CN109705634B - Attapulgite-based composite flame retardant modified by nitrogen-phosphorus-containing organic matter and preparation and application thereof - Google Patents
Attapulgite-based composite flame retardant modified by nitrogen-phosphorus-containing organic matter and preparation and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
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Abstract
The invention discloses an attapulgite-based composite flame retardant modified by nitrogen-phosphorus-containing organic matters, and a preparation method and an application thereof, wherein spiro pentaerythritol diphosphoric acid dichloride and 4,4 '-diaminodiphenylmethane are grafted on attapulgite through 4,4' -diphenylmethane diisocyanate, so that the attapulgite-based composite flame retardant is prepared, and can be used as a flame retardant in the fireproof application of polylactic acid materials. The composite flame retardant can be compounded into a polylactic acid matrix through a simple solution blending method, so that the mechanical property of the polylactic acid material can be improved, and the flame retardant property of the polylactic acid material can also be improved.
Description
Technical Field
The invention relates to a preparation method of a flame retardant, in particular to an attapulgite-based composite flame retardant modified by nitrogen-phosphorus-containing organic matters, and preparation and application thereof, belonging to the field of flame retardants.
Background
Polylactic acid (PLA) gradually comes into the sight of people as a polyester linear polymer material which is nontoxic, pollution-free, has good biocompatibility and can be decomposed and absorbed by organisms. The material which is known as green plastic is applied to all aspects of daily life. However, pure polylactic acid is not good in flame retardant property, and only up to UL94The grade HB and the limiting oxygen index are also lower, and only a shallow carbonized layer is formed during combustion, and then the carbonized layer is quickly liquefied, dripped and diffused for combustion, and is easy to move to cause larger accidents. In order to expand the application range and better meet certain applications in the fields of aviation, electronic appliances, automobiles and the like, more and more researchers are developing the research on the flame retardant modification of polylactic acid in recent years.
Attapulgite is also known as palygorskite and called universal clay, and structurally, the attapulgite is a porous layer chain silicate mineral, and the microstructure of the attapulgite generally comprises three layers of basic unit rod crystals, rod bundles generated by rod crystal aggregation and aggregate formed by rod crystal bundle aggregation. The attapulgite serving as a natural one-dimensional nano material is rich in reserves and excellent in performance, has strong rigidity due to the unique structure, has high temperature resistance as other inorganic clays, is filled into a polymer as a filler, improves the mechanical strength of the composite material, and reduces the cost.
Although the ATT is filled into the polylactic acid matrix, a series of mechanical properties of the material can be improved, but the flame retardant property of the polylactic acid cannot be improved. Therefore, a method for improving the flame retardant property of polylactic acid is desired to be developed. MDI has isocyanate groups with strong activity, MDA and PDD have N, P elements, and N, P elements in the polymer can improve the flame retardant property of the polymer.
Disclosure of Invention
The invention aims to provide an attapulgite-based composite flame retardant modified by nitrogen-phosphorus-containing organic matters, and preparation and application thereof. Pure attapulgite almost has no flame retardant property to the material, but because the attapulgite is a good filler, the mechanical property of the material can be improved by filling the attapulgite in a polymer, and the cost can be reduced. The technical problem to be solved by the invention is to synthesize a flame retardant, and graft the flame retardant on attapulgite, so that the attapulgite has a flame retardant effect on polymers.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention discloses a preparation method of an attapulgite-based composite flame retardant modified by nitrogen and phosphorus-containing organic matters, which is characterized by comprising the following steps: firstly, 4' -diphenylmethane diisocyanate MDI and attapulgite ATT are reacted to prepare attapulgite MDI-ATT containing isocyanate groups; then reacting 4,4' -diaminodiphenylmethane MDA with MDI-ATT to prepare attapulgite MDA-ATT containing amino; finally, the spiro pentaerythritol diphosphoric acid diphosphoryl chloride PDD reacts with amino on MDA-ATT, so that the attapulgite-based composite flame retardant PDATT modified by nitrogen-phosphorus containing organic matters is obtained; wherein, PDD is obtained by reacting phosphorus oxychloride with pentaerythritol.
