CN1239453C - Polyether ketone kind rigid largering monomer, polymer and synthesis method - Google Patents
Polyether ketone kind rigid largering monomer, polymer and synthesis method Download PDFInfo
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- CN1239453C CN1239453C CN 200310116016 CN200310116016A CN1239453C CN 1239453 C CN1239453 C CN 1239453C CN 200310116016 CN200310116016 CN 200310116016 CN 200310116016 A CN200310116016 A CN 200310116016A CN 1239453 C CN1239453 C CN 1239453C
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Abstract
The present invention belongs to a high molecular material field, more particularly relates to a rigid macrocyclic monomer, a dioolymer and a polymer which comprise biphenyl structures and belong to a polyaryletherketone class, and to a synthetic method for the rigid macrocyclic monomer and the polymer. Firstly, the present invention designs and synthetizes a kind of novel hydroquinone comprising chlorophenyl. The hydroquinone is used as a monomer to react with 4, 4'-difluorodiphenyl ketone to synthetize a fluorine terminated linear trimer. Then the trimer react (chlorophenyl hydroquinone, and bisphenol-A or bi-2-naphthol are used as raw materials) with bisphenol. Under the katalysis of anhydrous potassium carbonate, DMF is used as a solvent, and improved pseudo high dilution technique is used to synthetize a great variety of cyclic oligomers comprising one or multiple of chlorophenyl. Then the obtained cyclic oligomers are coupled under the catalysis condition of triphenylphosphine, zinc powder and nickelous bromide, and cyclic polymer is obtained. The present invention designs and prepares a series of rigid macrocyclic dioolymers and polymers which have high stability and stable nanometer scale cavities and belong to a polyaryletherketone class.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the synthetic method of a kind of poly aryl ether ketone rigid macrocyclic monomer, dipolymer and polymer of biphenyl contenting structure and rigid macrocyclic monomer, polymkeric substance.
Background technology
Design and synthetic research about polyaryletherketone and polyarylsulphone rigid macrocyclic molecule, be to solve special engineering plastics resin such as polyaryletherketone for the ring-opening polymerization by such macrocycle molecule at first because of high melt viscosity, when forming matrix material, have problem such as very big processing difficulties and propose 1.From the eighties in last century till now, the synthetic and ring-opening polymerization of poly aryl ether ketone macrocycle molecule has obtained going deep into extensive studies, especially in fields 2 such as novel poly aryl ether ketone special engineering plastics research and development and special engineering plastics recyclings.During superincumbent research was used, the poly aryl ether ketone macrocycle molecule mainly was that the raw material as ring-opening polymerization uses, and did not have enough knowledge for the researching value people of macrocycle molecule itself.But, no matter be that design and synthetic all tools with macromolecular material of stabilized nanoscale size and certain light, electricity, magnetic property have very important significance in the research of advanced subject such as molecule assembling or nano-machine along with the rise of nanosecond science and technology.Poly aryl ether ketone rigid macrocyclic molecule has advantages such as high stability, stabilized nano yardstick hole and hole controlled amount and is regarded as the nano structural material that a class gets a good eye prospect because of it.Wherein, how to make this class macrocycle molecule ordered arrangement and then realize that certain functionalization becomes present research focus 3.
Summary of the invention
First purpose of purpose of the present invention provides a kind of Resorcinol that contains the chloro phenyl;
It is a kind of by containing chloro phenyl Resorcinol and 4, the end capped linear tripolymer of 4 '-difluorodiphenyl reactive ketone synthetic fluorine that second purpose of the present invention provides;
The 3rd purpose of the present invention provides a kind of poly aryl ether ketone rigid macrocyclic oligopolymer that contains the chloro phenyl and preparation method thereof;
The 4th purpose of the present invention provides a kind of dimer and polymer and dimer and polymeric preparation method by the poly aryl ether ketone rigid macrocyclic oligopolymer preparation that contains the chloro phenyl.
The present invention at first designs and synthesizes out a kind of novel Resorcinol that contains the chloro phenyl, is monomer and 4 with it, and 4 '-difluorodiphenyl reactive ketone synthesizes the end capped linear tripolymer of fluorine; React with bis-phenol again, thereby on macrocycle molecule, introduced this active group of chlorophenyl, synthesize the big ring of the poly aryl ether ketone that contains one and two chlorophenyl, made the dipolymer and the polymer of the poly aryl ether ketone rigid macrocyclic oligopolymer of biphenyl contenting structure at last by the nickel catalyzed coupling reaction of chlorobenzene.
