CN115626985A - A kind of novel Mo base polymer and its preparation method and application - Google Patents

Abstract

The invention belongs to the technical field of polymer materials, and relates to a novel Mo-based polymer and a preparation method and application thereof. The preparation method includes the following steps: dissolving phosphorous acid and polyethyleneimine in concentrated acid, heating until the temperature rises to 100-130°C, adding formaldehyde solution dropwise, and reacting under reflux for 2-10 hours, cooling to room temperature, adding Neutralizer to adjust the pH value to neutral, filter and collect the precipitate, wash and dry to obtain polyethyleneimine derivatives; add polyethyleneimine derivatives, ammonium octamolybdate and water into the reaction bottle, reflux reaction, after reaction The precipitate was obtained by filtration, washed and dried to obtain a new Mo-based polymer. The method for preparing the Mo-based polymer in the invention is simple and easy to realize industrialized production, and the prepared Mo-based polymer is used as a flame retardant, which is green, environmentally friendly and more efficient.

Description

A kind of novel Mo base polymer and its preparation method and application

technical field

The invention belongs to the technical field of polymer materials, and relates to a novel Mo-based polymer and its preparation method and application.

Background technique

In recent years, with the enhancement of people's awareness of fire prevention, the demand for flame retardants has risen sharply, and the research and development of flame retardant materials has become increasingly active in various countries around the world, and various flame retardant products have come out continuously. The silicon-based flame retardant contains a large amount of silicon and oxygen elements, which can endow the material with excellent thermal and mechanical properties, and can also form a dense silicon dioxide layer similar to ceramics when burning, which can effectively isolate oxygen and heat and reduce the diffusion of combustible gases. Inhibit the combustion process; however, the flame retardant effect of a single silicon-based flame retardant is limited, and it is generally used in conjunction with other flame retardants. Halogenated flame retardants, mainly gas-phase flame retardants, have good flame retardant effects, but they release toxic and corrosive gases during combustion, which poses great hidden dangers to humans and the environment. For this reason, in the two directives of the "Waste Electrical and Electronic Equipment Directive" (WEEE) and the "Directive on the Prohibition of Hazardous Substances in Electrical and Electronic Equipment" (RoHS) promulgated by the European Union in 2003, it is strictly forbidden to add harmful halogens such as polybrominated diphenyl ethers to electronic appliances. Department of flame retardants. Compared with halogenated flame retardants, inorganic flame retardants based on endothermic flame retardants and intumescent flame retardants (IFR) based on condensed phase flame retardants are currently recognized as environmentally friendly "green flame retardants" by the scientific and industrial circles. "Flame retardants, but this kind of flame retardants often need a higher amount of addition to make the material achieve the expected flame retardant effect, the flame retardant efficiency is low, and the mechanical properties and processing properties of the material are greatly damaged. At the same time, Poor thermal stability and low decomposition temperature cause difficulties in the processing and recycling of flame-retardant polymers.

Contents of the invention

The present invention aims at the deficiencies in the prior art. The present invention synthesizes a novel Mo-based polymer for the first time, which can exert excellent flame-retardant performance when applied to high molecular polymers.

One aspect of the present invention provides a novel Mo-based polymer, the Mo-based polymer has a general structural formula shown in the following formula I:

However, n is an integer of 1-1000.

Preferably, the Mo-based polymer is obtained by reacting polyethyleneimine derivatives with the general structural formula shown in the following formula II with ammonium octamolybdate in an aqueous medium;

However, n is an integer of 1-1000.

The polyethylenimine derivative is combined with the molybdate group in ammonium octamolybdate through the combination of proton-carrying amino group and molybdate group in water, so as to prepare the Mo-based polymer.

Preferably, the molar ratio of polyethyleneimine derivatives to ammonium octamolybdate is 1: (0.1-1).

Preferably, the polyethyleneimine derivative and ammonium octamolybdate are reacted under reflux and stirring at 100-120° C. for 5-10 hours in an aqueous medium.

Preferably, the polyethyleneimine derivatives are prepared by a method comprising the following steps: dissolving phosphorous acid and polyethyleneimine in concentrated acid, heating until the temperature rises to 100-130°C, adding formaldehyde solution dropwise, and refluxing After reacting for 2-10 hours, cool to room temperature, add a neutralizing agent to adjust the pH value to neutral, collect the precipitate by filtration, wash and dry to obtain polyethyleneimine derivatives.

Preferably, the molar ratio of phosphorous acid to amino groups in polyethyleneimine is (0.05-0.4):1.

Concentrated acids include, but are not limited to, concentrated hydrochloric acid, concentrated sulfuric acid, and the like.