Further, when the PDD is synthesized, the mass ratio of phosphorus oxychloride to pentaerythritol is 12.5: 1; when MDI-ATT is synthesized, the mass ratio of MDI to ATT is 1: 2; when the MDA-ATT is synthesized, the mass ratio of MDI-ATT to MDA is 2: 1; when PDATT is synthesized, the mass ratio of MDA-ATT to PDD is 2: 1.
Furthermore, the preparation method of the attapulgite-based composite flame retardant modified by the nitrogen-phosphorus-containing organic matter comprises the following steps:
Adding ATT into a three-neck flask, adding anhydrous DMF, and performing ultrasonic treatment to uniformly disperse ATT; introducing nitrogen to remove air in the three-neck flask, adding MDI, heating the oil bath kettle to 80 ℃ under the protection of nitrogen, and carrying out magnetic stirring reaction for 1 h; after the reaction is finished, washing unreacted MDI with anhydrous DMF, and then drying and grinding to prepare MDI-ATT;
step 2, grafting MDA to MDA-ATT to prepare MDA-ATT
Adding MDI-ATT and MDA into a three-neck flask, and adding anhydrous DMF for dispersion; introducing nitrogen to remove air in the three-neck flask, heating the oil bath kettle to 55 ℃ under the protection of the nitrogen, and carrying out magnetic stirring reaction for 12 hours; after the reaction is finished, sequentially washing with anhydrous DMF and acetone, drying and grinding to obtain MDA-ATT;
step 3, preparing PDATT
3a Synthesis of PDD by Oxidation
Taking pentaerythritol particles and phosphorus oxychloride liquid, adding the pentaerythritol particles and the phosphorus oxychloride liquid into a three-neck flask, and mixing; gradually heating the mixture to 110 ℃, magnetically stirring the mixture to react for 12 hours under the protection of nitrogen, and absorbing HCl gas generated by the reaction by using NaOH aqueous solution; after the reaction is finished, obtaining a product through suction filtration, sequentially washing the product with carbon tetrachloride and ethanol, drying the product to constant weight, and grinding the product to obtain PDD;
3b, adding MDA-ATT and PDD into a three-neck flask, and then adding acetonitrile for dispersion; and introducing nitrogen to remove air in the three-neck flask, under the protection of nitrogen, heating the oil bath kettle to 80 ℃, carrying out reflux reaction for 2 hours, dropwise adding a drop of pyridine, reacting for 3 hours, stopping the reaction, cooling to room temperature, repeatedly washing, drying and grinding the product by using ethanol to obtain the PDATT.
The invention further discloses an application of the attapulgite-based composite flame retardant prepared by the preparation method, and the attapulgite-based composite flame retardant is used as a flame retardant in the fireproof application of polylactic acid materials. When in use, the attapulgite-based composite flame retardant is filled into the polylactic acid matrix by a solution blending method.
The spiro pentaerythritol diphosphoric acid diphosphoryl chloride and 4,4' -diaminodiphenylmethane which are grafted on the attapulgite-based composite flame retardant contain nitrogen and phosphorus elements, so the attapulgite-based composite flame retardant is a nitrogen-phosphorus synergistic flame retardant; in the combustion process of the polylactic acid, the attapulgite-based composite flame retardant is decomposed into phosphoric acid or polyphosphoric acid to promote the surface of the polylactic acid to be rapidly dehydrated and carbonized to form a carbonized layer, the flame retardant can be decomposed into nonvolatile glass materials, and meanwhile, nitrogen elements are decomposed to absorb heat and generate non-combustible gas to reduce the oxygen concentration at the flame in the combustion process, thereby playing a flame retardant role.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, isocyanate groups with strong activity on MDI are used for reacting with ATT and MDA, and MDA and PDD are grafted to ATT through amido bonds, so that the ATT contains a certain amount of N, P elements; because ATT is used as a one-dimensional material, has certain rigidity, has high temperature resistance as the same as other inorganic clay, and is used as a filler to be filled into a polylactic acid matrix, the mechanical strength of the composite material is improved, and the cost is reduced; therefore, the attapulgite-based composite flame retardant synthesized by the invention is filled in polylactic acid, so that the mechanical property of the polylactic acid material can be improved, and the flame retardant property of the polylactic acid material can also be improved.
