CN105121110B - Micropelletized resin, manufacture and use thereof - Google Patents
Micropelletized resin, manufacture and use thereof Download PDFInfo
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- CN105121110B CN105121110B CN201480020444.XA CN201480020444A CN105121110B CN 105121110 B CN105121110 B CN 105121110B CN 201480020444 A CN201480020444 A CN 201480020444A CN 105121110 B CN105121110 B CN 105121110B
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- 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
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- 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
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- 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
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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
The invention provides a micropelletized resin, a manufacture and a use thereof. The resin composition comprises pellets having a diameter of less than about 1 mm, for example, 0.75+-0.24 mm, and a length/ diameter (UD) ratio of from 0.5 to 2.0. It is further provided a method for manufacturing such a micropelletized resin composition, and use of the micropelletized resin composition comprising perfluorosulfonic acid ion exchange resin as catalyst for conversion of organic compounds, for example, in polymerization to manufacture polyether glycol or copolyether glycol.
Description
Technical field
The present invention relates to novel partculate resin combination.The diameter of the pellet of the micronized resin combination is less than about
1mm, such as 0.75 ± 0.24mm, and length/diameter (L/D) is than being 0.5 to 2.0.The micronized resin combination can be wrapped
Exchanger resin containing perfluorosulfonic acid ion.The invention further relates to be used to manufacture the effective ways of the micronized resin combination, with
And the micronized resin combination for example, makes at least one tetrahydrofuran or at least as the conversion for organic compound
A kind of tetrahydrofuran and at least one other polymerization of cyclic ethers are manufacturing the purposes of the catalyst of PTMEG or copolyether glycol.
Background technology
It is for about 3.0 to 3.5mm that normal resin compositionss pellet is manufactured in the following manner diameter：By extrudable resin
Compositionss pass through at elevated temperatures annular die head melting extrusion to prepare the strands of extrusion, then in a water bath cool down it
And cut into extrudate pellet.
Many publications series description perfluorosulfonic acid resins and its as the catalyst material for polyreaction purposes.Its
Include that United States Patent (USP) discloses 2009/0118456, its open Perfluorinated ion containing pendant sulfonic acid and hydroxy-acid group exchanges poly-
The purposes of compound；U.S. Patent No. 6,040,419, the purposes of its open polymer containing fluorinated sulfonic, the polymer
Containing at least 0.05 equivalent fluorinated sulfonic group/kg polymer；WO 95/19222, its disclosure is containing pendant sulfonic acid and carboxylic acid group
The purposes of the perfluorinated ion-exchange polymer of group；And U.S. Patent No. 5,118,869, it is open containing sulfonic acid group
The purposes of the admixture of fluoride resin and the fluoride resin containing hydroxy-acid group.Equally, U.S. Patent No. 5,403, No. 912 disclosures
The purposes of the perfluorinated resin sulfonic acid being made up of fluoropolymer main chain.United States Patent (USP) disclose 2008/0071118 be disclosed in it is a series of
There is purposes of the perfluoro alkyl sulfonic acid group as the resin of side chain in possible catalyst.United States Patent (USP) discloses 2003/
The purposes of the 176630 open polymer comprising α-fluosulfonic acid.Commercial standard perfluorosulfonic acid resin pellet be diameter be for about 3.0 to
The extrudate of 3.5mm.
The copolymer of THF and cyclic ethers is known in the art.Their preparation is for example disclosed in United States Patent (USP) by Pruckmayr
In No. 4,139,567 and U.S. Patent No. 4,153,786.This analog copolymer can be for example, by being described in by P.Dreyfuss
Any of methods of cyclic ether polymerization in " Polytetrahydrofuran " (Gordon＆Breach, N.Y.1982) is making
It is standby.Such polymerization includes by strong proton or lewis acid, by heteropoly acid and by perfluorinated sulfonic acid or acid resin entering
Row catalysis.In some cases, such as disclosed in U.S. Patent No. 4,163,115, using polymerization accelerant, such as carboxylic acid
Acid anhydride may be favourable.
No. 4,120,903 and No. 4,139,567 disclosure of U.S. Patent No. is by comprising poly- containing fluorosulfonic acid groups
THF and alkylene oxide or cyclic acetal copolymerization is set to prepare copolyether as chain terminating agent using water or alkane glycol on the catalyst of compound
Glycol.
