CN109912799B - Phosphorus-containing organic silicon flame retardant and preparation and application thereof - Google Patents
Phosphorus-containing organic silicon flame retardant and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a phosphorus-containing organosilicon flame retardant, which is prepared by taking gamma-aminopropyltriethoxysilane (KH-550), formaldehyde and phosphorous acid as raw materials and simultaneously performing Mannich reaction and intermolecular cross-linking polymerization, and has a structure represented by a structural formula (I):
the phosphorus-containing organic silicon flame retardant can well play the synergistic flame-retardant effect of silicon/phosphorus, and can be applied to a PET material to prepare a PET flame-retardant composite material, so that the flame-retardant property of the PET material can be obviously improved, the smoke suppression property of the PET material can be improved, and the smoke yield of the PET during combustion can be reduced.
Description
Technical Field
The invention belongs to the technical field of preparation of organic silicon flame retardants, and relates to a phosphorus-containing organic silicon flame retardant and a preparation method thereof.
Background
The main cause of death from fire is not the thermal hazard, but the inhalation of toxic fumes. The smoke not only can reduce the visibility of the environment, but also can paralyze the nerves of the human body by the toxic gas contained in the smoke, so that the escape and rescue actions are very difficult. In addition, the higher heat in the flue gas can accelerate flame propagation and also can bring thermal hazards to trapped people. Therefore, it is important to improve the smoke suppression of the material, thereby reducing the release of smoke and toxic gases, and maintaining the life safety of people.
Polyethylene terephthalate (PET) is an important semicrystalline thermoplastic polyester, and is widely used in packaging materials and home textiles due to its low price, excellent mechanical properties, and good dimensional stability. However, the Limiting Oxygen Index (LOI) of PET itself is low, only about 21%, and it is flammable material, and it is very easy to cause fire, thus greatly limiting some potential applications of PET. In addition, PET still has comparatively serious molten droplet phenomenon when burning, and can produce a large amount of black smoke and toxic gas, and is great to environment and human harm. Therefore, in order to widen the application field of PET and maintain environmental and life safety, it is necessary to modify PET to improve the flame retardant and smoke suppressing properties of PET.
Additive flame retardants are currently the focus of research. For PET, conventional additive-type flame retardants mainly include inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide; phosphorus-based flame retardants such as ammonium polyphosphate (APP), triphenyl phosphate (TPP), 9, 10-dioxa-10-phospha non-10-oxide (DOPO); nitrogen-based flame retardants such as melamine, melamine phosphate. However, various flame retardants have certain disadvantages. The inorganic flame retardant has good flame retardant effect, but has larger addition amount, and the mechanical property of the material is damaged while the flame retardant property of the material is improved. The phosphorus flame retardant has the disadvantages of poor thermal stability and easy hydrolysis. The nitrogen flame retardant has poor dispersibility in the material and strict requirements on particle size and particle size distribution.
The organic silicon flame retardant is a semi-inorganic high molecular material which takes-Si-O-Si-bond as a molecular main chain and has a side group connected with an organic group. As a high-efficiency, low-toxicity and environment-friendly halogen-free flame retardant, the halogen-free flame retardant has excellent thermal stability, almost all has a burning point above 300 ℃, has flame retardancy, and has little influence on the processability and physical and mechanical properties of plastic rubber.
The organosilicon flame retardant is not good when being used as a flame retardant additive alone, and is often used as a flame retardant synergist. The reason for this is that the organosilicon flame retardant cannot promote the carbonization of the substrate during combustion, and thus a relatively continuous and dense carbon layer is formed.
