CN101072809A - Substituted polyphenylenes via supported transition metal catalysis - Google Patents
Substituted polyphenylenes via supported transition metal catalysis Download PDFInfo
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Abstract
Substituted polyphenylenes and methods for producing such substituted polyphenylenes using supported transition metal catalysis are provided.
Description
Invention field
The present invention relates to a kind of method/technology for preparing the polyhenylene of replacement, more particularly, relate to a kind of method for preparing the polyhenylene that replaces with the transition-metal catalyst of load.
Background of invention
Penylene polymkeric substance and multipolymer show the performance of multiple hope, comprise high strength and rigidity, anti-solvent and erosion resistance and high use temperature.Therefore described polymkeric substance usually has the inflexible skeleton structure, also can be used for preparing molecular composite material.Because the polymer molecule solvability of growing up reduces, and can be precipitated out from reaction solvent under low polymerization degree (DP), therefore, the polyhenylene of synthetic macromolecule amount is very difficult.
Realized the deliquescent raising of required polyhenylene by on phenyl-Ji monomer, introducing side group, disclosed such in for example following United States Patent (USP): 5,886,130,5,227,457,5,824,744,5,830,945 and 5,976,437.The polyhenylene of the replacement of preparing according to the instruction of above-mentioned patent has demonstrated the mechanical property of many hope.
Aryl compound forms biaryl compound by the C-C coupling or polyarylate has very important significance on synthetic.Many currently known methodss can carry out this coupling, the Liv Ullmann coupling that comprises aryl iodide and aromatic bromide is (referring to P.E.Fanta, " The UllmanSynthesis of Biaryls ", Synthesis, 9,9-21,1974), realize the coupling (A.Suzuki of aromatic bromide and aryl iodide and aryl boric acid and ester with palladium catalyst, Acc.Chem.Res., 15,178,1982), the reductive coupling (T.Yamamoto and A.Yamamoto, Chem.Lett., the 353-356 that aryl halide and magnesium are undertaken with nickel catalyzator by Grignard reagent, 1977), the reductive coupling (I.Colon and D.R.Kelsey, J.Org.Chem., 51 that aryl muriate and zinc are carried out with the triphenylphosphine nickel catalyzator, 2627-2637,1986; With United States Patent (USP) 4,326,989) and the oxidative coupling (L.F.Fieser and M.Fieser, Reagents for Organic Synthesis, the 1st volume, 390,1967) of realizing phenol with iron (III) or air and copper catalyst.
Some reaction methods can be used to prepare the polyhenylene of replacement by the aryl coupling.Simple method depend on 1, the reduction condensation of 4-dihalogenated aromatic compounds, itself or undertaken by Grignard reagent, perhaps directly in the presence of reductive agent such as metallic zinc, carry out.Use catalyzer, as two (triphenylphosphine) nickelous chloride (II) or 1,4-two chloro-2-butylene.Right-bromine aryl boric acid can be used the palladium-based catalyst coupling.Polyhenylene also prepares by the method for not unique acquisition contraposition key, and as the Di Ersi-Alder condensation of two-acetylene and two-pyrone, the 1 polymerization then carry out virtueization, and the oxypolymerization of benzene.
Therefore, for the polyhenylene that preparation replaces, there are a lot of possible methods.The coupling that to be used for industrial polyhenylene synthetic core technology be dihalo an aromatic substance of metal catalytic.For example, the nickel catalyzed coupling is reflected in some United States Patent (USP)s and all described, comprise, and United States Patent (USP) 5,227,457,5,886,130 and 5,824,744, its disclosure all is hereby incorporated by.
Usually, this method uses nickel catalyzator in conjunction with triphenylphosphine (TPP) part and metallic zinc reductive agent, comes coupling dihalo an aromatic substance in polar aprotic solvent such as N,N-dimethylacetamide (DMAc) or N-Methyl pyrrolidone (NMP).This reaction can represent that wherein Y is a substituting group with figure below, and X is a halogen:
Though the method shown in the last figure can prepare the polyhenylene of the replacement of commercial quantities,, from synthesizing, making and environmental, it is disadvantageous that this technology has many aspects.
