WO2007058247A1 - Compose de clathrate d’une molecule de fluoropolyether - Google Patents

Compose de clathrate d’une molecule de fluoropolyether Download PDF

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Publication number
WO2007058247A1
WO2007058247A1 PCT/JP2006/322836 JP2006322836W WO2007058247A1 WO 2007058247 A1 WO2007058247 A1 WO 2007058247A1 JP 2006322836 W JP2006322836 W JP 2006322836W WO 2007058247 A1 WO2007058247 A1 WO 2007058247A1
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WO
WIPO (PCT)
Prior art keywords
group
compound
inclusion
fluoropolyether
cyclodextrin
Prior art date
Application number
PCT/JP2006/322836
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English (en)
Japanese (ja)
Inventor
Keiko Hirata
Haruhiko Mohri
Hirokazu Aoyama
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Daikin Industries, Ltd.
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Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2007058247A1 publication Critical patent/WO2007058247A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • 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
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine

Definitions

  • a fluoropolyether molecule is included as a guest compound in a host compound molecule having a ring structure or a helical structure and having a hydrophobic group inside the structure. It is related to the inclusion compound.
  • Cyclodextrin one of the polysaccharide compounds, is a cyclic oligomer of glucose and has a hydrophilic group on the outside of the ring and a hydrophobic pore on the inside. Therefore, the hydrophobic compound on the inside of the ring It is known to contain.
  • the main ones are a-cyclodextrin, j8-cyclodextrin, and y-cyclodextrin in which 6, 7, and 8 darcoviranose residues are linked by ⁇ -1, 4 glycosidic bonds.
  • the inner diameter of the ring varies depending on the type of cyclodextrin, and thus the size of the guest compound that is easily included is also different.
  • a typical guest molecule hydrophobic polymer
  • polydimethylsiloxane ⁇ known (Okumura, H., Kawaguchi, Y., Harada , A., Macromolecules, 2003, 36, 6422-6429.), Mixed with a saturated aqueous solution of cyclodextrin and a hydrophobic polymer.
  • a polyortaxene molecule in which polyethylene glycol molecules are clasped into the openings of ⁇ -cyclodextrin molecules is a compound or gel rich in high water absorption, uniform expansion, elasticity, viscoelasticity, etc. It is also known to give a product (Patent No. 3475252) ⁇
  • a specific example of a fluoropolymer, in particular a perfluoropolyether can be obtained.
  • there are still problems such as the heat resistance of compounds and gels rich in elasticity and viscoelasticity, chemical resistance, and compatibility with fluoropolymers.
  • Fluoropolyether is particularly excellent in water and oil repellency, antifouling, and lubricity. However, it does not dissolve in some fluorinated solvents such as perfluorinated hexane, either alone or in particular. It is only used as a fluorinated solution. However, the above characteristics are difficult to dispose of as an additive. Because it dissolves only certain fluorinated solvents and has poor compatibility with hydrocarbon resins, it can be used as an additive. Is limited.
  • the present inventors focused on clathrate compounds that have been studied for some fluorine-based compounds, and as a result of intensive studies on molecules having a fluoroether unit, the fluoroether unit is a cyclodextrin. In particular, it was found that a good inclusion complex with ⁇ -cyclodextrin was formed, and further studies were made to complete the present invention.
  • a fluoropolyether molecule is included as a guest compound in a host compound molecule having a ring structure or a helical structure and having a hydrophobic group inside the structure. Related to the inclusion.
  • a fluoropolyether compound is encapsulated in a host compound molecule having a ring structure or a helical structure characterized by inclusion of a hydrophobic compound and having a hydrophobic group inside the structure.
  • fluorine atoms are taken into the inside of the host compound ring, while carbon atoms, hydrogen atoms,
  • the poor solubility and poor compatibility of the fluoropolyether compound can be overcome.
  • a polysaccharide compound is exemplified, and examples thereof include cyclodextrin which is a polysaccharide having a ring structure, amylose having a helical structure, and the like. Among these, ⁇ -cyclodextrin forms a good inclusion complex.