No one of above-mentioned publication publication teaches are less than about 1mm comprising at least about 90% diameter, and such as 0.75
, than the pelletized resin compositionss of the pellet for 0.5 to 2.0, the pellet has basic for ± 0.24mm and length/diameter (L/D)
The surface of Smooth.No one of above-mentioned publication publication teaches are used to manufacture the side of such micronized resin combination
Method, or for converting organic compound in the presence of such pelletized resin compositionss of catalytically effective amount under conversion condition for validity
The method of thing.
The content of the invention
It is an object of the invention to provide the micronized resin combination of size uniform.Other purposes of the present invention are to provide use
In the effective ways for manufacturing the micronized resin combination, and the micronized resin combination conduct in acid form
For the conversion of organic compound, for example, make at least one tetrahydrofuran or at least one tetrahydrofuran and it is at least one other
Polymerization of cyclic ethers is manufacturing the purposes of the catalyst of PTMEG or copolyether glycol.
These and other objects provide the embodiment party comprising micronized resin combination by present invention realization, the present invention
Case, the micronized resin combination is less than about 1mm comprising at least about 90% diameter and length/diameter (L/D) is than being 0.5
To 2.0 pellet, the pellet has substantially smooth surface.Another embodiment includes pelletized resin compositionss, its
In at least about 90%, the diameter of the pellet of e.g., from about 95% to about 100% is for about 0.75 ± 0.24mm.Another reality of the present invention
Scheme is applied comprising pelletized resin compositionss, the pelletized resin compositionss include perfluorosulfonic acid ion exchanger resin.
Another embodiment of the invention includes the method for manufacturing micronized resin combination product, and it includes：
Viscosity is greater than about into 1x104The extrudable resin combination of Pascal (Pa.s) is extruded to form crowded by suitable die melt
Go out thing strands, cool down the extrudate strands to form the extrudate strands of cooling, the extrudate strands for making the cooling are entered
To form pelletized resin product in pelletier system, the pelletier system include having more than 12 teeth, such as 14 to 28
The rotor of tooth, such as 24 teeth, at least one ionized air jet and the vacuum in the exit of the pelletier system are taken out
Gas, thus the pelletized resin product at least about 90% diameter be less than about 1mm, e.g., from about 0.75 ± 0.24mm and L/D ratio and be
0.5 to 2.0, the pellet of the pelletized resin product has substantially smooth surface.
Another embodiment of the invention provides micronized resin combination, and its diameter for including at least about 50% is less than
About 1mm and length/diameter (L/D) are than for 0.5 to 2.0 pellet, the pellet has substantially smooth surface.Another
Embodiment includes pelletized resin compositionss, and wherein at least about 60%, the diameter of e.g., from about 75% or 80% pellet is for about
0.75±0.24mm.In another embodiment, the diameter of most of pellet is less than about 1mm and length/diameter (L/D) compares
For 0.5 to 2.0.
Another embodiment of the invention is comprising in the micro- of the size uniform in acid form of catalytically effective amount
In pelletized resin compositionss by organic compound conversions be converted product, such as be for about 200 dongles for manufacturing mean molecule quantity
To about 30,000 dalton PTMEG or copolyether glycol method, it include making comprising at least one tetrahydrofuran or
The reactant mixture of at least one tetrahydrofuran and at least one other cyclic ethers is under polymerization condition for validity in catalytically effective amount
In the presence of micronized resin combination comprising perfluorosulfonic acid ion exchanger resin, and optionally in acyl cation precursor, carboxylic
The step of being polymerized in the presence of acid and/or chain terminating agent.
Specific embodiment
Detailed description below is provided and is in order at the purpose of illustration certain embodiments of the present invention, and be not construed as this
The concept of invention is limited to these specific embodiments.Should describe and be specific to for particular, this is merely for illustration
Purpose, and be not construed as restricted.
The present invention relates to specific novel partculate resin combination, for manufacturing having for the micronized resin combination
Efficacious prescriptions method, and the work for example in manufacture PTMEG or copolyether glycol of the micronized resin combination in acid form
It is the purposes of the catalyst of conversion for organic compound.
The granules of the present invention are the extrusion with controlled physical dimension and the resin being granulated.They can be cylinder
Shape, another kind of physical form that is spherical or being determined by its final use.
