CN101519399A - Aromatic ring-shaped polyether-ketone oligomer and preparation method thereof - Google Patents
Aromatic ring-shaped polyether-ketone oligomer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an aromatic ring-shaped polyether-ketone oligomer and a preparation method thereof. Under 'pseudo-high dilution' condition, Friedel-Crafts-Karrer electrophilic reaction is utilized to open up a new route of taking carbon tetrachloride and substituted aromatic hydrocarbon monomers as basic raw materials to synthesize commercial, helicrystalline macrocylic oligomers of high-performance PEEK and PEK, namely the aromatic ring-shaped polyether-ketone oligomer with high yield. The aromatic ring-shaped oligomer can be melted and subjected to ring opening polymerization under the initiation of an anion initiator to obtain high-performance linear polyaryletherketone by using a cyclic structure and low melt viscosity peculiar to the aromatic ring-shaped oligomer. By the combination of low cost and high performance, the aromatic ring-shaped polyether-ketone oligomer and the synthetic route thereof has important application in the field of preparation of high-performance composite materials.
Description
Technical field:
The invention belongs to the presoma of high-performance polymer---aromatic ring-shaped polyether-ketone oligomer and preparation method thereof.
Background technology:
Aromatic polyether ketone (sulfone) is the high-performance polymer material of a class excellent performance, has advantages such as physical strength height, high temperature resistant, anti-solvent, is widely used in national defense industry and other high-technology field.Because the softening temperature of this base polymer is higher, particularly high melt viscosity has greatly restricted their application in fields such as little manufacturing, fibre reinforced composites.A kind of solution route is synthetic earlier corresponding aromatic ring-shaped oligopolymer, utilizes distinctive ring texture of cyclic oligomer and low melt viscosity, under initiator causes, carries out ring-opening polymerization fast and prepares polyaryletherketone (sulfone).Therefore, from 1989, General Electric Apparatus Co.(U.S.A.) has announced utilization " false high rare " technology synthetic aroma cyclic polycarbonates and has successfully carried out ring-opening polymerization that this has had since the technology of revolutionary meaning, the ring-type performed polymer of development aromatic polyether ketone (sulfone) is subjected to scientific research personnel's extensive concern, and cyclic polyether ketone (sulfone) oligopolymer of a series of novel textures obtains preparation.It is pointed out that in these work,, be mostly that the monomer that adopts structure to be beneficial to into the phenyl ring that contains an ortho position or a position replacement of ring sets out for preparation cyclic polyether ketone (sulfone) oligopolymer of high yield; In the ring-opening polymerization product, the existence of an ortho position or a position has destroyed the regularity of macromolecular chain, has reduced polymer properties.Therefore, how high productivity synthesizes the aromatic ring-shaped polyether-ketone oligomer of full aligning structure, particularly commercially obtained large-scale application, had the more excellent polyether-ether-ketone of semi-crystalline state structure, performance (PEEK), the ring prepolymer of polyetherketone (PEK) and PEKK polymkeric substance such as (PEKK), have crucial meaning in this area.Be the contraposition bond structure in traditional employed reaction monomers of the method for preparing linear polymer, make into its difficulty of circumpolar.Aromatic ring-shaped polyether-ketone for synthetic full aligning structure, people such as Gibson [Macromolecules, 1996,29 (16)] change synthetic route, earlier the bis-phenol of synthetic long-chain and two fluorine monomers to be discharging the tension force of ring, and then have syntheticly obtained that size is big, the less ring-type PEEK of tension force.Because this reaction scheme is tediously long, each step reaction all can have certain loss, and it is lower that the result causes into the ring rate.[PolymerBulletin, 1999,42] such as the Changchun Chen Tian of applied chemistry institute high post have designed the novel method that the ketoimine route synthesizes the less PEEK ring-type performed polymer of ring size, and cyclisation produce rate is lower.