Xylonite and the like (preparation of phosphorus-silicon-containing flame-retardant PET and structure and performance research thereof [ J)]The synthetic fiber industry, 2016, 39(2): 39-43), introduces flame retardant [ (6-oxo-6H-dibenzo [ c, e ] on PET molecular chain by copolymerization method][1,2]Oxaphosphohexa-6-yl) methyl]Succinic acid (DDP) to prepare phosphorus-containing flame-retardant PET composite material, and then SiO is introduced by a blending method2Thus obtaining the PET composite material containing phosphorus and silicon. The flame retardant property of the PET composite material prepared by the method is greatly improved, but the grafting copolymerization difficulty is increased along with the increase of the content of DDP in a system, and the DDP can inhibit the crystallization of PET molecules, and meanwhile, the copolymerization method has harsh conditions and higher experimental difficulty. In addition, SiO is used2The blending method introduces Si element due to SiO2Belonging to inorganic substances, and deteriorating the mechanical properties of the PET matrix.
CN 105732987a relates to an isocyanate group-containing organopolysiloxane compound, a method for producing the same, an adhesive, a pressure-sensitive adhesive, and a coating agent, which are obtained by an ene-thiol addition reaction of an organopolysiloxane compound having a mercapto group and an isocyanate compound having a polymerizable group. The method has simple process and good feasibility, but the flame retardant contains halogen elements such as bromine and the like, generates toxic gas during combustion, and is safe and unfavorable for people and environment.
CN 107698765A discloses a nitrogen-containing phosphorus-silicon flame retardant and a preparation method thereof, wherein the preparation method comprises the following two steps: 1) nucleophilic substitution of phenol and hexachlorocyclotriphosphazene to synthesize the cyclotriphosphazene derivative partially substituted by phenol; 2) and (3) nucleophilic substitution is further carried out on the cyclotriphosphazene derivative and hydroxyl silicone oil, so as to prepare the nitrogen-containing phosphorus-silicon flame retardant. The method for preparing the nitrogen-phosphorus-containing silicon cyclotriphosphazene flame retardant is simple to operate and mild in synthesis conditions, but the reaction raw material hexachlorocyclotriphosphazene belongs to a volatile toxic compound, so that certain danger exists in the experimental process, and the chlorine-containing components cannot be completely removed by post-reaction treatment.
Disclosure of Invention
The invention aims to provide a novel phosphorus-containing organic silicon flame retardant without toxic components and a preparation method of the phosphorus-containing organic silicon flame retardant.
The invention also provides the application of the phosphorus-containing organic silicon flame retardant in the PET material.
The phosphorus-containing organic silicon flame retardant is prepared by taking gamma-aminopropyltriethoxysilane (KH-550), formaldehyde and phosphorous acid as raw materials, introducing a phosphorus-containing group on an amino group of the gamma-aminopropyltriethoxysilane through a Mannich reaction, and performing intermolecular cross-linking polymerization, and has a structure represented by the following structural formula (I):
the phosphorus-containing organic silicon flame retardant represented by the structural formula (I) can be named poly N, N-dimethylene phosphate amino propyl siloxane (PDPSI).
Furthermore, the molar ratio of the raw material gamma-aminopropyltriethoxysilane (KH-550) to the formaldehyde to the phosphorous acid is 1: 1.5-3: 2-3.5. The weight average molecular weight of the prepared phosphorus-containing organic silicon flame retardant is 5K-14K, the number average molecular weight is 3K-10K, and the molecular weight distribution is 3-7.
Specifically, the phosphorus-containing organosilicon flame retardant is prepared by the following method: in the presence of hydrochloric acid, adding gamma-aminopropyltriethoxysilane (KH-550) into a phosphorous acid aqueous solution, then adding a formaldehyde solution to perform aminomethylation reaction of amino, formaldehyde and phosphorous acid, introducing a phosphorus-containing group on the amino of the gamma-aminopropyltriethoxysilane, and simultaneously performing intermolecular cross-linking polymerization of a silicon-oxygen bond under the catalytic action of hydrochloric acid, thereby preparing the poly-N-dimethylene phospho-aminopropylsiloxane (PDPSI).
More specifically, in the preparation method, the mixed solution of phosphorous acid and KH-550 is subjected to reflux reaction at 75-85 ℃ under an acidic condition, and then formaldehyde solution is added to continue the reflux reaction.
Wherein the refluxing reaction time of the mixed solution of the phosphorous acid and the KH-550 is preferably 0.8-1.5 h. And after adding the formaldehyde solution, continuously carrying out reflux reaction for 3-5 h.
