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WO2017069795A1 - Membranes de séparation de gaz à base de polymères fluorés et perfluorés - Google Patents

Membranes de séparation de gaz à base de polymères fluorés et perfluorés Download PDF

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Publication number
WO2017069795A1
WO2017069795A1 PCT/US2016/017365 US2016017365W WO2017069795A1 WO 2017069795 A1 WO2017069795 A1 WO 2017069795A1 US 2016017365 W US2016017365 W US 2016017365W WO 2017069795 A1 WO2017069795 A1 WO 2017069795A1
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Prior art keywords
component
monomer
gas
copolymer
membranes
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Application number
PCT/US2016/017365
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English (en)
Inventor
Yoshiyuki Okamoto
Yasuhiro Koike
Hao Zhang
Zhenjie He
Timothy C. Merkel
Original Assignee
Membrane Technology And Research, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/921,382 external-priority patent/US9643124B2/en
Application filed by Membrane Technology And Research, Inc. filed Critical Membrane Technology And Research, Inc.
Priority to CN201680076091.4A priority Critical patent/CN109152981B/zh
Publication of WO2017069795A1 publication Critical patent/WO2017069795A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene

Definitions

  • the invention relates to membrane-based gas separation processes.
  • the invention relates to gas separatio processes using copolymer membranes containing partially iluorinated or perfluorinated monomers.
  • TFE tetrafluoroethylene
  • U.S. Patent No. 3,308,107 discloses a similar dioxolane derivative, perfluoro-2-inethyiene-4-methyl-L3-dioxblane, Homopolymers and copolymers of perfluoro ⁇ 2-methylene-4--meihyl ⁇ L3-dioxolane with TFE are also disclosed.
  • U.S. Patent No. 5,051,114 also to Du Pont, discloses the testing of ' poly-[perfluoro-2 ⁇ methylene-4-m ethyl- 1,3 -dioxolane] for use in a membrane for gas separation. The results indicated that this material exhibited gas permeabilities 2,5 to 40 times lower as compared to dipolymer membranes of perfluoro-2 J 2-dimethyl-l,3-dioxo1e and TFE, but had higher selectivities.
  • the present invention relates to a process for separating components of a gas mixture whereby the gas mixture is passed across an improved separatio membrane having a selective layer formed from a copolymer comprising of at least one dioxolane monomer and a second monomer,
  • the invention is a process for separating two components, A and B, of a gas mixture having a ratio (Rf) of A:B , comprising:
  • Membranes previously developed for gas separation processes have incorporated the use of amorphous homopo!ymers of perfl uorinated dioxoles, dioxoianes, or cyclic acid ethers, or copolymers of these with retrafluoroethylene.
  • these membranes lack adequate selectivity for certain gas separations, such as treatment of natural gas.
  • the invention is a process for separating two components, A and B, of a gas mixture having a ratio (Rf) of A;B, comprising;
  • Ri, R 2> R 3 , R , R 5 and Rg are each independently hydrogen or fluorine, and a second monomer;
  • An important feature of the present invention is to balance the crystalline and amorphous phases of the copolymer material, if the copolymer is too crystalline or tightly packed, the membrane selective layer may have undesirably low. permeability. Conversely, a looser, open or more flexible structure may result in a membrane with high fluxes, but poor selectivity. Therefore, the second monomer should be one that counterbalances the characteristics of the first dioxolane monomer.
  • the second monomer may be a second dioxolane.
  • Representative, non-limiting dioxolanes may be selected from the group consisting of the structures found in Table ⁇ , above.
  • the second dioxolane may be perfluorinated, as shown, for example, in Table 1 , or may be partially iluorinaied, having at least one hydrogen atom replaced by a fluorine. atom.
  • the second monomer may be a dioxane.
  • Examples of representative, non-limiting diosanes are those shown in Table 2, below:
  • the dioxane component may be only partially fluorinated or fully fluorinated. Therefore, in certain embodiments, the monomers selected to prepare the material comprising the membrane selective layer may be a combination of partially fluorinated or perfluorinated dioxolanes and partially fluorinated or perfluorinated dioxanes,
  • the second monomer may be tetrafruoroethyiene (TFE),
  • the resulting copolymer may have a glass transition temperature Tg(c) that is higher or lower than the glass transition temperature of a homopolymer, Tg(h), of the first dioxoiane monomer,
  • Tg(c) is normally at least 5°C, preferably 1G°C, lower or higher than the Tg(h)
  • An important advantage of the present invention is that copolymerization of partially or perfluorinated dioxoiane monomers with a second monomer, such as a perfluorinated dioxane, in the membrane can result in higher selectivity for desired gases than can be obtained using prior art membranes that incorporate TFE or cyclic perfluorinated omopolyrners.
  • the membranes and processes of the invention are useful for man gas separation applications.
  • Specific examples include, but are not limited to the separation of various gases, for example, nitrogen, helium, carbon dioxide, and hydrogen from methane. Such separations are important in natural gas processing, for example.
  • the gas mixture may contain at least two components, designated component A and component B, that are to be separated from each other and optionally another component or components in the stream.
  • the permeating desired gas may be either a valuable gas that is desired to retrieve as an enriched product, or a contaminant that is desired to remove.
  • the permeate stream or the residue stream, or both may be the useful -products of the process.
