CN112920317B - Complex containing copper ions and molybdate ions and preparation method thereof - Google Patents
Complex containing copper ions and molybdate ions and preparation method thereof Download PDFInfo
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- CN112920317B CN112920317B CN202110115698.1A CN202110115698A CN112920317B CN 112920317 B CN112920317 B CN 112920317B CN 202110115698 A CN202110115698 A CN 202110115698A CN 112920317 B CN112920317 B CN 112920317B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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Abstract
The invention discloses a complex containing copper ions and molybdate ions and a preparation method thereof, wherein sodium p-styrenesulfonate and acryloyloxyethyl trimethyl ammonium chloride are used as monomers, N' -methylene bisacrylamide is used as a cross-linking agent, alpha-ketoglutaric acid is used as an initiator, an organic substance matrix is obtained through polymerization reaction under the catalysis of ultraviolet light, and then the organic substance matrix is sequentially soaked in ferric ion solution and molybdate solution for a long time, so that Cu is enabled to be dissolved in the molybdate solution2+C with organic matrix6H5O3S‑Formation of stable ionic bonds, MoO4 2‑And N, N, N-trimethylethylammonium ion (C)4H11N+) Forming stable ionic bond, drying to obtain complex containing iron ion and molybdate ion, and grinding into powder for use. The invention has simple preparation process, low raw material price, low process cost and high reaction efficiency, and the prepared product is widely used, particularly used as a flame-retardant smoke suppressant and has excellent flame-retardant smoke suppressant performance.
Description
Technical Field
The invention belongs to the field of polymers, relates to a preparation method of a complex, and particularly relates to a complex containing copper ions and molybdate ions and a preparation method of the complex.
Background
Synthesis of the first Metal carbonyl Complex Fe (CO) with L.Mond5Further research has led to the discovery of metal carbonyl anions containing negative valences as well as monovalent, divalent, trivalent, or tetravalent transition metals. The interaction between metal ions and macromolecules is one of the domestic and foreign research hotspots, wherein the metal ion complex has excellent characteristics: the structure is definite, the multifunctional group is provided, and the macromolecule characteristic and the metal ion characteristic are provided.
Due to the special configuration of the metal ion complex, the metal ion complex has various applications in the aspects of catalyst synthesis, drug synthesis, electrochemical application, compounding with a flame retardant and the like, so that the metal ion complex provides wider application prospects in the fields of supramolecular chemistry, biology, medicine and the like. Meanwhile, the research content and the research in the related field are paid extensive attention, and the synthesis of the metal ion complex is still a great challenge in the chemical field.
Before the work of this patent application, there has been no report of copper-containing and molybdate ion complexes, neither patent literature nor scientific paper.
Disclosure of Invention
The invention aims to provide a complex containing copper ions and molybdate ions and a preparation method thereof, and the complex can be used as a flame-retardant smoke suppressant for a polymer plate.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a complex containing copper ions and molybdate ions is characterized by comprising the following steps:
step 1, adding sodium p-styrene sulfonate, an acryloyloxyethyl trimethyl ammonium chloride solution, N, N' -methylene bisacrylamide and alpha-ketoglutaric acid into distilled water, and stirring until the materials are completely dissolved to obtain a reaction solution;
and 2, carrying out photocatalytic crosslinking reaction on the reaction solution under the irradiation of ultraviolet light to obtain an organic polymer, namely the organic matrix for introducing metal ion coordination.
Step 3, soaking the organic substance matrix in the step 2 in a copper ion solution to ensure that the copper ions and C of the organic substance matrix6H5O3S-Forming a stable ionic bond;
step 4, soaking the organic matrix soaked in the step 3 in molybdate ion solution to ensure that MoO4 2-And N, N, N-trimethyl ethylammonium radical ions of the organic matter matrix form stable ionic bonds;
and 5, drying the organic substance matrix soaked in the step 4 to obtain the complex containing copper ions and molybdate ions.
Preferably, in the step 1, the dissolution is performed under water bath conditions, wherein the temperature of the water bath is 50-70 ℃.
Preferably, in the step 2, the specific method is as follows: after the reaction solution is dripped into a designated mould, the mould is placed under an ultraviolet lamp for irradiation crosslinking for 8 to 20 hours.
Preferably, in the step 3, the copper ion solution is an aqueous solution of any one or a combination of several of copper nitrate, copper sulfate, copper chloride and copper bromide.
Preferably, in step 4, the molybdate ion solution is an aqueous solution of alkali metal molybdate.