At first, reduction reaction is non-homogeneous in essence in the nickel Catalytic processes, comprises solid-liquid interface, and wherein solid zinc particle must play the effect of the reductive agent that is used for the solvent radical reaction.It is all multifactor that in fact this technology make that the degree of reaction and speed are vulnerable to, and as the influence of particle diameter, shape and the quality of zinc, these all are difficult to control and monitor.
The second, the commercially available oxidized zinc of zinc particle (ZnO) part is wrapped quilt, and they must be removed so that zinc obtains activation, so that can carry out substitution reaction effectively.The reactivation process of zinc has a lot of defectives.For example, Zinc oxide particles is remained with the form of impurity, then cause forming various by products during chemical removal zinc oxide.For example, a kind of activation method of zinc is to use hydrochloric acid (HCl), and its corrodibility is very strong and poisonous, can generate volatile hydrogen as by product.
The 3rd, nickel itself is known carcinogenic substance, and this forces manufacturers must follow numerous environment expensive and consuming time and safety regulations.
The 4th, with regard to being used for effectively carrying out catalyst for reaction, catalyst packing need use quite excessive TPP part.TPP is expensive, is expendable at present; Therefore, increased the cost of this technology.
The 5th, the reaction pair water electrode is responsive.For example, as a rule, the acceptable water yield generally is lower than 50ppm.But the polar aprotic solvent that is used for this technology is the height moisture absorption, and this is just to making and the sizable challenge of operation formation.
Though be not intended to prepare the polyhenylene of replacement, had numerous novel aryl compound couplings that makes of having researched and proposed to form the route of diaryl recently.Example comprise people such as Mukhopadhyay publish article (J.Chem.Soc., Perkin Trans.2,1999,2481-2484); (Organic Process Research and Development, 7,2003,641); (Tetrahedron, 55,1999,14763); (J.Chem.Soc., Perkin Trans.2,2000,1809-1812), its disclosure is hereby incorporated by.
In the broadest sense, these new routes use metal catalysts, for example load on the palladium on the carbon base body, Pd (C), or load on rhodium on the carbon base body, Rh (C) finishes the coupling of aryl-aryl.In these routes, raw material remains halogenated aryl, and a lot of common reductive agents have been used for the regeneration of catalyzer, comprise, for example, zinc, formate, and hydrogen.The solid-liquid reaction is often promoted by phase-transfer catalyst such as polyoxyethylene glycol (PEG).Importantly, these reactions are water-fast and air usually, makes that reaction conditions can be not too strict, and can not necessarily carry out in Aquo System.
Comprise heterogeneous catalyst, for example, palladium/carbon, the reaction of Pd (C) has been used for preparing biphenyl by single halogenated aryl molecule.Unfortunately, the conversion of single halogenated aryl material causes uncontrollably generating two kinds of products in these reactions: the 1) coupling of the halogenated aryl molecule of Xi Wanging, for example, two chlorobenzene molecules are coupled together and form the biphenyl molecule, with 2) reduction of undesirable halogenated aryl material, for example, chlorobenzene is reduced into benzene.Below provide representational reaction process, coupling product and undesirable reduzate of hope wherein is shown simultaneously, X represents halogen, and Y represents one or more substituting groups.
In principle, the metal catalyst of load such as Pd (C) and Rh (C) can be used for the polyhenylene by corresponding phenyl-dihalide preparation replacement.In order to make the progressively synthetic abundant high molecular weight polymers with useful mechanical property that generates, the coupling efficiency of reaction must be more a lot of greatly than the reduction of halogen sense substituent.Otherwise the polymer chain that is reflected at growth becomes sufficiently long so that product just is terminated (being reduced) before having useful performance.
