CN1215065C - Method for synthesizing aromatic cyclic oligomer - Google Patents
Method for synthesizing aromatic cyclic oligomer Download PDFInfo
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- CN1215065C CN1215065C CN 03105019 CN03105019A CN1215065C CN 1215065 C CN1215065 C CN 1215065C CN 03105019 CN03105019 CN 03105019 CN 03105019 A CN03105019 A CN 03105019A CN 1215065 C CN1215065 C CN 1215065C
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Abstract
The present invention belongs to a method for synthesizing aromatic cyclic oligomers. Under the condition of false high dilution, the method uses Fried-Craft acylation reaction, the Lewis acid of anhydrous aluminium nuriate, etc. is used as a catalyst, the Lewis base of N-methyl pyrrolidine, etc. is used as a cocatalyst, and cyclization product yield is 90%; the aromatic cyclic oligomer has a specific annular structure and low melt viscosity and can carry out fusion ring-opening polymerization with the initiation of an anionic initiator, and high-performance linear aroamtic polyether ketone (sulfone) is obtained. The aromatic cyclic polyether ketone (sulfone) oligomer has the advantage of low cost and high performance, so the oligomer and a synthetic route thereof have wide application prospect in the field of preparing high-performance composite materials.
Description
Technical field
The invention belongs to the synthetic method of aromatic ring-shaped 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 non-volatility small molecules generation determine it in preparation high performance composite field and the Process Technology of Polymer technology such as the reaction injection molding of a new generation, aspects such as resin transfer moulding have important use and are worth.
Linear fragrant poly aryl ketone (sulfone) is the commercial performance resins of a class, has excellent chemical stability and machining property, and purposes is extremely extensive.But high melt temperature, and melt viscosity is big has limited it in machine-shaping with the application on being used for aspect the composite matrix resin; 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.And in the bibliographical information of synthetic aroma cyclic polyether ketone oligopolymer, adopt last method more, and this method tool cost height, adopting two expensive fluorine monomers is initial reactant, reaction such as at high temperature carries out at shortcoming; And this route of cationoid reaction has the potential 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 "; it is that the acylations annulation takes place under the catalyst action at aluminum chloride that this technology adopts the diacid chloride of long-chain and cationoid reaction 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%.But the potential low cost that this route of cationoid reaction has, advantages such as reaction conditions gentleness, the feasibility on synthetic aroma ring-type poly aryl ketone (sulfone) oligopolymer have obtained demonstration.Chinese patent 02123917.7 discloses a kind of preparation method of aromatic cyclic polyketone oligomer; adopt the friedel-crafts acylations; the phthalyl chloride that is easy to into ring with reaction structure is a starting raw material; synthesized a class ring-type polyketone oligopolymer; productive rate can reach 80%, and is suitable with the result of pyrosol nucleophilic condensation polymerization synthetic route.
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 oligopolymer.
In the method for the electric polycondensation synthesizing linear poly aryl ketone of friedel-crafts parent, in reaction process, add a spot of Lewis base and help improving the molecular weight of product and reaction is carried out fully.The present invention is in adopting this method synthetic aroma cyclic oligomer, adding a spot of Lewis base in reaction process is promotor, with the phthalyl chloride is the initial action monomer, the one-tenth ring rate of reactant can be brought up to more than 90% and improve the purity of cyclisation thing; And to being the initial action monomer with the m-phthaloyl chloride, synthetic performance more excellent between bit architecture linear polyketone (sulfone) performed polymer---the preparation of cyclic oligomer has same effect.
Synthetic cyclic oligomer of the present invention have a following structure:
R ' is hydrogen or methyl
R is
Wherein when containing ortho position phenyl-diformyl group in the structure, then form ortho position fragrance polyketone or ortho position fragrance polyketone sulfone cyclic oligomer; A fragrant polyketone in position or a position fragrance polyketone sulfone cyclic oligomer between between containing in the structure, then forming during the phenyl-diformyl group of position.