Preferably, in the formaldehyde aqueous solution, the mass percentage of formaldehyde is 35-45 wt%.

As a neutralizing agent, diethanolamine can be mentioned.

Another aspect of the present invention provides the preparation method of above-mentioned novel Mo-based polymer, comprises the following steps:

Add polyethyleneimine derivatives, ammonium octamolybdate and water into a reaction bottle, reflux for reaction, filter after reaction to obtain a precipitate, wash and dry the precipitate to obtain a new Mo-based polymer.

In the preparation method, the molar ratio of polyethyleneimine derivatives and ammonium octamolybdate is 1: (0.1-1).

In the preparation method, the reflux reaction temperature is preferably 100-120° C., and the reflux reaction time is preferably 5-10 hours.

In the preparation method, washing the precipitate includes washing with absolute ethanol and hot water in sequence.

Another aspect of the present invention also provides the application of the above-mentioned novel Mo-based polymer in polymers.

High molecular polymers include but not limited to thermoplastic elastomers, rubber and engineering plastics, etc.; thermoplastic elastomers include but not limited to SBS, SEBS, EPDM, EPR, POE, etc., rubbers include but not limited to styrene-butadiene rubber, butadiene rubber, Neoprene, nitrile rubber, ethylene propylene rubber, butyl rubber, etc. Engineering plastics include but not limited to polypropylene, polyethylene, polyvinyl chloride, ABS, etc.

Mo-based polymers are used as flame retardants in high-molecular polymers, which can effectively improve the flame-retardant properties of high-molecular polymers.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The present invention has prepared and synthesized a kind of general formula Mo-based polymer with the structure shown in formula I for the first time;

(2) The present invention has prepared novel Mo-based polymers by reacting polyethyleneimine derivatives and ammonium octamolybdate in aqueous medium with general structural formula shown in the following formula II;

(3) Mo-based polymers are used as flame retardants in high molecular polymers, which can effectively improve the flame retardant properties of high molecular polymers;

(4) The method for preparing Mo-based polymers in the present invention is simple and easy to realize industrial production, and the prepared Mo-based polymers are used as flame retardants, which are green, environmentally friendly, and more efficient.

Description of drawings

Fig. 1 is the infrared spectrogram of the PEIP-Mo of embodiment 1 and the PEIP of comparative example 1;

Fig. 2 (a) is the TG curve of PEIP-Mo of embodiment 1 and the PEIP of comparative example 1, Fig. 2 (b) DTG curve of PEIP, PEIP-Mo.

Detailed ways

The technical solutions of the present invention will be further described below through specific embodiments and drawings. It should be understood that the specific embodiments described here are only used to help understand the present invention, and are not intended to specifically limit the present invention. Unless otherwise specified, the raw materials used in the examples of the present invention are commonly used raw materials in the art, and the methods used in the examples are conventional methods in the art.

Example 1

The novel Mo-based polymer of embodiment 1 is prepared by the following steps:

In a 250ml three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, add 0.02mol of phosphorous acid, 100ml of concentrated hydrochloric acid with a mass fraction of 37%, and polyethyleneimine (1mmol) with a degree of polymerization of 100. When heating to 110°C and starting to reflux, add 32ml of 37wt% formaldehyde solution dropwise to the three-necked flask at a rate of two drops per second, drop it into the flask within 1h, then continue the reaction for 7h under reflux, and cool down after the reaction to room temperature, and neutralized to neutrality with ethylene glycol amine, and the precipitate was collected by filtration, washed three times with absolute ethanol, and finally, dried under vacuum for 4 hours, and dried to obtain polyethylene glycol with the general structure shown in formula II. Amine derivative (PEIP); 73% yield.

Add 0.3 mol of ammonium octamolybdate and 1 mol of the polyethyleneimine derivative prepared above into a single-necked flask, and add 100 ml of deionized water into the flask, slowly raise the temperature to 110°C, reflux and stir for 7 hours, and cool to room temperature , filtered to obtain the precipitate, washed twice with absolute ethanol, then filtered again with hot water at 70°C, and then freeze-dried for 24 hours to a constant weight to obtain a new type of Mo-based polymer (PEIP-Mo), which was blue-green and produced The rate is 72%.

Comparative example 1

The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 only prepared polyethyleneimine derivatives (PEIP) with the general structure shown in Formula II.

