CN115626985A - Novel Mo-based polymer and preparation method and application thereof - Google Patents
Novel Mo-based polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high molecular materials, and relates to a novel Mo-based polymer, and a preparation method and application thereof. The preparation method comprises the following steps: dissolving phosphorous acid and polyethyleneimine in concentrated acid, heating to 100-130 ℃, then dropwise adding a formaldehyde water solution, carrying out reflux reaction for 2-10 h, cooling to room temperature, adding a neutralizer to adjust the pH value to be neutral, filtering and collecting precipitate, cleaning, and drying to obtain a polyethyleneimine derivative; adding polyethyleneimine derivative, ammonium octamolybdate and water into a reaction bottle, carrying out reflux reaction, filtering after reaction to obtain a precipitate, and cleaning and drying the precipitate to obtain the novel Mo-based polymer. The method for preparing the Mo-based polymer is simple and easy to realize industrial production, and the prepared Mo-based polymer is used as a flame retardant, is green and environment-friendly and has higher efficiency.
Description
Technical Field
The invention belongs to the technical field of high molecular materials, and relates to a novel Mo-based polymer, and a preparation method and application thereof.
Background
In recent years, with the increasing awareness of fire prevention, the demand for flame retardants has increased dramatically, and research and development of flame retardant materials have been actively conducted in countries around the world, and various flame retardant products have been developed. The silicon flame retardant contains a large amount of silicon-oxygen elements, so that the material has excellent thermal property and mechanical property, and can form a compact silicon dioxide layer similar to ceramic during combustion, thereby effectively isolating oxygen and heat and reducing the diffusion of combustible gas, and further inhibiting the combustion process; however, a single silicon-based flame retardant has a limited flame retardant effect, and is generally used in combination with other flame retardants. Although the halogen flame retardant mainly based on gas-phase flame retardance has a good flame-retardant effect, toxic and corrosive gases are released during combustion, and great hidden danger exists for human beings and the environment. Therefore, in the two commands of ' scrap electronic and electric equipment command ' (WEEE) and ' harmful substance forbidding in electronic and electric appliances ' command ' (RoHS) issued in 2003 in the european union, the addition of harmful halogen flame retardants such as polybrominated diphenyl ethers to electronic and electric appliances is strictly prohibited. Compared with halogen flame retardants, inorganic flame retardants mainly based on heat absorption flame retardance and Intumescent Flame Retardants (IFR) mainly based on condensed phase flame retardance are recognized as environment-friendly flame retardants in the scientific and industrial fields at present, but the flame retardants usually need higher addition amount to enable the material to achieve the expected flame retardant effect, have lower flame retardant efficiency, greatly damage the mechanical property and the processing property of the material, and simultaneously have poor thermal stability and low decomposition temperature, thereby causing the processing and recycling difficulties of the flame-retardant high polymer.
Disclosure of Invention
Aiming at the defects in the prior art, the invention synthesizes a novel Mo-based polymer for the first time, and the novel Mo-based polymer can play an excellent flame retardant role when being applied to high molecular polymers.
One aspect of the present invention provides a novel Mo-based polymer having a general structural formula as shown in formula I below:
wherein n is an integer of 1 to 1000.
Preferably, the Mo-based polymer is obtained by reacting polyethyleneimine derivatives with a structural general formula shown as the following formula II with ammonium octamolybdate in an aqueous medium;
wherein n is an integer of 1 to 1000.
The polyethyleneimine derivative is combined with molybdate radical in ammonium octamolybdate through amino with proton in water, thereby preparing the Mo-based polymer.
Preferably, the molar ratio of polyethyleneimine derivative to ammonium octamolybdate is 1: (0.1-1).
Preferably, the polyethyleneimine derivative is reacted with ammonium octamolybdate in an aqueous medium under reflux at 100 to 120 ℃ for 5 to 10 hours.
Preferably, the polyethyleneimine derivative is prepared by a method comprising the following steps: dissolving phosphorous acid and polyethyleneimine in concentrated acid, heating to 100-130 ℃, then dropwise adding a formaldehyde water solution, carrying out reflux reaction for 2-10 h, cooling to room temperature, adding a neutralizer to adjust the pH value to be neutral, filtering and collecting precipitates, cleaning, and drying to obtain the polyethyleneimine derivative.