In the preparation method, the reaction product is precipitated by excessive absolute ethyl alcohol, and the phosphorus-containing organic silicon flame retardant can be obtained.
More specifically, the precipitate obtained is dried at 100 ℃ for 10h to finally obtain white powder of the phosphorus-containing organosilicon flame retardant.
The phosphorus-containing organic silicon flame retardant is prepared by introducing phosphorus element into the organic silicon flame retardant. The organic silicon has stronger hydrophobicity, can solve the defect that the phosphorus flame retardant is easy to hydrolyze, and can improve the compatibility of the flame retardant and a substrate and overcome the defect that the phosphorus flame retardant is easy to separate out by taking the organic silicon as a semi-inorganic material; meanwhile, the introduction of the phosphorus flame retardant also improves the catalytic carbon formation capability of the organic silicon flame retardant. Therefore, the phosphorus-containing organic silicon flame retardant prepared by the invention can better play the synergistic flame-retardant role of silicon/phosphorus.
The phosphorus-containing organic silicon flame retardant has the advantages of simple synthetic route, mild reaction process and controllable reaction conditions, and the prepared phosphorus-containing organic silicon flame retardant does not contain toxic components.
The phosphorus-containing organic silicon flame retardant prepared by the invention is applied to the PET material to prepare the PET flame-retardant composite material, so that the flame retardant property of the PET material can be obviously improved, the smoke suppression property of the PET material is improved, and the smoke output of the PET during combustion is reduced.
Specifically, the PET flame-retardant composite material is prepared by a melting and blending method of a phosphorus-containing organic silicon flame retardant and PET slices.
More specifically, the phosphorus-containing organic silicon flame retardant and the PET slices are subjected to melt blending at 255-265 ℃, wherein the phosphorus-containing organic silicon flame retardant accounts for 1-5% of the mass of the PET flame-retardant composite material.
The PET flame-retardant composite material prepared by the invention not only improves the flame retardance of PET, but also reduces the smoke output of PET during combustion and improves the smoke suppression performance of the PET.
The phosphorus-containing organic silicon flame retardant prepared by the invention can reduce the heat release rate of the polymer, improve the flame retardance, reduce the smoke output, inhibit the diffusion of smoke and improve the smoke suppression property. Meanwhile, the double effects of flame retardance and smoke suppression are exerted, and the fire hazard during the combustion of the polymer is greatly reduced.
Drawings
FIG. 1 is SEM and EDS spectra of PDPSI prepared in example 1.
FIG. 2 is an FT-IR spectrum of PDPSI prepared in example 1.
FIG. 3 is a thermogravimetric plot of the preparation of PDPSI of example 1.
FIG. 4 is a thermogravimetric plot of a PDPSI/PET composite.
FIG. 5 is a graph of Heat Release Rate (HRR) and Total Heat Released (THR) for a PDPSI/PET composite.
FIG. 6 is a plot of smoke generation rate (SPR) and Total Smoke Production (TSP) for the PDPSI/PET composite.
Figure 7 is a digital photograph of carbon residue from the PDPSI/PET composite.
FIG. 8 is a SEM image of carbon residue of the PDPSI/PET composite material.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1.
5g phosphorous acid was weighed and added to a beaker containing 10ml distilled water, and stirred to be sufficiently dissolved.
4.5g of gamma-aminopropyltriethoxysilane (KH-550) was weighed, slowly added to the above phosphorous acid solution with a dropper, and dissolved by stirring uniformly.
Adding the mixed solution into a three-neck flask provided with a spherical condenser tube and a stirrer, cooling, refluxing, heating in water bath to 80 ℃, adding 5ml of concentrated hydrochloric acid, refluxing for 1h, slowly adding 5ml of 37wt% formaldehyde solution, and continuously refluxing for 3.5 h.