The Resorcinol structural formula that contains the chloro phenyl of the present invention's design is:
The synthetic method of the designed Resorcinol that contains the chloro phenyl is as follows among the present invention: the mol ratio of reactant is: (p-Chlorobenzoic acid amide: Sodium Nitrite: para benzoquinone: hydrogenchloride=1: 1: 1.01-1.03: 3-6; The mole number of used sodium bicarbonate is the mole number that the mole number of hydrogenchloride deducts p-Chlorobenzoic acid amide).At first, one mole p-Chlorobenzoic acid amide is dissolved in the solution that is prepared by 340-510 milliliter concentrated hydrochloric acid and 500-1000 ml distilled water, place to 5 ℃ of ice-water baths above freezing at subzero 10 ℃ and to separate out amine salt in 10-30 minute, maintain the temperature under subzero 10 ℃ of-5 ℃ of conditions, splash into the distilled water solution of one mole of Sodium Nitrite 40-60%, drip the back and continue to stir 0.25-1 hour under ice-water bath, obtain diazonium salt solution, the gained diazonium salt solution maintains the temperature at about 0 ℃; The para benzoquinone that in another beaker, adds 336 grams-504 gram sodium bicarbonate and 1.01-1.03 mole, add the 2000-4000 ml distilled water, adding a certain amount of ice cube again makes system temperature drop to 0-15 ℃, to make diazonium salt solution all splashes into, and constantly add ice cube maintenance system temperature at 0-15 ℃, after dripping off, after continuing to be reacted to room temperature, react again after 2-4 hour and make the chlorophenyl para benzoquinone; With the chlorophenyl para benzoquinone 70-90 ℃ of drying in baking oven that makes, productive rate 90-98%.
Preparation contains in the reaction of chloro phenyl Resorcinol, and the mol ratio of chlorophenyl para benzoquinone and zinc powder is 1: 1-4, hydrogenchloride (85 milliliters of concentrated hydrochloric acids contain 1 mole of hydrogenchloride) is 1.5-3 with the mol ratio of zinc powder: 1.In the three-necked bottle of a logical nitrogen protection, add ethanol; the zinc powder of 1 mole of chlorophenyl para benzoquinone and 1-4 mole (making that the volumetric molar concentration that replaces para benzoquinone is 0.3mol/L-2mol/L); be heated to backflow under stirring; begin concentrated hydrochloric acid is splashed into; after dripping off; keep refluxing and continue to react 2-6 hour; stop heating; under nitrogen protection, place room temperature; remove by filter zinc powder with common B and qualitative filter paper, under water bath condition, ethanol is removed in underpressure distillation with filtrate; after the gained pale solid drying; use the toluene recrystallization, get white crystal and be the Resorcinol that contains the chloro phenyl, productive rate is 80-90%.
The structural formula of the poly aryl ether ketone rigid macrocyclic oligopolymer that contains the chloro phenyl of the present invention's design is as follows, mainly is the chlorophenyl of having introduced greater activity on poly aryl ether ketone rigid macrocyclic molecule:
Trans (IV)
Formula (I) is for containing bisphenol-A and the macrocyclic oligomer thing that contains chloro phenyl Resorcinol structure, formula (II) is for containing binaphthol and the macrocyclic oligomer thing that contains chloro phenyl Resorcinol structure, formula (III) and (IV) for containing the macrocyclic oligomer thing of chlorophenyl Resorcinol structure has cis and trans two kinds of structures.The big ring monomer of said structure formula can have two kinds of synthetic methods: (1) is earlier by containing chloro phenyl Resorcinol and excessive 4,4 '-difluorodiphenyl reactive ketone makes the end capped linear tripolymer that contains the chloro phenyl of fluorine, again by equimolar should linearity tripolymer and bisphenol-A or binaphthol or contain chloro phenyl Resorcinol, utilize improved pseudo-high dilution technique reaction to obtain containing chloro phenyl poly aryl ether ketone rigid macrocyclic product.(2) earlier by bisphenol-A monomer or binaphthol or contain chloro phenyl Resorcinol, with excessive 4,4 '-difluorodiphenyl reactive ketone makes the end capped tripolymer of fluorine, utilizes improved pseudo-high dilution technique reaction to obtain containing chloro phenyl poly aryl ether ketone rigid macrocyclic product by equimolar this tripolymer and the Resorcinol that contains the chloro phenyl again.So-called improved pseudo-high dilution technique is meant reactant solution is added drop-wise in the big excessive solvent system with extremely slow speed and goes, thereby causes false high rare condition of reaction system moment to obtain the macrocyclic oligomer thing 4 of high yield.