Preferably, the molar ratio of phosphorous acid to amino groups in the polyethyleneimine is (0.05 to 0.4): 1.
concentrated acids include, but are not limited to, concentrated hydrochloric acid, concentrated sulfuric acid, and the like.
Preferably, the mass percentage of formaldehyde in the formaldehyde aqueous solution is 35 to 45wt%.
The neutralizing agent may be exemplified by diethanolamine.
Another aspect of the present invention provides a method for preparing the above-described novel Mo-based polymer, comprising the steps of:
adding polyethyleneimine derivative, ammonium octamolybdate and water into a reaction bottle, carrying out reflux reaction, filtering after reaction to obtain a precipitate, and cleaning and drying the precipitate to obtain the novel Mo-based polymer.
In the preparation method, the molar ratio of the polyethyleneimine derivative to the ammonium octamolybdate is 1: (0.1-1).
In the preparation method, the reflux reaction temperature is preferably 100-120 ℃, and the reflux reaction time is preferably 5-10 hours.
In the preparation method, the cleaning of the precipitate comprises sequentially cleaning with absolute ethyl alcohol and hot water.
In another aspect, the present invention also provides the use of the above-described novel Mo-based polymer in a high molecular weight polymer.
High molecular polymers include, but are not limited to, thermoplastic elastomers, rubbers, engineering plastics, and the like; thermoplastic elastomers include, but are not limited to, SBS, SEBS, EPDM, EPR, POE, and the like, rubbers include, but are not limited to, styrene-butadiene rubber, neoprene rubber, nitrile rubber, ethylene-propylene rubber, butyl rubber, and the like, and engineering plastics include, but are not limited to, polypropylene, polyethylene, polyvinyl chloride, ABS, and the like.
The Mo-based polymer is used as a flame retardant in a high molecular polymer, and the flame retardant property of the high molecular polymer can be effectively improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention prepares and synthesizes a Mo-based polymer with a structural general formula shown in formula I for the first time;
(2) The invention prepares a novel Mo-based polymer by reacting polyethyleneimine derivatives with a general structural formula shown as the following formula II with ammonium octamolybdate in an aqueous medium;
(3) The Mo-based polymer is used as a flame retardant in a high molecular polymer, so that the flame retardant property of the high molecular polymer can be effectively improved;
(4) The method for preparing the Mo-based polymer is simple and easy to realize industrial production, and the prepared Mo-based polymer is used as a flame retardant, is green and environment-friendly and has higher efficiency.
Drawings
FIG. 1 is an infrared spectrum of PEIP-Mo of example 1 and PEIP of comparative example 1;
FIG. 2 (a) is a TG curve of PEIP-Mo of example 1 and PEIP of comparative example 1, and FIG. 2 (b) is a DTG curve of PEIP, PEIP-Mo.
Detailed Description
The technical solutions of the present invention are further described below by way of specific embodiments and drawings, it should be understood that the specific embodiments described herein are only for the purpose of facilitating understanding of the present invention, and are not intended to be specific limitations of the present invention. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1
The novel Mo-based polymer of example 1 was prepared by the following steps:
adding 0.02mol of phosphorous acid, 100ml of concentrated hydrochloric acid with the mass fraction of 37% and polyethyleneimine (1 mmol) with the polymerization degree of 100 into a 250ml three-neck flask provided with a magnetic stirrer, a thermometer and a reflux condenser, dropwise adding 32ml of 37wt% formaldehyde aqueous solution into the three-neck flask at the speed of two drops per second when the solution is heated to 110 ℃ and starts to reflux, dropwise adding the solution into the flask within 1h, then continuing to react for 7h under the reflux state, cooling to room temperature after the reaction is finished, neutralizing to neutrality by using ethylene glycol amine, filtering and collecting precipitates, washing the precipitates by using absolute ethyl alcohol for three times, finally drying for 4 h under vacuum, and drying to obtain the polyethyleneimine derivative (PEIP) with the structural general formula shown in formula II; the yield was 73%.
Adding 0.3mol of ammonium octamolybdate and 1mol of the polyethyleneimine derivative prepared in the previous step into a single-neck flask, adding 100ml of deionized water into the flask, slowly heating the system to 110 ℃, refluxing and stirring for 7 hours, cooling to room temperature, filtering to obtain a precipitate, washing for 2 times by using absolute ethyl alcohol, performing suction filtration once by using hot water at 70 ℃, and then freeze-drying for 24 hours to constant weight to obtain the novel Mo-based polymer (PEIP-Mo), wherein the novel Mo-based polymer is blue-green and the yield is 72%.