  • the invention is a process for separating two components, A and B, of a gas mixture wherein component A is hydrogen and component B is metiiane.
  • a gas mixture may be found in a steam reforming process.
  • the process of the invention may be used to recover hydrogen from synthesis gas, to remove carbon dioxide from synthesis gas, or to adjust the ratio -of hydrogen to carbon monoxide in synthesis gas.
  • the invention is a. process for separating two components, A and B, of a gas mixture wherein component A is carbon dioxide and component B is methane. This process may be involved in carbon capture and storage or used in the separation of C ⁇ 3 ⁇ 4 from natural gas.
  • the invention is a process for separating two components. A and B, of a gas mixture wherein component A is nitrogen and component B is methane. This process may be involved in removing nitrogen from nitrogen-contaminated natural gas.
  • the invention is a process for separating two components, A and
  • component A is helium and component B is methane.
  • This process may be useful for producing helium through natural gas extraction and subsequent purification.
  • the term "gas” as used herein means a gas or a vapor.
  • the term "polymer' as used herein generally includes, but is not limited to, homopolymers, copolymers, such as. for example, block, graft, random and alternating copolymers, terpolyrners, etc. and blends and modifications thereof.
  • the term “polymer * shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotaciic and atactic symmetries,
  • partially tluorinated as used herein means that at least one hydrogen atom attached to the polymer backbone or side chain is replaced by a fluorine atom.
  • highly fluorrnated means that at least 90% of the total number of halogen and hydrogen atoms attached to the polymer backbone; or side chains are fluorine atoms.
  • the in vention relates to a process for separating two components, A and B, of a gas mixture.
  • the separation is carried out by running a stream of the gas mixture across a membrane that is selective for the desired component to be separated from another component.
  • the desired component to be separated into the permeate may be either Component A or Component B.
  • the process results, therefore, in a permeate stream enriched in the desired component and a residue stream depleted in that component.
  • At least the selective layer responsible for the gas discrim nating properties of the membrane is made from a glassy copolymer.
  • the copolymer should be substantially amorphous. Crystalline polymers are typically essentially insoluble and thus render membrane making difficult, as well a exhibiting generally very low gas permeabilities. Crystalline polymers are not normally suitable for the selective layer, therefore.
  • the selective layer copolymer should be fl orinated, and generally the degree of ftaorination should be high to increase the chemical inertness and resistance of the material. By high, we mean having a fluorine:carhon ratio of atoms in. the polymer of at least 1 :1 , Most preferably, the polymer is periluorinated, even if the perfluorinated structure .has less than a 1 :1 fluorine:carbon ratio.
  • Various .materials may be used fo the eopolymerie selective layer to meet, the characterizing requirements. These include copolymers comprising a first dioxolane monomer and a second monomer.
  • dioxolane monomers as described herein are characterized, by a 1 ,3 -dioxolane ring, having the general form:
  • Preferred dioxolane monomers may be selected from perfIuoro-2-methyIene- 1 ,3-dioxo ane or derivatives thereof containing various substituent groups at the fourth and fifth positions of the dioxolane ring. These monomers are represented by the stmctures found in Table 1 , above.
  • a homopolymer of perftuoro-2-methy!ene-! ,3-dioxolane (Monomer H) is crystalline in nature, which was confirmed by Mikes et aL "Characterization and Properties of Semicrystatline and Amorphous Perfluoropolymer: poly(perfluoro-2-tnethylene-l 3 3-dioxoiane : )," Polymers for Advanced Technologies, v. 22, pp. 1272-1277 (2011 ). This crystallinity reflects the ability of the repeat unit in the homopolymer of Monomer H to pack tightly, fonning ordered stmctures. As a. result, Monomer H does not dissolve in fluorinated solvents.
  • the second monomer is a partially fluorinated dioxolane chosen from the group consisting of the m onomers found in Table 1, except for Monomer H,
  • the second monomer is a dioxane.
  • Preferred dioxane monomers as described herein are characterized by a 1,3-dioxane ring having the general form:
  • dioxane isomers such as 1 ,2-dioxane and 1,4-dioxane, may be used as the second monomer, having the general form:
  • Rj-R are each independently hydrogen, fluorine, or a perfluoroalkyl group having 1 to 7 carbons
  • a potential synthetic route for perfluoro-2-methylene-5-cyclopentyl-l ,3 -dioxane is shown below:
  • the bicyclic hydrocarbon precursor (1) is obtained.
  • Precursor (1 ) can be easily fluorinated and transformed to perfluoro potassium salt (2), the final monomer is obtained via salt (2)'s thermal decomposition.
  • dioxolanes can be prepared, by acetalization of aldehydes and ketalization of ketones with ethylene glycol.
  • Formulations embracing those suitable for use in the invention are described in Liu et al, and U.S. Patent Nos. 3,308,107; 5,051 ,1 14; 7,582,714; 7,635,780; 7,754,901 ; and 8,168,808, incorporated herein by reference.
  • Preparation of dioxane monomers is also described in Liu et al.
  • the homopolymers and copolymers of the monomers in Table 1 and Table 2 may be prepared by direct fluorination of hydrocarbon precursors and polymerized using perfluoro dibenzoyl peroxide as a free radical initiator to yield a linear polymer, or by another convenient method.
  • the resulting polymers are soluble in fluorinated solvents, such as hexafluorobenzene, perfliioro-hexane, and fluorinated FC43 (3MTM).
