CN105254653A - PX based inorganic super-molecular substance synthesis and preparation method - Google Patents
PX based inorganic super-molecular substance synthesis and preparation method Download PDFInfo
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- CN105254653A CN105254653A CN201510693042.2A CN201510693042A CN105254653A CN 105254653 A CN105254653 A CN 105254653A CN 201510693042 A CN201510693042 A CN 201510693042A CN 105254653 A CN105254653 A CN 105254653A
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Abstract
The invention discloses a PX based inorganic super-molecular substance synthesis and preparation method. The PX based inorganic super-molecular substance synthesis and preparation method uses p-xylene as a raw material and comprises the steps of oxidation, selective reduction, alkaline polymerization, metal ion complexing and vacuum drying. By adopting the steps, the PX based inorganic super-molecular substance synthesis and preparation method is convenient to operate and adopts simple equipment, and the silver ion binding rate of a synthesized inorganic super-molecular compound is beyond imagination and is unbelievable. The inorganic super-molecular compound can be applied to the fields of medicines, industrial electric conduction and the like through proper modification and has better market expectation. Thus, the PX based inorganic super-molecular substance synthesis and preparation method has the advantages that operation is convenient, equipment is simple and the silver ion binding rate of the synthesized inorganic super-molecular compound is high.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic super molecular compound, particularly relate to the method based on a kind of inorganic supramolecule material of PX synthesis preparation.
Background technology
P-Xylol (PX) is a kind of important industrial chemicals, p-Xylol is mainly used in producing terephthalic acid (PTA), polyethylene terephthalate cruel (PET) is obtained further with the rear dehydrating condensation of ethylene glycol (MEG) reaction, it can be used for producing poly-cruel fiber and then producing textiles, also can be used as the raw materials for production such as solvent and conduct medicine, spices, ink, but consumption is less.In recent years, due to poly-cruel fibrid excellent property, its output occupies the first place of synthon, is expected to rise day by day in the market of p-Xylol.
Inorganic macromolecule complex has very important effect in analytical chemistry, industrial application, in biology, the separation of the ion in such as analytical chemistry, the titration etc. of metal ion, the extraction etc. of coordination catalysis, metal in industrial application, be a lot of biomolecules in biology be all title complex, and the combination of the oxyphorase of iron content and oxygen and carbon monoxide, a lot of enzyme and the chlorophyllous normal operation containing magnesium also all be unable to do without title complex mechanism.
Summary of the invention
The object of the invention is to provide that a kind of easy to operate, equipment is simple for prior art, the inorganic super molecular compound of synthesis is for the high method based on a kind of inorganic supramolecule material of PX synthesis preparation of the combination rate of silver ions.
The present invention solves the problems of the technologies described above adopted technical scheme: based on the method for a kind of inorganic supramolecule material of PX synthesis preparation, comprising with p-Xylol is raw material, wherein: there are following steps:
1) p-Xylol getting 1 parts by volume mixes with the nitric acid of 0.2 to 1 parts by volume and is oxidized;
2) tetrahydrofuran (THF) of 0.8 to 1.2 parts by volume is added again;
3) then diborane gas is passed into;
4) basic solution mixing is added;
5), under reheating the condition of 20 to 50 DEG C, polyreaction 2 to 5 hours, then cools to stirring at room temperature;
6) stir being heated to the silver nitrate solution added in solution under the condition of 55 DEG C.Adopt above-mentioned steps, easy to operate, equipment inorganic super molecular compound that is simple, synthesis is beyond imagination for the combination rate of silver ions, makes us unexpected.By suitable modification, multiple field such as medicine, industry conduction can be applied to, there are good market expectations.