Specific embodiment comprises: at first be the trimerical preparation of the end capped linearity of fluorine, wherein contain chloro phenyl Resorcinol monomer and 4, the mol ratio of 4 '-difluoro benzophenone, catalyzer Anhydrous potassium carbonate is 1: 2-20: 2-10, dissolving 4, the solvent of 4 '-difluoro benzophenone is dimethyl formamide or N,N-DIMETHYLACETAMIDE, its consumption is 4, and the 1-3 of 4 '-difluoro benzophenone quality doubly.Step is; in the three-necked bottle of a logical nitrogen protection; add excessive 4; 4 '-difluoro benzophenone; add dimethyl formamide or N,N-DIMETHYLACETAMIDE again; make 4, the volumetric molar concentration of 4 '-difluoro benzophenone is 2mol/L-10mol/L, adds 50-100 milliliter toluene or dimethylbenzene in order to take the water that reaction generates out of.Under mechanical stirring, heat, when beginning to reflux etc. system, to contain the monomeric dimethyl formamide of chloro phenyl Resorcinol or dimethylacetamide solution (mass concentration 50-80%) splashes into, drip the back and continue reaction 2-8 hour, reaction finishes, it is excessive 4 that underpressure distillation is removed, and 4 '-difluoro benzophenone obtains the tripolymer product;
Its structural formula is as follows:
Synthesizing of ring, the mol ratio of tripolymer and biphenol monomer and Anhydrous potassium carbonate is in the reaction: 1: 1: 2-10.The tripolymer and the biphenol monomer (bisphenol-A that wait amount of substance of reaction will be participated in, binaphthol or chlorophenyl Resorcinol) be made into the solution that concentration is 0.01-0.06mol/L (solvent is dimethyl formamide or N,N-DIMETHYLACETAMIDE), in reaction vessel, add solubilizing reaction thing solvent for use 4-6 solvent doubly again, toluene or dimethylbenzene with the 50-100 milliliter, to be dissolved in the tripolymer of dimethyl formamide or N,N-DIMETHYLACETAMIDE and biphenol monomer solution after beginning to reflux is added drop-wise in the reaction system with the speed of 0.5-1ml/min, keep under toluene or the refluxing xylene band water condition, dropwise the back and continue reaction 4-8 hour, fritted sand funnel with G3 after reaction finishes removes by filter potassium carbonate powder, mother liquor is removed the solvent of 90-95% with the water pump underpressure distillation, surplus solution is poured in the 1000-4000 ml distilled water, add 40-200 milliliter concentrated hydrochloric acid breakdown of emulsion and obtain white flocks, filter with G3 fritted sand funnel, products therefrom distilled water boiling washing filtered while hot then, after repeating 3-5 time, products therefrom was dried 10-24 hour for 80-100 ℃ with vacuum drying oven, product after the oven dry is a stationary phase with GF254 (60 type) silica gel, methylene dichloride is a developping agent, separate to obtain the big ring product of the pure poly aryl ether ketone that contains the chloro phenyl by the isolating method of silicagel column, productive rate is 50-70%.