  • the bonding of the monomers occurs outside the main dioxolane or dioxane ring, typically by breaking of the double methylene bond attached to the second position (or in some cases the third position) in the five- or six-member ring. This process is different than dioxole polymerization, which occurs by the opening of a double bond within a five-member ring.
  • n is a positive integer
  • the copolymer may comprise more than two partially fi orodi oxo lane monomers, hi certain embodiments, the copolymer may comprise more than one partially fiuorinated or perfluorinated dioxane monomers.
  • the separation membrane has a selective layer comprising a copolymer formed from a first dioxolane monomer having the formula
  • the separation membrane has a selective layer comprising a copolymer formed from a first dioxolane monomer that is partially fluorinated, having the following formula:
  • Ri, R 2 , R-j, R 4 , Yi and R ( , are each independently hydrogen or fluorine, and a second dioxolane monomer selected from Table 1, wherein the second dioxolane monomer is not Monomer H, [0060]
  • the dioxane- monomers of Table 2 are more bulky and frustrate polymer chain packing, yielding a selective layer with higher free volume and higher gas permeability.
  • the resulting copolymer is not as crystalline as a dioxoiane homopolymer and has a higher glass transition temperature.
  • the copolymer has a glass transition temperature, Tg ⁇ e), that is higher, at least 5 °C higher, preferably at least 10°C higher, than a homopolymer made from the first dioxoiane monomer having a homopolymer glass transition temperature, Tg(h).
  • the copolymer is an ideal rando copol mer.
  • the selective layer of the separation membrane may comprise a copolymer formed from a partially fluormated dioxoiane monomer selected from the group consisting of the structures found in Table 1 and a dioxole monomer, such as those found in Teflon ⁇ AF and Hyflon® AD, or a polyp erfluoro (alkenyl vinyl ether) monomer, such as that used to make Cytop®.
  • the selective layer of the separation membrane may comprise a copolymer formed from a partially .fluormated or peril uorinated dioxoiane monomer of Table 1 and tetrafliioroethylene (TFE) that does not appreciably crystaiize as in the case of a homopolymer.
  • TFE tetrafliioroethylene
  • the copolymer chosen for the selective layer can be used to form films .or membranes by any convenient technique known in the art, and may take diverse forms. Because the polymers are glassy and rigid, an unsupported .film, tube or fiber of the polymer may be usable in principle as a single-layer membrane. However, such single-layer films will normally be. too thick to yield acceptable transmembrane flux, and in practice, the separation membrane usually comprises a very thin selective layer t at forms part of a thicker structure. This may be, for example, an . integral asymmetric membrane, comprising a dense skin region that forms the selective layer and a microporous support region. Such membranes were originally developed by Loeb and Sourirajan, and their preparation in flat sheet or hollow . fiber- form is now conventional in the art and is described, for example, in U.S. Patent Nos. 3,133,132 to Loeb, and 4,230,463 to Henis and Tripodi.
  • the membrane may be a composite membrane, that is,, a membrane having multiple layers.
  • Modem composite membranes typically comprise a highly permeable hut relatively non-selective support membrane, which provides mechanical strength, coated with a thin selective layer of another material that is primarily responsible for the separation properties.
  • a composite membrane is made by solution-casting the support membrane, then solution-coating the selective layer.
  • General preparation techniques for making composite membranes of this type are well known, and are described, for example, i ' U.S. Patent No. 4,243,70 to Riley et ah, incorporated herein by reference.
  • the membrane may take flat-sheet,, tube or holiow-fiber form.
  • the most preferred support, membranes are those with an asymmetric structure, which provides a smooth, comparatively dense surface on which to coat the selective layer. Support membranes are themselves frequently cast onto a backing web of paper or fabric.
  • a composite membrane by solution-casting the polymer directly onto a non-removable backing web, as mentioned above, in hollow-fiber form, multilayer composite membranes may be made by a coatmg procedure as taught, for example, in U.S. Patent. Nos. 4,863,761 ; 5,242,636; and 5,156,888, or by using a double-capillary spinneret of the type taught m U.S. Patent Nos. 5,141,642 and 5,318,417.
  • a gutter layer may optionally be used between the support membrane and the selective layer, for example to smooth the support surface and channel fluid to the support membrane pores.
  • the support membrane is first coated with the gutter layer, then with the periluo.ro selective layer as described herein.
  • the thickness of the selective layer or skin of the membranes can be chosen according to the proposed use, but will generally be no thicker than 5 ⁇ , and typically no thicker than 1 ⁇ . It is preferred that the selective layer be sufficiently thin that the membrane provide a pressure-normalized hydrogen flux, as measured with pure hydrogen gas at 25°C, of at least about 100 GPU (where 1 GPU ⁇ l l O "6 cni 3 (STP)/cm 2 ⁇ s ⁇ cmHg), more preferably at least about 200 GPU and most preferably at least about 400 GPU. In a preferred embodiment, the- selective layer thickness is no greater than about 0.5 ⁇ , and most preferably between about 0.3 ⁇ and 0.5 ⁇ -m.
  • the membranes exhibit a combination of good mechanical properties, thermal stability, and high chemical resistance.