The pellet of the micronized resin combination of the present invention equably has less than about 1mm, such as 0.75 ± 0.24mm's
Diameter and 0.5 to 2.0, preferably 0.75 to 1.25 length/diameter (L/D) ratio.The micronized resin combination can be included
The perfluorosulfonic acid ion exchanger resin being for example disclosed in U.S. Patent No. 4,433,082, the case is incorporated by reference into this
Wen Zhong.The pellet of the micronized resin combination equably at least about 90%, for example, at least about 95%, e.g., from about 95% to
100% diameter is less than about 1mm, such as 0.75 ± 0.24mm, and with 0.5 to 2.0, preferably 0.75 to 1.25 length/straight
Compare in footpath (L/D).The pellet has the basic glazing indicated by the visual evaluation of the microphotograph under the enlargement ratio of about 50X
Sliding surface.
The survey that the diameter and L/D ratios of the micronized resin combination passes through the microphotograph under the enlargement ratio of about 50X
Measure evaluation to indicate.
The granules of the present invention can include perfluorosulfonic acid ion exchanger resin, such as in U.S. Patent No. 4,433,082
Any one disclosed in (being herein incorporated by reference), or particularly SolvayThe granules pass through
Extrudable polymer comprising the resin is extruded into manufacture by the die melt of extruder.It should be noted that being used for
The resin of extrusion takes the form of perfluor sulfonyl fluorine.It is the thermoplastic that can be processed at elevated temperatures.Extrusion
Machine is not particularly critical, as long as it is effectively from high viscosity, i.e. greater than about 1x104The material manufacture extrudate strands of Pa.s.
However it has been found that the percentage ratio of the perforated area in feed rate and extrusion die is important.Extruder can be for example single
Screw extruder or double screw extruder.Because fluoropolymer such as perfluorosulfonic acid ion exchanger resin has 1x104Extremely
1x105The high viscosity of Pa.s, therefore, double screw extruder be preferably as its devolatilization (devolitize) more preferably, and
And if extrudable polymer feed takes powder type, then its surge is obtained more preferably.Feed rate in die head is necessary for 2.75
To 4.25lb/hr, e.g., from about 3.2lb/hr.Perforated area in die head is necessary for 0.8 ± 0.1mm.With extrudate strands from
Extruder die head occurs, and it is cooled down by dry calibration or water cooling.The strands of cooling subsequently enter pelletier system,
In pelletier system, it is set to form the granules of the present invention.
Pelletier system is extremely important for the manufacture of the micronized resin combination of the present invention.To realize micronized resin
The required property of compositionss, there is provided at least one is directly entered the ionized air jet in the cutting chamber of pelletier system.Additionally,
Use to have in the inside of the cutting chamber of pelletier system and be more than 12 teeth, such as 14 to 28 teeth, such as rotor of 24 teeth,
Rather than with the convention rotor of 12 teeth, to minimize room in turbulent flow.Further, in the exit of pelletier system
Vacuum suction is used under about 850 to about 1000 millibars.It has been found that rotor more than ionized air jet, gear ratio routine and true
The granules minimized in pelletier system that use of sky pumping are piled up, so as to reduce the probability of " cutting again " granules.
It is being converted into for example in such as U.S. Patent No. No. 4,330,654 and No. 4,437,952 and in http://
Www.ion-power.com/res/Nafion%20＆%20XL%20MEA/N AFION_R-1100_R-1000.pdf are (each
Be herein incorporated by reference) shown in acid form after, the micronized resin combination can serve as organising
Compound conversion reaction, such as esterification, etherificate and the catalyst being polymerized.Purposes of the micronized resin combination as esterification catalyst
Embodiment comprising make alcohol (such as methanol) and acid (such as acetic acid) connect at reaction conditions with the catalyst of catalytically effective amount
Touch to produce methyl acetate, the reaction condition includes such as 100 to 160 DEG C of temperature and the pressure of 150 to 300mmHg.
Micronized resin combination is included as the embodiment of the purposes of catalyst for etherification makes such as 1,4- butanediols effective with catalysis
The catalyst of amount contacts to produce THF at reaction conditions, the reaction condition include such as 100 to 180 DEG C of temperature and
The pressure of 200 to 1500mmHg.The micronized resin combination of the present invention is extremely important as the purposes of polymerization catalyst.It is this
The embodiment of purposes includes manufacture PTMEG or copolyether glycol.