Its synthesis mode is as follows,
A, contain dihydroxyphenyl propane and contain the synthetic of the big ring of chloro phenyl Resorcinol structure:
B, contain binaphthol and contain the synthetic of the big ring of chloro phenyl Resorcinol structure:
C, contain the synthetic of two big rings of chlorophenyl cis-trans-isomer:
The dimer of the poly aryl ether ketone macrocycle molecule of the biphenyl contenting structure of the present invention's design and polymeric structural formula are shown in (V), (VI), (VII):
The dimerization of the poly aryl ether ketone rigid macrocyclic oligopolymer of biphenyl contenting structure of the present invention and the synthetic method of polymer are described below: be raw material with the poly aryl ether ketone macrocyclic oligomer thing (I) that contains the chloro phenyl substituent, (II), (III) or (IV), make coupling catalyst with nickelous bromide, triphenyl phosphorus, zinc powder, with DMAC is solvent, the experience Preparation of Catalyst, feed intake, the process of coupling, aftertreatment, obtain the dimerization and the polymer of the poly aryl ether ketone rigid macrocyclic molecule of biphenyl contenting structure.Specific embodiment comprises:
To react used medicine and reaction there-necked flask; prolong; interface; equipment thorough dryings such as stirrer; to react with air is housed in the there-necked flask of induction stirring with high pure nitrogen and to catch up with only; under nitrogen protection; (with nickelous bromide in the catalyzer is reference to add the solvent N,N-DIMETHYLACETAMIDE; the volumetric molar concentration of nickelous bromide is 0.5mol/L-5mol/L in the solution) and a certain proportion of nickelous bromide; triphenyl phosphorus and zinc powder (triphenyl phosphorus: zinc powder: nickelous bromide=8-40: 3-40: 1) stir intensification; controlled temperature reacts about 45-65 ℃ and made the red-brown catalyzer in 0.5-2 hour; the poly aryl ether ketone rigid annular oligopolymer of again purifying being crossed (I) that contains the chloro phenyl substituent; (II); (III) or (IV) drop into; the contained chlorobenzene substituting group of linked reaction thing: nickelous bromide=1-25: 1, be warmed up to 80-100 ℃ of reaction reaction in 4-6 hour and finish.
The acidproof fritted sand funnel of mixing solutions with G4 filtered, and with 10-30 milliliter DMAC flushing zinc powder, mother liquid obtained after underpressure distillation boils off most of solvent discharging in distilled water, obtain white precipitate, this sedimentation and filtration, dry back are boiled, filtered with the ethanol boiling method, repeat 5-6 time, in baking oven, dry, obtain thick product.The thick product that thorough drying is crossed can obtain pure coupling product after silica gel chromatographic column separates.If what begin to feed intake usefulness is to contain the big ring of polyaryletherketone (I) of a chlorophenyl or (II), promptly obtain the dipolymer (V) encircled or (VI), contain the big ring (III) of chloro phenyl or (IV) if contain two, then obtain the polymer (VII) that encircles.
We have obtained containing the substituent poly aryl ether ketone rigid macrocyclic of one or two chlorophenyl molecule among the present invention, we can see the hole that this class macrocycle molecule has the stabilized nano size from the single crystal structure of macrocycle molecule, and we utilize chlorobenzene link coupled technology that these are contained dimer and the polymer that the coupling of the substituent rigid macrocyclic molecule of chlorophenyl obtains macrocycle molecule.
Description of drawings
Fig. 1: the soft electron impact mass spectra figure that contains chloro phenyl Resorcinol;
Fig. 2: the one dimension proton magnetic spectrum figure of biphenol monomer;
Fig. 3: by containing chloro phenyl Resorcinol and 4, the trimerical soft electron impact mass spectra figure of the end capped linearity of 4 '-difluoro benzophenone synthetic fluorine;
Fig. 4: the MALDI-TOF mass spectrum of monocycle (I);
Fig. 5: the single crystal structure figure of monocycle (I);
Fig. 6: the MALDI-TOF mass spectrum of monocycle (II);
Fig. 7: the one dimension proton magnetic spectrum figure of monocycle (II);
Fig. 8: monocycle (III) and MALDI-TOF mass spectrum (IV);
Fig. 9: the MALDI-TOF mass spectrum of dimer (V);
Figure 10: the MALDI-TOF mass spectrum of dimer (VI).
As shown in Figure 1, the theoretical molecular of biphenol monomer is 220, and test result fits like a glove with it.As shown in Figure 2, be the ownership of monomeric 9 different hydros, therefrom we can affirm that the structure of this biphenol monomer is as follows.
Following table is the ultimate analysis data of biphenol monomer of the present invention, and observed value is compared with theoretical value, and (error is only within ± 0.5%.
| Sample | Method | Carbon％ | Hydrogen％ |
| P-chlorophenyl Resorcinol | Calcd Foud | 65.32 65.24 | 4.11 3.97 |
As shown in Figure 3, the trimerical molecular weight 618 that records of this linearity conforms to theoretical molecular 618.Following table is trimerical ultimate analysis take off data, with the error of theoretical value within ± 0.5%.