For example, for Pd (C) or the catalytic technology of Rh (C), the highest coupling efficiency of report is 93%.Therefore, in this reaction, there is single halogenated aryl material of 7% to be reduced fully.This coupling degree between the dihalo aryl molecule will be equivalent to mean polymerisation degree (Dp) and have only 10-20.But, only at Dp greater than 50, be preferably greater than at 100 o'clock, polyhenylene just can obtain best performance.Therefore, according to the result of bibliographical information, heterogeneous metal catalyst appears to be not enough to prepare the polyhenylene of high-molecular weight replacement.
Therefore, need a kind of new, effectively, environmental sound, cost effective method prepares the polyhenylene of replacement.
Summary of the invention
The present invention relates to prepare the method for the polyhenylene of high-molecular weight replacement with heterogeneous metal supported catalyst.
In one embodiment, described method comprise make dihalo aryl or polyhalogenated aryl material under chosen temperature and the pressure, in the presence of the transition-metal catalyst of load, comprising in the reaction mixture of solvent and reacting, with between an aromatic substance, formerly halogen tie point place forms C-C, thereby form the polyhenylene polymkeric substance.
Method of the present invention can be used the phase-transfer catalyst that does not contain the acid proton that makes reaction terminating.
In addition, method of the present invention can be used side group, as aryl substituent, so that the polyhenylene chain of the replacement of growing up has solvability, polyreaction is proceeded to produce relative high-molecular weight degree.
Detailed Description Of The Invention
The present invention relates to prepare the method for the polyhenylene of high-molecular weight replacement with the transition-metal catalyst of load.
Provide the implication of following term and wording below:
Term used herein " polyhenylene that replaces " is meant, comprises the solubilizing group of penylene skeleton and quantity sufficient so that polymkeric substance dissolves in the polymkeric substance in the appropriate solvent.Term polyhenylene more generally should be believed to comprise the polyhenylene of replacement.
" solubilizing group " is meant when being connected on the described polymkeric substance as side chain and will makes polymkeric substance dissolve in the functional group in the appropriate solvent system.
" heterogeneous catalyst " is to be present in catalyzer in the homophase not with reaction medium.
" metal catalyst of load " comprises the metal that is suitable for catalyzed reaction that is attached on the inert solid matrix surface.
" halogenated aryl material " comprises one or more halogen atoms that are covalently bound on the aryl rings.Single halogenated aryl is meant an aromatic substance of the halogen atom with a connection, the dihalo aryl is meant an aromatic substance of the halogen atom with two connections, and polyhalogenated aryl is meant to have two or more an aromatic substance with the halogen atom of any arrangement mode connection.
The halogen atom of halogenated aryl material can be a fluorine, bromine, iodine, or preferred chlorine.The tie point of halogen is the reactive site that is used for transition metal-catalyzed aryl coupling in the polymerization process of the present invention.Therefore, dihalo an aromatic substance is for example, to be used to form the monomer of polyhenylene based polyalcohol.The monomeric halogen atom of dihalo aryl type can connect with a contraposition or a position each other, but cannot connect at the ortho position.For the polyhalogenated aryl material, halogen atom can be connected on aromatics (aryl) ring with any arrangement mode.In order to finish polymerization, do not need all halogens of polyhalogenated aryl material all to react.
" phase-transfer catalyst " (PTC) is meant that promotion is at the interface or the molecular species of the reaction of alternate generation.Under the situation of the metal-catalyzed polymerization of load, PTC works on the interface of solid catalyst and liquid phase reaction medium.
Disclosed here polymerization process of the present invention can comprise or not comprise phase-transfer catalyst (PTC).When using PTC, preferred use does not comprise the PTC of acid proton, because this kind of proton termination reaction unfriendly.Preferred PTC includes but are not limited to, ether, as polyoxyethylene glycol, glyme, polyglycol, crown ether, etc.; Quaternary ammonium salt such as benzyl trimethyl ammonium halide, benzyl triethyl ammonium ammonium halide, benzyl tripropyl ammonium halide, benzyl tributyl ammonium halide, tetramethyl-ammonium halide, tetraethyl-ammonium halide, the tetrapropyl ammonium halide, tetrabutyl ammonium halide, triethyl butyl ammonium halide, tributyl ethyl ammonium halide, trimethylammonium hexadecyl ammonium halide, four hexyl ammonium halides, the benzyl dimethyl alkyl ammonium halide, cetyl trimethyl halogeno-amine, dimethyl diallyl ammonium halide, cetyl pyridinium halogenide, the lauryl pyridinium halide, etc.; salt, as ethyl triphenyl halogenation , butyl triphenyl halogenation , methyl triphenyl halogenation , tetrabutyl halogenation , tetraphenyl halogenation , benzyl triphenyl halogenation , etc.; And other well known to a person skilled in the art phase transfer reagent, if they not disturbance reponse (as, they do not have the acid proton that can cause reaction terminating).