Comparative example 1
Comparative example 1 is different from example 1 in that comparative example 1 only produces a polyethyleneimine derivative (PEIP) having a general structural formula as shown in formula II.
Infrared spectroscopic analysis and thermogravimetric analysis were performed on the PEIP-Mo of example 1 and the PEIP of comparative example 1, and FIG. 1 is an infrared spectrum of the PEIP-Mo of example 1 and the PEIP of comparative example 1. PEIP-Mo showed 1168cm -1 The peaks left and right due to the P = O group in the PEIP side chain. At the same time, 1056cm -1 Another peak appears to the left and right, due to the P — O group in the PEIP side chain. And in the range of 1967-2331cm -1 There is a wide and shallow band, revealing the presence of protonated amino groups in the PEIP-Mo. PEIP-Mo at 889cm -1 A strong set of peaks appears to the left and right, due to the shock absorption peaks of Mo = O double bond in ammonium octamolybdate, at 580-817cm -1 The peak between them is the vibration absorption peak of Mo-O-Mo bond. In addition, at 1468cm -1 A peak appears on the left and right, which is weaker in PEIP-Mo, because the group and Mo-O-in ammonium octamolybdate combine with each other to weaken NH 2 + Absorption peak of group. It can be seen that the spectrum of PEIP-Mo covers roughly the spectrum of ammonium octamolybdate and PEIP. This indicates that the proposed flame retardant, PEIP-Mo, was successfully synthesized.
FIG. 2 (a) is a TG curve of PEIP-Mo of example 1 and PEIP of comparative example 1, and FIG. 2 (b) is a DTG curve of PEIP, PEIP-Mo; the detailed data include the onset temperature (T) of decomposition onset ) Maximum decomposition temperature (T) max ) And percent residue at 800 ℃ are summarized in table 1.
TABLE 1 TGA data for PEIP and PEIP-Mo in nitrogen
| Sample (I) | T onset a (℃) | T max b (℃) | Residual mass at 800 ℃ (%) |
| PEIP-Mo | 221 | 218，306， | 59.4 |
| PEIP | 187 | 188，300，510 | 22.6 |
T onset a (° c) represents the temperature at which 95% remains after decomposition.
T max b (° c) represents the peak temperature of the DTG.
As shown in FIG. 2 (a) and Table 1, with the addition of Mo, the initial decomposition temperature (T) of PEIP-Mo onset ) The temperature was 221 ℃. In fact, PEIP has the lowest T onset I.e. 187 c, which means that the bond between PEIP and Mo increases the thermal stability of the PEIP-Mo.
T of residues at 800 ℃ with PEIP-Mo onset The values have the same trend. The residue of PEIP-Mo at 800 ℃ is much higher than that of PEIP, 59.4%. The residue consisted of ammonium molybdate, indicating that the addition of molybdenum contributed significantly to the amount of residue. The residual mass of PEIP at 800 ℃ is very small, only 22.6%, indicating that molybdenum plays its role in the process of char formation.
Fig. 2 (b) shows that the PEIP-Mo undergoes a multi-step thermal degradation process. PEIP-Mo exhibits two major weight loss stages that can be attributed to the dehydration of PEIP and the formation of a char layer. Pure PEIP corresponds to the addition of zero Mo, dehydration of PEIP still occurs, but the degree of crosslinking may not be as great as that of PEIP-Mo, so PEIP continues to decompose at higher temperatures (510 ℃) until a more stable residue is formed, thus, PEIP forms minimal residue.
Example 2
The novel Mo-based polymer of example 2 was prepared by the following steps:
0.01mol of phosphorous acid, 100ml of concentrated hydrochloric acid with the mass fraction of 37% and 1mmol of polyethyleneimine with the polymerization degree of 100 are added into a 250ml three-neck flask provided with a magnetic stirrer, a thermometer and a reflux condenser, when the solution is heated to 110 ℃ and the reflux is started, 30ml of formaldehyde aqueous solution with the mass fraction of 37wt% is dripped into the three-neck flask at the speed of two drops per second, the solution is dripped into the flask within 1h, then the reaction is continued for 5h under the reflux state, the reaction is cooled to the room temperature after the reaction is finished and is neutralized by ethylene glycol amine, the precipitate is collected by filtration, the precipitate is washed three times by absolute ethyl alcohol, and finally, the reaction product is dried for 4 h under vacuum, and the polyethyleneimine derivative (PEIP) with the structural general formula shown in the formula II is obtained by drying.
