CN1145621C - Aromatic cyclic polyketone oligomer and its preparing method - Google Patents
Aromatic cyclic polyketone oligomer and its preparing method Download PDFInfo
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- CN1145621C CN1145621C CNB021239177A CN02123917A CN1145621C CN 1145621 C CN1145621 C CN 1145621C CN B021239177 A CNB021239177 A CN B021239177A CN 02123917 A CN02123917 A CN 02123917A CN 1145621 C CN1145621 C CN 1145621C
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Abstract
The present invention belongs to aromatic cyclic polyketone oligomers and a new synthesizing and preparing method thereof. Under the condition of pseudo-high dilution, the method uses Fried-Craft acylation reaction, phthaloyl dichloride, substituted arene monomers, etc. are used as basic raw materials, and the present invention develops a new route for synthesizing cyclic prepolymers of high performance resin with high yield, namely the aromatic cyclic polyketone oligomer. The aromatic cyclic oligomer has a specific cyclic structure and low melt viscosity and can carry out fusion ring-opening polymerization with the initiation of an anionic initiator, and the high-performance linear aromatic polyketone is obtained. The aromatic cyclic polyketone oligomer has the advantages of low cost and high performance, so the oligomer and a synthesizing route thereof have wide application prospects in the field of preparing high-performance composite materials.
Description
Technical field: the synthetic and novel preparation method that the invention belongs to aromatic ring-shaped polyketone oligopolymer.
Background technology: the research field that high-tech areas such as aromatic ring-shaped oligopolymer synthetic is should modern space flight, aviation, electronics, machinery grow up to the demand of advanced composite material and in the eighties latter stage.Distinctive ring texture of aromatic ring-shaped oligopolymer and low melt viscosity, under initiator causes, can carry out ring-opening polymerization fast and in polymerization process characteristics such as no small molecule by-product generation determine it in preparation high performance composite field and the Process Technology of Polymer technology such as the reaction injection moulding of a new generation, aspects such as resin transfer moulding have important use and are worth.
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, and the ring-type performed polymer that is used for the various novel textures of composite matrix resin is seen in succession in report.The fragrant polyaryletherketone of linear high molecular weight, sulfone are the commercial performance resinss of a class, have excellent chemical stability and machining property, and purposes is extremely extensive.But high melt temperature and melt viscosity have determined it to run into the obstacle that can't overcome and limited its application greatly on machine-shaping and preparation technology; And first synthesis of cyclic oligopolymer not only satisfies the high-performance of polyaryletherketone resinoid again via this route of ring-opening polymerization, and can overcome this shortcoming fully.
Usually the method for synthesizing linear high-performance polyarylether ketone can reduce the reaction of two classes: one, pyrosol nucleophilic condensation polymerization; Two, the electric polycondensation of friedel-crafts parent.In the existing literature report, the last method of the many employings of synthetic aroma ring-type polyaryletherketone oligopolymer.Gibson is at [macromolecules; 1997; 30.] delivered and be entitled as " friedel-crafts acylations annulation synthesizing new macrocylc compound "; it is that the acylations annulation takes place under the catalyst action at aluminum chloride that this technology adopts the fragrant diacid chloride of long-chain and reactive monomer triphen diether; but become the ring rate not high; separate through column chromatography, obtaining 70 yuan of cyclic oligomer productive rates is 23%.And at preparation raw material 4-[(4 '-acyl chlorides)-phenoxy group]-step is loaded down with trivial details during sulfobenzide.Simultaneously, the fusing point of this oligopolymer is 393 ℃, so must be higher than fusion ring-opening polymerization under this temperature, these all limit it and are applied on the preparation matrix material.But this route of cationoid reaction has the potential low cost, advantages such as reaction conditions gentleness, and also this speed of response is fast, helps realizing " false high rare " condition etc., has feasibility on synthetic aroma ring-type poly aryl ketone oligopolymer.