On the method for synthesizing linear or ring-type polyaryletherketone, can reduce the reaction of two classes, promptly form the pyrosol nucleophilic reaction of ehter bond and the friedel-crafts cationoid reaction of formation ketonic bond.Compare with the pyrosol nucleophilic reaction, this route of cationoid reaction has low cost, and raw material sources are extensive, advantages such as reaction conditions gentleness.Gibson was at [macromolecules in 1997; 1997; 30] delivered and be entitled as " friedel-crafts acylations annulation synthesizing new macrocylc compound "; although the productive rate of cyclic products is 23%, confirmed that cationoid reaction has feasibility at synthetic aroma ring-type polyaryletherketone (sulfone) oligopolymer.Chinese patent 02123917.7,03105019.0 disclose the novel method of utilizing cationoid reaction to prepare aromatic cyclic polyketone oligomer, the phthalyl chloride or the isophthalyl chloride that are beneficial to into ring with structure are starting raw material, high productivity has prepared ring-type polyketone oligopolymer, but its ring-opening polymerization product contains the phenyl ring of an ortho position or a position replacement, causes polymer performance to descend.Therefore, raw material by cheapness sets out, utilize the friedel-crafts cationoid reaction, the aromatic ring-shaped oligopolymer of the synthetic full aligning structure of high productivity, challenging aspect theoretical, and cyclic oligomer prepares polyaryletherketone by the original position ring-opening polymerization, has in fields such as little manufacturing, fibre reinforced composites widely to use.
Summary of the invention:
The purpose of this invention is to provide a class aromatic ring-shaped polyether-ketone oligomer;
Another object of the present invention provides a kind of preparation method of aromatic ring-shaped polyether-ketone oligomer.
It is the initial action monomer that the present invention adopts tetracol phenixin, utilizes the friedel-crafts cationoid reaction, and high productivity has synthesized the cyclic oligomer of high-performance aromatic polyether ether ketone (PEEK), polyetherketone (PEK) and PEKK (PEKK).The work that contains the cyclic oligomer of full aligning structure with this area forefathers' synthetic is compared, and advantage of the present invention is: the monomer wide material sources, and with low cost, avoid using expensive two fluorine monomers; Synthesis step is simple, the cyclic oligomer of the full aligning structure of one-step synthesis; The reaction conditions gentleness is at room temperature carried out; Ring-opening polymerization has obtained commercial high-performance polyarylether ketone.
Synthetic cyclic oligomer of the present invention have a following structure:
Wherein: n=2-20;
R ' is hydrogen or methyl;
R is
Or
Wherein working as the R structure is:
-O-Ar-O-time, aromatic polyether ether ketone cyclic oligomer formed;
-O-Ar-CO-Ar-O-time, aromatic polyether ketone cyclic oligomer formed;
O-Ar-SO
2-Ar-O-time forms aromatic polyether ether ketone sulfone cyclic oligomer.
Concrete synthesis step is as follows:
(1) preparation of cyclic oligomer
Catalyzer placed have the reaction flask that the top connects the spherical condensation tube of calcium chloride tube and gas absorbing device, add solvent again to form " false high rare " environment, solvent is dithiocarbonic anhydride, Nitromethane 99Min. or oil of mirbane; In addition with tetracol phenixin and fragrant monomer wiring solution-forming, both mol ratios are 0.95-1.05:1, and wherein the add-on of solvent does not have strict the qualification, and general add-on is that solute can dissolve fully and gets final product; Fragrant monomer is 4,4 '-phenoxy group benzophenone, triphen diether, 4,4 ' (3 methyl) phenoxy group benzophenone, 4,4 '-phenoxy group sulfobenzide or 4,4 ' (3 methyl) phenoxy group sulfobenzide; The mol ratio of catalyzer and tetracol phenixin is 2.0-4.0:1, and catalyzer is aluminum chloride, iron trichloride, zinc chloride, boron fluoride; Feed exsiccant nitrogen, under the room temperature vigorous stirring, the slow average rate of solution is added drop-wise in the reaction flask of formation " false high rare " environment; After drips of solution added, continuation was stirred to make in 0.54.0 hour and is reacted completely; Add the dilute hydrochloric acid termination reaction, continue to stir 0.5-4.0 hour; After separatory gets organic phase, use distilled water wash again, to remove catalyzer; Concentrate, be added drop-wise in the methyl alcohol and precipitate, get cyclic polyether ketone oligopolymer.