  • the fluorocafbon polymers that form the selective layer are typically insoluble except ' in peril uorinated solvents and are resistant to acids, alkalis, oils, low-molecular-weight esters, ethers and ketones, aliphatic and aromatic hydrocarbons, and oxidizing agents, making them suitable for use not only in the presence of C3+ hydrocarbons, but in many other hostile environments.
  • the membranes of the invention may be prepared in any known membrane form and housed in any convenient type of housing and separation unit. We prefer to prepare the membranes in flat-sheet form and to house them in spiral-wound modules. However, flat-sheet membranes ma also be mounted in plate-and- frame modules or in any other way, if the membranes are prepared in the fonn of hollow fibers or tubes, they may be potted in cylindrical housings or otherwise.
  • the membrane separation unit comprises one or more membrane modules.
  • the number of membrane modules required will vary according to the volume of gas to be treated, the composition of the feed gas, the desired compositions of the permeate and residue streams, the operating pressure of the system., and the available membrane, area per module.
  • Systems may contain as few as one membrane module or as many as several hundred or more.
  • the modules may be housed individually in pressure vessels or multiple elements may be mounted together in a sealed housing of appropriate diameter and length.
  • the membranes and processes of the invention are useful in applications for producing hydrogen or chemicals from hydrocarbon feedstocks, such as reforming or gasification processes followed by separation or chemical synthesis.
  • Steam reforming is well known in the chemical processing arts, and involves the formation of various gas mixtures commonly known as synthesis gas or syngas from a light hydrocarbon feedstock, steam: and optionally other gases, such as air, oxygen or nitrogen.
  • Synthesis gas usually contains at least hydrogen, carbon dioxide, carbon monoxide and methane, but the exact composition can be varied depending on its intended use.
  • Plant design and process operating conditions thus differ in their details, but the steam reforming process always includes a basic steam/hydrocarbon reforming reaction step, carried out at high temperature and elevated pressure, and one or more subsequent treatments of the raw synthesis gas. to remove carbon dioxide or make other adjustments to the gas composition.
  • the processes of the invention are expected to be especially useful in carrying out such treatments.
  • the invention is a process for separating carbon dioxide from methane, especially if the mixture also contains Cj + hydrocarbon vapors.
  • a mixture might be encountered during the processing of natural gas, of associated gas from oil wells, or of certain petrochemical streams, for example.
  • the processes of the invention are expected to be useful as part of the gas treatment train, either in the field or at a gas processing plant, for example.
  • the invention is a process for recovering helium from natural gas.
  • Helium is a rare gas on Earth. Almost all of the commercial helium requirements are supplied by extraction from helium-containing natural gas by low temperature fractional distillation processes. The resulting helium rich gases are further purified of refined using additional cryogenic distillation steps or by pressure swing adsorption (PSA) processes which selectively remove other gases. These final refining steps result in commercial grades of helium in excess, of 99.9%.
  • PSA pressure swing adsorption
  • the processes of the invention are expected to be useful in replacing or supplementing one or more of the unit operations in the helium recovery plant,
  • the invention is a process for separating nitrogen from natural gas.
  • the goal will often be to reduce the nitrogen content, of the natural gas to no more than about 4% nitrogen, which is an acceptable total inerts value for pipeline gas. In other circumstances, a higher or lower nitrogen target value may be required.
  • the processes of the invention are expected to be useful in field or plant equipment as stand alone or supplementary units to meet the desired nitrogen concentration target,
  • the invention is a process for separating oxygen from nitrogen.
  • Oxygen is used to enhance the combustion of all fuels, enabling improved burning zone control, and lowering emissions.
  • the present invention is expected to yield enriched oxygen that can be used advantageously in combustion processes, such as kilns, or when using low-grade fuels, where reduction in ballast nitrogen is beneficial.
  • the invention is a proces for separating water from alcohols, such as ethanol, particularly bioethanol produced from natural sources.
  • alcohols such as ethanol
  • bioethanol produced from natural sources.
  • a major drawback to more economical use of bioethanol as a fuel is the energy used to grow the feedstock, to ferment it, and to separate a dry ethanol product from the fennentation broth.
  • the processes of the invention are expected to be useful in lowering the energy costs associated with ethanol separation (dehydration).
  • Composite membranes were prepared using a homopolymer of monomer B and a copolymer of perfluora ⁇ 2-metliylene"4-methyl--l ! 3,”dioxQlane (monomer B) and perfTuoro-2-rn ethylene- 1 ,3-dioxane,
  • perfluoro selective layers were coated onto support membranes, either on a small coater or by hand coating, and the membranes were finished by oven drying. Samples of each finished composite membrane were then cut into 1.2.6cm 2 stamps.
  • the membranes were tested in a permeation test-cell apparatus with pure gases at room temperature and 50 psig feed pressure. The gas fluxes through the membranes were measured, and the permeances and selectivities were calculated.
  • the perfluorodioxolane/perfmorodioxane copolymer helps to increase membrane selectivity, which is higher than the selectivity of a membrane