Summary of the invention: the purpose of this invention is to provide the aromatic ring-shaped polyketone oligopolymer of a class;
Another object of the present invention provides a kind of preparation method of aromatic ring-shaped polyketone oligopolymer.
It is the initial action monomer that the present invention adopts the phthalyl chloride that is beneficial to into ring on the structure, it not only makes the monomer wide material sources, cost reduces, and become the ring rate to bring up to 80%, the cyclic oligomer that obtains is made up of the homologue of the different macrocylc compound of a series of polymerization degree, it has low relatively softening temperature thereby has reduced the temperature of ring-opening polymerization, this technology for the preparation matrix material provides wide process window, makes this annulation route have important application prospects in preparation high performance composite field.
Synthetic cyclic oligomer of the present invention have a following structure:
Wherein: n=2-10
R ' is hydrogen or methyl
R is-O--CH
2-
Wherein when containing the Ar-O-Ar key in the R structure, then form aromatic polyether ketone cyclic oligomer.In the R structure, contain Ar-SO
2Then form fragrant polyketone sulfone cyclic oligomer during-Ar key.As Ar-O-Ar and Ar-SO
2-A exists down simultaneously, then forms aromatic polyether ketone sulfone cyclic oligomer.
Concrete synthesis step is as follows:
(1) preparation of cyclic oligomer
Catalyzer is placed the reaction flask of the spherical condensation tube that has top connection calcium chloride tube and gas absorbing device, add quantitative solvent again, in addition with phthalyl chlorine and monomer wiring solution-forming, both mol ratios are 0.90-1.05, wherein the add-on of solvent does not have strict the qualification, and general add-on is that solute can melt fully and gets final product; The mol ratio of catalyzer and phthalyl chlorine is 2.0-4.0, catalyzer is aluminum chloride, iron trichloride, zinc chloride, boron fluoride, under the room temperature vigorous stirring, the slow average rate of solution is added drop-wise in the reaction flask to form " false high rare " environment, continue to stir 0.5-4.0 hour, add the dilute hydrochloric acid termination reaction; After separatory gets organic phase, use distilled water wash again, to remove catalyzer; Solvent evaporated obtains crude product, with the chloroform washing, gets cyclic oligomer.
(2) ring-opening polymerization of cyclic oligomer
Take by weighing initiator and cyclic oligomer, its mol ratio is: 0.001-0.05, initiator are biphenyl bis-phenol potassium or cesium fluoride, and thorough mixing is heated to the oligopolymer fusion under nitrogen atmosphere, react 20-60 minute, obtain the linear polyketone of high-molecular weight.
The present invention adopts " false high rare " principle, uses commercial cheap raw material, and by above-mentioned annulation, but the synthesized polymer degree of high yield is the mixture of the cyclic oligomer of 2-10, and wherein product is with dimer, and tripolymer is main.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 suitable with this route of nucleophilic reaction.
Embodiment is as follows:
The preparation of embodiment 1 polyetherketoneetherketoneketone cyclic oligomer
With 3.34g (0.025mol) aluminum trichloride (anhydrous) and 200mLl, the 2-ethylene dichloride places and has the 500mL there-necked flask that the top connects the spherical condensation tube of calcium chloride tube and gas absorbing device.With 2.0302g (0.01mol) phthalyl chlorine and 3.3642g (0.01mol) 4,4 ' the phenoxy group benzophenone is dissolved in 50mL1, in the 2-ethylene dichloride, under room temperature and the vigorous stirring solution slow average rate in 8 hours is added drop-wise in the there-necked flask, dropwise, continue to stir 2 hours, add the dilute hydrochloric acid termination reaction of 50mL 0.1M.After separatory gets organic phase, again with 100mL distillation washing 3 times, to remove catalyzer.Solvent evaporated obtains pale yellow powder, washes 2 times with the 5mL chloroform, gets cyclic oligomer 3.97g, and productive rate is 85%.