(2) ring-opening polymerization of cyclic oligomer
Take by weighing initiator and cyclic oligomer, its mol ratio is: 0.01-0.05:1, initiator are biphenyl bis-phenol potassium, potassium phenylate, salt of wormwood or cesium fluoride, thorough mixing, under nitrogen atmosphere, be heated to the oligopolymer fusion, reacted 20-60 minute, obtain the linear polyaryletherketone of high-molecular weight.
The present invention adopts " false high rare " principle, use commercial cheap raw material, by Friedel-Crafts reaction, but the synthesized polymer degree of high yield is the mixture of the aromatic ring-shaped polyether-ketone oligomer of 2-20, and wherein product is based on dimer, tripolymer and the tetramer.Because oligopolymer is made up of the different macrocylc compound of the polymerization degree, so can make ring-opening polymerization carry out under relatively low temperature.This route is than pyrosol nucleophilic reaction synthetic aroma cyclic oligomer, and it is low to have a cost, advantages such as reaction conditions gentleness, and also productive rate is higher than the nucleophilic reaction route.
Embodiment is as follows:
The preparation of embodiment 1 polyetherketone cyclic oligomer
6.68g (0.05mol) aluminum trichloride (anhydrous) and 500mL dithiocarbonic anhydride placed have the 1L there-necked flask that the top is connected the spherical condensation tube of calcium chloride tube and gas absorbing device.With 3.0812g (0.02mol) tetracol phenixin and 7.3258g (0.02mol) 4,4 '-phenoxy group benzophenone is dissolved in the 100mL dithiocarbonic anhydride, under room temperature and the vigorous stirring solution slow average rate in 8 hours is added drop-wise in the there-necked flask, dropwises, continued stirring reaction 2 hours; The dilute hydrochloric acid termination reaction that adds 80mL 0.1M continues to stir 2 hours.After separatory gets organic phase, again with 100mL distillation washing 3 times, to remove catalyzer.Concentrate, be added drop-wise in the methyl alcohol and precipitate, get cyclic oligomer, product is a pale yellow powder, and productive rate is 87%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.3,1177.9,1569.8,1961.7,2354.1, correspond to the protonated molecular ion peak of dimer to six aggressiveness of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 2 polyether-ether-ketone cyclic oligomers
Reaction monomers 5.2442g (0.02mol) triphen diether is substituted 4,4 '-phenoxy group benzophenone, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a pale yellow powder, productive rate 74%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=577.4,865.5,1153.5,1441.4,1729.9,2018.1, correspond to the protonated molecular ion peak of the dimer of cyclic oligomer respectively to heptamer, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 3 polyether-ether-ketone cyclic oligomers
Reaction monomers 5.2442g (0.02mol) triphen diether is substituted 4,4 '-phenoxy group benzophenone, solvent substitutes dithiocarbonic anhydride with Nitromethane 99Min., other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a faint yellow solid, productive rate 78%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=577.6,865.4,1154.0,1441.7,1729.8,2018.0,2306.1, correspond to the protonated molecular ion peak of dimer to eight aggressiveness of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 4 methyl polyetherketone cyclic oligomers
Reaction monomers 7.8820g (0.02mol) 4,4 '-(3-methyl) phenoxy group-benzophenone is substituted 4,4 '-phenoxy group benzophenone, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 85%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=841.3,1261.7,1682.0,2101.7,2522.1,2942.1 correspond to the protonated molecular ion peak of the dimer of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree to heptamer.
The preparation of embodiment 5 polyether etherketone sulfone cyclic oligomers
With reaction monomers 8.0476g (0.02mol) 4,4 '-phenoxy group sulfobenzide substitutes 4,4 '-phenoxy group benzophenone, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow solid, productive rate 92%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=857.1,1285.7,1714.0,2141.9,2569.9,2998.1, correspond to the protonated molecular ion peak of the dimer of cyclic oligomer respectively to heptamer, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 6 methyl polyether etherketone sulfone cyclic oligomers
Reaction monomers 8.6476g (0.02mol) 4,4 '-(3-methyl) phenoxy group-sulfobenzide is substituted 4,4 '-phenoxy group benzophenone, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a faint yellow solid, productive rate 90%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=913.5,1369.1,1825.4,2282.0,2737.9, correspond to the protonated molecular ion peak of dimer to six aggressiveness of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 7 polyetherketone cyclic oligomers
With tetracol phenixin and 4,4 '-phenoxy group benzophenone mol ratio is replaced by 0.95, and promptly two monomeric consumptions are respectively 3.0812g (0.02mol) and 6.9538g (0.019mol), other feed intake and reaction conditions and treatment step with embodiment 1, get pale yellow powder, productive rate is 65%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.5,1177.8,1569.6,1961.7, correspond to the protonated molecular ion peak of the dimer of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree to pentamer.