Adding 0.5mol of ammonium octamolybdate and 1mol of the polyethyleneimine derivative prepared in the previous step into a single-neck flask, adding 100ml of deionized water into the flask, slowly heating the system to 115 ℃, refluxing and stirring for 5 hours, cooling to room temperature, filtering to obtain a precipitate, washing 3 times with absolute ethyl alcohol, performing suction filtration once with hot water at 75 ℃, and then freeze-drying for 24 hours to constant weight to obtain the novel Mo-based polymer (PEIP-Mo).
Example 3
The novel Mo-based polymer of example 3 was prepared by the following steps:
0.04mol of phosphorous acid, 100ml of concentrated hydrochloric acid with the mass fraction of 37 percent and 1mmol of polyethyleneimine with the polymerization degree of 100 are added into a 250ml three-neck flask provided with a magnetic stirrer, a thermometer and a reflux condenser, when the solution is heated to 110 ℃ and the reflux is started, 40ml of 40wt percent formaldehyde aqueous solution is dripped into the three-neck flask at the speed of two drops per second, the mixture is dripped into the flask within 30min, then the reaction is continued for 6h under the reflux state, the reaction is cooled to the room temperature after the reaction is finished and is neutralized by ethylene glycol amine, the precipitate is collected by filtration, washed three times by absolute ethyl alcohol, and finally dried for 5h under vacuum to obtain the polyethyleneimine derivative (PEIP) with the structural general formula shown in the formula II.
Adding 0.6mol of ammonium octamolybdate and 1mol of the polyethyleneimine derivative prepared in the previous step into a single-neck flask, adding 100ml of deionized water into the flask, slowly heating the system to 105 ℃, refluxing and stirring for 8 hours, cooling to room temperature, filtering to obtain a precipitate, washing 3 times with absolute ethyl alcohol, performing suction filtration once with hot water at 80 ℃, and then freeze-drying for 24 hours to constant weight to obtain the novel Mo-based polymer (PEIP-Mo).
Comparative example 2
Comparative example 2 differs from example 1 in that:
preparing polyethyleneimine derivatives in the same manner as in example 1, adding 0.3mol of ammonium octamolybdate and 1mol of the polyethyleneimine derivatives prepared above into a single-neck flask, adding 100ml of deionized water into the flask, stirring at room temperature for 7h, filtering to obtain precipitates, washing with anhydrous ethanol for 2 times, performing suction filtration with hot water at 70 ℃ once, and freeze-drying for 24 h to constant weight to obtain the product.
Application example 1
100 parts of chloroprene rubber and 10 parts of PEIP-Mo of example 1 are firstly mixed and blended in an internal mixer at a rotor speed of 60 ℃ and 60r/min, then are milled at room temperature, are cured on a vulcanizing machine after the rubber materials are mixed uniformly, and are cut according to the size required by the test and then are subjected to subsequent test.
Application example 2
Application example 2 differs from application example 1 in that application example 2 is a mixture of 100 parts of neoprene and 15 parts of the PEIP — Mo of example 1.
Application example 3
Application example 3 differs from application example 1 in that application example 3 is 100 parts of chloroprene rubber mixed with 20 parts of the PEIP-Mo of example 1.
Application example 4
Application example 4 differs from application example 1 in that application example 4 is a mixture of 100 parts of neoprene and 12 parts of the PEIP — Mo of example 2.
Application example 5
Application example 5 differs from application example 1 in that application example 5 is 100 parts of chloroprene rubber mixed with 16 parts of PEIP-Mo of example 3.
Comparative application example 1
Comparative application example 1 is different from application example 1 in that the PEIP-Mo of example 1 is not added to comparative application example 1.
Comparative application example 2
Application comparative example 2 is different from application example 1 in that 10 parts of the PEIP of comparative example 1 are added to application comparative example 2.
