CN1264925C - Method for preparing polysulfoneamide/claynano composite material - Google Patents
Method for preparing polysulfoneamide/claynano composite material Download PDFInfo
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- CN1264925C CN1264925C CNB031514545A CN03151454A CN1264925C CN 1264925 C CN1264925 C CN 1264925C CN B031514545 A CNB031514545 A CN B031514545A CN 03151454 A CN03151454 A CN 03151454A CN 1264925 C CN1264925 C CN 1264925C
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- polysulfonamides
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- diaminodiphenylsulfone
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Abstract
The present invention relates to a method for preparing a polysulfonamides / clay nanometer composite material, which belongs to the technical field of the manufacture process of a composite material composed of an organic high molecular polymer and an inorganic filling material. The method of the present invention is characterized in that the present invention adopts the monomer solution intercalation in-situ polymerization technology, and the process mainly has the steps that organic clay is added into an organic solvent and then is stirred at a high speed; furthermore, a clay dispersion solution is formed; aromatic diamine is added into the clay dispersion solution, and then the mixed solution is stirred, is dissolved, and is cooled into negative 8 to 10 DEG C; thereby, a monomer intercalation solution is formed; the low temperature monomer intercalation solution is stirred and then is added with terephthaloyl chloride so as to carry out the polycondensation, and then the solution is neutralized by alkali and then is filtered; thereby, a product is formed. The composite material manufactured by the method of the present invention has the fine mechanical performance, and is suitable for manufacturing protective clothes and military dress used for various majors after the composite material is manufactured into fiber.
Description
Technical field
The present invention relates to a kind of preparation method of polysulfonamides/clay nanocomposites, be particularly related to the preparation method of Polyphenylene Sulfone acid amides/clay nanocomposites, the manufacturing process technology field of the matrix material that genus organic high molecular polymer and mineral filler are formed.
Background technology
The organic high molecular polymer polysulfonamides is to use engineering plastics more widely, has premium propertiess such as resistance to chemical attack, radiation hardness, high temperature resistant, uninflammability and electrical isolation.Can make good filtering material, also can be used for the insulation paper of motor.Especially be made into textile fibres, more, can be used to make some special spe-cial-purpose uniforms, as antigravity suit, pressure compensating suit, fighting uniform and bunker clothing etc. because it has high-strength, lightweight, resistant to elevated temperatures characteristics.Also can be used for making military supplies such as steel helmet.But,, be one of important topic of current material subject so how to improve the over-all properties of polysulfonamides resin because the mechanical property of polysulfonamides does not still satisfy requirement.
How improve on the molecular weight of polymkeric substance in most of doses at the emphasis of research at present, do not see the relevant report that adopts nanotechnology to prepare polysulfonamides and the matrix material of clay as yet.
Summary of the invention
The object of the present invention is to provide a kind of method that improves the polysulfonamides mechanical property.Further purpose of the present invention provides the preparation method of the matrix material of a kind of polysulfonamides resinous polymer and mineral filler clay composition.
The preparation method of a kind of polysulfonamides/clay nanocomposites of the present invention is characterized in that adopting the technology of monomer solution intercalation in-situ polymerization, and the processing step of present method is as follows:
A. raw material is prepared: main raw material and weight percent are: aromatic diamines 40-60%, p-phthaloyl chloride 60-40%; In addition, press above-mentioned raw materials total amount 100% and add organic clay for benchmark, the add-on of this organic clay is 0.1-10%;
B. organic clay is incorporated in the N,N-dimethylacetamide solvent, high-speed stirring forms clay dispersion solution;
C. aromatic diamines is joined in the above-mentioned clay dispersion solution, stir on the limit, the limit dissolving, and be cooled to 15 ℃～-25 ℃; Under low-temperature condition, continue to stir 30 minutes, make to form monomer intercalation solution; Aromatic diamines is a diaminodiphenylsulfone(DDS);
D. in above-mentioned low temperature monomer intercalation solution, add p-phthaloyl chloride while stirring, make it carry out polycondensation, finally form nano composite material;
E. with alkali neutralization and filtration, promptly get product.
Above-mentioned clay is a kind of layer silicate mineral, its essential mineral composition is the layer aluminosilicate of the montomorillonite of 85-93%, and this clay is through n-alkyl amino acid, n=6-12, properties-correcting agent is handled, and is the organic clay that forms after ten diamino acid ion exchange treatment.