  • R 1 and R 2 are the same force or different, and each has a bond, a functional group Z 1 and may be substituted with a fluorine atom; a divalent hydrocarbon group; Y 1 and Y 2 is the same or different, and all are H, a halogen atom or a functional group Z 2 ; n is 2 to: an integer of LOO; — (RfO) 1 is a formula (2):
  • xi to X 12 are the same or different and all are H, CH, F or CF, ⁇ to X
  • any one of 6 is F or CF
  • any one of X 7 to X 1Q is F or CF
  • X U to X 12 is F or CF
  • nl, n2 and n3 are the same or different
  • the inclusion compound is sometimes called an inclusion complex or an inclusion body.
  • the fluoropolyether that is a guest compound may have a fluoropolyether unit in its molecule.
  • the inclusion structure occurs in this fluoropolyester unit! /.
  • Fluoropolyether as a preferable good guest compound is represented by the formula (1):
  • xi to X 12 are the same or different and all are H, CH, F or CF, ⁇ to X
  • Any force one 6 is F or CF
  • any force one of X 7 to X 1Q is F or CF
  • X U to X 12 is F or CF
  • nl, n2 and n3 are the same or different
  • ⁇ -cyclodextrin When ⁇ -cyclodextrin is used as a combination of the three compounds, especially as a host compound molecule, it is necessary to have a perfluoroether unit, which is F, in terms of size compatibility with the pores of ⁇ -cyclodextrin. I also like power.
  • Displacement force 2 units or all units may be combined.
  • the RfO unit must contain the Rf ⁇ unit alone or in combination with Rf 2 0 and / or Rf 3 0. Compared with ⁇ -cyclodextrin, it is easier to be included in ⁇ -cyclodextrin, and it is desirable to have a strong spot power.
  • Preferable ⁇ is 2 to 50, more preferably 11 to 30, from the viewpoint of the viscosity of the fluoropolyether.
  • nl is 0-50, more preferably 11-30, n2 is 0-50, more preferably 7-36, and n3 is preferably 0-50, more preferably 0-20.
  • — ( ⁇ ⁇ ⁇ )-(Rf 2 0)-(Rf ⁇ )-(Rf 2 0)-(v, x, y and z are positive vxyz
  • Y 1 and Y 2 are the same or different and all are H, a halogen atom or a functional group Z 2 .
  • R 1 and R 2 are the same or different and both have a bond, a functional group Z 1, and may be substituted with a fluorine atom. It is a hydrocarbon group.
  • R 1 and R 2 may be a divalent hydrocarbon group having a relatively small number of carbon atoms (for example, 1 to 10 carbon atoms, or even 1 to 2 carbon atoms), and V, one or both of them are polymers. Chain (number average molecular weight 100
  • R 1 and R 2 include the following types.
  • Preferred examples include CF—, —CF CF—, and —CF CF CH—.
  • Examples of commercially available products include the demnum series manufactured by Daikin Industries, Ltd., the NORELTA series manufactured by NOK CRUBA, the Fomblin series manufactured by Solvay, and the Crite Tux series manufactured by DuPont.
  • polymer chains examples include chains containing acrylic units, styrene units, butyl ether units, a -olefin units, and non-fluorinated polyether units.
  • R 3 is H or an organic group which may contain halogen, for example, F, CF, H or CH; R 4 is H or an organic group
  • R 4 may have a fluorine atom! /, But may be a hydrocarbon group, a non-fluorinated polyether chain (polyoxyethylene chain, polyoxypropylene chain, etc.) and the like.
  • polymer chain for example, a fluoropolyether bonded to a side chain of a non-fluorinated polymer:
  • RfO, n and r are the same as described above; R 5 and R 6 are the same or different and may be substituted with a fluorine atom; Y 3 is exemplified by those represented by Y 1 or Y 2 ).