The preparation of embodiment 2 polyetherketoneetherketoneketone cyclic oligomers
Methylene chloride is substituted 1, the 2-ethylene dichloride, other monomeric charge when reaction conditions and treatment step must pale yellow powder with embodiment 1, and productive rate is 73%.
The preparation of embodiment 3 polyetherketoneetherketoneketone cyclic oligomers
The solvent Nitromethane 99Min. is substituted 1, the 2-ethylene dichloride, other monomeric charge when reaction conditions and treatment step must cyclic oligomer with embodiment 1, and productive rate is 69%.
The preparation of embodiment 4 polyetherketoneetherketoneketone cyclic oligomers
Solvent oil of mirbane is substituted 1, the 2-ethylene dichloride, other monomeric charge when reaction conditions and treatment step must pale yellow powder with embodiment 1, and productive rate is 64%.
The preparation of embodiment 5 polyetherketoneetherketoneketone cyclic oligomers
Solvent dithiocarbonic anhydride is substituted 1, the 2-ethylene dichloride, other monomeric charge when reaction conditions and treatment step must pale yellow powder with embodiment 1, and productive rate is 61%.
The preparation of embodiment 6 polyetherketoneetherketoneketone cyclic oligomers
Catalyzer FERRIC CHLORIDE ANHYDROUS 4.06g (0.025mol) 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 70%.
The preparation of embodiment 7 polyetherketoneetherketoneketone cyclic oligomers
Catalyzer Zinc Chloride Anhydrous 3.41g (0.025mol) 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 58%.
The preparation of embodiment 8 polyetherketoneetherketoneketone cyclic oligomers
Catalyzer boron fluoride 1.70g (0.025mol) 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 preparation of embodiment 9 polyetherketoneetherketoneketone cyclic oligomers
Catalyzer aluminum trichloride (anhydrous) consumption is brought up to 4.68g (0.035mol), other monomeric charge when reaction conditions and treatment step with embodiment 1, pale yellow powder, productive rate is 76%.
The preparation of embodiment 10 polyetherketoneetherketoneketone cyclic oligomers
With phthalyl chlorine and 4,4 ' phenoxy group benzophenone mol ratio is replaced by 0.95, and promptly two monomeric consumptions are respectively 2.0302g (0.01mol) and 3.1960g (0.095mol), other feed intake and reaction conditions and treatment step with embodiment 1, get pale yellow powder, productive rate is 71%.
The preparation of embodiment 11 polyetherketoneetherketoneketone cyclic oligomers
With phthalyl chlorine and 4,4 ' phenoxy group benzophenone mol ratio is replaced by 1.05, and promptly two monomeric consumptions are respectively 2.0302g (0.01mol) and 3.5324g (0.0105mol), other feed intake and reaction conditions and treatment step with embodiment 1, get pale yellow powder, productive rate is 52%.
The preparation of embodiment 12 polyetherketoneetherketoneketone 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 55%.
The preparation of embodiment 13 polyetherketoneetherketoneketone 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 86%.
The preparation of embodiment 14 PEKK cyclic oligomers
Reaction monomers 1.7021g (0.01mol) phenyl ether 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 70%.
The preparation of embodiment 15 poly aryl ketone ketone cyclic oligomers
Reaction monomers 1.6824g (0.01mol) ditane 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 54%.
The preparation of embodiment 16 polyether ether ketone ketone cyclic oligomers
Reaction monomers 2.6221g (0.01mol) 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 81%.
The preparation of embodiment 17 polyether ether ketone ketone cyclic oligomers
Reaction monomers 2.6221g (0.01mol) triphen diether is substituted 4,4 ' the phenoxy group benzophenone, solvent substitutes 1 with methylene dichloride, the 2-ethylene dichloride, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a faint yellow solid, productive rate 76%.
The preparation of embodiment 18 methyl polyetherketoneetherketoneketone cyclic oligomers
Reaction monomers 3.6440g (0.01mol) 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 75%.
