WO2010101337A1 - Hexafluoropropylene oxide polymer compositions and a preparing method of hexafluoropropylene oxide polymer using hexafluoropropylene oligomer - Google Patents

Hexafluoropropylene oxide polymer compositions and a preparing method of hexafluoropropylene oxide polymer using hexafluoropropylene oligomer Download PDF

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WO2010101337A1
WO2010101337A1 PCT/KR2009/004191 KR2009004191W WO2010101337A1 WO 2010101337 A1 WO2010101337 A1 WO 2010101337A1 KR 2009004191 W KR2009004191 W KR 2009004191W WO 2010101337 A1 WO2010101337 A1 WO 2010101337A1
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hexafluoropropylene
hexafluoropropylene oxide
oxide polymer
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Soo-Bok Lee
In Jun Park
Jong-Wook Ha
Kwang Won Lee
Sang Goo Lee
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Korea Research Institute of Chemical Technology KRICT
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Publication of WO2010101337A1 publication Critical patent/WO2010101337A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/28—Hexyfluoropropene
    • 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
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • 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
    • 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
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens

Definitions

  • the HFPO is used in the amount of 300-700 weight parts, more preferably 400-600 weight parts relative to 100 weight parts of the HFP.
  • the amount of the HFPO is less than 300 weight parts, the weight average molecular weight of the HFPO polymer may be insufficient.
  • the amount is more than 700 weight parts, HFPO polymer with a relatively low molecular weight may increase.
  • the reaction is conducted at 20-40 0 C, more preferably 25-35 0 C.
  • reaction rate may be insufficient.
  • temperature is higher than 40 0 C, a large amount of HFP oligomer trimer may be produced.

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  • Health & Medical Sciences (AREA)
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Abstract

The present invention relates to hexafluoropropylene oxide polymer composition and a process of preparing of hexafluoropropylene oxide polymer by an anionic polymerization, and in particular the hexafluoropropylene oxide polymer composition comprises an anionic initiator, a polar solvent, hexafluoropropylene and hexafluoropropylene oxide. The hexafluoropropylene oxide polymer is prepared under particular reaction conditions by using the composition, hexafluoropropylene oxide polymer prepared by using the composition according to a preparation process herein has a weight average molecular weight (Mw) of 1,500-4,000 at -10-20 °C.

