+

WO1999003910A1 - Complexes de polymeres organosilicies de forme tubulaire et procede d'obtention de ceux-ci - Google Patents

Complexes de polymeres organosilicies de forme tubulaire et procede d'obtention de ceux-ci Download PDF

Info

Publication number
WO1999003910A1
WO1999003910A1 PCT/CN1998/000126 CN9800126W WO9903910A1 WO 1999003910 A1 WO1999003910 A1 WO 1999003910A1 CN 9800126 W CN9800126 W CN 9800126W WO 9903910 A1 WO9903910 A1 WO 9903910A1
Authority
WO
WIPO (PCT)
Prior art keywords
tube
organosilicon
polymer
poly
polymeric complex
Prior art date
Application number
PCT/CN1998/000126
Other languages
English (en)
Inventor
Rongben Zhang
Hui Xu
Ping Xie
Letian Wang
Ze Li
Xinyu Cao
Ming Cao
Daorong Dai
Original Assignee
Institute Of Chemistry, Chinese Academy Of Sciences
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
Application filed by Institute Of Chemistry, Chinese Academy Of Sciences filed Critical Institute Of Chemistry, Chinese Academy Of Sciences
Priority to AU83303/98A priority Critical patent/AU8330398A/en
Publication of WO1999003910A1 publication Critical patent/WO1999003910A1/fr

