EP1558663A1 - Procede de synthese du polydimethylcetene par polymerisation cationique du type friedel et craft du dimethylcetene - Google Patents
Procede de synthese du polydimethylcetene par polymerisation cationique du type friedel et craft du dimethylceteneInfo
- Publication number
- EP1558663A1 EP1558663A1 EP03767880A EP03767880A EP1558663A1 EP 1558663 A1 EP1558663 A1 EP 1558663A1 EP 03767880 A EP03767880 A EP 03767880A EP 03767880 A EP03767880 A EP 03767880A EP 1558663 A1 EP1558663 A1 EP 1558663A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- catalytic system
- group
- taken
- cok
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/005—Polyesters prepared from ketenes
-
- 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
- C08F4/00—Polymerisation catalysts
Definitions
- the subject of the invention is a process for the synthesis of a polymer, polydimethylketene (abbreviated as PDMK in the text below) from dimethyl ketene (abbreviated as DMK in the following text) as a comonomer.
- PDMK polydimethylketene
- DMK dimethyl ketene
- the synthesis of this polymer is carried out by a process of cationic catalytic polymerization involving an initiator, a catalyst and a co-catalyst.
- the invention also relates to the polymer obtained by said process.
- the first polymerization of DMK was described by H. Staudinger in 1925. It operated at a temperature of -80 ° C to 0 ° C in the presence of trimethylamine as catalyst.
- the product obtained has been described as a trimer cyclic compound containing 3 units of monomers (A) and 2 units of monomers (B), amorphous and non-crystallizable.
- the patent GB-893,308 discloses the synthesis of a crystalline polymer resulting from the polymerization of units (A) and (B) at a temperature between -80 ° C and -20 ° C with aluminum-based catalysts ( AICtefC ⁇ Hs), AICI (C 2 H 5 ) 2, AI (C-.Hs) CI 2 , AI (OC 3 H7) Br 2 ,
- AIBr 3 AICl3.0 (C 2 H5) 2, AIEt 3 ), based on Beryllium (Be (C 2 H 5 ) 2) or based on zinc (Zn ⁇ H).
- the patent GB-987,370 relates to an improvement of the previous patent. It provides a process for the synthesis of PDMK containing more than 93% by weight of ⁇ -ketone motif by carrying out the synthesis in a solvent having a high dielectric constant and in the presence of AIBr 3 or AICI 2 Et.
- the solvents used are nitrobenzene , toluene, dichloromethane, 1, 1, 1, 2-tetrachloroethane and 1, 1-dichloroethylene.
- the state of the art in the field of cationic polymerization of dimethyl ketene does not state the use on the one hand of an initiator or initiator (I), nor of a cocatalyst (coK).
- the catalyst generally used is a Lewis acid suspended alone in a solvent or a mixture of solvents. In some cases, the Lewis acid is dissolved in a polar solvent or a mixture of solvents, at least one of which is polar.
- the Applicant has now found that according to the operating conditions for the polymerization of DMK, it is possible to selectively direct the polymerization towards the formation of a polymer of ⁇ -ketonic structure with very good yields> 65% and in the presence of solvents usual, inexpensive and not presenting the degree of danger of the solvents mentioned above.
- the applicant has placed itself in cationic catalysis requiring a catalyst soluble in the solvent used. It also got rid of the problems of peroxide formation in order to allow a safe production of PDMK as well as problems of transfer reactions parasitizing the results and leading to the formation of low molecular weight chains. These different parameters allow a large-scale synthesis of PDMK.
- the subject of the invention is a cationic catalysis system comprising an initiator (I), a catalyst (K) and a co-catalyst (CoK).
- the catalytic system is characterized in that the co-catalyst (CoK) is an agent releasing the active polymerization center from its counter anion generated by the reaction between the catalyst (K) and the initiator ( I).
- CoK co-catalyst
- the catalytic system is characterized in that the co-catalyst (CoK) is a molecule having at least one double bond depleted in electron by an electro-attracting group.