| Sample | Method | Carbon％ | Hydrogen％ |
| Tripolymer | Calcd Foud | 73.97 74.02 | 3.76 3.85 |
As shown in Figure 4, the measured value of monocycle (I) molecular weight is 805, conforms to theoretical value 805; As shown in Figure 5, the measured value of the molecular weight of monocycle (II) is 863, conforms to theoretical value 863, and wherein 845 is M+Na
+Molecular weight peaks.As shown in Figure 7, the ownership that has shown monocycle (II) hydrogen.Because the complex structure of this compound, its structure determine it is by one dimension hydrogen spectrum, carbon spectrum; The analysis-by-synthesis of the relevant spectrum of two dimension hydrogen hydrogen, the relevant spectrum of carbon carbon, the relevant spectrum of hydrogen carbon obtains.
| Nuclear and numbering | Chemical shift (ppm) | Nuclear and numbering | Chemical shift (ppm) |
| H2，H6 H3，H5 H8 H10 H11 H14，H18 H15，H17 H20，H24 H21，H23 H26 H27 | 7.306 7.441 7.318 7.078 7.159 6.674 7.627 7.592 6.995 7.244 7.907 | H29，H40 H30，H39 H31，H38 H32，H37 H42 H43 H46，H50 H47，H49 H52，H56 H53，H55 | 7.899 7.432 7.341 7.341 7.916 7.268 7.025 7.664 7.774 6.905 |
As shown in Figure 8, monocycle (III) and (IV) measured value of molecular weight be 797, conform to theoretical value 797,647 is the molecular weight of the CCA of used matrix among the figure; As shown in Figure 9, the measured value of dimer (V) molecular weight is 1539, conforms to theoretical value 1539, and 1561 is M+Na among the figure
+Molecular weight; As shown in figure 10, the measured value of dimer (VI) molecular weight is M+H=1655, conforms to theoretical value 1655, and 1677 is M+Na among the figure
+Molecular weight, 1693 is M+Ka
+Molecular weight.
Embodiment
Embodiment 1:
In 1000 milliliters beaker, add 0.2 mole of p-Chlorobenzoic acid amide and 100 ml distilled waters and 50 milliliters of concentrated hydrochloric acids, heating condition is dissolving down, putting to room temperature is reduced to about 0 ℃ temperature under stirring and cryosel bath condition, 0.2 mole of Sodium Nitrite of dropping is dissolved in the solution in 75 ml distilled waters under the agitation condition, continues to stir 15 minutes.In another beaker, put into 0.2 mole of para benzoquinone, 0.4 mole gram sodium bicarbonate, 50 gram trash ice and 500 ml waters, the above-mentioned diazonium salt solution that makes under agitation splashes into, and adds trash ice frequently and keeps temperature of reaction below 15 ℃, adds the back and continues to stir and rise to room temperature and stirred 2 hours again, filter with B and qualitative filter paper, it is inferior to repeat to give a baby a bath on the third day after its birth with 1000 ml distilled waters again, dries to such an extent that chlorophenyl para benzoquinone 38.05 restrains productive rate 87%.
Embodiment 2:
In 1000 milliliters three-necked bottle, add 0.5 mole contain chloro phenyl para benzoquinone, splash into 138 milliliters of concentrated hydrochloric acids behind 86 gram zinc powders and 500 milliliter of 95% alcohol heating reflux, drip the back and continued back flow reaction 4 hours.Remove by filter zinc powder with B and qualitative filter paper, mother liquor gets pale solid with water pump pressure reducing and steaming ethanol, behind the vacuum drying, gets the Resorcinol that 84 gram white crystals contain the chloro phenyl, productive rate 80% with 500 milliliters of toluene recrystallizations.
Embodiment 3:(is to contain chloro phenyl Resorcinol and excessive 4, and 4 '-difluorodiphenyl reactive ketone is an example)
Be to connect stirring, water-taker, reflux and constant pressure funnel on 1 liter the three-necked bottle at volume; bottle is interior with 4 of 1 mole of 350 milliliters of DMF dissolving; 4 '-difluoro benzophenone adds Anhydrous potassium carbonate and 50 milliliters of toluene of 0.5 mole, stirring and refluxing band water under the protection of high pure nitrogen.In system with p.s. 1 speed splash into the DMF solution (250 milliliters) of chlorophenyl Resorcinol (0.1 mole), drip the back and continue a stirring and refluxing and made in 3 hours and react completely.The cooled and filtered desalination, boil off about 300ml DMF, in surplus solution impouring 4000ml distilled water, obtain white precipitate after adding 50ml concentrated hydrochloric acid breakdown of emulsion, be put in the pallet in baking oven 50-70 ℃ of drying behind the suction filtration 48 hours.Thick product adopts underpressure distillation to steam fluorine ketone, utilizes fat extraction device extracting 24 hours, separates out white solid be tripolymer from ethanolic soln with 300 milliliters of ethanol, and 100 ℃ of dryings of vacuum drying oven 10 hours must white products 45g (productive rate: 72%).