The proper metal catalyzer comprises, but is not limited to Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, and other transition-metal catalysts well known to those skilled in the art.Preferably, catalyst concn is between 0.01 mole of %-100 mole %.Catalyst concn be connected to the aryl monomeric unit on halogen atom quantity or the mole relevant.Thus, the catalyzer of 100 moles of % is meant stoichiometric catalyst atoms with respect to reactive halogen atom.Using reductive agent is to be used for regenerated catalyst, thereby makes the catalyzer that can use low concentration in reaction.
Possible support of the catalyst includes but are not limited to, carbon, silicon-dioxide, silica gel, polymer support, hydrated metal oxide, crystal titanate, ceramic monolith, aluminum oxide, silica-alumina, molecular sieve, and other carriers well known to those skilled in the art.
Suitable reductive agent includes but are not limited to, formate, hydrogen, Zn, Mg, Mn and other proper metal, and other reductive agents well known to those skilled in the art.In addition, also can use other method of reducing, as electrochemical reduction.
The preparation method of replacement polyhenylene of the present invention can comprise or not comprise to the reaction in add alkali.When using alkali, suitable alkali includes but are not limited to, pyridine, and hydroxide salt, tertiary amine, hydride salt, carbonate, and well known to those skilled in the art other do not form the alkali of acid conjugate acid basically.The concentration that increases alkali will increase speed of reaction up to the highest, and this depends on the concentration of catalyzer and matrix.
Coupled reaction is carried out in solution or suspension in the reactor that stirs, and temperature is preferably about 0 ℃-Yue 250 ℃, and more preferably from about 25 ℃-Yue 200 ℃, most preferably from about 60 ℃-Yue 150 ℃.
Pressure is not crucial concerning the method for invention; Therefore, can use and be higher than normal atmosphere or be lower than normal atmosphere and normal atmosphere.When using gas as reductive agent, pressure may influence the concentration of reductive agent, like this, may wish to use the mixture of rare gas element and reducing gas.
Reaction times is not very crucial, because many reactions just were through with less than 2 hours.The existence of temperature of reaction, alkali will influence the reaction times, and usually, under the alkali concn condition of higher temperature and increase, reaction is very fast.Because reaction is irreversible basically, so the time does not have maximum value.
Stir speed (S.S.) is very important, and this is because it must be high fully with the supported catalyst that suspended effectively.Absolute stir speed (S.S.) will depend on reactor, not react the not too effectively top speed that becomes but do not exist will make when speed surpasses a certain value.
Reaction solvent should be selected to such an extent that make resulting polymers dissolve in reaction medium.Appropriate solvent comprises polar aprotic solvent, as N,N-DIMETHYLACETAMIDE (DMAc), and dimethyl formamide, N-Methyl pyrrolidone (NMP), methyl-sulphoxide, tetramethylene sulfone, etc.; Aromatic solvent such as toluene, benzene, dimethylbenzene etc.; Aliphatic hydrocarbon comprises pentane, hexane, dodecane etc.; Saturated aliphatics and cyclic aliphatic ether, as ether, diglyme, tetrahydrofuran (THF) etc.; Aromatic oxide, as phenyl ether, etc.; Water; The homogeneous solvent mixture; With heterogeneous solvent mixture, comprise suspension, emulsion, miniemulsion, and microemulsion, wherein said nonhomogeneous system can be stable by well known to a person skilled in the art suitable tensio-active agent, needs only not disturbance reponse system (that is, tensio-active agent is not tart or can not makes described catalyst deactivation) of described tensio-active agent.Therefore, the solvent system that can be used for preparing the polyhenylene of replacement according to the present invention can be monophasic, for example, and the NMP-aqueous systems; Or biphase, for example, phenylate/aqueous systems.