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un processus permettant de séparer des composants d'un mélange gazeux à l'aide de membranes copolymères de séparation de gaz. Ces membranes utilisent une couche sélective composée à partir de copolymères de monomères dioxolane partiellement fluoré ou perfluoré et un deuxième monomère, tel qu'un dioxane ou un dioxolane partiellement fluoré. Les membranes ainsi obtenues présentent des performances de sélectivité supérieures pour des paires de gaz d'intérêt tout en maintenant une perméance rapide aux gaz en comparaison à des membranes préparées à l'aide de perfluoropolymères classiques, tels que le Téflon® AF, l'Hyflon® AD et le Cytop®.
PCT/US2016/017365 2015-10-23 2016-02-10 Membranes de séparation de gaz à base de polymères fluorés et perfluorés WO2017069795A1 (fr)

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CN201680076091.4A CN109152981B (zh) 2015-10-23 2016-02-10 基于氟化和全氟化的聚合物的气体分离膜

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US14/921,382 2015-10-23
US14/921,382 US9643124B2 (en) 2014-02-19 2015-10-23 Gas separation membranes based on fluorinated and perfluorinated polymers

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CN108047189A (zh) * 2017-12-11 2018-05-18 博容新材料（深圳）有限公司 一种含氟二氧杂己环烯烃、其均聚物及其制备方法
CN108517025A (zh) * 2018-03-23 2018-09-11 博容新材料（深圳）有限公司 一种无定形含氟聚合物及其制备方法

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TWI745233B (zh) * 2021-02-03 2021-11-01 台光電子材料股份有限公司 樹脂組合物及其製品
CN113786743B (zh) * 2021-09-28 2023-07-18 常熟三爱富中昊化工新材料有限公司 气体分离膜、其制备方法和用途
CN114984773B (zh) * 2022-06-29 2023-09-01 江苏久膜高科技股份有限公司 一种油气回收复合膜及其制备方法

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