Description

HEXAFLUOROPROPYLENE OXIDE POLYMER COMPOSITIONS AND A PREPARING METHOD OF HEXAFLUOROPROPYLENE OXIDE POLYMER USING HEXAFLUOROPROPYLENE OLIGOMER
The present invention relates to hexafluoropropylene oxide polymer composition comprising an anionic initiator, a polar solvent, hexafluoropropylene and hexafluoropropylene oxides, and also to a process of preparing hexafluoropropylene oxide polymer having a weight average molecular weight (Mw) of 1,500-4,000 at -10-20 ℃ under particular reaction conditions by using the composition according to an anionic polymerization method.
Polymer of hexafluoropropylene oxide is a known material. If end groups are removed from a hexafluoropropylene oxide polymer comprising only carbon, fluorine and oxygen, it becomes superior in thermal stability, antioxidation, mechanical stability, anticorrosive property, etc. The hexafluoropropylene oxide polymer can be used even at extremely low or high temperature, and is widely used in vacuum pumps, automobiles, memory hard disks for storing information, high-performance diluents for the use in aerospace engineering, due to its lubricative durability. Its application has been also expanded into various areas such as greases, release agents, liquids with a relatively low refractive index and oils. In particular, researches have been performed on how to prevent reflection by using an end-function-modified polymer with a weight average molecular weight of 400-1,000. Applicability of a polymer with a weight average molecular weight of 2,000-6,000 to an anti-fingerprint agent is also under study.
U. S. patent Nos. 3,412,148 and 3,322,826 disclose processes of preparing polymers of hexafluoropropylene oxide. In these processes, an anionic initiator is prepared and hexafluoropropylene is used as a diluent. As a result, hexafluoropropylene oxide is polymerized into a polymer with a weight average molecular weight of about 5,500. For using hexafluoropropylene as a diluent, reaction should be conducted at an extremely low temperature such as -30 ℃ or lower. A recent study reports the results of research activities using various polar solvents and under various reaction temperatures [Macromolecules, 2009, 42 (3), 612-619].
However, there has been no research report regarding a process of polymerizing hexafluoropropylene oxide by directly using hexafluoropropyl oligomer.
The present inventors have performed intensive researches to overcome the aforementioned problems of the conventional anionic polymerization method of preparing hexafluoropropylene oxide (HFPO) polymer. As a result, they have succeeded in selecting suitable compositions used in the process, their mixing ratio and reaction conditions, thereby finally achieving a process of preparing hexafluoropropylene oxide polymer having a weight average molecular weight (Mw) 1,500-4,000 at -10-20 ℃ with a high yield. The present invention aims to provide HFPO polymer composition and a process of preparing of HFPO polymer with a high yield.
To overcome the technical problems, in an aspect, the present invention discloses a hexafluoropropylene oxide polymer composition comprising an anionic initiator, a polar solvent, hexafluoropropylene, and hexafluoropropylene oxide.
In another embodiment, the present invention discloses a HFPO polymer herein has a structure of Formula 1:
[Formula 1]
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)COF
wherein n is an integer of 8-25.
In a further aspect, the present invention discloses a process of preparing hexafluoropropylene oxide polymer, the process comprising (a) preparing hexafluoropropylene oligomer by introducing hexafluoropropylene to a mixture of an anionic initiator and a polar solvent at 20-40 ℃ and under nitrogen atmosphere; and (b) preparing hexafluoropropylene oxide polymer of Formula 1 by introducing hexafluoropropylene oxide to a reactor where the step (a) is conducted at an average rate of 1.5-2.5 g/min at -10-20 ℃:
[Formula 1]
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)COF:
wherein n is an integer of 8-25.
By using a process of preparing HFPO polymer as disclosed in the present invention, HFPO polymer having a weight average molecular weight of 1,500-4,000 can be easily obtained at -10 ℃ to 20 ℃, which is much higher than the temperature of the conventional process (-30 ℃). The yield is high and molecular weight distribution is relatively uniform.
Fig. 1 shows the GPC results of HFP oligomer prepared Example 1.
Hereunder is provided a detailed description of the present invention.
As used herein, the terms of hexafluoropropylene, hexafluoropropylene oligomer and hexafluoropropylene oxide are referred to as 'HFP', 'HFP oligomer' and 'HFPO', respectively. The present invention discloses a HFPO polymer composition comprising an anionic initiator, a polar solvent, hexafluoropropylene (HFP), and hexafluoropropylene oxide (HFPO). In an embodiment, a HFPO polymer has a structure of Formula 1 below:
[Formula 1]
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)COF
wherein n is an integer of 8-25, preferably 10-25.
Fluorinated metal, preferably at least one fluorinated metal selected from the group consisting of cesium fluoride (CsF) and potassium fluoride (KF), can be used as the anionic initiators, which is one of the ingredients in the present invention. The anionic initiator is used in the amount of 2-5 weight parts, more preferably 2.5-4 weight parts relative to 100 weight parts of the HFP. When the amount of the anionic initiator is less than 2 weight parts, the production of hexafluoropropylene oligomer becomes small and reaction rate decreases. When the amount is more than 5 weight parts, reaction heat may be uncontrollable due to the increase in the reaction rate.
Tetraethyleneglycolmethylether may be used as the polar solvent. The polar solvent is used in the amount of 2-10 weight parts, more preferably 2.5-8 weight parts relative to 100 weight parts of the HFP. When the amount of the polar solvent is less than 2 weight parts, the reaction rate may be insufficient and a large amount of hexafluoropropylene trimer may be produced. When the amount is more than 10 weight parts, although the reaction rate increases, a large amount of hexafluoropropylene trimer may be produced.
The HFP is a reactant used for the production of hexafluoropropylene (HFP) oligomer, which anionically reacts with the anionic initiator and serves as a diluent. The produced HFP oligomer contains hexafluoro trimer comprising at least one hexafluoro dimer selected from the group consisting of 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent-2-ene and 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)pent-2-ene and 1,1,1,3,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)pent-2-ene.