For optimizing technique scheme, the measure taked also comprises: in step 1), and the concentration of nitric acid is 60% to 85%; Step 1) oxidization time is 0.5 to 2 hour.Preferably the concentration of 0.5 parts by volume is the nitric acid of 65%, is oxidized 1 hour, tetrahydrofuran (THF) 1 parts by volume.Polymeric reaction temperature preferably 30 DEG C, polymerization reaction time is advisable for 3 hours, and after cooling to room temperature, churning time is 1 hours.Add the churning time after Silver Nitrate to be advisable with about 2h.For the ease of packaging and transport, can carry out to reaction product the packing box preservation carrying out product under the condition of 110 DEG C after vacuum-drying to constant weight again.Use the nitric acid of 65% through row complete oxidation, be completely oxidized to terephthalic acid.In step 3), under passing into the condition maintaining normal temperature in diborane gas process; The flow velocity of diborane gas is 3 parts by volume/h to 20 parts by volume/h; The reaction times passed into is 2 to 4 hours.The preferably reaction times of 3 hours.The adaptive diborane gas flow velocity of 100ml p-Xylol is not preferably had to be 0.5L/h.Use diborane reductive agent through row reduction, hydroxyl can be reduced into of the side chain of a terephthalic acid hydroxy-acid group.In step 3), pass in diborane gas process and maintain 30 DEG C.The polymerisate that diborane gas can ensure to obtain low polymerization is added in this condition.In step 4), basic solution includes but not limited to that concentration is the ammoniacal liquor of 3 to 10mol/L.Preferred 8mol/L ammoniacal liquor.The ammoniacal liquor of 3 to the 10mol/L of 30 to 50ml is joined with the p-Xylol of 100ml.The alkali used is the ammoniacal liquor of 8mol/L, and the amount of ammoniacal liquor is excessive.In step 6), the concentration of Silver Nitrate is 0.1 to 1mol/L.Preferred silver nitrate concentration is 0.1mol/L, joins this concentration Silver Nitrate about 25ml be advisable with 100ml p-Xylol.Process add free argent ion can be formed with ammoniacal liquor [Ag2]+.In case of heating [Ag2]+inorganic super molecular compound can be formed with the P-hydroxybenzoic acid be polymerized low in solution.
Owing to present invention employs, there are following steps:
1) p-Xylol getting 1 parts by volume mixes with the nitric acid of 0.2 to 1 parts by volume and is oxidized;
2) tetrahydrofuran (THF) of 0.8 to 1.2 parts by volume is added again;
3) then diborane gas is passed into;
4) basic solution mixing is added;
5), under reheating the condition of 20 to 50 DEG C, polyreaction 2 to 5 hours, then cools to stirring at room temperature;
6) stir being heated to the silver nitrate solution added in solution under the condition of 55 DEG C.Adopt above-mentioned steps, easy to operate, equipment inorganic super molecular compound that is simple, synthesis is beyond imagination for the combination rate of silver ions, makes us unexpected.By suitable modification, multiple field such as medicine, industry conduction can be applied to, there are good market expectations.Thus the present invention has that easy to operate, equipment is simple, the inorganic super molecular compound of synthesis is for the high advantage of the combination rate of silver ions.
Embodiment
Below in conjunction with attached embodiment, the present invention is described in further detail.