After the reaction was completed, the reaction solution was poured into a beaker, and an excess amount of anhydrous ethanol was added to precipitate and rapidly stirred to obtain a white solid powder. And (3) carrying out suction filtration on the solid powder, washing the solid powder twice by using absolute ethyl alcohol, drying the solid powder for 10 hours at the temperature of 100 ℃, and grinding the solid powder to prepare the phosphorus-containing organic silicon flame retardant poly N, N-dimethylene phospho-aminopropyl siloxane (PDPSI).
In the embodiment, the weight average molecular weight of the PDPSI is 10-14K, the number average molecular weight is 8-10K, and the molecular weight distribution is 4-7.
The microscopic morphology of the PDPSI was analyzed by Scanning Electron Microscopy (SEM) and the results are shown in FIG. 1. As can be seen from the figure, the PDPSI has a certain degree of agglomeration and the particle size is about 1-3 μm. And the PDPSI contains abundant C, N, O, P, Si elements and the like as can be seen by element analysis of an energy spectrometer (EDS).
The structure of the PDPSI was analyzed in conjunction with the FT-IR spectrum shown in FIG. 2. 2988cm-1And 2883cm-1Is a long-chain methylene group- (CH)2)3Middle C-H stretching vibration absorption peak, 706cm-1And 750cm-1Is the in-plane rocking vibration absorption peak of methylene; 2606cm-1And 2753cm-1The peak at (A) is assigned to the vibration absorption peak of phosphorus hydroxyl (P-OH) and is 1017cm-1The position is the absorption peak of the P = O bond, thus indicating the presence of a phosphate group; 1135cm-1And 1208cm-1Is the stretching vibration absorption peak of Si-O-Si, 3400cm-1Is the vibration absorption peak of Si-OH. The EDS and FT-IR analysis results prove that the phosphorus-containing organic silicon flame retardant PDPSI prepared by the invention has a structure shown in a structural formula (I).
The decomposition temperature and the char-forming ability are important factors in judging whether the flame retardant can exert a flame-retardant effect on the polymer. The high decomposition temperature can improve the thermal stability of the composite material, and the good carbon forming capability can promote the formation of a stable carbon layer when the matrix is burnt. The thermal stability of PDPSI under nitrogen was analyzed by thermogravimetric analysis and the results are shown in figure 3. From the thermogravimetric plot, the initial decomposition temperature (T) of PDPSI5%) The temperature was 261 ℃. The PDPSI has a large number of hydroxyl groups on the surface, so that the PDPSI has the advantages of high stability and high stabilityThe initial decomposition temperature is low, and the existence of terminal Si-OH can cause the molecular chain depolymerization of PDPSI, generate a large amount of cyclic organosilicon oligomer, and simultaneously, hydroxyl groups can be dehydrated and condensed to form a cross-linked network structure. However, the initial decomposition temperature of the PDPSI is still higher than the processing temperature (255 ℃) of PET, so that the processing requirement is met. Moreover, the carbon residue of the PDPSI at 800 ℃ is as high as 62.17 percent, which indicates that the PDPSI has better carbon forming capability.
Example 2.
2.5g phosphorous acid was weighed into a beaker containing 10ml distilled water and stirred to dissolve it sufficiently.
4.5g of gamma-aminopropyltriethoxysilane (KH-550) was weighed, slowly added to the above phosphorous acid solution with a dropper, and dissolved by stirring uniformly.
Adding the mixed solution into a three-neck flask provided with a spherical condenser tube and a stirrer, cooling, refluxing, heating in water bath to 80 ℃, adding 5ml of concentrated hydrochloric acid, refluxing for 1h, slowly adding 3.5ml of 37wt% formaldehyde solution, and continuously refluxing for 3 h.
After the reaction was completed, the reaction solution was poured into a beaker, and an excess amount of anhydrous ethanol was added to precipitate and rapidly stirred to obtain a white solid powder. And (3) carrying out suction filtration on the solid powder, washing the solid powder twice by using absolute ethyl alcohol, drying the solid powder for 10 hours at the temperature of 100 ℃, and grinding the solid powder to prepare the phosphorus-containing organic silicon flame retardant poly N, N-dimethylene phospho-aminopropyl siloxane (PDPSI).