The HFPO is used in the amount of 300-700 weight parts, more preferably 400-600 weight parts relative to 100 weight parts of the HFP. When the amount of the HFPO is less than 300 weight parts, the weight average molecular weight of the HFPO polymer may be insufficient. When the amount is more than 700 weight parts, HFPO polymer with a relatively low molecular weight may increase.
Hereunder is provided a detailed description of a process of preparing HFPO polymer by using HFPO polymer composition through an anionic polymerization.
The present invention discloses a process of preparing hexafluoropropylene oxide polymer, the process comprising (a) preparing hexafluoropropylene oligomer by introducing hexafluoropropylene to a mixture of an anionic initiator and a polar solvent at 20-40 ℃ and under nitrogen atmosphere; and (b) preparing hexafluoropropylene oxide polymer of Formula 1 by introducing hexafluoropropylene oxide to a reactor at an average rate of 1.5-2.5 g/min at -10-20 ℃:
[Formula 1]
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)COF:
wherein n is an integer of 8-25, preferably 10-25.
Anionic initiator, polar solvent, HFP, HFP oligomer and types and amounts of HFPO are the same as described above regarding the HFPO polymer composition.
The step (a) is to prepare a HFP oligomer at 20-40 ℃ and under nitrogen atmosphere. The reaction is conducted at 20-40 ℃, more preferably 25-35 ℃. When the temperature is lower than 20 ℃, reaction rate may be insufficient. When the temperature is higher than 40 ℃, a large amount of HFP oligomer trimer may be produced. The produced HFP oligomer are hexafluoro dimer and hexafluoro trimer, and preferably contains at least two entities selected from the group consisting of 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent-2-ene, 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)pent-2-ene and 1,1,1,3,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)pent-2-ene. The HFP oligomer produced during the step (a) is preferred to contain hexafluoro dimer and hexafluoro trimer in a weight ratio of 20-40 : 80-60. The weight ratio of the dimer to the trimer is either lower than 20 : 80 or higher than 40 : 60, weight average molecular weight of HFPO polymer may decrease.
The step (b) is to prepare HFPO polymer of Formula 1 through an anionic polymerization by introducing HFPO at -10-40 ℃ to a reactor where the step (a) is conducted. For obtaining HFPO polymer with a weight average molecular weight of 3,000-4,000, reaction temperature is preferred to be controlled within -10-10 ℃. When the temperature is lower than -10 ℃, HFP oligomer acts as diluent insufficiently, thus failing to allowing HFPO polymer to grow. When the temperature is higher than 10 ℃, the dissociation of fluoride anions increase and the portion of HFPO polymer with a relatively low molecular weight also increases. In contrast, for obtaining HFPO polymer with a weight average molecular weight 1,500-3,000, reaction temperature is preferred to be maintained within 10-20 ℃. When the reaction temperature during the step (b) is lower than 10 ℃, HFPO polymer may grow more than desired. When the temperature is higher than 20 ℃, the dissociation of fluoride anions may increase, thus in turn increasing HFPO polymer with a relatively low molecular weight.
The HFPO is preferred to be introduced at an average rate of 1.5-2.5 g/min, more preferably at a rate of 1.8-2.2 g/min. If the rate is higher than the upper limit, the anionic reaction may proceed insufficiently. Meanwhile, if the introduction is slower than the lower limit, the production time may increase. After HFPO is introduced at the aforementioned average rate for 8-10 hours, either continuously or discontinuously, thus allowing anionic polymerization to proceed, the reaction is allowed to stand sufficiently for the termination of reaction.
After the termination of reaction, fluorinated metal is removed through filtration, and HFP oligomer, HFPO with a relatively low molecular weight and solvent (tetraethyleneglycoldimethylether) are moved in a distillation tower equipped with a reboiler (2 L), a pack column (Φ=50 x 1200 L), a reflux condenser and a vacuum line, thus affording HFPO polymer.
Thus obtained HFPO polymer has a weight average molecular weight of 1,500-4,000, more preferably 2,000-4,000 within the temperature of -10-20 ℃.
EXAMPLES
The present invention will be described based on the following Examples. However, the present invention is not limited by the same.
Example 1
Tetraethylene glycol dimethylether (a polar solvent, 10 g) and dried cesium fluoride (an anionic initiator, 5 g) were introduced into a reactor equipped with a temperature controller, a stirrer and a pressure gauge under nitrogen atmosphere. The reactor was maintained at 30 ℃ using circulatory cooler, and HFP 200g was introduced for the anionic reaction, thus affording HFP oligomer. Thus prepared HFP oligomer was ascertained to contain 35 wt% of hexafluoro dimer and 65 wt% of hexafluoro trimer as analysed by using a GPC (gel permeation chromatography, Younglin Instruments) equipped with a Jordi DVB column and a refractive index detector (step 1, Fig. 1).
After the reaction of preparing HFP oligomer was completed, the temperature in a reactor was maintained at 40 ℃. Then, a total of 1,000 g of HFP was introduced for 9 hours at a rate of 1.85 g/min, and anionic polymerization was conducted (step 2). After the reaction was completed, the reactor was allowed to stand for 30 minutes, a small amount of product mixture was separated through a valve on a lower part of the reactor.
The product mixture was analysed using the aforementioned GPC without additional filtration, thus ascertaining that the weight average molecular weight is 1,700.
Examples 2-8 and Comparative Examples 1-7
HFPO polymer was prepared as described in Example 1 except that reaction conditions and compositions were adjusted as shown in Table 1.
Table 1
Figure PCTKR2009004191-appb-I000001
Table 2
Figure PCTKR2009004191-appb-I000002
It was confirmed that a process of preparing HFPO polymer disclosed in the present invention enables HFPO polymer with a weight average molecular weight of 1,500-4,000 in a relatively high yield. HFPO polymer composition of the present invention and its preparation process are applicable to a variety of areas such as a vacuum pump, an automobile, a memory hard disk, a diluent for the use in aerospace engineering, grease, a release agent, liquid with a relatively low refractive index and oils.