The preparation of embodiment 8 polyetherketone cyclic oligomers
With tetracol phenixin and 4,4 '-phenoxy group benzophenone mol ratio is replaced by 1.05, and promptly two monomeric consumptions are respectively 3.0812g (0.02mol) and 7.6817g (0.021mol), other feed intake and reaction conditions and treatment step with embodiment 1, get pale yellow powder, productive rate is 52%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.1,1177.7,1569.6,1961.4, correspond to the protonated molecular ion peak of the dimer of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree to pentamer.
The preparation of embodiment 9 polyetherketone cyclic oligomers
The solvent Nitromethane 99Min. is substituted dithiocarbonic anhydride, and other monomeric charge when reaction conditions and treatment step must pale yellow powder with embodiment 1, and productive rate is 75%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.3,1177.8,1569.6,1961.6,2354.7, correspond to the protonated molecular ion peak of dimer to six aggressiveness of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 10 polyetherketone cyclic oligomers
Solvent oil of mirbane is substituted dithiocarbonic anhydride, and other monomeric charge when reaction conditions and treatment step must cyclic oligomer with embodiment 1, and productive rate is 63%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.4,1177.6,1569.7,1961.8,2355.0, correspond to the protonated molecular ion peak of dimer to six aggressiveness of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 11 polyetherketone cyclic oligomers
Catalyzer FERRIC CHLORIDE ANHYDROUS 8.12g (0.05mol) is substituted aluminum trichloride (anhydrous), and other monomeric charge when reaction conditions and treatment step must yellow powder with embodiment 1, and productive rate is 67%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.3,1177.6,1569.7,1961.6,2354.9, correspond to the protonated molecular ion peak of dimer to six aggressiveness of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 12 polyetherketone cyclic oligomers
Catalyzer Zinc Chloride Anhydrous 6.82g (0.05mol) is substituted aluminum trichloride (anhydrous), and other monomeric charge when reaction conditions and treatment step must pale yellow powder with embodiment 1, and productive rate is 46%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.2,1177.5,1569.6 the dimer that corresponds to cyclic oligomer respectively is to tetrameric protonated molecular ion peak, shows that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 13 polyetherketone cyclic oligomers
Catalyzer boron fluoride 3.40g (0.05mol) is substituted aluminum trichloride (anhydrous), and other monomeric charge when reaction conditions and treatment step must pale yellow powder with embodiment 1, and productive rate is 71%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.3,1177.6,1569.7,1961.8,2353.9,2746.1, correspond to the protonated molecular ion peak of the dimer of cyclic oligomer respectively to heptamer, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 14 polyetherketone cyclic oligomers
Catalyzer aluminum trichloride (anhydrous) consumption is brought up to 10.02g (0.075mol), other monomeric charge when reaction conditions and treatment step with embodiment 1, pale yellow powder, productive rate is 90%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.3,1177.8,1569.4,1961.7,2353.6,2745.9, correspond to the protonated molecular ion peak of the dimer of cyclic oligomer respectively to heptamer, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 15 polyetherketone cyclic oligomers
The dropping time is replaced by 4 hours, monomeric charge when reaction conditions and treatment step with embodiment 1, pale yellow powder, productive rate is 72%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.4,1177.8,1569.6,1960.9,2354.1, correspond to the protonated molecular ion peak of dimer to six aggressiveness of cyclic oligomer respectively, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The preparation of embodiment 16 polyetherketone cyclic oligomers
The dropping time is replaced by 12 hours, monomeric charge when reaction conditions and treatment step with embodiment 1, pale yellow powder, productive rate is 91%.The main fignal center of the laser mass spectrometry spectrogram of product is positioned at: m/z=785.1,1177.6,1569.2,1961.6,2353.4,2745.8, correspond to the protonated molecular ion peak of the dimer of cyclic oligomer respectively to heptamer, show that product is made up of the different cyclic oligomer of a series of polymerization degree.