Infrared spectrum analysis and thermogravimetric analysis were performed on the PEIP-Mo of Example 1 and the PEIP of Comparative Example 1. FIG. 1 is the infrared spectrogram of the PEIP-Mo of Example 1 and the PEIP of Comparative Example 1. PEIP-Mo exhibits a peak around 1168 cm ^-1 , which is attributed to the P=O group in the side chain of PEIP. Meanwhile, another peak appeared around 1056 cm, which was attributed to the PO group in the side chain of ^PEIP . And there is a broad and shallow band at ^1967–2331 cm, revealing the presence of protonated amino groups in PEIP-Mo. PEIP-Mo has a group of strong peaks around 889cm- ¹ , which is attributed to the vibration absorption peak of the Mo=O double bond in ammonium octamolybdate, and the peak between 580-817cm ^-1 is Mo-O- The vibrational absorption peak of the Mo bond. In addition, a peak appears around 1468cm ^-1 , which appears weaker in PEIP-Mo, because the group and Mo-O- in ammonium octamolybdate combine with each other, weakening the absorption peak of the _NH2 ⁺ group . It can be found that the spectrum of PEIP-Mo roughly covers the spectrum of ammonium octamolybdate and PEIP. It can be explained that the envisaged flame retardant PEIP-Mo was successfully synthesized.

Fig. 2 (a) is the TG curve of the PEIP-Mo of embodiment 1 and the PEIP of comparative example 1, the DTG curve of Fig. 2 (b) PEIP, PEIP-Mo; Detailed data includes the onset temperature (T _onset ) of decomposition, Table 1 summarizes the maximum decomposition temperature (T _max ) and the percent residue at 800°C.

Table 1 TGA data of PEIP and PEIP-Mo in nitrogen

sample T_onset^a(℃) T_max^b(°C) Residual mass at 800°C (%) PEIP-Mo 221 218, 306, 59.4 PEIP 187 188, 300, 510 22.6

_Tonset ^a (°C) represents the temperature at which 95% remains after decomposition.

T _max ^b (°C) represents the peak temperature of DTG.

As shown in Fig. 2(a) and Table 1, with the addition of Mo, the initial decomposition temperature (T _onset ) of PEIP-Mo was 221 °C. In fact, PEIP has the lowest _Tonset , which is 187 °C, which means that the combination between PEIP and Mo will increase the thermal stability of PEIP-Mo.

The residue at 800 °C has the same trend as the _Tonset value of PEIP-Mo. The residue of PEIP-Mo at 800 °C is much higher than that of PEIP, which is 59.4%. The residue consisted of ammonium molybdate, which indicated that the addition of molybdenum contributed greatly to the amount of residue. The residual mass of PEIP at 800°C is very small, only 22.6%, indicating that molybdenum plays a role in the carbonization process.

Figure 2(b) shows that PEIP-Mo undergoes a multi-step thermal degradation process. PEIP-Mo exhibits two main weight loss stages, which can be attributed to the dehydration of PEIP and the formation of char layer. Pure PEIP is equivalent to adding zero parts of Mo, and the dehydration of PEIP will still occur, but the degree of crosslinking may not be like that of PEIP-Mo, so PEIP continues to decompose at a higher temperature (510 °C) until more Stable residue, therefore, PEIP forms minimal residue.

Example 2

The novel Mo-based polymer of embodiment 2 is prepared by the following steps:

In a 250ml three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, add 0.01mol of phosphorous acid, 100ml of concentrated hydrochloric acid with a mass fraction of 37%, and polyethyleneimine (1mmol) with a degree of polymerization of 100. When heating to 110°C and starting to reflux, add 30ml of 37wt% formaldehyde solution dropwise to the three-necked flask at a rate of two drops per second, drop it into the flask within 1h, then continue to react for 5h under reflux, and cool down after the reaction to room temperature, and neutralized to neutrality with ethylene glycol amine, and the precipitate was collected by filtration, washed three times with absolute ethanol, and finally, dried under vacuum for 4 hours, and dried to obtain polyethylene glycol with the general structure shown in formula II. Amine Derivatives (PEIP).

Add 0.5 mol of ammonium octamolybdate and 1 mol of the polyethyleneimine derivative prepared above into a single-necked flask, and add 100 ml of deionized water into the flask, slowly raise the temperature to 115°C, reflux and stir for 5 hours, and cool to room temperature , The precipitate was obtained by filtration, washed three times with absolute ethanol, then filtered once with hot water at 75°C, and then freeze-dried for 24 hours to a constant weight to obtain a new type of Mo-based polymer (PEIP-Mo).

Example 3

The novel Mo-based polymer of embodiment 3 is prepared by the following steps:

In a 250ml three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, add 0.04mol of phosphorous acid, 100ml of concentrated hydrochloric acid with a mass fraction of 37%, and polyethyleneimine (1mmol) with a degree of polymerization of 100. When heating to 110°C and starting to reflux, drop 40ml of 40wt% formaldehyde solution into the three-necked flask at a rate of two drops per second, drop it into the flask within 30min, then continue to react for 6h under reflux, and cool down after the reaction to room temperature, and neutralized to neutrality with ethylene glycol amine, the precipitate was collected by filtration, washed three times with absolute ethanol, and finally, dried under vacuum for 5 hours, and dried to obtain polyethylene glycol with the general structure shown in formula II Amine Derivatives (PEIP).