Embodiment 4:
0.02 mole and the 0.02 mole bisphenol-A of the end capped tripolymer of fluorine that contains the chloro phenyl is dissolved in 500 milliliters of dimethyl formamides, adds Anhydrous potassium carbonate 5.52 grams in one 3000 milliliters three-necked bottle, 2000 milliliters of dimethyl formamides, 100 milliliters of toluene.Reaction system is led to nitrogen protection; system reflux band water is after 2 hours under the electronics agitation condition, the speed of reactant solution (the trimerical dimethyl formamide solution of fluorine end-blocking that contains the chloro phenyl) 1ml/ second splashed into reaction system, after dripping off; reacted 4 hours, reaction finishes again.Fritted sand funnel with G3 removes by filter salt of wormwood, boils off most of dimethyl formamide under mother liquor decompression (10 mmhg) condition, remains 150 ml solns, be poured in 3000 ml distilled waters, add 100 milliliters of concentrated hydrochloric acid breakdowns of emulsion again, obtain flocks, filter with G3 fritted sand funnel, get thick product, use 600 ml distilled waters each again, boil heat filtering then, repeat 3 times, product after the filtration is with vacuum drying oven 100 ℃ of dryings 24 hours again, white powder.The thick product GF254 of gained, 60 type silica gel are stationary phase, methylene dichloride is a developping agent, separates big ring 8.7 grams of poly aryl ether ketone that obtain containing the chloro phenyl, productive rate 54% by filling out silicagel column certainly.Structural formula is as (I).
Embodiment 5:
By bisphenol-A and excessive 4, the Resorcinol that 0.02 mole and 0.02 mole of the tripolymer that 4 '-difluoro benzophenone makes contains the chloro phenyl repeats the operation steps of embodiment 4, finally also obtains the big ring of poly aryl ether ketone (I) 8.05 grams, productive rate 50%.
Embodiment 6:
Change the bisphenol-A among the embodiment 4 into di-how phenol (amount of substance is constant), repeat the operation steps of embodiment 4, finally can obtain the big ring of poly aryl ether ketone (II) 10.01 grams, productive rate 57%.
Embodiment 7:
Tripolymer among the embodiment 5 is changed into by di-phenol and excessive 4 how, and the tripolymer that 4 '-difluorodiphenyl reactive ketone makes repeats the operation steps of embodiment 4, finally can obtain the big ring of poly aryl ether ketone (II) 10.88 grams, productive rate 63%.
Embodiment 8:
Change the bisphenol-A among the embodiment 4 into contain the chloro phenyl Resorcinol, repeat the operation steps of embodiment 4, finally can obtain big ring of poly aryl ether ketone (III) or (IV) 7.94 grams, 49.8%.
Embodiment 9:
With volume is that 100 milliliters of three-necked bottles place thermostat water bath, connects vacuum shelf interface, reflux and peace bottle on it respectively, built-in magnetic stir bar.Add 0.45 gram triphenyl phosphorus, 0.45 gram zinc powder, 0.05 gram nickelous bromide and 30 milliliters of DMAC in the system in advance, installed powder 3.62 grams of big ring monomer (I) in the peace bottle in advance.After the system of having checked is airtight, make system vacuumize (vacuum tightness is the 4-10 mmhg) repeatedly, logical nitrogen several times after, with heating in water bath, wait to reach 50 ℃, in the peace bottle, be injected into 3 milliliters of saturated DMAC of logical nitrogen in order to dissolve in big ring monomer (I) and the impouring system in the lump, constant temperature was in 80 ℃ of reactions 3 hours, the cooling back removes by filter zinc powder with the acidproof fritted sand funnel of G4, thick product was separated out in discharging after decompression steamed most of DMAC in distilled water, thick product must be through vacuum drying oven 100 ℃ of oven dry 24 hours, utilize hand-stuff silicagel column to separate (used silica gel is the agent of GF25460 type silica gel) again, developping agent is methylene dichloride-tetrahydrofuran (THF) (volume ratio is 100: 3), vacuum-drying gets white products, and promptly poly aryl ether ketone rigid macrocyclic (V) 5.19 restrains productive rate 75%.