In the embodiment, the weight average molecular weight of the PDPSI is 5-14K, the number average molecular weight is 3-10K, and the molecular weight distribution is 3-7.
Example 3.
3.3g phosphorous acid was weighed into a beaker containing 10ml distilled water and stirred to dissolve it sufficiently.
4.5g of gamma-aminopropyltriethoxysilane (KH-550) was weighed, slowly added to the above phosphorous acid solution with a dropper, and dissolved by stirring uniformly.
Adding the mixed solution into a three-neck flask provided with a spherical condenser tube and a stirrer, cooling, heating in a water bath under reflux to 85 ℃, adding 5ml of concentrated hydrochloric acid, carrying out reflux reaction for 0.8h, slowly adding 6ml of 37wt% formaldehyde solution, and continuing to carry out reflux reaction for 5 h.
After the reaction was completed, the reaction solution was poured into a beaker, and an excess amount of anhydrous ethanol was added to precipitate and rapidly stirred to obtain a white solid powder. And (3) carrying out suction filtration on the solid powder, washing the solid powder twice by using absolute ethyl alcohol, drying the solid powder for 10 hours at the temperature of 100 ℃, and grinding the solid powder to prepare the phosphorus-containing organic silicon flame retardant poly N, N-dimethylene phospho-aminopropyl siloxane (PDPSI).
In the embodiment, the weight average molecular weight of the PDPSI is 7-14K, the number average molecular weight is 4-10K, and the molecular weight distribution is 3-7.
Example 1 is applied.
The PET chips were dried in a vacuum drum dryer at 120 ℃ for 12h and the PDPSI prepared in example 1 was dried in an electrothermal forced air dryer at 100 ℃ for 6 h.
According to the mass ratio of PDPSI to the composite material slices of 1%, 2%, 3%, 4% and 5%, adding the dried PDPSI with different masses into a side feeding port of a double-screw extruder, adding PET through a main feeding port, controlling the melt temperature to be 270-280 ℃ and the melt pressure to be 0.6-1.5 MPa, carrying out melt blending through the double-screw extruder, carrying out wire drawing and grain cutting, and preparing the PDPSI/PET composite material slices containing different mass fractions, namely PP-1, PP-2, PP-3, PP-4 and PP-5.
Under the same conditions, pure PET slices were prepared without adding PDPSI.
Thermogravimetric analysis is adopted to research the thermal degradation behavior of the PET and PDPSI/PET composite material under the nitrogen atmosphere, and the specific result is shown in figure 4.
As can be seen from FIG. 4, the initial decomposition temperature of pure PET was 438.2 ℃, the rate of thermal weight loss was maximized at 476.5 ℃ and the amount of carbon residue was 13.4% at 800 ℃.
Compared with pure PET, the initial decomposition temperature, the maximum thermal weight loss temperature and the 800 ℃ carbon residue amount of the PDPSI/PET composite material are increased. Particularly, the initial decomposition temperature of PP-5 is delayed by 41.9 ℃, the carbon residue at 800 ℃ is 17.0 percent and is improved by 26.9 percent, which shows that the thermal stability of PET is improved and the carbon forming capability of PET at high temperature is enhanced by adding PDPSI.
As can be seen from the thermal degradation behavior of the PDPSI in FIG. 3, the initial decomposition temperature of the PDPSI itself is 261 deg.C, much lower than that of pure PET. Theoretically, if no chemical reaction between the PDPSI and PET occurs, the initial decomposition temperature of the PDPSI/PET composite material should be advanced. Therefore, it is presumed that the crosslinking structure is formed by the dehydration of the hydroxyl group of the PDPSI and the carboxyl group at the end of the PET molecular chain, and at the same time, the network structure formed by the dehydration and condensation of the PDPSI covers the PET surface, which protects the underlying substrate, thereby delaying the initial decomposition temperature of the PDPSI/PET composite material and increasing the carbon residue thereof.