Add 0.6 mol of ammonium octamolybdate and 1 mol of the polyethyleneimine derivative prepared above into a one-necked flask, and add 100 ml of deionized water into the flask, slowly raise the temperature to 105°C, reflux and stir for 8 hours, and cool to room temperature , The precipitate was obtained by filtration, washed three times with absolute ethanol, then filtered once with hot water at 80°C, and then freeze-dried for 24 hours to a constant weight to obtain a new type of Mo-based polymer (PEIP-Mo).

Comparative example 2

The difference between comparative example 2 and embodiment 1 is:

Prepare polyethyleneimine derivatives with the method of embodiment 1, then add 0.3mol ammonium octamolybdate, 1mol above-mentioned prepared polyethyleneimine derivatives in a single-necked flask, and add 100ml deionized water in the flask, Stir at room temperature for 7 hours, filter to obtain the precipitate, wash twice with absolute ethanol, then filter once with hot water at 70°C, and freeze-dry for 24 hours to a constant weight to obtain the product.

Application Example 1

100 parts of chloroprene rubber and 10 parts of PEIP-Mo of Example 1 were mixed in an internal mixer at 60°C and a rotor speed of 60r/min, and then opened at room temperature until the rubber was mixed. After uniformity, it is cured on a vulcanizing machine, and the obtained film is cut according to the size required by the test for subsequent testing.

Application Example 2

The difference between application example 2 and application example 1 is that in application example 2, 100 parts of chloroprene rubber are mixed with 15 parts of PEIP-Mo of example 1.

Application Example 3

The difference between application example 3 and application example 1 is that in application example 3, 100 parts of chloroprene rubber are mixed with 20 parts of PEIP-Mo of example 1.

Application Example 4

The difference between application example 4 and application example 1 is that in application example 4, 100 parts of chloroprene rubber are mixed with 12 parts of PEIP-Mo of example 2.

Application Example 5

The difference between application example 5 and application example 1 is that in application example 5, 100 parts of chloroprene rubber are mixed with 16 parts of PEIP-Mo of example 3.

Application Comparative Example 1

The difference between Application Comparative Example 1 and Application Example 1 is that the PEIP-Mo of Example 1 is not added in Application Comparative Example 1.

Application Comparative Example 2

The difference between Application Comparative Example 2 and Application Example 1 is that 10 parts of PEIP of Comparative Example 1 are added to Application Comparative Example 2.

Application Comparative Example 3

The difference between Application Comparative Example 3 and Application Example 1 is that 10 parts of ammonium octamolybdate was added in Application Comparative Example 3.

Application Comparative Example 4

The difference between Application Comparative Example 4 and Application Example 1 is that 10 parts of the product of Comparative Example 2 are added to Application Comparative Example 4.

The flame retardant properties of the products of Application Examples 1-5 and Application Comparative Examples 1-4 are shown in Table 2.

Table 2 Flame retardant properties of the products of application examples 1-5 and application comparative examples 1-4

Oxygen Index% vertical burn rating Smoke density level SDR Application Example 1 35.3 UL94 V-1 twenty one 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 no grade 35 Application Comparative Example 2 32.5 UL94V-2 41 Application Comparative Example 3 31.1 no grade twenty four Application Comparative Example 4 31.9 UL94V-2 36

It can be seen from the above table 2 that the PEIP-Mo prepared in Examples 1-3 is applied to chloroprene rubber, which can well improve the flame retardancy of the chloroprene rubber material. In application comparative example 4, the mixture of PEIP and ammonium octamolybdate is mixed with chloroprene rubber, and the flame retardant performance is significantly lower than that of application example 1, indicating that PEIP and ammonium octamolybdate need to undergo a chemical reaction before they can be used as flame retardants. Improve the flame retardant properties of materials.

Finally, it should be noted that the specific embodiments described herein are only examples to illustrate the spirit of the present invention, rather than limiting the implementation of the present invention. Those skilled in the technical field to which the present invention belongs may make various modifications or supplements to the described embodiments, or replace them in similar ways, and it is not necessary and impossible to give a full example of all the embodiments here. However, the obvious changes or variations derived from the essential spirit of the present invention still belong to the protection scope of the present invention, and interpreting them as any additional limitation is contrary to the spirit of the present invention.

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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