For manufacturing the PTMEG or copolyether glycol that number-average molecular weight is for about 200 dalton to about 30,000 dalton
Method include making at least one tetrahydrofuran or at least one tetrahydrofuran and at least one other cyclic ethers (such as alkylene oxide)
In the micronized resin combination comprising the present invention under the polymerization condition for validity of the temperature including e.g., from about 0 DEG C to about 80 DEG C
In the presence of catalyst, optionally the step of being polymerized in the presence of acyl cation precursor, carboxylic acid and/or chain terminating agent.Therefore, this
Bright embodiment is provided by manufacturing the polymerization of the reactant mixture comprising tetrahydrofuran (THF) and optional comonomer
The method of poly- (tetramethylene ether) glycol (PTMEG), its copolymer and their ester, it includes making at least one tetrahydrofuran exist
Including urging in the micronized resin combination comprising the present invention under the polymerization condition for validity of e.g., from about 0 DEG C to about 80 DEG C of temperature
In the presence of agent, optionally the step of being polymerized in the presence of acyl cation precursor, carboxylic acid and/or chain terminating agent.
Therefore, it is for about 650 dalton to about that another embodiment of the invention is provided for manufacturing number-average molecular weight
4000 dalton and viscosity are for about the method for poly- (tetramethylene ether-copolymerization-alkylene ether) glycol of 80cP to about 4000cP,
It includes making at least one tetrahydrofuran and at least one alkylene oxide have in the polymerization of the temperature including e.g., from about 0 DEG C to about 80 DEG C
Under the conditions of effect in the presence of the catalyst of the micronized resin combination comprising the present invention, optionally in acyl cation precursor, carboxylic
The step of being polymerized in the presence of acid and/or chain terminating agent.
Therefore, it is for about 650 dalton to about that another embodiment of the invention is provided for manufacturing number-average molecular weight
4000 dalton and viscosity are for about the method for poly- (tetramethylene ether-copolymerization-ethyleneether) glycol of 80cP to about 4000cP,
It includes making at least one tetrahydrofuran and oxirane in the polymerization condition for validity of the temperature including e.g., from about 0 DEG C to about 80 DEG C
Under comprising the present invention micronized resin combination catalyst in the presence of, optionally acyl cation precursor, carboxylic acid and/or
The step of being polymerized in the presence of chain terminating agent.
After polymerization procedure, recovery number-average molecular weight is for about 200 dalton to about 30,000 dalton, e.g., from about 650 roads
The dalton of Er Dun to about 4,000 and viscosity are for about the PTMEG and copolyether glycol of 80cP to about 4000cP.In the reaction
In generally consume the THF of about 25 weight % to about 40 weight %.High percentage is consumed in the reaction, and for example 50 weight % are to about
" other cyclic ethers " in the polymerization procedure raw material of 100 weight %, such as alkylene oxide (such as EO).In embodiment of the present invention
In, remove unreacted raw material tetrahydrofuran, other cyclic ethers, the dimer (if present) of such as alkylene oxide, alkylene oxide, and
What is existed is any compared with low boiling component.
Unless otherwise stated, term " polymerization " used herein includes term " copolymerization " in its implication.
Unless otherwise stated, term " PTMEG " used herein refers to polytetramethylene ether diol.PTMEG
Referred to as polyoxybutylene glycols.Unless otherwise stated, the term " copolyether glycol " for being used with odd number herein refers to tetrahydrochysene furan
Mutter and at least one other cyclic ethers, the copolymer of such as alkylene oxide, it is also referred to as polyoxy butylidene polyether polyols.Copolymerization
The example of ether glycol is the copolymer of tetrahydrofuran and oxirane.Also referred to as poly- (the tetramethylene-altogether of this copolyether glycol
Poly- ethyleneether) glycol.
Unless otherwise stated, term " THF " used herein refers to tetrahydrofuran, and include in its implication
Can be with the alkyl-substituted tetrahydrofurans of the Jing of THF copolymerization, such as 2- methyltetrahydrofurans, 3- methyltetrahydrofurans and 3- ethyls
Tetrahydrofuran.Unless otherwise stated, term " alkylene oxide " used herein refer in its alkylene oxide ring containing two,
Three or the compound of four carbon atom.Alkylene oxide can be for example following substituent groups of unsubstituted or Jing：1 to 6 carbon
The straight chain or branched-alkyl of atom, or the aryl that the alkyl and/or alkoxyl of unsubstituted or Jing 1 or 2 carbon atoms replaces,
Or the halogen atom of such as chlorine or fluorine.The example of such compound includes oxirane (EO)；1,2 epoxy prapane；1,3- rings
Ethylene Oxide；1,2- epoxy butanes；1,3- epoxy butanes；2,3- epoxy butanes；Styrene oxide；2,2- pair-chloromethyl -1,3- rings
Ethylene Oxide；Epoxychloropropane；Perfluoroalkyl ethylene oxide, such as (1H, 1H- perfluoropentyl) oxirane；With and combinations thereof.