The method according to this invention depends on the polyhenylene polymeric chain of growing up and remains in the solution to reach required high molecular.In this, there are many methods to can be used for implementing the present invention.At many United States Patent (USP)s, for example, United States Patent (USP) 5,227 discloses use solubilizing group (aryl substituent) in 457,5,646,231 and 5,721,335 and has dissolved the polyhenylene polymer chain of growing up, and these disclosures all are hereby incorporated by.
The present invention is used to form soluble polyhenylene polymkeric substance, and it comprises the solubilising side group that is connected on the polyhenylene polymer backbone.As disclosed in the above referenced patent, known arrangement that a variety of solubilizing groups are arranged and type can form a large amount of possible monomers of polymeric of the present invention that are used for.-kind more than dihalo aryl or polyhalogenated aryl material can be included in the described polymerization, thereby form multipolymer with two or more repeating units.All dihalo aryl and polyhalogenated aryl monomeric substance also not all need to comprise solubilizing group.For example, can make dihalo aryl monomer with solubilising side group, as 2,5-dichlorobenzene ketone and the second dihalo aryl monomer that does not have solubilizing group, as 1, the copolymerization of 3-dichlorobenzene.Have big that the molar fraction of the material of solubilizing group must be enough, before reaching the polymerization degree of hope, from reaction medium, be precipitated out to prevent polymkeric substance.
Can introduce the inconsistent solvability aryl substituent of reaction system of some and prior art with the method according to this invention, make its outstanding side on described polymer backbone.For example, the polyhenylene with the solubilizing group that comprises ehter bond can prepare with the method disclosed in the present astoundingly.The general example of this polymkeric substance is as follows, and wherein R is an alkyl, aryl, alkaryl, aralkyl, alkyl or aryl acid amides, aryl ketones, alkoxyl group, polyoxyalkylene, polyhenylene ether, polyphenylene sulfide, polyphenylene ethylene, polyvinyl chloride, polyalkyl methacrylate, polyacrylonitrile, poly-alkyl vinyl ether, polyvinyl alcohol, polyvinyl acetate (PVA), perfluoroalkyl, perfluoro alkoxy, polyester, polymeric amide, polyimide, Polyfluoroalkyl (polyfluoroalkyl), polyfluoro aryl, polyfluoro alkoxyl group, sulphonamide, aryl ester, alkyl ester, sulphonate, alkyl sulfonate esters, aryl sulfone.
Be water-proof and can in protonic solvent, carry out again in addition according to polymerization process provided by the invention.For protonic solvent, as water or alcohol, can use ionizable side group, make the polymer molecule of growing up have solvability as pyridyl or sulfonic group.
In addition, because have higher temperature of reaction, so other monomer also can be by method polymerization of the present invention.For example, some will dissolve under higher temperature at insoluble monomer under the temperature of reaction of prior art, and can use the method polymerization of the metal catalyst of load.
The method of the metal supported catalyst that use practice according to the present invention provides can produce lot of advantages, comprising:
(1) saves solid zinc reductive agent.In method disclosed by the invention, can use dissolved reductive agent (as, formate or preferred hydrogen), so just eliminated liquid-solid interface, make the reaction more may command that becomes.Save expensive zinc powder and reduced cost, and no longer need activation step;
(2) save the carcinogenic nickel of use.
(3) save use TPP or other solvability part, significantly reduced the material cost of technology;
(4) the metal catalyst reusable edible of load, this makes the amount of technology cost and generation refuse that whole the reduction be arranged.With
(5) react not only anti-air but also water-fast, thereby reduced the manufacturing cost and the Operating Complexity of technology.