Concrete synthesis step is as follows:
(1) preparation of cyclic oligomer
Catalyzer is placed the reaction flask that has top connection calcium chloride tube and gas absorbing device, and the amount of visual response thing adds solvent again; Stir down promotor is added drop-wise in the reaction flask; Catalyzer is aluminum chloride, iron trichloride or zinc chloride; Promotor is N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide or hexamethyl phosphonic amide; In addition benzene diacid chloride and substituted arene monomer are mixed with solution, wherein the add-on of solvent is that solute can dissolve fully and gets final product; 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, continues to stir 0.5-4.0 hour, add the dilute hydrochloric acid termination reaction; After separatory gets organic phase, use distilled water wash again, remove catalyzer; Concentrate, be added drop-wise in the methyl alcohol and precipitate, get cyclic oligomer;
Wherein: the mol ratio of catalyzer and benzene diacid chloride is 2.5-6.0: 1,
The mol ratio of promotor and benzene diacid chloride is 0.5-2.0: 1,
The mol ratio of substituted arene monomer and benzene diacid chloride is 0.90-1.05: 1,
Solvent is 1,2-ethylene dichloride, methylene dichloride, dithiocarbonic anhydride, Nitromethane 99Min. or oil of mirbane;
(2) ring-opening polymerization of cyclic oligomer
Take by weighing initiator and cyclic oligomer, its mol ratio is: 0.001-0.05: 1, and initiator is biphenyl bis-phenol potassium or cesium fluoride, thorough mixing, under nitrogen atmosphere, be heated to the oligopolymer fusion, reacted 20-60 minute, obtain high-molecular weight linear polyether ketone or linear polyether ketone sulfone.
The present invention adopts " false high rare " principle, Friedel-Crafts reaction is used in the preparation cyclic oligomer has carried out systematic research, optimize reaction conditions, with chloroparaffin commonly used cheap etc. is solvent, adopting commercial phthalyl chloride or m-phthaloyl chloride is the initial action monomer, the monomer wide material sources further reduce cost; The reaction conditions gentleness is carried out in room temperature; Greatest feature of the present invention is, add minor N-methyl-2-pyrrolidone, N in the reaction process, dinethylformamide, N, Lewis bases such as N-N,N-DIMETHYLACETAMIDE or hexamethyl phosphonic amide are promotor, the one-tenth ring rate of reactant can be brought up to more than 90% and improve the purity of cyclisation thing; And to performance more excellent between bit architecture linear polyketone (sulfone) performed polymer---the preparation of cyclic oligomer has same effect.Cyclic oligomer obtained by this method is that the polymerization degree is the homologue composition of the macrocylc compound of 2-10, wherein product is based on dimer, tripolymer, reduced the temperature of ring-opening polymerization, can make ring-opening polymerization under relatively low temperature, carry out, for the complete processing at the preparation matrix material provides wide process window, make this annulation route have important application prospects in preparation high performance composite field.
Embodiment
Embodiment 1 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
With 4.68g (0.035mol) aluminum trichloride (anhydrous) and 200mL 1, the 2-ethylene dichloride places and has the spherical condensation tube that the top is connected with calcium chloride tube, connects on drying tube in the 500mL there-necked flask of a gas absorbing device again.Stir down the 1.0mL N-Methyl pyrrolidone is added drop-wise in the there-necked flask, with 2.0302g (0.01mol) phthalyl chlorine and 4.0238g (0.01mol) 4,4 ' the phenoxy group sulfobenzide is dissolved in 50mL 1, 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.Concentrate, be added drop-wise in the methyl alcohol and precipitate, get cyclic oligomer 5.05g, productive rate is 95%.
Embodiment 2 contains the preparation of the polyetherketoneetherketoneketone cyclic oligomer of ortho position ketone ketone structure
Reaction monomers 3.3642g (0.01mol) 4,4 ' phenoxy group benzophenone is substituted 4,4 ' phenoxy group sulfobenzide, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a pale yellow powder, productive rate 93%.
Embodiment 3 contains the preparation of the PEKK cyclic oligomer of ortho position ketone ketone structure
Reaction monomers 1.7021g (0.01mol) phenyl ether is substituted 4,4 '-the phenoxy group sulfobenzide, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a pale yellow powder, productive rate 81%.
Embodiment 4 contains the preparation of the methyl polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Reaction monomers 4.3052g (0.01mol) 4,4 '-(3-methyl) phenoxy group-sulfobenzide is substituted 4,4 ' phenoxy group sulfobenzide, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 92%.
Embodiment 5 contains the preparation of the methyl polyetherketoneetherketoneketone cyclic oligomer of ortho position ketone ketone structure
Reaction monomers 3.9444g (0.01mol) 4,4 '-(3-methyl) phenoxy group-benzophenone is substituted 4,4 ' phenoxy group sulfobenzide, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 93%.
Embodiment 6 contains the preparation of the methyl polyether ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Reaction monomers 2.6231g (0.01mol) triphen diether is substituted 4,4 ' phenoxy group sulfobenzide, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 88%.
The preparation of the polyethersulfone ether ketone ketone cyclic oligomer of position ketone ketone structure between embodiment 7 contains
Reaction monomers 2.0302g (0.01mol) isophthalyl chloride is substituted phthalyl chlorine, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 64%.