In the process the THF as reactant can be any commercially available THF.Generally, THF has less than about 0.03
The water content of weight % and the less than about peroxide content of 0.005 weight %.If THF contains unsaturated compound, its
Concentration should cause them not have adverse effect to the polymerization of the present invention or its polymerizate.For example, for some should
With, it is preferred that the copolyether glycol product of the alkylene oxide with high molar concentration of the present invention has low APHA color, example
Such as less than about 100 APHA units.Optionally, THF can contain oxidation retarder, such as Yoshinox BHT (BHT), in case
Only form undesirable by-product and color.If desired, can use one or more can replace with the Jing alkyl of THF copolymerization
THF as co-reactant, in an amount of from THF about 0.1 weight % to about 70 weight %.The reality of the alkyl-substituted THF of such Jing
Example includes 2- methyltetrahydrofurans, 3- methyltetrahydrofurans and 3- ethyltetrahydrofuran.
As noted above, in the method for the invention the alkylene oxide as reactant can be contained in its alkylene oxide ring
There is the compound of two, three or four carbon atom.Alkylene oxide can be that unsubstituted or Jing such as alkyl, aryl or halogen are former
What son replaced.It may be selected from such as oxirane；1,2 epoxy prapane；1,3- expoxy propane；1,2- epoxy butanes；2,3- epoxies
Butane；1,3- epoxy butanes；2,2- bischloromethyloxetanes；Epoxychloropropane with and combinations thereof.Preferably, alkylene oxide tool
There are the less than about water content of 0.03 weight %, the less than about total aldehyde content of 0.01 weight % and less than about 0.002 weight %
Acidity (as acetic acid).Alkylene oxide should have low colourity and nonvolatile residue.
Optional acyl cation precursor in for the method for the present invention can at reaction conditions produce THF
Any compound of acetyl oxonium ion." acyl cation " used herein is referred to by structure R-C+The ion that=O is represented, its
Middle R is the alkyl of hydrogen or 1 to 16 carbon atom, the alkyl of preferably 1 to 16 carbon atom.The representative of acyl cation precursor is acetyl
Halogenide and carboxylic acid anhydrides.The carboxylic acid anhydrides that carboxylic moiety contains 1 to 16 carbon atom be it is preferred, particularly 1 to 4 carbon atom
Those.The non-limiting examples of such anhydride are acetic anhydride, propionic andydride and the first and second anhydride.Due to its efficiency herein preferably
The anhydride for using is acetic anhydride.Acyl cation precursor typically at least initially with about 0.1 weight % to about 15 weight %, preferably from about
0.7 weight % to the concentration of about 10 weight % is present in reactant mixture.
The molecular weight of polymer product can by optionally adding 1 to 16 carbon atom in reactant mixture, preferably 1 to
The aliphatic carboxylic acid of 5 carbon atoms is any limitation as.Acetic acid is preferred for the present invention due to its low cost and effectiveness.Acyl cation
The weight ratio of precursor/carboxylic acid should be about 20:1 to about 0.1:1, preferably from about 10:1 to about 0.5:In the range of 1.In general, making
Carboxylic acid is more, then the molecular weight of product is lower.When deployed, aliphatic carboxylic acid generally with about 0.1 weight % to about 10 weights
Amount %, preferably from about 0.5 weight % to the concentration of the THF of about 5 weight % is added in reactant mixture.
It should be noted that because preferred acyl cation precursor acetic anhydride is with THF and catalyst reaction obtains corresponding
Acid, therefore, acid need not be individually added in this case, but it is typically desired for the molecular weight control this measure for improving.For
Obtain the product of the commercial desired number-average molecular weight with 650 to 30,000 dalton, it is preferred that acyl cation precursor
With carboxylic acid with the reaction mass of about 0.5 weight % to about 20 weight %, the combined concentration of preferably from about 1 weight % to about 10 weight %
In being present in reactant mixture.