In the process, the invention carries out CONE Calorimetry (CONE) test on the PDPSI/PET composite material so as to further analyze the flame retardant property of the composite material. The CONE method can be used for simulating the combustion condition of the material in a real fire and characterizing the combustion behavior of the material through a series of parameters.
First, fig. 5 shows a graph of Heat Release Rate (HRR) (a) and Total Heat Released (THR) (b) of the PDPSI/PET composite. HRR is one of the important fire performance parameters of a material, and the smaller the value, the lower the risk level of the material when burning. As can be seen from FIGS. 5(a) and (b), the addition of PDPSI significantly reduced the HRR and THR of the PDPSI/PET composite.
The peak values of the heat release rate (PHRR) and THR of pure PET were 513.22kW/m, respectively2And 71.9MJ/m2When the amount of the PDPSI added is 3%, the PHRR of the PP-3 is 147.88kW/m2Compared with pure PET, the THR is reduced by 71.19 percent and 29.06 percent. The PDPSI is added, so that a continuous and compact carbon layer is formed on the surface of the base body when the PET is burnt, the transmission of oxygen is inhibited, and the lower base body is protected from being burnt.
Next, FIG. 6 is a graph of the smoke generation rate (SPR) (a) and Total Smoke Production (TSP) (b) of the PDPSI/PET composite. As seen in FIG. 6(a), the addition of PDPSI significantly suppressed the release of smoke, indicating that PDPSI has some smoke suppression effect. As seen in FIG. 6(b), the Total Smoke Production (TSP) of the PDPSI/PET composite is significantly lower than that of pure PET.
When the addition amount of the PDPSI is 3 percent, the TSP of the PP-3 is 11.1m2Compared with pure PET, the product has 22.92% lower effect. The possible flame-retardant and smoke-suppression mechanism is analyzed as follows: at the initial stage of combustion of the PDPSI/PET composite material, the flame retardant PDPSI is firstly heated and decomposed to generate phosphide, so that the matrix is promotedAromatization reaction, thereby forming a carbon layer to cover the surface of the substrate and protecting the lower substrate from being combusted; meanwhile, under the catalysis of phosphoric acid, the terminal Si-OH of the PDPSI has dehydration condensation reaction with the terminal-OH of a PET molecular chain besides self dehydration condensation, so that an interpenetrating network structure is formed, and the continuity and compactness of a carbon layer are improved; the P = O bond unit generated by the phosphate group can be bonded with a reaction point with an oxidation tendency on the surface of the carbon layer, so that the carbon layer is passivated, and the permeability of the carbon layer is reduced; moreover, because the surface energy of Si atoms is low, the Si atoms can also migrate to the surface of a substrate in the combustion process, and a layer of SiO is formed on the surface of a generated carbon layer2The layer further enhances the thermal oxygen stability and compactness of the carbon layer. The compact and continuous carbon layer with good thermal stability plays roles in isolating oxygen transmission and inhibiting heat diffusion, thereby effectively protecting the lower-layer matrix and achieving the purposes of inflaming retarding and smoke inhibiting.
Figures 7 and 8 provide digital photographs and SEM images, respectively, of carbon residue after cone calorimetry testing of the PDPSI/PET composite. Wherein, A-1, B-1, C-1, D-1, E-1, F-1 in figure 7 and A-2, B-2, C-2, D-2, E-2, F-2 in figure 8 correspond to materials PET and PP-1, PP-2, PP-3, PP-4, PP-5 respectively.
According to the A-1/A-2 of PET, the residual carbon content of pure PET after combustion is small, a complete carbon layer is difficult to form to cover the surface of a matrix, and the formed carbon layer is formed by stacking a plurality of thin fragments, so that the carbon layer is loose, the surface of the carbon layer has a plurality of holes, and the heat diffusion and the oxygen transmission cannot be effectively isolated. By contrast, after the PDPSI is added into the PET matrix, the residual carbon amount of the PDPSI/PET composite material after combustion is obviously increased (B-1-F-1 in figure 7), which shows that the PDPSI can improve the carbon forming capability of PET.