Above-mentioned aromatic diamines is Ursol D, mphenylenediamine, any one or two kinds of in 4 ' 4 diaminodiphenylsulfone(DDS)s, 3 ' 3 diaminodiphenylsulfone(DDS)s.
Above-mentioned neutralization alkali is calcium oxide, be neutralized to pH value is 6-7.
Among the present invention, typical polysulfonamides is to be formed by diaminodiphenylsulfone(DDS) and p-phthaloyl chloride polycondensation, and its chemical equation is:
In above-mentioned representative instance, when aromatic diamines was 4 ' 4 diaminodiphenylsulfone(DDS)s and/or 3 ' 3 diaminodiphenylsulfone(DDS)s, then polysulfonamides specifically was expressed as the Polyphenylene Sulfone acid amides.
The present invention has adopted the technology of monomer solution intercalation in-situ polymerization, a kind of monomer is inserted between the clay layer, add another monomer subsequently and make it to carry out polycondensation, length along with polymer molecular chain when the restricted clearance polymerization constantly increases, make the interfloor distance of clay platelet also constantly increase, restraint force between the adjacent sheets is weakened, so that clay layer is fully strutted even is peeled off, and be dispersed in the polymeric matrix with nanoscale, by Coulomb's force and the strong interaction of polymer formation, finally form Organic simultaneously.This material is with the rigidity of inorganics, and the toughness and the workability of dimensional stability and thermotolerance and organic polymer ideally combine.Can give the many employing traditional methods of material unapproachable premium properties.
The advantage of the inventive method is that technology is simple, and is workable, easy to make and with low cost.
The prepared product of the inventive method is polysulfonamides/clay nanocomposites, through precipitation bath solidify, operations such as drawing-off, washing, drying, densification, coiling handle, can make polysulfonamides/clay nanocomposites fiber, this is a kind of novel high-performance fiber.
Conventional polysulfonamides fibre 2.3cN/dtex (2.4 gram/dawn)
Polysulfonamides/clay nanocomposites fiber 2.9cN/dtex (3.1 gram/dawn)
Embodiment
After now embodiments of the invention being described in.
Embodiment one:
A. raw material is prepared: main raw material is 4 ' 4 two amido sulfobenzides, 3 ' 3 two amido sulfobenzides, p-phthaloyl chloride, organic clay.Organic clay is the organic clay that the layer aluminosilicate of montomorillonite and ten diamino acid properties-correcting agent is carried out becoming after the ion exchange treatment organic modification.
B. 3 gram organic claies and 300 are restrained the high speed tissue mincer that N ' N---dimethylacetamide solvents are put into a 1000ml, with the rotating speed high speed shear that per minute 12000 changes, the time is 20 minutes, makes it form clay dispersion suspensoid solution.
C. above-mentioned suspensoid is poured in the four neck reactors of 500ml, is added 4 ' 4 two amido sulfobenzide and 0.03mol (7.5 gram) 3 ' 3 diaminodiphenylsulfone(DDS)s of 0.09mol (22.35 gram) while stirring, be cooled to-8 ℃--10 ℃; Continue at low temperatures to stir 30 minutes.
D. add the p-phthaloyl chloride of 0.12mol (24.4 gram) in above-mentioned cryogenic fluid while stirring, high-speed stirring makes it carry out polycondensation; React and close cooling pump after 3 minutes, it is heated up naturally.
E. continue reaction after 1 hour, it is 6-7 that the adding calcium oxide is neutralized to pH value; Through filtering discharging, promptly get product at last.
Polymkeric substance is measured the interplanar distance and the transmission electron microscope observation clay layer thickness of the d001 face diffraction peak of material medium clay soil through the X diffraction, show that clay is strutted even dissociated, and lamellar spacing only is 20-80nm, is dispersed in the polysulfonamides matrix with nanoscale.