The preparation of embodiment 19 polyethersulfone ether ketone ketone cyclic oligomers
With reaction monomers 4.0238g (0.01mol) 4,4 ' phenoxy group-sulfobenzide substitute 4,4 ' phenoxy group benzophenone, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow solid, productive rate 86%.
The preparation of embodiment 20 methyl polyethersulfone ether ketone ketone cyclic oligomers
Reaction monomers 4.3238g (0.01mol) 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 79%.
The ring-opening polymerization of embodiment 21 polyetherketoneetherketoneketone cyclic oligomers
Take by weighing 0.5g cyclic oligomer and 0.01g cesium fluoride thorough mixing, heat in logical nitrogen test tube, at 305 ℃, the oligopolymer fusion was reacted 40 minutes down, obtained high-molecular weight linear polyether ether ketone ketone ketone polymer.
The ring-opening polymerization of embodiment 22 polyethersulfone ether ketone ketone cyclic oligomers
Take by weighing 0.5g cyclic oligomer and 0.01g cesium fluoride thorough mixing, heat in logical nitrogen test tube, at 300 ℃, the oligopolymer fusion was reacted 40 minutes down, obtained high-molecular weight linear polyether sulfone ether ketone ketone polymer.
The ring-opening polymerization of embodiment 23 polyetherketoneetherketoneketone cyclic oligomers
Initiator is substituted cesium fluoride by 0.005g biphenyl bis-phenol potassium, and polymerization time is 30 minutes, and other treatment step obtains high-molecular weight linear polyether ether ketone ketone ketone polymer with embodiment 21.
Claims (3)
1. aromatic cyclic polyketone oligomer has following structure:
In the formula: polymerization degree n=2-10;
R ' is hydrogen or methyl;
R is:
-O- -CH
2-
2. aromatic cyclic polyketone oligomer according to claim 1 is characterized in that described aromatic cyclic polyketone oligomer is a primary product with dimer and tripolymer.
3. the preparation method of the described aromatic cyclic polyketone oligomer of claim 1, key step is:
Catalyzer is placed the reaction flask of the spherical condensation tube that has top connection calcium chloride tube and gas absorbing device, phthalyl chloride and a kind of substituted arene class monomer are dissolved in the solvent, both mol ratios are 0.90-1.05, the mol ratio of catalyzer and phthalyl chlorine is 2.0-4.0, under stirring at room, the slow average rate of solution is added drop-wise in the reaction flask, continue to stir 0.5-4.0 hour, add the dilute hydrochloric acid termination reaction, after separatory gets organic phase, use distilled water wash, solvent evaporated obtains crude product, with the chloroform washing, get cyclic oligomer;
Described catalyzer is aluminum chloride, iron trichloride, zinc chloride or boron fluoride;
Described solvent is 1,2-ethylene dichloride, methylene dichloride, dithiocarbonic anhydride, Nitromethane 99Min. or oil of mirbane;
Described substituted arene class monomer is a phenyl ether, ditan, 1,4-two phenoxy group benzene, 1,4-(3-methylphenoxy) benzene, 4,4 '-phenoxy group benzophenone, 4,4 '-phenoxy group sulfobenzide, 4,4 '-(3-methylphenoxy) benzophenone or 4,4 '-(3-methylphenoxy) sulfobenzide.
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| CN101519399B (en) * | 2009-03-27 | 2012-05-23 | 武汉工程大学 | Aromatic ring-shaped polyether-ketone oligomer and preparation method thereof |
| CN101519400B (en) * | 2009-03-27 | 2012-05-23 | 武汉工程大学 | Macrocyclic aryl thioether ether sulfone oligomer and preparation method thereof |
| WO2019181829A1 (en) * | 2018-03-22 | 2019-09-26 | 帝人株式会社 | Cyclic poly(arylene ether ketone) and production method therefor |
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