  • the host ich compound may be a compound having a ring structure or a helical structure and having a hydrophobic group inside the structure and capable of including a fluoropolyether molecule.
  • Specific examples include polysaccharide compounds having a ring structure or a helical structure and a hydrophobic group inside the structure, and synthetic compounds such as calixarene and crown ether. .
  • polysaccharide compounds having a ring structure and having a hydrophobic group inside the structure include ⁇ -cyclodextrin, j8-cyclodextrin, ⁇ cyclodextrin, oral amylose, and these Derivatives (modified products) of ⁇ -cyclodextrin or derivatives thereof are preferred because they form a particularly stable inclusion compound with a fluoropolyether molecule.
  • Derivatives of polysaccharide compounds having a ring structure include, for example, those in which all or part of the hydroxyl groups of the polysaccharide compounds are acetylated, methyl etherified, 2-hydroxyethylated, etc. And a polymer compound having a polysaccharide compound having a cyclic structure as a side chain (pendant) of the polymer.
  • Examples of the polysaccharide compound having a helical structure and having a hydrophobic group inside the structure include amyloses.
  • Amylose is a linear molecule contained in starch, and has a structure in which a glucose is linked by a 1,4 daricoside bond.
  • amylose crystal structures There are two known amylose crystal structures: double helix (A, B type) and single helix (V type).
  • the oil and fat component contained in the granule is included in the helical structure and exists as an inclusion compound.
  • Bociek et al. Have studied the structure of amylose by inclusion of palmitate, hexanoic acid, etc. (Gidley. MJ, Bociek. SMJAm. Chem. Soc, 1988, 110, 3820-382 9).
  • V-amylose is preferred because it has a structure similar to cyclodextrin and can include a wide range of guest compound molecules.
  • host compounds described in JP-A-09-241248 such as calixarene and crown ether, are known and can include a fluoropolyether molecule. Can be used in the present invention.
  • the ratio of the host compound molecule to the fluoropolyether molecule in the clathrate compound varies depending on the type, structure, number, molecular weight, etc. of the fluoroether unit (RfO). It is usually in the range of iZi to iZiooo, and further iZi to iZioo, in terms of the molar ratio of host compound molecules (hereinafter sometimes referred to as “inclusion ratio” t).
  • the inclusion ratio of the fluoropolyether molecule ⁇ ⁇ -cyclodextrin molecule molar ratio is 1 to 1 to 20
  • the point of stability is also preferable.
  • the clathrate compound of the present invention is obtained by adding a guest compound molecule in a saturated aqueous solution of a water-soluble compound molecule and leaving it alone after being irradiated with ultrasonic waves, or host compound molecules and guest compound molecules. It can manufacture by the method of kneading, adding water little by little to this mixture.
  • the inclusion complex of the present invention is usually obtained in a solid form (powder form). Therefore, the clathrate compound of the present invention can be used as a modifier for various materials using the properties of fluoropolyether in the powder state as it is.
  • the present invention also relates to a powder of the clathrate compound of the present invention alone or a powder (composition) containing the clathrate compound.
  • the particle size of the powder may be appropriately selected depending on the material to be blended, the production method, etc. Usually, it is in the range of 0.001 to 100 / ⁇ ⁇ .
  • the additives may be those usually used in powder compositions, for example, flame retardants, antistatic agents, thickeners, surface active agents. And preservatives.
  • the amount of inclusion compound in the powder composition is the type, degree, A wide range of 0.01-99.99% by mass based on fluoropolyether can be adopted as appropriate depending on the type of material to be modified.
  • the present invention also relates to a liquid composition containing the inclusion compound of the present invention and a solvent.
  • the solvent may be any solvent that can dissolve or disperse the host compound. Therefore, the solvent that can be used depends on the host compound.
  • the host compound is a polysaccharide compound
  • the inclusion of a fluoropolyether as a guest compound makes it extremely difficult for the fluoropolyether to dissolve or disperse. Since it can be uniformly dissolved or dispersed in an ionic solvent, it can be easily blended into a material having an affinity only for a powerful polar solvent that could not be uniformly mixed in the prior art.