Embodiment: based on the method for a kind of inorganic supramolecule material of PX synthesis preparation, comprising with p-Xylol is raw material, and it has following steps:
1) p-Xylol getting 1 parts by volume mixes with the nitric acid of 0.2 to 1 parts by volume and is oxidized;
2) tetrahydrofuran (THF) of 0.8 to 1.2 parts by volume is added again;
3) then diborane gas is passed into;
4) basic solution mixing is added;
5), under reheating the condition of 20 to 50 DEG C, polyreaction 2 to 5 hours, then cools to stirring at room temperature;
6) stir being heated to the silver nitrate solution added in solution under the condition of 55 DEG C.Adopt above-mentioned steps, easy to operate, equipment inorganic super molecular compound that is simple, synthesis is beyond imagination for the combination rate of silver ions, makes us unexpected.By suitable modification, multiple field such as medicine, industry conduction can be applied to, there are good market expectations.In step 1), the concentration of nitric acid is 60% to 85%; Step 1) oxidization time is 0.5 to 2 hour.The concentration of preferred 0.5 parts by volume of the present embodiment is the nitric acid of 65%, is oxidized 1 hour, tetrahydrofuran (THF) 1 parts by volume.Polymeric reaction temperature preferably 30 DEG C, polymerization reaction time is advisable for 3 hours, and after cooling to room temperature, churning time is 1 hours.Add the churning time after Silver Nitrate to be advisable with about 2h.For the ease of packaging and transport, can carry out to reaction product the packing box preservation carrying out product under the condition of 110 DEG C after vacuum-drying to constant weight again.Use the nitric acid of 65% through row complete oxidation, be completely oxidized to terephthalic acid.In step 3), under passing into the condition maintaining normal temperature in diborane gas process; The flow velocity of diborane gas is 3 parts by volume/h to 20 parts by volume/h; The reaction times passed into is 2 to 4 hours.The present embodiment preferably reaction times of 3 hours.The present embodiment does not preferably have the adaptive diborane gas flow velocity of 100ml p-Xylol to be 0.5L/h.Use diborane reductive agent through row reduction, hydroxyl can be reduced into of the side chain of a terephthalic acid hydroxy-acid group.In step 3), pass in diborane gas process and maintain 30 DEG C.The polymerisate that diborane gas can ensure to obtain low polymerization is added in this condition.In step 4), basic solution includes but not limited to that concentration is the ammoniacal liquor of 3 to 10mol/L.The preferred 8mol/L ammoniacal liquor of the present embodiment.The ammoniacal liquor of 3 to the 10mol/L of 30 to 50ml is joined with the p-Xylol of 100ml.The alkali used is the ammoniacal liquor of 8mol/L, and the amount of ammoniacal liquor is excessive.In step 6), the concentration of Silver Nitrate is 0.1 to 1mol/L.The preferred silver nitrate concentration of the present embodiment is 0.1mol/L, joins this concentration Silver Nitrate about 25ml be advisable with 100ml p-Xylol.Process adds free argent ion can form [AgNH with ammoniacal liquor
3]
2+.[AgNH in case of heating
3]
2+inorganic super molecular compound can be formed with P-hydroxybenzoic acid of being polymerized low in solution.
Further illustrated by example:
(1) be oxidized: measure the paraxylene feedstock of 100ml in 500ml there-necked flask, the nitric acid adding 65% of 50ml is oxidized, oxidation 1h.
(2) selective reduction: the tetrahydrofuran (THF) adding 100ml again in there-necked flask, passes into diborane gas under the condition of normal temperature, and flow velocity is 0.5L/h, reaction 3h.
(3) alkaline polymerization: the ammoniacal liquor 50ml adding 8mol/L, be heated under the condition of 30 DEG C, polyreaction 3h, cools to stirring at room temperature 1h.
(4) complexing of metal ion: be heated to the silver nitrate solution 25ml stirring 2h adding 0.1mol/L under the condition of 55 DEG C in solution.
(5) vacuum-drying: to reaction product under the condition of row 110 DEG C vacuum-drying to constant weight.
the mensuration of free metal example
Precipitation titration: Fo Erhadefa-ferriammonium sulfate [NH
4fe (SO
4)
2] indicator, initial SCN-+Ag+=AgSCN ↓ (white) K
sp=1.0 × 10-12
Terminal SCN-+Fe
3+=FeSCN
2+(redness) K surely=138
Indicator is made, with 0.0500mol/L thiocyanation (NH with ferriammonium sulfate (NH4Fe (SO4) 2)
4sCN) standardized solution makes titrating solution.As instillation NH
4during SCN standardized solution, first produce AgSCN white precipitate.Ag
+after ion quantitative deposition, an excessive NH
4fe3 in SCN standardized solution and indicator
+when ionic bond generates red coordination ion 2+, namely reach titration end point.
Specific experiment step
Sampling: get in the volumetric flask of polyreaction sample 100ml and 250ml completely.
Titration: with ferriammonium sulfate (NH
4fe (SO
4)
2) make indicator, with 0.0500mol/L thiocyanation (NH
4sCN) standardized solution carries out titration as titrating solution.