- CoK co-catalyst
- the catalytic system is characterized in that the catalyst (K) comprises an element (M) belonging to columns IB, IIB and A, IIIB and IIIA, IVB and IVA, VB and VA, VIIIB of the table of periodic classification of the elements.
- the catalytic system is characterized in that the element (M) is taken from the group containing the chemical elements B, Ti, Sn, Al, Hf, Zn, Be, Sb, Ga, In, Zr , V, As and Bi.
- the catalytic system is characterized in that the catalyst (K) is a Lewis acid of general formula R n MX 3 - n for M an element belonging to column IIIA, of general formula MX 4 for M an element belonging to columns VA, IVA and IVB and of general formula MXs for M an element belonging to column VB with: - R a monovalent radical taken from the group containing trifluoromethylsulphonate, hydrocarbon groups of 1 to 12 carbon atoms of carbon alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl and alkoxy types;
- X a halogen atom taken from the group F, Cl, Br and I; - n an integer from 0 to 3.
- the catalytic system is characterized in that the catalyst is taken from the group comprising TiCU, ZrCU, SnC, VCI, SbFs, AlC, AlBr 3 , BF 3 , BCb, FeCb, EtAICI ⁇ , EtuAICIi s, And 2 AICI, AIMes and AIEts.
- the catalytic system is characterized in that the initiator (I) can be a monofunctional molecule (11), a difunctional molecule (12), a molecule substituted by one or more halogen atoms (13) or Brônsted acid (14).
- the subject of the invention is also a process for the cationic polymerization of monomers from C3 to C10 involving a catalytic system as described above.
- the method is characterized in that the monomers are taken from the group comprising dimethyl ketene, isobutylene, but-1-ene, 4-methylpent-1-en, oct-1-en, 2-methylbut-1 -ene, 3-methylbut-1-ene, 2-methylbut-2-ene, styrene, styrenes substituted by alkyl radicals such as a-methylstyrene, p-methylstyrene, halogen-substituted styrenes such as p-chlorostyrene, propylene , isopentene, vinyl monomers in general and vinyl ethers in particular, diolefins or cyclodiolefins with conjugated dienes such as 1, 3-butadiene, 2,3-dimethyl-1,3-butanediene, hexanediene, myrcene, 6,6 -dimethyl-fulvene, piperylene, isopre
- the invention also relates to the polymer capable of being obtained by the process described above and also relates to the use of the catalytic system defined above.
- the catalytic system thus generated either before the polymerization or in situ makes it possible to avoid the formation of trimer which occurs during the polymerization of DMK in the presence of a Lewis acid alone. Indeed, the species which initiates the polymerization produces a neutral end which thus avoids the formation of the intermediate zwitterion in the trimer.
- This process therefore makes it possible to work in apolar or medium polar solvents, the toxicity of which is compatible with large-scale use, unlike the polar solvents mentioned above, without the formation of trimer.
- the catalytic system makes it possible to control the nature of the chain ends by choosing the nature of the initiator or initiator. It is thus possible to introduce at the end of the chain a functionality which is not reactive in cationic polymerization but which allows a subsequent modification of the polymer.
- branched or star polymers can also be generated using an initiator with functionality greater than 2.
- the co-catalyst (CoK) of the catalytic system (1 + K + CoK) allows, depending on its nature, to solubilize the catalyst. (K) even in a weakly polar medium and soluble even at high concentrations of the order of 1 M of acid
- Lewis as catalyst (K) while it is generally difficult to dissolve this acid in solvents of low polarity.
- solubility of AICb in the absence of the cocatalyst does not exceed 1.5 ⁇ 10 ⁇ 3 M in dichloromethane.
- the catalytic system according to the invention exhibits an increased catalytic activity, hence the possibility of use the catalyst in a smaller quantity.