  • the polar solvent includes hydrocarbon alcohols such as methanol and ethanol; fluorine-containing alcohols such as hexafluoroisopropanol and pentafluoropropanol; hydrocarbons such as acetic acid.
  • hydrocarbon alcohols such as methanol and ethanol
  • fluorine-containing alcohols such as hexafluoroisopropanol and pentafluoropropanol
  • hydrocarbons such as acetic acid.
  • Fluoric carboxylic acids such as trifluoroacetic acid; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, pyridine, acetone, and water depending on the host compound.
  • nonpolar solvent examples include hexane and benzene.
  • liquid composition of the present invention usual additives such as a flame retardant, an antistatic agent, a thickener, a surfactant and a preservative may be added.
  • concentration of the inclusion complex in the liquid composition of the present invention may be selected as appropriate depending on the type and degree of properties to be modified, the type of solvent, and the type of material to be modified.
  • a wide range of 0.01 to 99.99% by mass on the basis of olopolyether can be adopted.
  • Dissolution or dispersion in a solvent can be easily carried out by a method such as stirring, heating, and ultrasonic waves, and a liquid group in which an inclusion compound and further a fluoropolyether are uniformly dispersed in the solvent. A composition is obtained.
  • the powder (or powder composition) and liquid composition of the present invention may be directly applied to the surface of various articles as a surface modifier, or may be blended with various polymers to form a fluoropolymer. You can show the characteristics of Tell.
  • the present invention also relates to a polymer composition containing the inclusion complex of the present invention and a polymer.
  • the polymer to be modified by adding the clathrate compound of the present invention is not particularly limited, and the clathrate compound is not limited.
  • uniform blending is possible if it has an affinity with the host compound.
  • the host compound is a polysaccharide compound
  • a polymer having a polar group that could not be uniformly blended conventionally such as acrylic resin, epoxy resin, polyester resin, etc.
  • the concentration of the clathrate compound in the polymer composition of the present invention is 0 on the basis of fluoropolyether, which may be appropriately selected depending on the type and degree of properties to be modified, the type of polymer to be modified, etc. 01-99. A wide range of 99% by mass can be used.
  • the compound can be easily blended into the polymer solution by adding a liquid composition or a powder composition containing the inclusion complex to the polymer solution and stirring the mixture. As a result, a polymer composition in which fluoropolyether is uniformly dispersed in the polymer can be obtained.
  • the powerful polymer composition may be used as a molding material as it is, or may be used as various modifiers by pulverizing a powder frame or pellets.
  • the clathrate compound of the present invention is useful as an antifouling agent, lubricant, etc. in the form of a powder (or a powder composition), a liquid composition, a polymer composition, etc.
  • a powder or a powder composition
  • a liquid composition e.g., a polymer composition
  • the compound of the present invention is used in the same manner as the compound and the gel-like substance having high absorbency, uniform expansibility, and elasticity or viscoelasticity as described in Japanese Patent No. 3475252. It can also be used as a material.
  • the compound and gel-like substance comprising the fluoropolyether of the present invention can be a material having excellent heat resistance, chemical resistance and compatibility with fluoropolymers.
  • Fluoropolyether with a basic skeleton of nl (nl 22-26) and a carboxyl group at one end (number average molecular weight 4000)
  • Fluoropolyether with CF 3 as the basic skeleton and a perfluoroalkyl group at the end (number average molecular weight 3500)
  • Measurement conditions MAS rotation speed 7kHz. room temperature.
  • PFPE-1 (7 mg, 0.0019 mmol) was added dropwise as a fluoropolyether to a saturated aqueous solution of ⁇ -cyclodextrin ( ⁇ cyclodextrin 0.5 g, 0.386 mmol / 2 ml). After applying ultrasonic waves for about 15 minutes, it was left overnight. Thereafter, the precipitate was collected by suction filtration, and the precipitate was dried overnight at 60 ° C. under reduced pressure to obtain 28 mg of a powdery white solid.