Preferably, the molybdate ion solution is one or a mixture of several of lithium molybdate, sodium molybdate, potassium molybdate, rubidium molybdate, cesium molybdate, francium molybdate and magnesium molybdate.
Preferably, the soaking time in step 3 and step 4 is 2-4 days.
Preferably, the molar ratio of the sodium p-styrene sulfonate, the acryloyloxyethyl trimethyl ammonium chloride solution, the N, N' -methylene bisacrylamide and the alpha-ketoglutaric acid is 450-550: 550-650: 0.5-1.5.
A complex comprising a copper ion and a molybdate ion, wherein: the compound is prepared by any one of the preparation methods, and the molecular structural formula is as follows:
in the above formula, x and y are the numbers of structural units and are positive integers.
The application of the complex containing copper ions and molybdate ions is characterized in that: a flame-retarding smoke-suppressing agent for the polymer plate.
The invention has the beneficial effects that:
the invention uses sodium p-styrenesulfonate and acryloyloxyethyl trimethyl ammonium chloride as monomers, N' -methylene bisacrylamide as a cross-linking agent and alpha-ketoglutaric acid as an initiator to carry out polymerization reaction under the catalysis of ultraviolet light to obtain an organic substance matrix, and then the organic substance matrix is sequentially soaked in a cupric ion solution and a molybdate radical solution for a long timeLiquid, so that Cu is2+C with organic matrix6H5O3S-Formation of stable ionic bonds, MoO4 2-And N, N, N-trimethylethylammonium ion (C)4H11N+) Forming stable ionic bond, drying to obtain the complex containing copper ions and molybdate ions, and grinding into powder for use. The invention has simple preparation process, low raw material price, low process cost and high reaction efficiency, and the prepared product is widely used, particularly used as a flame-retardant smoke suppressant and has excellent flame-retardant smoke suppressant performance.
Drawings
FIG. 1 is an XPS energy spectrum of a complex containing copper ions and molybdate ions prepared in example 1.
Fig. 2 is an XRD energy spectrum of the complex containing copper ions and molybdate ions prepared in example 1.
FIG. 3 is an FTIR spectrum of a complex containing copper ions and molybdate ions prepared in example 1.
FIG. 4 is a TG diagram of a complex containing copper ions and molybdate ions prepared in example 1.
Detailed Description
The embodiments of the present invention are not limited to the following examples, which can make the present invention more fully understood by those skilled in the art.
Example 1:
weighing sodium p-styrenesulfonate (NaSS), acryloyloxyethyl trimethyl ammonium chloride solution (DMAEA-Q), N, N' -Methylene Bisacrylamide (MBAA) and alpha-Ketoglutaric Acid (KA) according to a certain molar ratio (500:593:1:1) to synthesize an organic matrix capable of introducing metal ions, and the specific operation is as follows: 2.9055g of DMAEA-Q, 2.6062g of NaSS, 0.0039g of MBAA and 0.0037g of KA (the molar ratio of the four is equal to about 500:593:1:1) are weighed, the mixture is mixed, then distilled water is added to the mixture to reach a constant volume of 10ml, and the mixture is placed into a 60 ℃ water bath kettle to be continuously stirred until the mixture is completely dissolved. Dripping the solution into a designated mold, irradiating under an ultraviolet lamp for 12h for illumination crosslinking, and soaking in CuCl after organic matrix is formed2In solution (1mol/L, 50ml) for 3 days, make Cu2+C with organic matrix6H5O3S-Forming stable ionic bond, and soaking in Na2MoO4In solution (1mol/L, 50ml) for 3 days, make MoO4 2-And N, N, N-trimethylethylammonium ion (C)4H11N+) Forming stable ionic bonds, drying to obtain the complex, grinding into powder to be tested.
XPS spectrogram data: common XPS signals correspond to the elements S2 p, C1S, N1S and O1S for organic substrates in Cu (DN) Mo at 164eV, 285eV, 402eV and 530.6eV, respectively, and additional XPS signals correspond to the elements Mo 3d and Cu 2p3 for Cu (DN) Mo at 232.1eV and 932.5eV, indicating the successful incorporation of copper and molybdenum elements into organic substrates.
XRD energy spectrum data: the XRD curve of Cu (DN) Mo is disordered and has low crystallinity, and the disordered amorphous structure in the pattern indicates that Cu (DN) Mo does not contain CuCl2，Na2MoO4And CuMoO4And the like.