- FIG. 1 represents the initiation phase of the cationic polymerization
- AIBr 3 as catalyst (k), tert-butyl chloride as initiator (I) and o-chloranyl as co-catalyst (CoK).
- the cationic catalysis system involves an initiator (I), a catalyst (K) and a co-catalyst (CoK).
- Our cationic catalysis system is not limited to the polymerization of DMK.
- Other monomers can also be polymerized with this system such as isobutylene, but-1-ene, 4-methylpent-1-ene, oct-1-ene, 2-methylbut-1-ene, 3-methylbut-1-ene, 2-methylbut-2-ene, styrene, styrenes substituted by alkyl radicals such as a-methylstyrene, p-methylstyrene, halogen-substituted styrenes such as p -chlorostyrene, propylene, isopentene, vinyl monomers in general and vinyl ethers in particular, diolefins and cyclodiolefins with conjugated dienes such as 1, 3-butadiene, 2,3-dimethyl-l, 3- butanediene, hexanediene, myrcene, 6,6-dimethyl-fulven
- the solvent in which the polymerization takes place also plays an important role. It must not only promote the separation of the charges but also solvate the growing chains to slow down the precipitation while not hindering the approach of the monomer by the formation of solvent cage. If the polar solvents favor the dissociation of the pairs of ions by their high dielectric constant and therefore increase the proportion of reactive free ions, they also preferentially solvate the active centers and therefore limit conversions by hampering the approach of the monomer. In general, there should not be any obstacles to the solvation of the active centers by the DMK.
- the DMK will preferentially solvate the growing chains but the reactions transfer will be favored by the solvent, the use of a complexing agent then makes it possible to limit these reactions in order to obtain high molar masses.
- the polymerization can therefore take place in a solvent of saturated or unsaturated, aliphatic or alicyclic hydrocarbon type and substituted or unsubstituted.
- the reaction can also take place in a mixture of such solvents.
- hydrocarbons such as hexanes, heptanes, toluene, methylcyclohexane, ethylcyclohexane, propylcyclohexane, alkyl chlorides
- initiator (I) or initiator it is chosen from the conventional initiators included in the composition of the Friedel and Craft systems for the cationic polymerization of olefins, it can be:
- (11) mono-functional that is to say having a single chemical function and having the following general chemical formula: Ri-CO-X, R1-COO-R2 and R1-O-R2 with the groups Ri and R2 taken from the group comprising the following elements: a hydrogen atom, an alkyl / aryl group such as CH 3 , CH-.CH2, (CH 3 ) 2 CH, (CH 3 ) 3 C, C ⁇ Hs and substituted aromatic rings, Ri and R2 groups may be the same or different, and X equal to a halogen atom (F, Cl, Br, I); - (12) di-functional, that is to say having two chemical functions and having the following general chemical formula: X1-CO-R-CO-X2,
- R3 is taken from the group comprising alkyl groups having from 1 to 8 carbon atoms and alkene and phenylalkyl groups (alkyl radical) having from 2 to 8 carbon atoms, RI,
- R2, R3 can also be of the adamantyl or bornyl form with X being in a tertiary carbon position; or of the following general chemical formula:
- R5 is taken from the group comprising alkyl groups having from 1 to 8 carbon atoms and alkene groups having from 2 to 8 carbon atoms
- R6 is taken from the group comprising alkyl groups having from 1 to 8 carbon atoms and alkene or phenylakyl groups (alkyl radical) having from 2 to 8 carbon atoms
- R4 taken from the group comprising phenylene, biphenyl, a, ⁇ -diphenylalkane groups and - (CFteJn - with n an integer from 1 to 10; or of the following general chemical formula:
- a protic acid such as for example CF3.SO-.H, H2SO4 or HCIO4, HBr, HCI, and HI.