  • the obtained solid was analyzed by the above-mentioned method, and confirmed to be an inclusion complex of PFPE-1 and ⁇ -cyclodextrin.
  • (CF CF) unit (CF CF CF O) is -129ppm, (CF CF CF O) is -83ppm
  • the powder X-ray diffraction pattern of the white solid of Example 1 is different from the spectrum of ⁇ -cyclodextrin alone, and the diffraction pattern (Li, J., Toh. KC, Ni, X “Zhou, Z” Leong, KW Macromolecules, 2001, 34, 8829-8831.), And it was confirmed that an inclusion complex was formed.
  • Example 1 when the state change was observed with a microscope at 30 to 280 ° C, the white solid of Example 1 was observed to have a phenomenon estimated to be melted at around 230 ° C. This phenomenon can be ruled out by the fact that PFPE-1, which was included by the start of the decomposition of ⁇ -cyclodextrin, precipitates.
  • Example 1 the amount of PFPE-1 mixed was changed as shown in Table 1, and the inclusion state was examined. The results are shown in Table 1. In the table, ⁇ -CD is ⁇ -cyclodextrin. [0097] [Table 1]
  • Example 2 The same procedure as in Example 1 was conducted except that PFPE-2 was used as a fluoropolyether in the amount shown in Table 2 against a saturated aqueous solution of ⁇ -cyclodextrin ( ⁇ -cyclodextrin 0.5 g, 0.386 mmol / 2 ml). A powdery white solid was obtained, confirmed to be an inclusion complex of PFPE-2 and ⁇ -cyclodextrin by the same analysis method as in Example 1, and the inclusion ratio was calculated. The results are shown in Table 2.
  • PFPE-3 which has a different structure from PFPE-1 and PFPE-2, as a fluoropolyether against a saturated aqueous solution of ⁇ -cyclodextrin ( ⁇ cyclodextrin 0.5 g, 0.386 mmol / 2 ml). 077 mmol)
  • ⁇ -cyclodextrin 0.5 g, 0.386 mmol / 2 ml.
  • a powdery white solid was obtained in the same manner as in Example 1, except that it was used. The precipitate was much less than in Examples 1 and 2 with the same molar amounts of PFPE-1 and PFPE-2. Subsequently, it was confirmed by the same analysis method as in Example 1 that it was an inclusion complex of PFP E-3 and ⁇ -cyclodextrin.
  • Example 2 The same procedure as in Example 1 was performed except that 309 mg (0.077 mmol) of PFPE-1 was used as a fluoropolyether with respect to a saturated aqueous solution of ⁇ -cyclodextrin (j8-cyclodextrin 438 mg, 0.386 mmo 1/24 ml). Thus, a powdery white solid was obtained. The precipitate was much smaller than when the same molar amount of ⁇ -cyclodextrin was used. Subsequently, it was confirmed by the same analysis method as in Example 1 that it was an inclusion complex of PFPE-1 and ⁇ -cyclodextrin.
  • ⁇ -cyclodextrin j8-cyclodextrin 438 mg, 0.386 mmo 1/24 ml
  • Example 1 For the inclusion compound number 1 of Example 1, the inclusion compound number 2-3 of Example 2, and the inclusion compounds of Example 3 and Example 4, hexafluoroisopropanol (HFIP), dimethylformamide Liquid compositions using (DMF) and dimethyl sulfoxide (DMSO) as solvents were prepared, and their solubility (dispersibility) was investigated. In addition, the solubility (dispersibility) of each of y-cyclodextrin, ⁇ -cyclodextrin, and PFPE-1 to PFPE-3 was also investigated. The results are shown in Table 3.