As instillation NH
4sCN solution just reaches terminal, illustrates that the silver ion content in the sample of synthesis is extremely low, also just describes silver ions and all form year inorganic macromolecular complex thing.
In sum, the method convenient experimental operation, equipment is simple, and the inorganic super molecular compound of synthesis is high for the combination rate for silver ions.
Although describe the present invention in conjunction with preferred embodiment; so itself and be not used to limit the present invention; any those skilled in the art; without departing from the spirit and scope of the present invention; can implement various change, the displacement of coordinator and amendment here to the theme listed, therefore protection scope of the present invention be as the criterion when the scope limited depending on proposed claim.
Claims (6)
1., based on the method for a kind of inorganic supramolecule material of PX synthesis preparation, comprising with p-Xylol is raw material, it is characterized in that: have following steps:
1) p-Xylol getting 1 parts by volume mixes with the nitric acid of 0.2 to 1 parts by volume and is oxidized;
2) tetrahydrofuran (THF) of 0.8 to 1.2 parts by volume is added again;
3) then diborane gas is passed into;
4) basic solution mixing is added;
5), under reheating the condition of 20 to 50 DEG C, polyreaction 2 to 5 hours, then cools to stirring at room temperature;
6) stir being heated to the silver nitrate solution added in solution under the condition of 55 DEG C.
2. the method based on a kind of inorganic supramolecule material of PX synthesis preparation according to claim 1, it is characterized in that: in step 1), the concentration of described nitric acid is 60% to 85%; Oxidization time described in step 1) is 0.5 to 2 hour.
3. the method based on a kind of inorganic supramolecule material of PX synthesis preparation according to claim 1, is characterized in that: in step 3), described pass into the condition maintaining normal temperature in diborane gas process under; The flow velocity of described diborane gas is 3 parts by volume/h to 20 parts by volume/h; The described reaction times passed into is 2 to 4 hours.
4. the method based on a kind of inorganic supramolecule material of PX synthesis preparation according to claim 1, it is characterized in that: in step 3), described passing in diborane gas process maintains 30 DEG C.
5. the method based on a kind of inorganic supramolecule material of PX synthesis preparation according to claim 1, it is characterized in that: in step 4), described basic solution includes but not limited to that concentration is the ammoniacal liquor of 3 to 10mol/L.
6. the method based on a kind of inorganic supramolecule material of PX synthesis preparation according to claim 1, it is characterized in that: in step 6), the concentration of described Silver Nitrate is 0.1 to 1mol/L.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333743A (en) * | 1998-12-22 | 2002-01-30 | 三星综合化学株式会社 | Production method of aromatic carboxylic acids |
| CN1469856A (en) * | 2000-10-10 | 2004-01-21 | ������˹��Ů����ѧ | Oxidation of alkyl-aromatic compounds |
-
2015
- 2015-10-21 CN CN201510693042.2A patent/CN105254653A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333743A (en) * | 1998-12-22 | 2002-01-30 | 三星综合化学株式会社 | Production method of aromatic carboxylic acids |
| CN1469856A (en) * | 2000-10-10 | 2004-01-21 | ������˹��Ů����ѧ | Oxidation of alkyl-aromatic compounds |
Non-Patent Citations (4)
| Title |
|---|
| J. MA ET AL.: "Modulated calorimetry of poly(1,4-oxybenzoate), poly(2,6-oxynaphthoate), and their copolymers", 《THERMOCHIMICA ACTA》 * |
| JIANJUN QU ET AL.: "Wear behavior offilled polymers for ultrasonic motor in vacuum environments", 《WEAR》 * |
| 方炎等: "苯甲酸的羟基取代物在银纳米颗粒表面的吸附行为的研究", 《光散射学报》 * |
| 罗洋辉等: "对羟基苯甲酸（PHBA）的超分子合成（水合物、共晶和有机盐）研究", 《中国化学会第十六届大环化学暨第八届超分子化学学术讨论会论文集》 * |
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Application publication date: 20160120 |