Claims (8)

  1. Hexafluoropropylene oxide polymer composition comprising an anionic initiator, a polar solvent, hexafluoropropylene, and hexafluoropropylene oxide.
  2. The hexafluoropropylene oxide polymer composition of claim 1, wherein the hexafluoropropylene oxide polymer is a polymer of Formula 1:
    [Formula 1]
    CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)COF:
    wherein n is an integer of 8-25.
  3. The hexafluoropropylene oxide polymer composition of claim 1, which comprises 2-5 weight parts of the anionic initiator and 2-10 weight parts of the polar solvent relative to 100 weight parts of the hexafluoropropylene.
  4. The hexafluoropropylene oxide polymer composition of claim 1 or 3, wherein the anionic initiator is at least one fluorinated metal selected from the group consisting of cesium fluoride and potassium fluoride, and the polar solvent is tetraethyleneglycoldimethylether.
  5. A process of preparing hexafluoropropylene oxide polymer, the process comprising:
    (a) preparing hexafluoropropylene oligomer by introducing hexafluoropropylene to a mixture of an anionic initiator and a polar solvent at 20-40 ℃ and under nitrogen atmosphere; and
    (b) preparing hexafluoropropylene oxide polymer of Formula 1 by introducing hexafluoropropylene oxide to a reactor where the step (a) is conducted at an average rate of 1.5-2.5 g/min at -10-20 ℃:
    [Formula 1]
    CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)COF:
    wherein n is an integer of 8-25.
  6. The process of preparing hexafluoropropylene oxide polymer of claim 5, wherein the hexafluoropropylene oligomer comprises hexafluoro dimer and hexafluoro trimer in a weight ratio of 20-40 : 80-60.
  7. The process of preparing hexafluoropropylene oxide polymer of claim 6, wherein the hexafluoro dimer is at least one selected from the group consisting of 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent-2-ene and 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)pent-2-ene, and the hexafluoro trimer is 1,1,1,3,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)pent-2-ene.
  8. The process of preparing hexafluoropropylene oxide polymer of claim 5 or 7, wherein a weight average molecular weight (Mw) of the hexafluoropropylene oxide polymer as measured at -10 - 20 ℃ is 1,500-4,000.
PCT/KR2009/004191 2009-03-06 2009-07-28 Hexafluoropropylene oxide polymer compositions and a preparing method of hexafluoropropylene oxide polymer using hexafluoropropylene oligomer Ceased WO2010101337A1 (en)