Drawings
FIG. 1 is the FI-IR spectrum of the product of each step in the process of synthesizing PDATT of example 1, wherein curves a, b, c, d correspond to sample pure ATT, MDI-ATT, PDD and PDATT, respectively.
FIG. 2 shows TEM spectra of pure ATT and PDATT in example 1 of the present invention, wherein a and b correspond to pure ATT and PDATT samples, respectively.
FIG. 3 is a TGA spectrum of pure ATT, PDD and PDATT of example 1 of the present invention.
FIG. 4 is a graph showing tensile breaking stresses of polylactic acid filled with pure ATT and PDATT at different ratios in example 1 of the present invention.
FIG. 5 is a graph showing tensile strengths of polylactic acid filled with pure ATT and PDATT at different ratios in example 1 of the present invention.
FIG. 6 is a graph showing the elastic modulus of polylactic acid filled with pure ATT and PDATT at different ratios in example 1 of the present invention.
FIG. 7 is a graph showing the Heat Release Rate (HRR) and total heat release amount (THR) of PDATT filled in polylactic acid at various ratios in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is described in detail by the following specific examples, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
Example 1
The attapulgite-based composite flame retardant is prepared by the following steps:
Putting 5g of ATT into a 250mL three-neck flask, adding 95g of anhydrous DMF, and performing ultrasonic treatment to uniformly disperse the ATT to obtain 5 wt% suspension; introducing nitrogen to remove air in the three-neck flask, adding 2.5g of MDI, heating the oil bath kettle to 80 ℃ under the protection of nitrogen, and carrying out magnetic stirring reaction for 1 h; after the reaction is finished, washing unreacted MDI with anhydrous DMF, drying for 24h in a vacuum oven at 80 ℃, and grinding to obtain MDI-ATT;
step 2, grafting MDA to MDA-ATT to prepare MDA-ATT
Weighing 5g of MDI-ATT and 10g of MDA, adding the MDI-ATT and the MDA into a 250mL three-neck flask, and dispersing by using 95g of anhydrous DMF; introducing nitrogen to remove air in the three-neck flask, heating the oil bath kettle to 55 ℃ under the protection of the nitrogen, and reacting for 12 hours under magnetic stirring; after the reaction is finished, washing the mixture twice by using anhydrous DMF and acetone in sequence, drying the mixture for 8 hours in a vacuum oven at the temperature of 80 ℃, and grinding the dried mixture to obtain the MDA-ATT.
Step 3, preparing the attapulgite-based composite flame retardant (PDATT)
3a Synthesis of PDD by Oxidation
6.8g of pentaerythritol particles and 85g of phosphorus oxychloride liquid were charged into a 250mL three-necked flask equipped with a peripheral condenser and a tail gas absorber and mixed. Gradually heating the mixture to 110 ℃, magnetically stirring the mixture to react for 12 hours under the protection of nitrogen, and absorbing HCl gas generated by the reaction by using NaOH aqueous solution; after the reaction is finished, obtaining a product through suction filtration, sequentially washing the product twice by using carbon tetrachloride and ethanol respectively, then drying the product at 80 ℃ to constant weight, and grinding the product to obtain white solid powder, namely PDD.
3b, adding 4g of MDA-ATT and 2g of PDD into a 100mL three-neck flask, and then adding 50mL of acetonitrile for dispersion; and introducing nitrogen to remove air in the three-neck flask, under the protection of nitrogen, heating the oil bath kettle to 80 ℃, carrying out reflux reaction for 2 hours, dropwise adding a drop of pyridine, reacting for 3 hours, stopping the reaction, cooling to room temperature, repeatedly washing the product with ethanol, drying in a vacuum oven at 80 ℃ for 10 hours, and grinding to obtain the PDATT.
The PDATT prepared in this example was added to polylactic acid PLA by melt blending method, specifically: dissolving PLA in trichloromethane, adding PDATT, mechanically stirring for 4h to uniformly disperse PDATT, and drying to constant weight. To compare the effect of PDATT addition on PLA performance, multiple samples were prepared at PDATT to PLA mass ratios of 1:199, 2:198, 3:197, and 4:196, which were respectively reported as 0.5 wt% PDATT/PLA, 1 wt% PDATT/PLA, 1.5 wt% PDATT/PLA, and 2 wt% PDATT/PLA. For comparison, the same amount of added sample was made by adding ATT to polylactic acid PLA.