  • HFIP hexafluoroisopropanol
  • a fluoropolyether molecule in a host compound molecule such as cyclodextrin, it can be dissolved in a conventional solvent having no affinity with fluoropolyether, such as a polar solvent, or Can be dispersed. In addition, it is possible to uniformly add a resin having a poor compatibility with the fluoropolyether compound. Furthermore, the phenomenon that the fluoropolyether compound encapsulated inside the host compound gradually precipitates on the surface (sustained release) is used for a long time. Antifouling and lubricating effects can be achieved.

Abstract

L’invention a pour objectif de réaliser une dissolution ou une dispersion d’un fluoropolyéther dans un solvant ne présentant aucune affinité pour le fluoropolyéther, par exemple un solvant polaire, ainsi que de réaliser un chargement uniforme dans une résine présentant une faible compatibilité avec le fluoropolyéther. L’invention concerne un composé de clathrate comprenant une molécule de composé hôte, telle que la cyclodextrine, ayant une structure cyclique ou en spirale, à l’intérieur de laquelle se trouve un groupement hydrophobe, lequel renferme une molécule de fluoropolyéther en tant que composé client.
PCT/JP2006/322836 2005-11-17 2006-11-16 Compose de clathrate d’une molecule de fluoropolyether WO2007058247A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011138211A1 (fr) * 2010-05-07 2011-11-10 Borealis Ag Procédé pour la préparation d'un système catalyseur métallocène solide et son utilisation pour la polymérisation d'oléfines
JP2012097131A (ja) * 2010-10-29 2012-05-24 Daikin Industries Ltd 表面処理剤と組成物、その処理加工品
EP3765091A4 (fr) * 2018-03-16 2022-01-19 Istanbul Medipol Universitesi Complexes d'inclusion appropriés pour être utilisés en tant qu'agent d'histotripsie
CN114797490A (zh) * 2022-07-04 2022-07-29 天津大学 一种分离阴离子盐的高选择性分离膜的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001083566A1 (fr) * 2000-04-28 2001-11-08 Center For Advanced Science And Technology Incubation, Ltd. Compose contenant du polyrotaxane reticule
JP2003532757A (ja) * 2000-05-11 2003-11-05 イーストマン ケミカル カンパニー アシル化シクロデキストリン：ゲスト分子包接錯体
WO2005052026A1 (fr) * 2003-11-28 2005-06-09 The University Of Tokyo Polyrotaxane et son procede de production

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001083566A1 (fr) * 2000-04-28 2001-11-08 Center For Advanced Science And Technology Incubation, Ltd. Compose contenant du polyrotaxane reticule
JP2003532757A (ja) * 2000-05-11 2003-11-05 イーストマン ケミカル カンパニー アシル化シクロデキストリン：ゲスト分子包接錯体
WO2005052026A1 (fr) * 2003-11-28 2005-06-09 The University Of Tokyo Polyrotaxane et son procede de production

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011138211A1 (fr) * 2010-05-07 2011-11-10 Borealis Ag Procédé pour la préparation d'un système catalyseur métallocène solide et son utilisation pour la polymérisation d'oléfines
EP2386583A1 (fr) * 2010-05-07 2011-11-16 Borealis AG Préparation d'un système catalytique solide
CN102884090A (zh) * 2010-05-07 2013-01-16 北欧化工公司 制备固体金属茂催化剂体系的方法以及该催化剂体系在烯烃聚合中的应用
US8822365B2 (en) 2010-05-07 2014-09-02 Borealis Ag Process for the preparation of a solid metallocene catalyst system and its use in polymerisation of olefins
JP2012097131A (ja) * 2010-10-29 2012-05-24 Daikin Industries Ltd 表面処理剤と組成物、その処理加工品
EP3765091A4 (fr) * 2018-03-16 2022-01-19 Istanbul Medipol Universitesi Complexes d'inclusion appropriés pour être utilisés en tant qu'agent d'histotripsie
CN114797490A (zh) * 2022-07-04 2022-07-29 天津大学 一种分离阴离子盐的高选择性分离膜的制备方法
CN114797490B (zh) * 2022-07-04 2022-10-25 天津大学 一种分离阴离子盐的高选择性分离膜的制备方法

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