Embodiment
Will be better understood in general introduction of the present invention and describe part described these and other feature and advantage of the present invention in detail by reference following examples.
Embodiment 1
In 1 liter of flask, with 30 gram (120 mmoles) 2, Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 33.75 gram (1350 mmole) NaOH, 7.0 gram polyoxyethylene glycol and 1.6 grams 10%: toluene (1: 1 v/v) and 250 milliliters of H
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 2
In 1 liter of flask, with 30 gram (120 mmoles) 2, Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 33.75 gram (1350 mmole) NaOH, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) and 250 milliliters of H
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 3
In 500 ml flasks, with 30 gram (120 mmoles) 2,5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 174.5 gram (1350 mmole) N, the Pd/C and 250 milliliters of NMP of (w/w) of N-diisopropylethylamine, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 4
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 136.6 gram (1350 mmole) triethylamines, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 5
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 136.6 gram (1350 mmole) triethylamines, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10% mixes with 250 milliliters of methyl-phenoxides.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 6
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 7
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, speed with 1 ml/min adds the solution that 5.33 gram (141 mmole) sodium borohydrides form in 180 milliliters of NMP, reinforced lasting other 3 hours, subsequently solution is filtered, be poured into the acetone (acetone of 4: 1 v/v ratios: reaction mixture), resulting polymers is condensed by vigorous stirring.By the filtering separation product.
Embodiment 8
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 136.6 gram (1350 mmole) triethylamines, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10% mixes with 250 milliliters of NMP.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 9
In 1 liter of flask, with 30 gram (120 mmoles) 2, Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 33.75 gram (1350 mmole) NaOH, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) and 250 milliliters of H
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, add 9.60 gram (141 mmole) sodium formiates at 180 milliliters of H with the speed of 1 ml/min
2The solution that forms among the O, reinforced lasting other 3 hours, subsequently solution is filtered, be poured into the acetone (acetone of 4: 1 v/v ratios: reaction mixture), resulting polymers is condensed by vigorous stirring.By the filtering separation product.
Embodiment 10
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 136.6 gram (1350 mmole) triethylamines, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10% mixes with 250 milliliters of NMP.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, add 9.60 gram (141 mmole) sodium formiates at 180 milliliters of H with the speed of 1 ml/min
2The solution that forms among the O, reinforced lasting other 3 hours, subsequently solution is filtered, be poured into the acetone (acetone of 4: 1 v/v ratios: reaction mixture), resulting polymers is condensed by vigorous stirring.By the filtering separation product.
Embodiment 11
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 136.6 gram (1350 mmole) triethylamines and 1.6 grams 10% mixes with 250 milliliters of NMP.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 12
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes and 1.6 grams 10% mixes with 250 milliliters of pyridines.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 13
In 500 ml flasks, with 30 gram (120 mmoles) 2, the Pd/C of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10% mixes with 250 milliliters of pyridines.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 14
In 1 liter of flask, with 30 gram (120 mmoles) 2, Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 186.6 gram (1350 mmole) salt of wormwood, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) and 250 milliliters of H
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, add 9.60 gram (141 mmole) sodium formiates at 180 milliliters of H with the speed of 1 ml/min
2The solution that forms among the O, reinforced lasting other 3 hours, subsequently solution is filtered, be poured into the acetone (acetone of 4: 1 v/v ratios: reaction mixture), resulting polymers is condensed by vigorous stirring.By the filtering separation product.
Embodiment 15
In 1 liter of flask, with 30 gram (120 mmoles) 2, Pd/C and 250 milliliters of methyl-phenoxides and 250 milliliters of H of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 186.6 gram (1350 mmole) salt of wormwood, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, add 9.60 gram (141 mmole) sodium formiates at 180 milliliters of H with the speed of 1 ml/min
2The solution that forms among the O, reinforced lasting other 3 hours, subsequently solution is filtered, be poured into the acetone (acetone of 4: 1 v/v ratios: reaction mixture), resulting polymers is condensed by vigorous stirring.By the filtering separation product.