- initiators (I) there may be mentioned, cumyl esters of hydrocarbon acids such as 2-acetyl-2-phenylpropane, alkylcumyl ethers such as 2-methoxy-2-phenylpropane, 1,4 di (2-methoxy-2-propyl) benzene, cumyl halides, particularly chlorinated chlorines such as 2-chloro-2-phenylpropane, (1-chloro-1-methylethyl) benzene, 1,4-di (2 -chloro-2-propyl) benzene, 1,3,5-tri (2-chloro-2-propyl) benzene, aliphatic halides particularly chlorinated such as 2-chloro-2,4,4-trimethylpentane (TMPCI ), 2-bromo-2,4,4-trimethylpentan
- the catalyst (K) is a Lewis acid, preferably a strong Lewis acid (such as for example: AlCb, AIBr 3 , EtAIC, BF 3 , BCb, SbFs, SiCU) in order to favor the ketone structure, of general chemical formula RnMX 3 -n, MX 4 or MX y depending on the nature of the element M with:
- a strong Lewis acid such as for example: AlCb, AIBr 3 , EtAIC, BF 3 , BCb, SbFs, SiCU
- M an element belonging to columns IB, IIB and A, IIIB and IIIA, IVB and IVA, VB and VA, VIIIB of the periodic table of elements, by way of example, the following elements may be cited for M: B, Ti, Sn, Al, Zn, Be, Sb, Ga, In, Zr, V, As, Bi.
- M belongs to the columns: • IIIA (formula R n MX 3 -n);
- VA and VB (formula MX y ); • IVA and IVB (MX 4 formula); R a monovalent radical taken from the group containing trifluoromethylslphonate, hydrocarbon groups of 1 to 12 carbon atoms of the alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl and alkoxy groups such as for example the following groups CH 3 , CH3CH2, (CI -b) 2CH, (Chb) 3C, CéH-, substituted aromatic rings, OCH3, OC2H5, OC3H7.
- arylalkyl and “alkylaryl” refer to a radical containing coupled aliphatic and aromatic structures, the radical being in position akyl in the first case and aryl in the second case.
- X a halogen taken from the group F, Cl, Br and I, preferably Cl.
- N an integer from 0 to 3 and y an integer from 3 to 5.
- EADC EtAIC
- EASC Eti.sAICti.s
- DEAC Et 2 AICI
- AIMe 3 and AIEt 3 Lewis acids can also be supported on clays, zeolites, silica or silica alumina, this allowing the recovery of the supported catalyst at the end of the reaction and therefore its recycling.
- Particularly preferred Lewis acids for our cationic polymerization system are AlCb, AIBr 3 , EADC, EASC, DEAC, BF 3 , TiCU.
- co-catalyst it is an agent releasing the active center of polymerization of the counter anion generated by the reaction between the catalyst (K) and the initiator (I).
- the active polymerization center is thus made more accessible thanks to the action of CoK.
- the cocatalyst is in particular a complexing agent serving to complex the counter anion generated by the reaction between the catalyst and the initiator which has the effect of releasing the active polymerization center.
- Examples that may be mentioned include o-chloranyl (3,4,5,6-tetrachloro-1,2,2-benzoquinone), p-chloranyl (2,3,5,6-tetrachloro- 1, 4- benzoquinone), nitrobenzene, trinitrobenzene or tetracyanoethylene.
- the polymerization reactor In order to carry out the polymerization of DMK into polydimethyl ketene (PDMK), the polymerization reactor is cooled to the polymerization temperature indicated in table 1 below.
- the DMK gas is purified (by absorption / desorption) with a neutral washing solvent such as for example an n-alkane or an aromatic and is then absorbed in the polymerization solvent.
- the mixture K, I, CoK is then either prepared in situ in the polymerization solvent before or after the absorption of DMK in the polymerization solvent, or is prepared in ex situ solution and then added to the polymerization reactor before or after absorption of DMK in the polymerization solvent.
- the ideal temperature range to obtain good chemoselectivity is -30 to -50 ° C.
- the polymerization can also be carried out at room temperature with very good results but in this case it is preferable to reduce the concentration of monomer.