The preparation of the polyetherketoneetherketoneketone cyclic oligomer of position ketone ketone structure between embodiment 8 contains
Reaction monomers 2.0302g (0.01mol) isophthalyl chloride is substituted phthalyl chlorine, reaction monomers 3.6440g (0.01mol) 4,4 '-phenoxy group-benzophenone substitute 4,4 ' phenoxy group sulfobenzide, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 62%.
The preparation of the methyl polyethersulfone ether ketone ketone cyclic oligomer of position ketone ketone structure between embodiment 9 contains
Reaction monomers 2.0302g (0.01mol) isophthalyl chloride is substituted phthalyl chlorine, 4.3052g (0.01mol) 4,4 '-(3-methyl) phenoxy group-sulfobenzide substitute 4,4 ' phenoxy group sulfobenzide, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 65%.
The preparation of the methyl polyetherketoneetherketoneketone cyclic oligomer of position ketone ketone structure between embodiment 10 contains
Reaction monomers 2.0302g (0.01mol) isophthalyl chloride is substituted phthalyl chlorine, 3.9444g (0.01mol) 4,4 '-(3-methyl) phenoxy group-benzophenone substitute 4,4 ' phenoxy group sulfobenzide, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 61%.
The preparation of the polyether ether ketone ketone cyclic oligomer of position ketone ketone structure between embodiment 11 contains
Reaction monomers 2.0302g (0.01mol) isophthalyl chloride is substituted phthalyl chlorine, 2.6231g (0.01mol) triphen diether substitute 4,4 ' phenoxy group benzophenone, other monomeric charge when reaction conditions and treatment step with embodiment 1.Product is a yellow powder, productive rate 60%.
Embodiment 12 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Catalyzer FERRIC CHLORIDE ANHYDROUS 5.68g (0.035mol) 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 79%.
Embodiment 13 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Catalyzer Zinc Chloride Anhydrous 4.77g (0.035mol) 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 70%.
Embodiment 14 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
With promotor N, dinethylformamide 0.8mL substitutes N-Methyl pyrrolidone, other monomeric charge when reaction conditions and treatment step with embodiment 1, yellow powder, productive rate is 84%.
Embodiment 15 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Promotor N,N-dimethylacetamide 1.0mL is substituted N-Methyl pyrrolidone, and other monomeric charge when reaction conditions and treatment step must yellow powder with embodiment 1, and productive rate is 88%.
Embodiment 16 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Catalyzer aluminum trichloride (anhydrous) consumption is brought up to 8.02g (0.06mol), other monomeric charge when reaction conditions and treatment step with embodiment 1, pale yellow powder, productive rate is 89%.
Embodiment 17 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Promotor N-Methyl pyrrolidone consumption is replaced by 2.0mL, and catalyzer aluminum trichloride (anhydrous) consumption is replaced by 6.01g (0.045mol), other monomeric charge when reaction conditions and treatment step with embodiment 1, pale yellow powder, productive rate is 85%.
Embodiment 18 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
With phthalyl chlorine and 4,4 ' phenoxy group sulfobenzide mol ratio is replaced by 0.95, and promptly two monomeric consumptions are respectively 2.0302g (0.01mol) and 3.8226g (0.095mol), other feed intake and reaction conditions and treatment step with embodiment 1, get pale yellow powder, productive rate is 75%.
Embodiment 19 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
With phthalyl chlorine and 4,4 ' phenoxy group sulfobenzide mol ratio is replaced by 1.05, and promptly two monomeric consumptions are respectively 2.0302g (0.01mol) and 4.2250g (0.0105mol), other feed intake and reaction conditions and treatment step with embodiment 1, get pale yellow powder, productive rate is 49%.
Embodiment 20 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
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 86%.
Embodiment 21 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
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 81%.
Embodiment 22 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
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 56%.
Embodiment 23 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
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 64%.
Embodiment 24 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
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 69%.
Embodiment 25 contains the preparation of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
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 95%.
Embodiment 26 contains the ring-opening polymerization of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Take by weighing 0.5g cyclic oligomer and 0.01g cesium fluoride thorough mixing, heat in logical nitrogen test tube, at 303 ℃, the oligopolymer fusion was reacted 35 minutes down, obtained high-molecular weight linear polyether ketone sulfone.
Embodiment 27 contains the ring-opening polymerization of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
The amount of initiator is replaced by 0.025g by 0.005g, and polymerization time is 20 minutes, and other treatment step obtains high-molecular weight linear polyether ketone sulfone with embodiment 26.