Data on FTIR spectrogram: infrared spectrogram of Cu (DN) Mo and organic complex, wherein Cu (DN) Mo is 3441.56cm-1And 1640.07cm-1The absorption peak is not disappeared, which indicates that-OH bond is still present in the product, so that the synthesized Cu (DN) Mo also contains crystal water. The organic complex is 1185.9cm-1Has an absorption peak, and the product has a Na-O-S network. Cu (DN) Mo at 1181.31cm-1A broad absorption peak is formed, which indicates that a Cu-O-S network is formed in the product. In addition, Cu (DN) Mo is 823.61cm-1Has a strong absorption peak, and the absorption peak of Mo ═ O bond is at 964cm-1On the left and right, it is shown that the strong absorption peak of the product is formed by tensile vibration of Mo-N bonds.
TG graph data: since Cu (DN) Mo contains a small amount of moisture and small molecules, water vapor and low molecular gaseous compounds are formed along with the continuous rising of the temperature, and the curves all have slight descending tendency between 30 ℃ and 300 ℃. The organic complexes in the flame retardant smoke suppressant begin to decompose between 320 ℃ and 480 ℃ and further the residual amount of Cu (DN) Mo is 64.2%. Meanwhile, Cu (DN) Mo has good thermal stability and is suitable for processing polymers.
Example 2:
weighing sodium p-styrenesulfonate (NaSS), acryloyloxyethyl trimethyl ammonium chloride solution (DMAEA-Q), N, N' -Methylene Bisacrylamide (MBAA) and alpha-Ketoglutaric Acid (KA) according to a certain molar ratio (530:620:1:1) to synthesize an organic matrix capable of introducing metal ions, and the specific operation is as follows: 3.3038g of DMAEA-Q, 2.7626g of NaSS, 0.0039g of MBAA and 0.0037g of KA are weighed, the materials are mixed, distilled water is added to the mixture, the volume is determined to be 10ml, and the mixture is placed into a water bath kettle at the temperature of 60 ℃ to be stirred continuously until the mixture is completely dissolved. Dripping the solution into a designated mold, irradiating under an ultraviolet lamp for 12h for illumination crosslinking, and soaking in CuNO after an organic matrix is formed3In solution (1mol/L, 50ml) for 3 days, make Cu2+C with organic matrix6H5O3S-Forming stable ionic bond, and soaking in Na2MoO4In solution (1mol/L, 50ml) for 3 days, make MoO4 2-And N, N, N-trimethylethylammonium ion (C)4H11N+) Forming stable ionic bonds, drying to obtain the complex, grinding into powder to be tested.
Example 3:
weighing sodium p-styrenesulfonate (NaSS), acryloyloxyethyl trimethyl ammonium chloride solution (DMAEA-Q), N, N' -Methylene Bisacrylamide (MBAA) and alpha-Ketoglutaric Acid (KA) according to a certain molar ratio (460:570:1:1) to synthesize an organic matrix capable of introducing metal ions, and the specific operation is as follows: 2.7928g of DMAEA-Q, 2.3977g of NaSS, 0.0039g of MBAA and 0.0037g of KA (the molar ratio of the four is equal to about 460:570:1:1) are weighed, distilled water is added to the mixture to reach a constant volume of 10ml, and the mixture is placed into a 60 ℃ water bath kettle to be continuously stirred until the mixture is completely dissolved. Dripping the solution into a designated mold, irradiating under an ultraviolet lamp for 12h for illumination crosslinking, and soaking in CuNO after an organic matrix is formed3In solution (1mol/L, 50ml) for 3 days, make Cu2+C with organic matrix6H5O3S-Forming stable ionic bond, and soaking in Na2MoO4In solution (1mol/L, 50ml) for 3 days, make MoO4 2-And N, N, N-trimethylethylammonium radicalIon (C)4H11N+) Forming stable ionic bonds, drying to obtain the complex, grinding into powder to be tested.