The ring-opening polymerization of embodiment 17 polyetherketone cyclic oligomers
Take by weighing 0.5g cyclic polyether ketone oligopolymer and 0.01g cesium fluoride thorough mixing, heat in logical nitrogen test tube, at 355 ℃, the oligopolymer fusion was reacted 40 minutes down, obtained the linear polyaryletherketone of high-molecular weight semi-crystalline state.
The ring-opening polymerization of embodiment 18 polyether etherketone sulfone cyclic oligomers
Take by weighing 0.5g cyclic polyether ether ketone sulfone oligopolymer and 0.01g biphenyl bis-phenol potassium thorough mixing, heat in logical nitrogen test tube, at 370 ℃, the oligopolymer fusion was reacted 30 minutes down, obtained the linear polyarylether ether ketone of high-molecular weight sulfone.
The ring-opening polymerization of embodiment 19 polyether-ether-ketone cyclic oligomers
Take by weighing 0.5g cyclic polyether ether ketone oligopolymer and 0.01g potassium phenylate thorough mixing, heat in logical nitrogen test tube, at 375 ℃, the oligopolymer fusion was reacted 50 minutes down, obtained the linear poly of high-molecular weight.
Claims (4)
1. aromatic ring-shaped polyether-ketone oligomer has following structure:
In the formula: n=2-20;
R ' is hydrogen or methyl;
R is:
2. the preparation method of the described aromatic ring-shaped polyether-ketone oligomer of claim 1, it is characterized in that: catalyzer is placed have the reaction flask that nitrogen inlet, top connect the spherical condensation tube of calcium chloride tube and gas absorbing device, add solvent again to form " false high rare " environment; In addition with tetracol phenixin and fragrant monomer wiring solution-forming, wherein the add-on of solvent is that solute can dissolve fully and gets final product; Feed exsiccant nitrogen, under stirring at room, the slow average rate of solution is added drop-wise in the reaction flask; Solution dropwises, and continues to react to make in 0.5-4.0 hour to react completely; Add the dilute hydrochloric acid termination reaction, continue to stir 0.5-4.0 hour; After separatory gets organic phase, use distilled water wash, to remove catalyzer; Under the nitrogen protection, concentrate, join in the methyl alcohol and precipitate, obtain the described aromatic ring-shaped polyether-ketone oligomer of claim 1;
Wherein: solvent is dithiocarbonic anhydride, Nitromethane 99Min. or oil of mirbane; Fragrant monomer is 4,4 '-phenoxy group benzophenone, triphen diether, 4,4 '-(3-methyl) phenoxy group-benzophenone, 4,4 '-phenoxy group sulfobenzide or 4,4 '-(3-methyl) phenoxy group-sulfobenzide; Catalyzer is aluminum chloride, iron trichloride, zinc chloride or boron fluoride; The mol ratio of tetracol phenixin and fragrant monomer is 0.95-1.05:1; The mol ratio of catalyzer and tetracol phenixin is 2.0-4.0:1.
3. the described aromatic ring-shaped polyether-ketone oligomer of claim 1 is used for the original position ring-opening polymerization and prepares the high-molecular weight linear polymer.
4. purposes according to claim 3 is characterized in that: take by weighing initiator and aromatic ring-shaped polyether-ketone oligomer, its mol ratio is: 0.001-0.05:1, thorough mixing, under nitrogen atmosphere, be heated to the oligopolymer fusion, reacted 20-60 minute, obtain the high-molecular weight linear polymer; Described initiator is biphenyl bis-phenol potassium, potassium phenylate, salt of wormwood or cesium fluoride.
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| CN1215065C (en) * | 2003-03-03 | 2005-08-17 | 中国科学院长春应用化学研究所 | Method for synthesizing aromatic cyclic oligomer |
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