area in the die is approximately 0.8 mm.
  • the extruded stands exiting the die are cooled in a water bath set at 12 to 15 °C.
  • the cooled strands are then micropelletized using a modified pelletizer system with one ionized air jet and a rotor with 24 teeth in the cutting chamber, an ionized air knife, and vacuum extraction maintained at about 1 ,000 mbar, resulting in perfluorosulfonic acid ion exchange resin micropellets at least 95 % thereof having a diameter of 0.75 + 0.24 mm, and length/diameter (L/D) ratio of about 1.0, as determined by microphotographs.
  • the resulting pellets have an essentially smooth surface as determined by microphotographs.
  • Continuous EO/THF polymerization is carried out at 55 °C and atmospheric pressure in a 000 ml glass reactor, with an effective working volume of 500 ml, equipped with a side outlet and a mechanical agitator with a speed of approximately 350 rpm.
  • the reaction mixture contains 27.0 wt % EO, 0.41 wt % deionized water, and balanced with THF.
  • the reaction mixture is fed by a pump to the top of the reactor through a dip tube.
  • the product mixture flows out of the reactor through the side outlet which is covered by polyethylene cloth to retain the catalyst.
  • the reactor capacity for the reaction mixture is therefore about 500 ml.
  • added are 25 grams (about 5 wt % of the reaction mixture) of the
  • perfluorosulfonic acid ion exchange resin micropellets of Example 1 in acidic form as catalyst The reactor is continuously agitated during the course of the experiment. Various feed rates are used, in the range of 1 ml/min to 3 ml/min. A small sample (2-3 ml) of the product is taken at intervals and dried in a vacuum oven for 3 hours at 120 °C for conversion measurements. The bulk of the product mixture is collected every few hours and the unreacted feed materials are removed using a rotary evaporator at a temperature of about 99 °C (boiling water bath) and partial vacuum to provide the polymerization products for analyses.
  • a rotary evaporator at a temperature of about 99 °C (boiling water bath) and partial vacuum to provide the polymerization products for analyses.
  • the polymerization product samples are measured for EO and THF conversion and the molecular weight of the product by GPC.
  • the APHA color of the product samples is determined to average about 12.
  • the EO conversions prove to be 75, 72, 69 and 66 percent, respectively.
  • the product molecular weight for these samples is determined to be 3450, 3250, 3050 and 2850, respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne une composition de résine sous forme de granulés ayant un diamètre inférieur à environ 1 mm, par exemple 0,75 + 0,24 mm, et un rapport longueur/diamètre (L/D) de 0,5 à 2,0. L'invention concerne en outre un procédé de fabrication d'une telle composition de résine en microgranulés et l'utilisation de ladite composition sous forme de résine échangeuse d'ions contenant de l'acide perfluorosulfurique comme catalyseur de conversion de composés organiques, par exemple dans la polymérisation pour fabriquer du polyéther glycol ou du co-polyéther glycol.
PCT/US2014/015541 2013-02-11 2014-02-10 Résine en microgranulés, sa fabrication et son utilisation WO2014124358A1 (fr)

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* Cited by examiner, † Cited by third party
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CN106565946A (zh) * 2015-10-12 2017-04-19 重庆建峰工业集团有限公司 聚四氢呋喃生产粗品中分离微量甲醇钠工艺

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112606255B (zh) * 2020-11-30 2023-03-24 山东东岳未来氢能材料股份有限公司 应用于催化领域的离子交换树脂的加工方法