Comparative application example 3
Comparative application example 3 differs from application example 1 in that 10 parts of ammonium octamolybdate were added to comparative application example 3.
Application comparative example 4
Comparative application example 4 is different from application example 1 in that 10 parts of the product of comparative example 2 are added to comparative application example 4.
The flame retardant properties of the products of practical examples 1 to 5 and practical comparative examples 1 to 4 are shown in Table 2.
TABLE 2 flame retardancy of products of practical examples 1-5 and practical comparative examples 1-4
| Oxygen index% | Vertical combustion class | Smoke density rating SDR | |
| Application example 1 | 35.3 | UL94 V-1 | 21 |
| Application example 2 | 37.4 | UL94 V-0 | 13 |
| Application example 3 | 39.8 | UL94 V-0 | 10 |
| Application example 4 | 35.8 | UL94 V-1 | 19 |
| Application example 5 | 39.6 | UL94 V-0 | 11 |
| Application comparative example 1 | 30.8 | Grade free | 35 |
| Comparative application example 2 | 32.5 | UL94 V-2 | 41 |
| Application contrastExample 3 | 31.1 | Grade free | 24 |
| Application comparative example 4 | 31.9 | UL94 V-2 | 36 |
As can be seen from the above table 2, the PEIP-Mo prepared in the examples 1-3 can be applied to the chloroprene rubber to well improve the flame retardant property of the chloroprene rubber material. In the application comparative example 4, the flame retardant property of the material obtained by mixing the chloroprene rubber with the mixture of the PEIP and the ammonium octamolybdate is significantly lower than that of the application example 1, which shows that the PEIP and the ammonium octamolybdate can be used as a flame retardant to improve the flame retardant property of the material after a chemical reaction.
Finally, it should be noted that the specific examples described herein are merely illustrative of the spirit of the invention and do not limit the embodiments of the invention. Various modifications, additions and substitutions for the embodiments described herein will occur to those skilled in the art, and all such embodiments are neither required nor possible. While the invention has been described with respect to specific embodiments, it will be appreciated that various changes and modifications may be made without departing from the spirit and scope of the invention, as defined by the appended claims.
Claims (10)
1. A novel Mo-based polymer, wherein the Mo-based polymer has the general structural formula shown in formula I below:
wherein n is an integer of 1 to 1000.
2. The Mo-based polymer according to claim 1, wherein the Mo-based polymer is obtained by reacting a polyethyleneimine derivative having a general structural formula shown in formula II below with ammonium octamolybdate in an aqueous medium;
wherein n is an integer of 1 to 1000.
3. The Mo-based polymer according to claim 2, wherein the molar ratio of polyethyleneimine derivative to ammonium octamolybdate is from 1: (0.1-1).
4. The Mo-based polymer according to claim 2, wherein the polyethyleneimine derivative is reacted with ammonium octamolybdate in an aqueous medium under reflux at 100 to 120 ℃ for 5 to 10 hours.
5. The Mo-based polymer according to claim 2, wherein the polyethyleneimine derivative is prepared by a process comprising the steps of: dissolving phosphorous acid and polyethyleneimine in concentrated acid, heating to 100-130 ℃, then dropwise adding a formaldehyde water solution, carrying out reflux reaction for 2-10 h, cooling to room temperature, adding a neutralizer to adjust the pH value to be neutral, filtering and collecting precipitates, cleaning, and drying to obtain the polyethyleneimine derivative.
6. The Mo-based polymer of claim 5 wherein the molar ratio of phosphorous acid to amino groups in polyethyleneimine is (0.05-0.4): 1.
7. the Mo-based polymer according to claim 5, wherein the mass percent of formaldehyde in the aqueous formaldehyde solution is 35 to 45 wt.%.
8. A method for preparing a novel Mo-based polymer according to claim 1, comprising the steps of:
adding polyethyleneimine derivative, ammonium octamolybdate and water into a reaction bottle, carrying out reflux reaction, filtering after reaction to obtain a precipitate, and cleaning and drying the precipitate to obtain the novel Mo-based polymer.
9. The method according to claim 8, wherein the molar ratio of polyethyleneimine derivative to ammonium octamolybdate is 1: (0.1-1);
and/or the reflux reaction temperature is 100-120 ℃, and the reflux reaction time is 5-10 hours.
10. Use of the novel Mo-based polymer of claim 1 in high molecular weight polymers.
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