Embodiment 16
In 1 liter of flask, with 30 gram (120 mmoles) 2, Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 186.6 gram (1350 mmole) salt of wormwood, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) and 250 milliliters of H
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, add 6.5 gram (141 mmole) ethanol at 180 milliliters of H with the speed of 1 ml/min
2The solution that forms among the O, reinforced lasting other 3 hours.Then solution is filtered, in acetone, condense and isolate polymkeric substance.
Embodiment 17
In 1 liter of flask, with 30 gram (120 mmoles) 2, Pd/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 186.6 gram (1350 mmole) salt of wormwood, 2.0 gram cetyl trimethylammonium bromides and 1.6 grams 10%: toluene (1: 1 v/v) and 250 milliliters of H
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, add 8.47 gram (141 mmole) 2-propyl alcohol at 180 milliliters of H with the speed of 1 ml/min
2The solution that forms among the O, reinforced lasting other 3 hours.Then solution is filtered, in acetone, condense and isolate polymkeric substance.
Embodiment 18
In 1 liter of flask, with 28.7 gram (120 mmoles) 2, Pd/C and 250 milliliters of NMP of (w/w) of 5-dichloro diphenyl ether, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 33.75 gram (1350 mmole) NaOH, 7.0 gram polyoxyethylene glycol and 1.6 grams 10%: toluene (1: 1 v/v) and 250 milliliters of H
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
Embodiment 19
In 1 liter of flask, with 30 gram (120 mmoles) 2, Rh/C and 250 milliliters of NMP of (w/w) of 5-dichlorobenzene ketone, 3.09 gram (21 mmole) Meta Dichlorobenzenes, 33.75 gram (1350 mmole) NaOH, 7.0 gram polyoxyethylene glycol and 1.55 grams 10%: toluene (1: 1 v/v) and 250 milliliters of H
2O mixes.At N
2Protection will be reacted vigorous stirring 20 minutes with overhead stirrer down under 100 ℃.After 20 minutes, introduce stable H
2Stream.Reaction was continued other 3 hours, and subsequent filtration solution is poured into acetone (4: 1 v/v ratio acetone: reaction mixture), by vigorous stirring resulting polymers is condensed.By the filtering separation product.
More than to the polyhenylene of exemplary replacement with to generate the description that the embodiment of the method for this replacement polyhenylene carries out be to illustrate of the present invention.But, will be conspicuous owing to change to those skilled in the art, the present invention not Plan Bureau is limited to above-mentioned specific embodiment.Scope of the present invention defines in following claim.
Claims (55)
1. method for preparing the polyhenylene polymkeric substance of replacement, it comprises:
Make dihalo aryl or polyhalogenated aryl material under chosen temperature and the pressure, in the presence of the transition-metal catalyst of load, comprising in the reaction mixture of solvent and reacting, with between an aromatic substance, formerly halogen tie point place forms C-C, thereby form polyhenylene polymkeric substance or multipolymer.
2. the method for claim 1 further comprises dihalo aryl or polyhalogenated aryl material are reacted to carry out catalyst regeneration in the presence of reductive agent.
3. the method for claim 2, wherein said reductive agent is selected from formate, hydrogen, Zn, the group that Mg and Mn form.
4. the process of claim 1 wherein to react and pass through electrochemical reducting reaction.
5. the process of claim 1 wherein that the transition metal that comprises loading transition metallic catalyst is selected from Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, and Cu.
6. the process of claim 1 wherein that described support of the catalyst comprises carbon.
7. the process of claim 1 wherein that described support of the catalyst comprises silicon-dioxide.
8. the process of claim 1 wherein that described support of the catalyst comprises polymer materials.
9. the process of claim 1 wherein that catalyst concn is between 0.01 mole of %-100 mole %.
10. the process of claim 1 wherein that catalyst concn is between 0.1 mole of %-75 mole %.
11. the process of claim 1 wherein that catalyst concn is between 0.25 mole of %-50 mole %.
12. the process of claim 1 wherein that catalyst concn is between 0.5 mole of %-25 mole %.