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US4139567A (en) 1977-03-30 1979-02-13 E. I. Du Pont De Nemours And Company Method for preparing copolyether glycols
US4153786A (en) 1977-03-30 1979-05-08 E. I. Du Pont De Nemours And Company Method for preparing ester end-capped copolyether glycols
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EP1195191A1 (fr) * 1999-03-18 2002-04-10 Hosokawa Micron Corporation Dispositif et procede de production de granules
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WO2006092337A1 (fr) * 2005-03-01 2006-09-08 Dsm Ip Assets B.V. Structure de gazon en plaques artificiel avec remplissage granulaire
EP1839737A1 (fr) * 2004-12-21 2007-10-03 Eisai R&D Management Co., Ltd. Dispositif de lit fluidise
US20080071118A1 (en) 2004-06-29 2008-03-20 Naoko Fujita Process for producing polyether polyol
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US4163115A (en) 1976-03-31 1979-07-31 E. I. Du Pont De Nemours And Company Preparation of esters of poly-(tetramethylene ether) glycol
US4120903A (en) 1977-03-30 1978-10-17 E. I. Du Pont De Nemours And Company Method for preparing poly(tetramethylene ether) glycol
US4139567A (en) 1977-03-30 1979-02-13 E. I. Du Pont De Nemours And Company Method for preparing copolyether glycols
US4153786A (en) 1977-03-30 1979-05-08 E. I. Du Pont De Nemours And Company Method for preparing ester end-capped copolyether glycols
US4330654A (en) 1980-06-11 1982-05-18 The Dow Chemical Company Novel polymers having acid functionality
US4433082A (en) 1981-05-01 1984-02-21 E. I. Du Pont De Nemours And Company Process for making liquid composition of perfluorinated ion exchange polymer, and product thereof
US4437952A (en) 1982-01-04 1984-03-20 E. I. Du Pont De Nemours & Co. Coextruded multilayer cation exchange membranes
JPH0292508A (ja) * 1988-09-29 1990-04-03 Nippon Petrochem Co Ltd 球形ミニペレットの製造法及びその装置
US5403912A (en) 1990-11-27 1995-04-04 Commonwealth Scientific And Industrial Research Organization Process for the production of poly(alkylene oxide)
US5118869A (en) 1991-02-13 1992-06-02 E. I. Du Pont De Nemours And Company Polymerizing tetrahydrofuran to produce polytetramethylene ether glycol using a modified fluorinated resin catalyst containing sulfonic acid groups
WO1995019222A1 (fr) 1994-01-12 1995-07-20 E.I. Du Pont De Nemours And Company Microcomposite poreux prepare a partir d'un polymere perfluore echangeur d'ions et d'un oxyde metallique, a l'aide d'un procede sol-gel
WO1996030180A1 (fr) * 1995-03-31 1996-10-03 Exxon Chemical Patents Inc. Articles expanses moules par rotation
US6040419A (en) 1996-01-24 2000-03-21 E. I. Du Pont De Nemours And Company Process for the polymerization of cyclic ethers
EP1195191A1 (fr) * 1999-03-18 2002-04-10 Hosokawa Micron Corporation Dispositif et procede de production de granules
JP2001149770A (ja) * 1999-12-01 2001-06-05 Hosokawa Micron Corp 粉粒体処理装置
US20030176630A1 (en) 2000-07-03 2003-09-18 Gerd Bohner Method for the single-step production of polytetrahydrofuran and tetrahydrofuran copolymers
EP1555102A1 (fr) * 2004-01-13 2005-07-20 JSP Corporation Procédé pour la fabrication des granules thermoplastiques
US20080071118A1 (en) 2004-06-29 2008-03-20 Naoko Fujita Process for producing polyether polyol
EP1839737A1 (fr) * 2004-12-21 2007-10-03 Eisai R&D Management Co., Ltd. Dispositif de lit fluidise
WO2006092337A1 (fr) * 2005-03-01 2006-09-08 Dsm Ip Assets B.V. Structure de gazon en plaques artificiel avec remplissage granulaire
US20090118456A1 (en) 2005-08-02 2009-05-07 Mcmaster University Chelating silicon-based polymers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106565946A (zh) * 2015-10-12 2017-04-19 重庆建峰工业集团有限公司 聚四氢呋喃生产粗品中分离微量甲醇钠工艺
CN106565946B (zh) * 2015-10-12 2019-01-29 重庆建峰工业集团有限公司 聚四氢呋喃生产粗品中分离微量甲醇钠工艺

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CN105121110A (zh) 2015-12-02

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