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WO2018197897A1 (en) * 2017-04-27 2018-11-01 Mexichem Fluor S.A. De C.V. Methods
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KR101067027B1 (en) * 2009-03-06 2011-09-23 한국화학연구원 Method for preparing hexafluoropropylene oxide polymer using hexafluoropropylene oxide polymer composition and hexafluoropropylene oligomer
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0834526A1 (en) * 1996-10-02 1998-04-08 Shin-Etsu Chemical Co., Ltd. Process for the polymerization of hexafluoropropene oxide
EP0947534A1 (en) * 1998-04-01 1999-10-06 Shin-Etsu Chemical Co., Ltd. Polymerization of hexafluoropropene oxide
EP1698650A1 (en) * 2005-03-02 2006-09-06 3M Innovative Properties Company Polymerization of hexafluoropropylene oxide

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3322826A (en) 1962-04-11 1967-05-30 Du Pont Polymerization of hexafluoropropylene epoxide
US3412148A (en) 1966-05-02 1968-11-19 Du Pont Polymerization of hexafluoropropylene oxide
EP0503294A3 (en) * 1991-02-14 1993-08-04 Hoechst Aktiengesellschaft Process for preparing perfluorpolyetheracrylfluorides
JP3533889B2 (en) * 1997-07-15 2004-05-31 ダイキン工業株式会社 Fluorovinyl ethers with terminal oxygen functional groups and their preparation
KR101067027B1 (en) * 2009-03-06 2011-09-23 한국화학연구원 Method for preparing hexafluoropropylene oxide polymer using hexafluoropropylene oxide polymer composition and hexafluoropropylene oligomer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0834526A1 (en) * 1996-10-02 1998-04-08 Shin-Etsu Chemical Co., Ltd. Process for the polymerization of hexafluoropropene oxide
EP0947534A1 (en) * 1998-04-01 1999-10-06 Shin-Etsu Chemical Co., Ltd. Polymerization of hexafluoropropene oxide
EP1698650A1 (en) * 2005-03-02 2006-09-06 3M Innovative Properties Company Polymerization of hexafluoropropylene oxide
EP1858952B1 (en) * 2005-03-02 2008-08-27 3M Innovative Properties Company Polymerization of hexafluoropropylene oxide

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018197897A1 (en) * 2017-04-27 2018-11-01 Mexichem Fluor S.A. De C.V. Methods
US11377432B2 (en) 2017-04-27 2022-07-05 Mexichem Fluor S.A.De C.V. Method for preparing a tetrafluoro-1,2-epoxypropane
US11718597B2 (en) 2017-04-27 2023-08-08 Mexichem Fluor S.A.De C.V. Method for preparing a tetrafluoro-1,2-epoxypropane
CN119735851A (en) * 2025-03-06 2025-04-01 慈溪埃弗龙密封件有限公司 A porous sealing gasket with high elastic recovery rate and preparation method thereof

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