13. the process of claim 1 wherein that catalyst concn is between 0.75 mole of %-10 mole %.
14. the process of claim 1 wherein that catalyst concn is between 1 mole of %-5 mole %.
15. the process of claim 1 wherein that the polyhenylene polymkeric substance of growing up remains in the solution by the solubilising side group on the polyhenylene polymer backbone.
16. the process of claim 1 wherein and carry out under the existence that is reflected at phase-transfer catalyst.
17. the method for claim 16, wherein said phase-transfer catalyst is a quaternary ammonium salt.
18. the method for claim 16, wherein said phase-transfer catalyst are salt.
19. the method for claim 16, wherein said phase-transfer catalyst does not comprise acid proton.
20. the process of claim 1 wherein that described reaction mixture comprises alkali.
21. the method for claim 20, wherein said alkali is pyridine.
22. the method for claim 20, wherein said alkali is hydroxide salt.
23. the method for claim 20, wherein said alkali is tertiary amine.
24. the method for claim 20, wherein said alkali is hydride salt.
25. the method for claim 20, wherein said alkali is carbonate.
26. the process of claim 1 wherein that temperature of reaction is maintained at about between 0 ℃-Yue 250 ℃.
27. the process of claim 1 wherein that temperature of reaction is maintained at about between 25 ℃-Yue 200 ℃.
28. the process of claim 1 wherein that temperature of reaction is maintained at about between 60 ℃-Yue 150 ℃.
29. the process of claim 1 wherein that reaction pressure is a normal atmosphere.
30. the process of claim 1 wherein that reaction pressure is lower than normal atmosphere.
31. the process of claim 1 wherein that reaction pressure is higher than normal atmosphere.
32. the process of claim 1 wherein to react and undertaken by solution polymerization.
33. the method for claim 32, wherein reaction solvent is a polar aprotic solvent.
34. the method for claim 32, wherein reaction solvent is an aromatic solvent.
35. the method for claim 32, wherein reaction solvent is an aliphatic hydrocarbon.
36. the method for claim 32, wherein reaction solvent is saturated aliphatics or cyclic aliphatic ether.
37. the method for claim 32, wherein reaction solvent is an aromatic oxide.
38. the method for claim 32, wherein reaction solvent is a water.
39. the method for claim 32, wherein reaction solvent is the homogeneous mixture of different solvents.
40. the method for claim 32, wherein reaction mixture comprises heterogeneous liquid mixture.
41. the method for claim 40, wherein reaction mixture is an emulsion.
42. the method for claim 40, wherein reaction mixture is a miniemulsion.
43. the method for claim 40, wherein reaction mixture is a microemulsion.
44. the method for claim 40, wherein reaction mixture is a suspension.
45. the method for claim 40, wherein reaction mixture comprises tensio-active agent.
46. the method for claim 45, wherein said tensio-active agent does not comprise acid proton.
47. the process of claim 1 wherein that described phase-transfer catalyst is ether or polyethers.
48. the process of claim 1 wherein that the polymerization degree of the polyhenylene polymkeric substance that forms is greater than about 20.
49. the process of claim 1 wherein that the polymerization degree of the polyhenylene polymkeric substance that forms is greater than about 40.
50. the process of claim 1 wherein that the polymerization degree of the polyhenylene polymkeric substance that forms is greater than about 60.
51. the process of claim 1 wherein that the polymerization degree of the polyhenylene polymkeric substance that forms is greater than about 80.
52. the process of claim 1 wherein that the polymerization degree of the polyhenylene polymkeric substance that forms is greater than about 100.
53. the process of claim 1 wherein that the polymerization degree of the polyhenylene polymkeric substance that forms is greater than about 120.
54. the process of claim 1 wherein that the polyhenylene polymkeric substance that forms is a homopolymer.
55. the process of claim 1 wherein that the polyhenylene polymkeric substance that forms is a multipolymer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53992704P | 2004-01-28 | 2004-01-28 | |
| US60/539,927 | 2004-01-28 | ||
| US11/045,416 | 2005-01-27 |
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