- the unreacted DMK is neutralized with ethanol and then the contents of the reactor are filtered.
- the PDMK is recovered, washed and then dried for 1 hour at 100 ° C. under vacuum.
- the polymer is white and mainly has a ⁇ -ketone structure (measurements made by IRTF).
- the polymerization process in cationic catalysis according to the invention can be carried out continuously with re-use of the solvent and of the unreacted monomer. The following results are obtained (see Table 1) according to the operating conditions indicated. Examples 1, 2, 3 and 4 were carried out according to the invention unlike Comparatives 1 and 2.
- the process according to the invention makes it possible to have a better efficiency of the catalyst and makes it possible to synthesize significantly larger quantities of PDMK unlike the operating conditions of Comp 1 and 2.
- the molar mass by weight (Mw) is equal to 300,000 g / mol
- the polymerization according to the invention therefore makes it possible to obtain greater homogeneity in the length of the chains, unlike the polymerization according to the prior art.
- the proportion of the ester and ketone units in the polymer is measured by infrared Fourier transform spectroscopy (abbreviated as IRTF).
- IRTF infrared Fourier transform spectroscopy
- DOl the Optical Density of the band at 1740 cm- '(characteristic band of the ester functions)
- D02. This measurement allows a comparison of the batches between them but is not a direct measurement of the proportion of each motif.
- Example 4 the manipulation described in Example 4 was tested with 2-iodo-2-methylpropane and leads to very similar results.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerization Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0213828 | 2002-11-05 | ||
FR0213828A FR2846660B1 (fr) | 2002-11-05 | 2002-11-05 | Systeme de catalyse cationique comprenant un initiateur,un catalyseur et un co-catalyseur |
PCT/FR2003/003266 WO2004044030A1 (fr) | 2002-11-05 | 2003-11-03 | Procede de synthese du polydimethylcetene par polymerisation cationique du type friedel et craft du dimethylcetene |
Publications (1)
Publication Number | Publication Date |
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EP1558663A1 true EP1558663A1 (fr) | 2005-08-03 |
Family
ID=32104462
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03767880A Withdrawn EP1558663A1 (fr) | 2002-11-05 | 2003-11-03 | Procede de synthese du polydimethylcetene par polymerisation cationique du type friedel et craft du dimethylcetene |
Country Status (8)
Country | Link |
---|---|
US (1) | US7105615B2 (fr) |
EP (1) | EP1558663A1 (fr) |
JP (1) | JP2006505658A (fr) |
CN (1) | CN100402576C (fr) |
AU (1) | AU2003292314B2 (fr) |
CA (1) | CA2504619A1 (fr) |
FR (1) | FR2846660B1 (fr) |
WO (1) | WO2004044030A1 (fr) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2875169B1 (fr) | 2004-09-15 | 2008-07-04 | Arkema Sa | Structure comprenant au moins une couche de polyethylene et au moins une couche de polymere barriere |
CN104558357B (zh) * | 2013-10-18 | 2018-02-13 | 中国石油化工股份有限公司 | 一种阳离子聚合方法 |