The complex containing iron ions and molybdate ions prepared by the invention has wide application, and is particularly used as a flame-retardant smoke suppressant added into a PVC (polyvinyl chloride) plate to produce a flame-retardant smoke suppressant sheet with the oxygen index of 39.1 and the maximum smoke density (Ds)max)340.28, reach smoke density value (Ds) ten minutes after burning10)324.71. The flame-retardant smoke-suppressing effect is good, wherein the pure PVC plate has an oxygen index of 35.2 and a maximum smoke density (Ds)max)637.66, reach smoke density value (Ds) ten minutes after burning10)633.40。
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Claims (10)
1. A preparation method of a complex containing copper ions and molybdate ions is characterized by comprising the following steps:
step 1, adding sodium p-styrenesulfonate and acryloyloxyethyl trimethyl ammonium chloride solution serving as monomers, N' -methylene bisacrylamide serving as a cross-linking agent and alpha-ketoglutaric acid serving as an initiator into distilled water, and stirring until the monomers are completely dissolved to obtain a reaction solution;
step 2, carrying out photocatalytic crosslinking reaction on the reaction solution under the irradiation of ultraviolet light to obtain an organic polymer, namely an organic matrix for introducing metal ion coordination;
step 3, soaking the organic substance matrix in the step 2 in a copper ion solution to ensure that the copper ions and C of the organic substance matrix6H5O3S-Forming a stable ionic bond;
step 4, soaking the organic matrix soaked in the step 3 in molybdate ion solution to ensure that MoO4 2-And N, N, N-trimethyl ethylammonium radical ions of the organic matter matrix form stable ionic bonds;
and 5, drying the organic substance matrix soaked in the step 4 to obtain the complex containing copper ions and molybdate ions.
2. The process of claim 1, wherein the copper ion-containing complex comprises: in the step 1, the dissolution is completed under the condition of water bath, and the temperature of the water bath is 50-70 ℃.
3. The process of claim 1, wherein the copper ion-containing complex comprises: in the step 2, the specific method is as follows: after the reaction solution is dripped into a designated mould, the mould is placed under an ultraviolet lamp for irradiation crosslinking for 8 to 20 hours.
4. The process of claim 1, wherein the copper ion-containing complex comprises: in the step 3, the copper ion solution is an aqueous solution of any one or a combination of more of copper nitrate, copper sulfate, copper chloride and copper bromide.
5. The process of claim 1, wherein the copper ion-containing complex comprises: in the step 4, the molybdate ion solution is an alkali metal molybdate aqueous solution.
6. The process of claim 1, wherein the copper ion-containing complex comprises: the molybdate ion solution is one or a mixture of several of lithium molybdate, sodium molybdate, potassium molybdate, rubidium molybdate, cesium molybdate, francium molybdate and magnesium molybdate.
7. The process of claim 1, wherein the copper ion-containing complex comprises: the soaking time in the step 3 and the step 4 is 2-4 days.
8. The process of claim 1, wherein the copper ion-containing complex comprises: the molar ratio of the sodium p-styrene sulfonate, the acryloyloxyethyl trimethyl ammonium chloride solution, the N, N' -methylene bisacrylamide and the alpha-ketoglutaric acid is 450-550: 550-650: 0.5-1.5.
9. A complex comprising a copper ion and a molybdate ion, wherein: the preparation method of any one of claims 1 to 8, wherein the molecular structural formula is as follows:
in the above formula, x and y are the numbers of structural units and are positive integers.
10. Use of the copper ion and molybdate ion containing complex of claim 9, wherein: a flame-retarding smoke-suppressing agent for the polymer plate.
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| CN104193891A (en) * | 2014-05-17 | 2014-12-10 | 中北大学 | Preparing method of gel microsphere material absorbing molybdate |
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| CN108404980A (en) * | 2018-02-06 | 2018-08-17 | 西北师范大学 | A kind of synthesis and application of the high performance high strength plural gel of load gold nano particle |
| CN108727738A (en) * | 2018-06-14 | 2018-11-02 | 中山市绿浪助剂有限公司 | Halogen-free low-smoke flame-retardant cable material and preparation method thereof |
| CN110790866A (en) * | 2018-12-03 | 2020-02-14 | 华东理工大学 | Preparation method of nanogel based on polyelectrolyte as template |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193891A (en) * | 2014-05-17 | 2014-12-10 | 中北大学 | Preparing method of gel microsphere material absorbing molybdate |
| CN108247808A (en) * | 2017-12-29 | 2018-07-06 | 江西绿洲环保新材料股份有限公司 | Fire-retardant medium-density plate of environment-friendly smoke-suppressing and preparation method thereof |
| CN108404980A (en) * | 2018-02-06 | 2018-08-17 | 西北师范大学 | A kind of synthesis and application of the high performance high strength plural gel of load gold nano particle |
| CN108727738A (en) * | 2018-06-14 | 2018-11-02 | 中山市绿浪助剂有限公司 | Halogen-free low-smoke flame-retardant cable material and preparation method thereof |
| CN110790866A (en) * | 2018-12-03 | 2020-02-14 | 华东理工大学 | Preparation method of nanogel based on polyelectrolyte as template |
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