Embodiment 10:
With volume is that 100 milliliters of three-necked bottles place thermostat water bath, connects vacuum shelf interface, reflux and peace bottle on it respectively, built-in magnetic stir bar.Add 0.45 gram triphenyl phosphorus, 0.45 gram zinc powder, 0.05 gram nickelous bromide and 30 milliliters of DMAC in the system in advance, installed big ring monomer (II) powder 3.88 grams in the peace bottle in advance.After the system of having checked is airtight, make system vacuumize (vacuum tightness is the 4-10 mmhg) repeatedly, logical nitrogen several times after, with heating in water bath, wait to reach 50 ℃, in the peace bottle, be injected into 3 milliliters of saturated DMAC of logical nitrogen in order to dissolve in big ring monomer (II) and the impouring system in the lump, constant temperature was in 80 ℃ of reactions 3 hours, cooled and filtered is removed zinc powder, thick product is separated out in discharging after steaming DMAC in water, separate through silicagel column, developping agent is methylene dichloride-tetrahydrofuran (THF) (volume ratio is 100: 3), and vacuum-drying gets white products, be poly aryl ether ketone rigid macrocyclic (VI) 5.68 grams, productive rate 76.3%.
Embodiment 11:
With volume is that 100 milliliters of three-necked bottles place thermostat water bath, connects vacuum shelf interface, reflux and peace bottle on it respectively, built-in magnetic stir bar.Add 0.45 gram triphenyl phosphorus, 0.45 gram zinc powder, 0.05 gram nickelous bromide and 30 milliliters of DMAC in the system in advance, installed big ring (III) or 3.58 grams of powder (IV) in the peace bottle in advance.After the system of having checked is airtight, make that system vacuumizes repeatedly, logical nitrogen several times after, with heating in water bath, wait to reach 50 ℃, in peace bottle, be injected into 3 milliliters of saturated DMAC of logical nitrogen in order to dissolve big ring (III) or (IV) and in the impouring system in the lump, constant temperature was in 80 ℃ of reactions 3 hours, cooled and filtered is removed zinc powder, thick product is separated out in discharging after steaming DMAC in water, separate through silicagel column, developping agent is methylene dichloride-tetrahydrofuran (THF) (volume ratio is 100: 3), obtains white products after the vacuum-drying, i.e. poly aryl ether ketone rigid macrocyclic (VII).
Reference:
1.(a)Tsuchida，E.；Shouji，E.；Yamamoto，K.Macromolecules 1993，26，7144.(b)Yamanoto，K；Jikei，M.；Miyatake，K.；Katoh，J.；Nishide，H.；Tsuchida，E.Macromolecules 1994，27，4317.2
2.(a)Howard M.Colquhoun
* and David F.Lewis Macromolecules 2002，35，6875-6882.(b)Howard M.Colquhoun
* and David F.Lewis Macromolecules2003，36，3775-3778
3.Ben.T.，Chen.C.H.；Cao.H.；Wang.X.Macromol.Rapid.Commun，2002，23，196
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Claims (5)
1, a class contains the poly aryl ether ketone rigid annular oligopolymer of chloro phenyl substituent, it is characterized in that having introduced on macrocycle molecule the chlorophenyl of greater activity, and its structural formula is as (I), (II), (III) or (IV):
(I) (II)
Trans
(III) (IV)
2, a kind of described poly aryl ether ketone rigid annular oligopolymer method that contains the chloro phenyl substituent of claim 1 for preparing: first method be earlier with chlorophenyl Resorcinol and amount of substance excessive 4,4 '-difluoro benzophenone is under the Anhydrous potassium carbonate catalytic condition, dimethyl formamide is that solvent makes the end capped tripolymer of fluorine, this bisphenol-A, binaphthol or chlorophenyl Resorcinol that contains the tripolymer of chloro phenyl side group and wait amount of substance utilizes the synthetic big ring of poly aryl ether ketone that obtains containing the chloro phenyl of improved pseudo-high dilution technique then; Second method be utilize earlier bisphenol-A, binaphthol or chlorophenyl Resorcinol diphenol monomer and amount of substance excessive 4,4 '-difluoro benzophenone is under the Anhydrous potassium carbonate catalytic condition, dimethyl formamide is that solvent makes tripolymer, reacts the big ring of poly aryl ether ketone that obtains containing the chloro phenyl with the chlorophenyl Resorcinol again.