CN104558342B (zh) * | 2013-10-18 | 2017-02-01 | 中国石油化工股份有限公司 | 一种阳离子聚合方法 |
CN104974293B (zh) * | 2014-04-04 | 2018-04-10 | 中国石油化工股份有限公司 | 一种阳离子聚合方法 |
CN105440231B (zh) * | 2014-08-07 | 2018-03-02 | 中国石油化工股份有限公司 | 一种嵌段共聚物的制备方法和嵌段共聚物 |
CN106032399B (zh) * | 2015-03-17 | 2018-07-20 | 中国石油化工股份有限公司 | 一种星形嵌段共聚物及其制备方法 |
CN106146706B (zh) * | 2015-04-22 | 2018-09-21 | 中国石油化工股份有限公司 | 一种阳离子聚合方法 |
CN106146697B (zh) * | 2015-04-22 | 2018-09-21 | 中国石油化工股份有限公司 | 一种阳离子聚合方法 |
CN106146705B (zh) * | 2015-04-22 | 2018-06-15 | 中国石油化工股份有限公司 | 一种卤化聚合物的制备方法 |
CN106146710B (zh) * | 2015-04-22 | 2018-12-28 | 中国石油化工股份有限公司 | 一种阳离子聚合方法 |
CN106146704B (zh) * | 2015-04-22 | 2018-12-28 | 中国石油化工股份有限公司 | 一种卤化聚合物的制备方法 |
CN106146703B (zh) * | 2015-04-22 | 2018-10-16 | 中国石油化工股份有限公司 | 一种阳离子聚合方法 |
CN106146696B (zh) * | 2015-04-22 | 2018-10-16 | 中国石油化工股份有限公司 | 一种阳离子聚合方法 |
CN106146698B (zh) * | 2015-04-22 | 2018-10-16 | 中国石油化工股份有限公司 | 一种卤化聚合物的制备方法 |
CN106146701B (zh) * | 2015-04-22 | 2018-09-21 | 中国石油化工股份有限公司 | 一种卤化聚合物的制备方法 |
CN106317349B (zh) * | 2015-07-08 | 2018-11-02 | 中国石油化工股份有限公司 | 一种苯乙烯-异单烯烃-苯乙烯三嵌段共聚物及其制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01278529A (ja) * | 1988-04-30 | 1989-11-08 | Cemedine Co Ltd | 複素環式化合物の開環方法及び重合方法 |
Family Cites Families (5)
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BE598508A (fr) | 1959-12-24 | |||
JPS54158489A (en) * | 1978-06-05 | 1979-12-14 | Mitsubishi Petrochem Co Ltd | Polymerization of olefin |
JP2003503558A (ja) * | 1999-06-25 | 2003-01-28 | バイエル アクチェンゲゼルシャフト | 極性および非極性モノマーの共重合法 |
US6512916B1 (en) * | 2000-02-23 | 2003-01-28 | America Connect, Inc. | Method for selecting markets in which to deploy fixed wireless communication systems |
DE10042118A1 (de) * | 2000-08-28 | 2002-03-14 | Bayer Ag | Verfahren zur Herstellung von Isoolefincopolymeren |
-
2002
- 2002-11-05 FR FR0213828A patent/FR2846660B1/fr not_active Expired - Fee Related
-
2003
- 2003-11-03 AU AU2003292314A patent/AU2003292314B2/en not_active Ceased
- 2003-11-03 CA CA002504619A patent/CA2504619A1/fr not_active Abandoned
- 2003-11-03 US US10/534,120 patent/US7105615B2/en not_active Expired - Fee Related
- 2003-11-03 JP JP2004550723A patent/JP2006505658A/ja active Pending
- 2003-11-03 WO PCT/FR2003/003266 patent/WO2004044030A1/fr active Application Filing
- 2003-11-03 EP EP03767880A patent/EP1558663A1/fr not_active Withdrawn
- 2003-11-03 CN CNB2003801083355A patent/CN100402576C/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01278529A (ja) * | 1988-04-30 | 1989-11-08 | Cemedine Co Ltd | 複素環式化合物の開環方法及び重合方法 |
Also Published As
Publication number | Publication date |
---|---|
FR2846660A1 (fr) | 2004-05-07 |
JP2006505658A (ja) | 2006-02-16 |
US7105615B2 (en) | 2006-09-12 |
CN100402576C (zh) | 2008-07-16 |
US20060014910A1 (en) | 2006-01-19 |
WO2004044030A1 (fr) | 2004-05-27 |
FR2846660B1 (fr) | 2006-07-07 |
AU2003292314B2 (en) | 2007-11-15 |
AU2003292314A1 (en) | 2004-06-03 |
CA2504619A1 (fr) | 2004-05-27 |
CN1735643A (zh) | 2006-02-15 |
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