Optional chain terminating agent in for the method for the present invention is selected from water, the alkane glycol containing 2 to about 10 carbon atoms
With and combinations thereof.Water and 1,4- butanediols are preferred with availability because it is inexpensive.These compounds can be applied in combination, with
Adjust the molecular weight of final product.
Catalyst is present in the polymerization procedure of the present invention with catalytically effective amount, and under normal conditions, catalytically effective amount is
The reactant mixture of finger about 0.01 weight % to about 30 weight %, preferably from about 0.05% to about 15%, even more preferably about 0.1%
To about 10% concentration.
, generally at about 0 DEG C to about 80 DEG C, e.g., from about 20 DEG C to about 70 DEG C, e.g., from about 30 DEG C to about for the polymerization procedure of the present invention
Carry out at 70 DEG C.Either in intermittently or serially mode, methods described is generally run at atmosheric pressure, but can use what is reduced
Pressure or elevated pressure are helping control the temperature of reactant mixture in course of reaction.For example, pressure used can be about
200mmHg to about 800mmHg, e.g., from about 300mmHg are to about 500mmHg.
Polymerization procedure to avoid the formation of peroxide, methods described can be carried out under inert gas atmosphere.It is adapted to
The non-limiting examples of noble gases used herein include nitrogen, carbon dioxide or rare gas.Additionally, methods described
Polymerization procedure also can be carried out in presence of hydrogen in the hydrogen pressure of about 0.1 to about 10 bar.
At the end of polyreaction, can be by filtering the catalysis of micronized amberlite oil/fat composition, being decanted or be centrifuged
Agent is separated from reactant mixture, and is reused.If methods described is run in a continuous manner, catalyst can be simple
Be allowed to stay in the reactor, while the fresh reactant of charging and removing product.
Following examples to the present invention and its illustrated using ability.The present invention covers other different embodiments, and
And its some details covers the modification of each apparent aspect, this is without departing from the spirit and scope of the present invention.Accordingly
Ground, should be considered as embodiment substantially exemplary and nonrestrictive.
Embodiment
Embodiment 1
Obtain the perfluorosulfonic acid ion exchanger resin pellet (Solvay of the business manufacture that average-size is 3 to 3.5mm) sample, and reserve a part of standby.Remainder is placed in the 18mm being made up of corrosion-resistant Langaloy same
To in the hopper of rotating twin-screw extruder, and extruded by the annular die head with 8mm nibs.Screw rod rpm is maintained at 33, and
And torque/the amperage of motor is maintained at 23%.150 DEG C are arrived under the die head temperature in 355 DEG C of exit at charging aperture, double spiral shells
Bar machine barrel is divided into 8 areas, and melt pressure is measured as 620psi.Feed rate in die head is maintained at about 3.2lb/hr.In die head
Perforated area be about 0.8mm.
The strands for leaving the extrusion of die head are cooled down in the water-bath for be set as 12 to 15 DEG C.Then, by the strands of cooling
Using improved pelletier system micronized, the pelletier system has an ionized air jet and tool in cutting chamber
There are the rotor of 24 teeth, ionized air knife and be maintained at about 1,000 millibar of vacuum suction, so that as passed through micro- photograph
What piece determined, a diameter of 0.75 ± 0.24mm and length of at least 95% perfluorosulfonic acid ion exchanger resin granules/straight
Footpath (L/D) ratio for about 1.0.As determined by microphotograph, gained pellet has substantially smooth surface.
Embodiment 2
Continuous EO/THF is aggregated under 55 DEG C and atmospheric pressure and is carried out in 1000ml glass reactors, the glass reaction
The effective working volume of device is 500ml, and equipped with side outlet and mechanical agitator, the speed of the mechanical agitator is for about
350rpm.Reactant mixture contains the EO of 27.0 weight %, the deionized water of 0.41 weight %, and remainder is THF.Will reaction
Mixture is fed to the top of reactor by pump by dip tube.Product mixtures are by side outlet outflow reactor, the side
Outlet polyethylene cloth covers to block catalyst.Therefore, the reactor capacity for reactant mixture is for about 500ml.Then
The perfluorosulfonic acid ion exchanger resin microgranule in acid form of 25 grams of (reactant mixtures of about 5 weight %) embodiments 1 of addition
Material is used as catalyst.The continuous-stirring reactor during experimentation.Using in the range of 1ml/min to 3ml/min it is various enter
Material speed.A small amount of Product samples (2 to 3ml) are taken at a time interval, and are dried 3 hours at 120 DEG C in vacuum drying oven
To measure conversion ratio.Most of product mixtures are collected every a few houres, and using rotary evaporator at about 99 DEG C (boiling water bath)
Temperature and partial vacuum under remove unreacted charging, with provide for analysis polymerizate.