3, the poly aryl ether ketone rigid annular oligopolymer method that contains the chloro phenyl substituent as claimed in claim 2, the steps include: to contain chloro phenyl Resorcinol monomer and 4,4 '-difluoro benzophenone, the mol ratio of Anhydrous potassium carbonate is 1: 2-20: 2-10, in the three-necked bottle of a logical nitrogen protection, add excessive 4,4 '-difluoro benzophenone, add dimethyl formamide or N,N-DIMETHYLACETAMIDE again, make 4, the volumetric molar concentration of 4 '-difluoro benzophenone is 2mol/L-10mol/L, add 50-100 milliliter toluene or dimethylbenzene in order to take the water that reaction generates out of, under mechanical stirring, heat, when beginning to reflux etc. system, with mass concentration 50-80% contain the monomeric dimethyl formamide of chloro phenyl Resorcinol or dimethylacetamide solution splashes into, drip the back and continue reaction 2-8 hour, reaction finishes, it is excessive 4 that underpressure distillation is removed, and 4 '-difluoro benzophenone obtains the tripolymer product; The mol ratio of tripolymer and biphenol monomer and Anhydrous potassium carbonate is 1: 1: 2-10, in reaction vessel, add solubilizing reaction thing solvent for use 4-6 solvent doubly, toluene or dimethylbenzene with the 50-100 milliliter, after beginning to reflux, will wait the tripolymer and the bisphenol-A of amount of substance, the concentration that binaphthol or chlorophenyl Resorcinol are made into is that the solution of 0.01-0.06mol/L is added drop-wise in the reaction system with the speed of 0.5-1ml/min, keep under toluene or the refluxing xylene band water condition, dropwise the back and continue reaction 4-8 hour, reaction finishes after-filtration and removes potassium carbonate powder, mother liquor is removed the solvent of 90-95% with the water pump underpressure distillation, surplus solution is poured in the 1000-4000 ml distilled water, add 40-200 milliliter concentrated hydrochloric acid breakdown of emulsion and obtain white flocks, filter products therefrom distilled water boiling washing filtered while hot then, after repeating 3-5 time, products therefrom was dried 10-24 hour for 80-100 ℃ with vacuum drying oven, product after the oven dry separates and obtains the big ring product of the pure poly aryl ether ketone that contains the chloro phenyl, and productive rate is 50-70%.
4, a kind of dimer and polymer that obtains through coupling by the poly aryl ether ketone rigid annular oligopolymer that contains the chloro phenyl substituent, its structural formula is shown in (V), (VI), (VII):
(V)
(VI)
n≥2
(VII)
5, a kind of described poly aryl ether ketone rigid macrocyclic dipolymer of chloro phenyl substituent and method of polymer of containing of claim 4 that prepare, the steps include: drying and under nitrogen protection, in dimethylacetamide solvent, add triphenyl phosphorus, zinc powder and nickelous bromide, its mol ratio is 8-40: 3-40: 1, and make that the nickelous bromide volumetric molar concentration is 0.5mol/L-5mol/L in the solution, stir and heat up, controlled temperature makes the red-brown catalyzer 45-65 ℃ of reaction 0.5-2 hour; The poly aryl ether ketone rigid annular oligopolymer of again purifying being crossed (I) that contains the chloro phenyl substituent, (II), (III) or (IV) drop into, the contained chlorobenzene substituting group of linked reaction thing: nickelous bromide=1-25: 1, be warmed up to 80-100 ℃ of reaction reaction in 4-6 hour and finish; Mixing solutions is filtered with funnel, and with 10-30 milliliter N,N-DIMETHYLACETAMIDE flushing zinc powder, mother liquid obtained after underpressure distillation boils off most of solvent discharging in distilled water, obtain white precipitate, this sedimentation and filtration, dry back are boiled, filtered with the ethanol boiling method, repeat 5-6 time, in baking oven, dry, obtain thick product, the thick product that thorough drying is crossed can obtain pure coupling product after silica gel chromatographic column separates.
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| CN102219648A (en) * | 2011-04-27 | 2011-10-19 | 吉林大学 | (4-(1-adamantyl))phenyl hydroquinone and preparation method thereof |
| CN102304119B (en) * | 2011-06-03 | 2013-10-16 | 吉林大学 | Amino-containing circular aryl ether ketone monomer, and synthesis method and application thereof |
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