It is noted that the carbon layers formed by E-1 and F-1 in FIG. 7 were fractured, and the analysis reason may be that the carbon layers were fractured due to stress concentration caused by non-uniform dispersion due to the large addition amount of the flame retardant.
From SEM images (B-2 to F-2 in FIG. 8) of carbon residue after combustion of the PDPSI/PET composite material, it can also be seen that, after the PDPSI flame retardant is added, the surface pores of the carbon layer are reduced and a plurality of honeycomb structures are formed. The carbon layer formed after combustion of the composite was more dense and continuous than pure PET (a-2 in fig. 8).
Therefore, when the PDPSI/PET composite material is combusted, the excellent carbon layer structure can fully isolate the transmission of oxygen and the diffusion of heat, and effectively protect the lower-layer matrix. Meanwhile, the compact carbon layer structure can well inhibit the release of smoke particles, thereby achieving the purposes of inflaming retarding and smoke inhibition.
EDS (electron-ray diffraction) elemental analysis of the residual carbon shows that the residual carbon contains flame-retardant elements such as N, P, Si and the like, and the PDPSI can participate in a carbon forming reaction when a matrix is combusted, so that the matrix is promoted to form a cross-linked reticular carbon layer to cover the surface of the matrix, and the function of protecting a polymer is achieved.
Claims (9)
1. A phosphorus-containing organosilicon flame retardant is prepared by taking gamma-aminopropyltriethoxysilane, formaldehyde and phosphorous acid as raw materials, introducing a phosphorus-containing group on an amino group of the gamma-aminopropyltriethoxysilane through a Mannich reaction, and performing intermolecular cross-linking polymerization, and has a structure represented by the following structural formula (I):
2. the phosphorus-containing organic silicon flame retardant of claim 1, wherein the molar ratio of the raw materials of gamma-aminopropyltriethoxysilane, formaldehyde and phosphorous acid for preparing the phosphorus-containing organic silicon flame retardant is 1: 1.5-3: 2-3.5, and the prepared phosphorus-containing organic silicon flame retardant has the weight-average molecular weight of 5-14K, the number-average molecular weight of 3-10K and the molecular weight distribution of 3-7.
3. The preparation method of phosphorus-containing organosilicon flame retardant of claim 1, comprising the steps of adding gamma-aminopropyltriethoxysilane into phosphorous acid aqueous solution in the presence of hydrochloric acid, then adding formaldehyde solution to perform aminomethylation reaction of amino group with formaldehyde and phosphorous acid, introducing phosphorus-containing group on amino group of gamma-aminopropyltriethoxysilane, and simultaneously performing intermolecular cross-linking polymerization of silicon-oxygen bond under the catalysis of hydrochloric acid to prepare the phosphorus-containing organosilicon flame retardant.
4. The preparation method of claim 3, wherein the mixed solution of phosphorous acid and gamma-aminopropyltriethoxysilane is refluxed at 75-85 ℃ under acidic condition, and then formaldehyde solution is added for continuous reflux reaction.
5. The preparation method of claim 4, wherein the reflux reaction time of the mixed solution of phosphorous acid and gamma-aminopropyltriethoxysilane is 0.8-1.5 h, and the reflux reaction is continued for 3-5 h after the formaldehyde solution is added.
6. Use of the phosphorus containing silicone flame retardant of claim 1 as a flame retardant for PET materials.
7. A PET flame-retardant composite material prepared by the phosphorus-containing organic silicon flame retardant of claim 1 and PET slices through a melt blending method.
8. The PET flame-retardant composite material according to claim 7, wherein the phosphorus-containing organosilicon flame retardant accounts for 1-5% of the mass of the PET flame-retardant composite material.
9. The PET flame-retardant composite material as claimed in claim 7 or 8, wherein the phosphorus-containing silicone flame retardant and the PET chips are melt-blended at 255-265 ℃.
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| CN111234235B (en) * | 2020-02-24 | 2022-05-13 | 桂林理工大学 | Oligomeric silicon-oxygen phosphate flame retardant and preparation method and application thereof |
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