Embodiment 28 contains the ring-opening polymerization of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
The amount of initiator is replaced by 0.0005g by 0.005g, and polymerization time is 60 minutes, and other treatment step obtains high-molecular weight linear polyether ketone sulfone with embodiment 26.
Embodiment 29 contains the ring-opening polymerization of the polyethersulfone ether ketone ketone cyclic oligomer of ortho position ketone ketone structure
Initiator is substituted cesium fluoride by 0.005g biphenyl bis-phenol potassium, and polymerization time is 40 minutes, and other treatment step obtains high-molecular weight linear polyether ketone sulfone with embodiment 26.
Embodiment 30 contains the ring-opening polymerization of the polyetherketoneetherketoneketone cyclic oligomer of ortho position ketone ketone structure
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 ketone.
The ring-opening polymerization of the polyetherketoneetherketoneketone cyclic oligomer of position ketone ketone structure between embodiment 31 contains
Take by weighing 0.5g cyclic oligomer and 0.01g cesium fluoride thorough mixing, heat in logical nitrogen test tube, at 320 ℃, the oligopolymer fusion was reacted 40 minutes down, obtained high-molecular weight linear polyether ketone sulfone.
The ring-opening polymerization of the polyethersulfone ether ketone ketone cyclic oligomer of position ketone ketone structure between embodiment 32 contains
Initiator is substituted cesium fluoride by 0.01g biphenyl bis-phenol potassium, and polymerization time is 35 minutes, and other treatment step obtains high-molecular weight linear polyether ketone sulfone with embodiment 29.
Claims (2)
1, a kind of method of synthetic aroma cyclic oligomer, it is characterized in that, with phthalyl chlorine or isophthalyl chloride is starting raw material, with aluminum trichloride (anhydrous), iron trichloride or zinc chloride is catalyzer, adopt Lewis base N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide or hexamethyl phosphonic amide are promotor, are applicable to the synthetic following cyclic oligomer that contains an adjacent benzene dicarbapentaborane or a benzene dicarbonyl structure that has:
Wherein: n=2-10; R ' is hydrogen or methyl;
R is:
-O-、-CH
2-、
2, the synthetic method of aromatic ring-shaped oligopolymer according to claim 1 is characterized in that synthesis step is as follows:
Catalyzer is placed the reaction flask that has top connection calcium chloride tube and gas absorbing device, and the amount of visual response thing adds solvent again; Stir down promotor is added drop-wise in the reaction flask; Catalyzer is aluminum chloride, iron trichloride or zinc chloride; Promotor is N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide or hexamethyl phosphonic amide; In addition benzene diacid chloride and substituted arene monomer are mixed with solution, wherein the add-on of solvent is that solute can dissolve fully and gets final product; 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, continues to stir 0.5-4.0 hour, add the dilute hydrochloric acid termination reaction; After separatory gets organic phase, use distilled water wash again, remove catalyzer; Concentrate, be added drop-wise in the methyl alcohol and precipitate, get cyclic oligomer;
Wherein: the benzene diacid chloride is phthalyl chlorine or isophthalyl chloride,
The mol ratio of catalyzer and benzene diacid chloride is 2.5-6.0: 1,
The mol ratio of promotor and benzene diacid chloride is 0.5-2.0: 1,
The mol ratio of substituted arene monomer and benzene diacid chloride is 0.90-1.05: 1,
Solvent is 1,2-ethylene dichloride, methylene dichloride, dithiocarbonic anhydride, Nitromethane 99Min. or oil of mirbane.
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| CN101519400B (en) * | 2009-03-27 | 2012-05-23 | 武汉工程大学 | Macrocyclic aryl thioether ether sulfone oligomer and preparation method thereof |
| CN101519399B (en) * | 2009-03-27 | 2012-05-23 | 武汉工程大学 | Aromatic ring-shaped polyether-ketone oligomer and preparation method thereof |
| AU2010337613B2 (en) | 2009-12-28 | 2013-08-01 | Toray Industries, Inc. | Cyclic polyphenylene ether ether ketone composition and method for producing the same |
| WO2019181829A1 (en) * | 2018-03-22 | 2019-09-26 | 帝人株式会社 | Cyclic poly(arylene ether ketone) and production method therefor |
| WO2022258332A1 (en) | 2021-06-09 | 2022-12-15 | Solvay Sa | Cyclic oligo(arylene ether)s, processes for their preparation and their use |
| WO2022258333A1 (en) | 2021-06-09 | 2022-12-15 | Solvay Sa | Cyclic oligo(arylene ether)s, processes for their preparation and their use |
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