For the molecular weight of EO and THF conversion ratios and product polymerizate sample is measured by GPC.Product sample
The APHA color of product is determined as average about 12.Under the feed rate of 1ml/min, 1.5ml/min, 2ml/min and 3ml/min,
EO conversion ratios are proved to respectively 75%, 72%, 69% and 66%.The molecular weight of product Jing of these samples is determined and is respectively
3450th, 3250,3050 and 2850.
Although the present invention is described with regard to specific embodiment, it is understood by one skilled in the art that can be to these
Embodiment carries out various modifications and variations, and this is without departing from the spirit and scope of the present invention.For example, although exemplified with some realities
Apply scheme, but other blend compositions it is also contemplated that.
Claims (6)
1. a kind of method for manufacturing pelletized resin composition product, it includes：Viscosity is more than into 1x104Pa.s's is extrudable
Resin combination is extruded to form extrudate strands by die melt, cools down the extrudate strands to form the extrusion of cooling
Thing strands, the extrudate strands for making the cooling are entered in pelletier system to form pelletized resin product, the comminutor system
System includes thering is the rotor for being more than 12 teeth, at least one ionized air jet and in the exit of the pelletier system
Vacuum suction, thus the pelletized resin product at least 50% diameter is 0.5 to 2.0 less than 1mm and L/D ratios, the granulation
The pellet of naval stores has smooth surface.
2. method according to claim 1, wherein the extrudable resin includes perfluorosulfonic acid ion exchanger resin.
3. method according to claim 1, wherein the pelletized resin product comprising a diameter of the 0.75 of at least 90% ±
The pellet of 0.24mm.
4. method according to claim 3, wherein the L/D ratios of the pelletized resin product are 0.75 to 1.25.
5. method according to claim 1, wherein the viscosity of the extrudable resin combination is 1x104Extremely
1x105Pa.s, and the rotor has 14 to 28 teeth.
6. method according to claim 1 and 2, wherein the pelletized resin product at least 90% diameter is less than 1mm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361763301P | 2013-02-11 | 2013-02-11 | |
| US61/763,301 | 2013-02-11 | ||
| PCT/US2014/015541 WO2014124358A1 (en) | 2013-02-11 | 2014-02-10 | Micropelletized resin, manufacture and use thereof |
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| CN105121110A CN105121110A (en) | 2015-12-02 |
| CN105121110B true CN105121110B (en) | 2017-05-03 |
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| CN201480020444.XA Active CN105121110B (en) | 2013-02-11 | 2014-02-10 | Micropelletized resin, manufacture and use thereof |
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|---|---|
| CN (1) | CN105121110B (en) |
| TW (2) | TW201443124A (en) |
| WO (1) | WO2014124358A1 (en) |
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| CN106565946B (en) * | 2015-10-12 | 2019-01-29 | 重庆建峰工业集团有限公司 | Polytetrahydrofuran, which produces, separates Trace Methanol sodium technique in crude product |
| CN112606255B (en) * | 2020-11-30 | 2023-03-24 | 山东东岳未来氢能材料股份有限公司 | Processing method of ion exchange resin applied to catalysis field |
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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 |
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| WO1996030180A1 (en) * | 1995-03-31 | 1996-10-03 | Exxon Chemical Patents Inc. | Foamed rotationally molded articles |
| EP1195191A1 (en) * | 1999-03-18 | 2002-04-10 | Hosokawa Micron Corporation | Device and method for producing granules |
| CN1647903A (en) * | 2004-01-13 | 2005-08-03 | 株式会社Jsp | Thermoplastic resin pellet, process for preparing thermoplastic resin pellets and expanded thermoplastic resin bead |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201443124A (en) | 2014-11-16 |
| CN105121110A (en) | 2015-12-02 |
| TW201636396A (en) | 2016-10-16 |
| WO2014124358A1 (en) | 2014-08-14 |
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