Claims (5)
1. the preparation method of a polysulfonamides/clay nanocomposites is characterized in that adopting the technology of monomer solution intercalation in-situ polymerization, and the processing step of present method is as follows:
A. raw material is prepared: main raw material and weight percent are: aromatic diamines 40-60%, p-phthaloyl chloride 60-40%; In addition, press above-mentioned raw materials total amount 100% and add organic clay for benchmark, the add-on of this organic clay is 0.1-10%;
B. organic clay is incorporated in the N,N-dimethylacetamide solvent, high-speed stirring forms clay dispersion solution;
C. aromatic diamines is joined in the above-mentioned clay dispersion solution, stir on the limit, the limit dissolving, and be cooled to 15 ℃～-25 ℃; Under low-temperature condition, continue to stir 30 minutes, make to form monomer intercalation solution; Aromatic diamines is a diaminodiphenylsulfone(DDS);
D. in above-mentioned low temperature monomer intercalation solution, add p-phthaloyl chloride while stirring, make it carry out polycondensation, finally form nano composite material;
E. with alkali neutralization and filtration, promptly get product.
2. the preparation method of a kind of polysulfonamides/clay nanocomposites according to claim 1, it is characterized in that described clay is a kind of layer silicate mineral, its essential mineral composition is the layer aluminosilicate of the montomorillonite of 85-93wt%, this clay is through the n-alkyl amino acid, n=6-12, properties-correcting agent is handled, and is the organic clay that forms after ten diamino acid ion exchange treatment.
3. the preparation method of a kind of polysulfonamides/clay nanocomposites according to claim 1 is characterized in that described aromatic diamines is Ursol D, mphenylenediamine, any one or two kinds of in 4 ' 4 diaminodiphenylsulfone(DDS)s, 3 ' 3 diaminodiphenylsulfone(DDS)s.
4. the preparation method of a kind of polysulfonamides/clay nanocomposites according to claim 1 is characterized in that described neutralization alkali is calcium oxide, to be neutralized to pH value be 6-7.
5. the preparation method of a kind of polysulfonamides/clay nanocomposites according to claim 1, when it is characterized in that described aromatic diamines is 4 ' 4 diaminodiphenylsulfone(DDS)s and/or 3 ' 3 diaminodiphenylsulfone(DDS)s, polysulfonamides specifically is expressed as the Polyphenylene Sulfone acid amides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031514545A CN1264925C (en) | 2003-09-29 | 2003-09-29 | Method for preparing polysulfoneamide/claynano composite material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031514545A CN1264925C (en) | 2003-09-29 | 2003-09-29 | Method for preparing polysulfoneamide/claynano composite material |
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| CN1528820A CN1528820A (en) | 2004-09-15 |
| CN1264925C true CN1264925C (en) | 2006-07-19 |
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| CNB031514545A Expired - Fee Related CN1264925C (en) | 2003-09-29 | 2003-09-29 | Method for preparing polysulfoneamide/claynano composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235552B (en) * | 2008-02-29 | 2010-06-09 | 上海大学 | Random copolymerization polysulfonamide spinning liquid and preparation method thereof |
| WO2015120809A1 (en) * | 2014-02-14 | 2015-08-20 | 上海特安纶纤维有限公司 | Fibre made from aromatic polymer containing sulfone group, yarn, fabric, and products, and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457019B (en) * | 2009-01-04 | 2011-06-08 | 上海大学 | Carbon nanotube/polysulfonamide nano composite material and preparation method thereof |
-
2003
- 2003-09-29 CN CNB031514545A patent/CN1264925C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235552B (en) * | 2008-02-29 | 2010-06-09 | 上海大学 | Random copolymerization polysulfonamide spinning liquid and preparation method thereof |
| WO2015120809A1 (en) * | 2014-02-14 | 2015-08-20 | 上海特安纶纤维有限公司 | Fibre made from aromatic polymer containing sulfone group, yarn, fabric, and products, and preparation method thereof |
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|---|---|
| CN1528820A (en) | 2004-09-15 |
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