Links

Classifications

    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

  • the present invention relates to a organosilicon material with tube-like structure, particularly, the present invention relates to a complex of tube-like organosilicon polymers and the method for producing the same.
  • the present invention relates to the synthesis of hybrid organic-inorganic polymeric materials.
  • the host of the complex is a synthetic tube-like organosilicon polymer.
  • the molecular dimension, chemical affinity, and molecular shape of the tube-like polymer can be easily adjusted in accordance with different requirements. Its solubility makes it possible to re-process the material conveniently.
  • the guest molecule which can be entrapped encompasses a wide variety of molecules, therefore building blocks for many functional materials can be obtained.
  • the present invention also relates to the preparation of functional supermolecular complexes using tube-like organosilicon polymers as host molecules.
  • Guest molecules either small molecules or polymers, having sonic, optical, electrical, magnetic, or other properties are entrapped inside the tube-like polymers to form the supermolecular complexes.
  • the tube-like polymeric complexes of this invention falls into two categories. In one of which a small molecule or a metal ion is entrapped; in the other one a polymer is entrapped. Their general structures are shown in figures 2 and 3, respectively.
  • the method for producing the tube-like organosilicon polymeric complexes of the present invention includes entrapping the guest molecules into the tube-like organosilicon polymers to form supermolecular complexes.
  • Guest molecules are either small molecules with functionalities or metal ions such as cyclohexanone, tetrahydrofuran (THF), N-(4-nitrophenyl)-2-proline (NPP), azobenzene or its derivatives, fullerene, Schiff bases or frans-stilbene, Pt(l-IV) ions, Eu(lll) ion, Tb(lll) ion, or K(l) ion; or polymers such as poly(ethylene glycol), poly(vinyl alcohol), poly(methylhydrosiloxane), polyaniline, poly pyrrol, polythiophene , poly(acyl imide) or its derivatives, or poly(acrylic acid) or its derivatives.
  • metal ions such as cyclohexanone, tetrahydrofuran (THF), N-(4-nitrophenyl)-2-proline (NPP), azobenzene or its derivatives, fullerene, Schiff bases or frans-stilbene
  • the entrapment in situ is carried out according to the following procedures.
  • the ladder-like organosilicon polymers, coupling reagents, guest molecules are dissolved in organic solvent. Catalyst is added to the system to induce the coupling reaction. Under the inert atmosphere, the reaction is run at 20 - 140°C, preferable at 40 - 80°C , for 2 - 100 hours, preferable for 20 - 60 hours, during which time the tube-like polymers are formed and the guest molecules are entrapped in situ inside the tube to give the supermolecular complexes.
  • Vi-T vinyl ladder-like polymer
  • Allyl-T allyl ladder-like polymer
  • H-T hydrogen ladder-like polymer
  • the molar ratio of the ladder-like polymer and the coupling reagent is in the range of 0.5 - 5.
  • the solvents may be used include toluene, xylene, ethylene glycol dimethyl ether, poly(vinyl ether), dimethyl o-phthalate, THF, 1 , 4-dioxane, cyclohexanone, acetone, alcohols and a mixture of above solvents.
  • the catalysts may be used include: platinum catalysts such as H ⁇ PtCl ⁇ H ⁇ O, C ⁇ 2 PtCI 2 , complex of Pt and Vi-SiMe 2 OSiMe 2 -Vi (Karstedt's catalyst), and complexse of Pt ° " ⁇ v and alkene compounds, mixture of Pt 2+ and ethyl acetoacetate/acetone; Pd catalysts such as (Ph 3 P) 4 Pd, (Ph 3 P) 2 PdCl2, (PHCN) 2 PdCI 2 ; Rh catalysts such as [RhCI(CO) 2 ], (Ph 3 P) 2 (CO)RhCI, (Ph 3 P) 3 RhCI, (Et 3 P) 2 (CO)RhCI; chelates of the above mentioned metals and metal colloid catalysts; alkali oxides and hydroxides, sodium alkoxides and phenoxides, organometallic compounds (Zn, Al, B etc); inorganic acid and strong organic
  • the displacement entrapment is performed according to the following procedures.
  • the tube-like organosilicon polymers and the guest molecules are dissolved in organic solvent(s).
  • the guest molecules are entrapped inside the tube-like organosilicon polymers by ultrasonic, heating, or by changing the polarity of the solvent, during which the guest molecule is entrapped into the cavity of the tube-like organosilicon polymer and the solvent molecules or other molecules originally entrapped inside the tube were replaced by the guest molecules.
  • the weight of guest molecules is 1 - 200% of that of tube-like organosilicon polymers.
  • the solvents may used include toluene, xylene, chloroform, ethylene glycol dimethyl ether, ploy(vinyl ether), dimethyl o-phthalate, THF, 1 , 4-dioxane, cyclohexanone, cyclohexanol, methanol, acetone, and acetonitrile.
  • the amount of the solvent used is 5 - 50 ml_ per gram of tube-like polymers.
  • the frequency of the ultrasonic used is in the range of 1 - 200 kHz.
  • the temperature is in the range of 20 - 200 °C.
  • tube-like polymeric complexes may be obtained by using the method of the present invention, which is useful in a variety of applications.
  • these complexes have unique structures which can be readily adjusted, they may act as building blocks for functional materials such as biosensors, supermolecular catalysts, supermolecualr separation membranes, novel nano- scale optical or electronical materials.
  • the polymeric complexes of the present invention is soluble in a variety of solvents, therefore allows to be further processed.
  • solvents include toluene, xylene, chloroform, ethylene glycol dimethyl ether, ploy(vinyl ether), dimethyl o- phthalate, THF, 1 , 4-dioxane, cyclohexanone, cyclohexanol, acetone, isopropanol, isobutanol, or a mixture thereof.
  • Figure 1 shows the general structure of tube-like organosilicon polymers, wherein 1 represents -CH 2 CH 2 -, -CH 2 (CH2)nCH2-, -(CH 2 CH2(SiMe2O) m CH 2 CH2-, -CH 2 CH 2 C6H 4 CH 2 CH 2 -, -CH 2 (CH 2 ) n OC 6 H 4 (CH 2 ) n CH 2 -, -O(CH 2 ) n C 6 H 4 (CH 2 )nO-, or OOC(CH 2 ) n C 6 H 4 (CH 2 ) n COO-.
  • Figure 2 shows the general structure of the tube-like organosilicon polymeric complex in which the entrapped molecules are small molecules or metal ions.
  • 1 represents the entrapped small molecules or metal ions
  • 2 represent the same thing as that 1 in figure 1 represents.
  • Figure 3 shows the general structure of the tube-like organosilicon polymeric complex in which the entrapped molecules are polymers. Wherein 1 represents the entrapped polymers, and 2 represents the same thing as that 1 in figure 1 represents.
  • the reaction temperature was controlled at 30 - 40°C for 36 hours.
  • the product was washed with water and methanol.
  • the IR spectrum of the product indicated the completeness of the reaction.
  • the peaks of poly(ethylene glycol) appeared in the 1 H-NMR spectrum and these peaks were broadened and shifted to up-field, indicating that poly(ethylene glycol) was entrapped inside the tube-like polymers.
  • the reaction was carried out at 40 - 50°C for 36 - 48 hours. After the reaction the majority of the solvent was evaporated and the product was precipitated from methanol for several times. The product was washed with methanol for several times. The IR spectrum of the product indicated the completeness of the reaction. The melting point peak of NPP disappeared on DSC measurement. The peaks of benzene appeared in the IR spectrum. All these results indicated that NPP was entrapped inside the tube-like polymers.
  • Example 1 Displacement entrapment of Schiff base type liquid crystal molecules
  • Example 12 Displacement entrapment of poly(acrylic acid)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne une matière organosiliciée présentant une structure tubulaire et plus particulièrement un complexe de polymères organosiliciés de forme tubulaire. On prépare ce complexe par deux procédés, à savoir le piégeage in situ et le piégeage par déplacement. Etant donné que les polymères de forme tubulaire présentant différentes dimensions moléculaires et affinités chimiques peuvent sélectivement piéger des molécules hôtes qui correspondent au polymère, on peut former différents complexes. Ces complexes peuvent être utilisés dans des dispositifs moléculaires, lors de la catalyse et de la séparation faisant intervenir la reconnaissance des molécules et lors d'autres opérations.
PCT/CN1998/000126 1997-07-17 1998-07-16 Complexes de polymeres organosilicies de forme tubulaire et procede d'obtention de ceux-ci WO1999003910A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU83303/98A AU8330398A (en) 1997-07-17 1998-07-16 Tube-like organosilicon polymeric complexes and the method for producing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 97112268 CN1206021A (zh) 1997-07-17 1997-07-17 有机硅管状高分子复合物及其制备方法
CN97112268.7 1997-07-17

Publications (1)

Publication Number Publication Date
WO1999003910A1 true WO1999003910A1 (fr) 1999-01-28

Family

ID=5172175

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN1998/000126 WO1999003910A1 (fr) 1997-07-17 1998-07-16 Complexes de polymeres organosilicies de forme tubulaire et procede d'obtention de ceux-ci

Country Status (3)

Country Link
CN (1) CN1206021A (fr)
AU (1) AU8330398A (fr)
WO (1) WO1999003910A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6423772B1 (en) 1999-07-16 2002-07-23 Institute Of Chemistry, Chinese Academy Of Sciences Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100384748C (zh) * 2006-06-13 2008-04-30 中国科学院上海硅酸盐研究所 用乙酸盐水解制备氢氧化物纳米材料的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110726A (ja) * 1983-11-18 1985-06-17 Mitsubishi Electric Corp シリコ−ン化合物の製法
JPS61278532A (ja) * 1985-06-05 1986-12-09 Mitsubishi Electric Corp 末端ヒドロキシフエニルラダ−ポリシロキサンの製法
EP0436844A2 (fr) * 1990-01-10 1991-07-17 Mitsubishi Denki Kabushiki Kaisha Polysiloxane phénylique à structure d'échelle de haute pureté terminé par des groupes hydroxyles et son procédé de préparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110726A (ja) * 1983-11-18 1985-06-17 Mitsubishi Electric Corp シリコ−ン化合物の製法
JPS61278532A (ja) * 1985-06-05 1986-12-09 Mitsubishi Electric Corp 末端ヒドロキシフエニルラダ−ポリシロキサンの製法
EP0436844A2 (fr) * 1990-01-10 1991-07-17 Mitsubishi Denki Kabushiki Kaisha Polysiloxane phénylique à structure d'échelle de haute pureté terminé par des groupes hydroxyles et son procédé de préparation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6423772B1 (en) 1999-07-16 2002-07-23 Institute Of Chemistry, Chinese Academy Of Sciences Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same

Also Published As

Publication number Publication date
CN1206021A (zh) 1999-01-27
AU8330398A (en) 1999-02-10

Similar Documents

Publication Publication Date Title
Montague et al. Synthesis of poly [bis (trifluoroethoxy) phosphazene] under mild conditions using a fluoride initiator
Krska et al. Synthesis of water-soluble carbosilane dendrimers
Kaes et al. Bipyridine: the most widely used ligand. A review of molecules comprising at least two 2, 2 ‘-bipyridine units
Slagt et al. Encapsulation of Hydrophilic Pincer− Platinum (II) Complexes in Amphiphilic Hyperbranched Polyglycerol Nanocapsules
Hearshaw et al. Organometallic and related metal-containing dendrimers
Schubert et al. Macromolecules containing bipyridine and terpyridine metal complexes: towards metallosupramolecular polymers
Chen et al. Biotin-terminated ruthenium bipyridine ring-opening metathesis polymerization copolymers: Synthesis and self-assembly with streptavidin
Grayson et al. Synthesis and surface functionalization of aliphatic polyether dendrons
Krishna et al. Synthesis of poly (propyl ether imine) dendrimers and evaluation of their cytotoxic properties
US20030113740A1 (en) Oligonucleotide-modified ROMP polymers and co-polymers
Vögtle Dendrimers II: architecture, nanostructure and supramolecular chemistry
KR101275968B1 (ko) 백금 착물의 폴리머화 배위 화합물의 제조 방법
WO2003087188A1 (fr) Polymers et copolymeres romp a modification oligonucleotidique
Liao et al. Organoruthenium dendrimers
Newkome et al. Synthesis of neutral metallodendrimers possessing adamantane termini: Supramolecular assembly with β-cyclodextrin
US6423772B1 (en) Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same
CN113121396A (zh) 一种可降解的含二硒基聚多巴胺及其制备方法与应用
Miyashita et al. Catalytic one-pot synthesis of end-functionalized poly (9, 9′-di-n-octylfluorenevinylene) s by acyclic diene metathesis (ADMET) polymerization using ruthenium–Carbene catalysts
US20060237365A1 (en) Silicone derivatized macromolecules
JP3793461B2 (ja) シルアルキレンシロキサンの重合方法
WO1999003910A1 (fr) Complexes de polymeres organosilicies de forme tubulaire et procede d'obtention de ceux-ci
WO2008069274A1 (fr) Polymère organique portant plusieurs structures cycliques organiques et une structure en chaîne passant à travers les structures cycliques, et son procédé de production
CN1284513A (zh) 一种由有机桥基梯形聚硅氧烷构成的管状高分子复合物及其制备方法
KR102483813B1 (ko) 하이퍼브랜치 폴리머, 금속 회수제, 금속 회수 방법 및 촉매 활성 방해제
Ding et al. Synthesis and characterization of hyperbranched poly (siloxysilane) possessing rhodamine B as terminal group

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM HR HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: KR

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载