FIG. 1 is the FI-IR spectrum of the product of each step in the process of synthesizing PDATT of this example, wherein the curves a, b, c, d correspond to pure ATT, MDI-ATT, PDD and PDATT of the sample, respectively. As can be seen from the figure, curve b is compared with curve a at 1648cm-1、1544cm-1And 2278cm-1A new peak appeared and 1648cm-1、1544cm-1Is a band of amide I and II, 2278cm-1Is an isocyanate group, indicating that one isocyanate group of MDI reacted with a hydroxyl group on the ATT surface and the other isocyanate group was exposed on the surface of the attapulgite. In FT-IR spectrum of PDATTAbsorption peak at 1513cm-1(C-C)，1230cm-1Is a P-O bond, 1027cm-1Is a P-O-C bond, 1085cm-1The spiro pentaerythritol diphosphorous dichloride is successfully grafted to the attapulgite by a P-N bond.
Fig. 2 is a TEM spectrum of PDATT and pure ATT of this example, and it can be seen that: the attapulgite has a smooth rod-like structure with the length of 300nm and the width of 2nm, and the surface of PDATT begins to be rough, so that successful grafting of MDI, MDA and PDD on the attapulgite is proved.
FIG. 3 is a TGA spectrum of pure ATT, PDD and PDATT of the attapulgite-based composite flame retardant of this example. As can be seen from the figure, there is a first large weight loss from 30 ℃ to 270 ℃ due to the fact that ATT and PDATT contain free water, the weight loss of ATT in this temperature range is caused by the loss of free water, and the weight loss of PDATT is caused by the decomposition of free water in ATT and grafted PDD; the second large weight loss of PDATT was due to loss of bound water in ATT and further decomposition of grafted PDD from 270 to 800 ℃.
FIG. 4 is a graph of tensile breaking stress of PLA filled with pure ATT and PDATT in different proportions for this example. Compared with pure PLA, the fracture stress of the polylactic acid composite material is obviously improved with the addition of ATT and PDATT, because the added ATT and PDATT are uniformly dispersed in the polylactic acid matrix, the load can be effectively transferred in the stretching process, and the fracture stress of the composite material is improved. When the addition amount of PDATT reaches 2%, the performance is reduced, and the performance is probably caused by the agglomeration phenomenon due to excessive addition amount of PDATT.
FIG. 5 is a graph of tensile strength of PLA filled with pure ATT and PDATT at different ratios in this example. Compared with pure PLA, when the polylactic acid is crystallized, ATT and PDATT serving as a flame retardant are added, so that the nucleating agent can be used, and the crystallinity of the polylactic acid is improved. Generally, the crystallinity increases, the hardness increases, and the tensile strength tends to decrease. PDATT decreases tensile strength more slowly than pure ATT.
FIG. 6 is a graph of elastic modulus of the PLA filled with pure ATT and PDATT at different ratios in this example. Compared with pure PLA, the elastic modulus of the polylactic acid composite material is reduced with the addition of ATT and PDATT serving as a flame retardant, and the elastic modulus is reduced because the movement of polylactic acid molecular chains is hindered due to the addition of inorganic particle materials.
FIG. 7 is a graph of Heat Release Rate (HRR) and Total Heat Release (THR) for PDATT of this example filled in PLA at various ratios. Compared with pure PLA, the heat release rate and the total heat release amount of the polylactic acid composite material are obviously reduced with the addition of the flame retardant PDATT, which shows that the heat release behavior of the polylactic acid composite material can be greatly inhibited by adding PDATT into PLA, and the flame retardant property of the PLA composite material is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (3)
1. A preparation method of an attapulgite-based composite flame retardant modified by nitrogen and phosphorus-containing organic matters is characterized by comprising the following steps:
firstly, 4' -diphenylmethane diisocyanate MDI and attapulgite ATT are reacted to prepare attapulgite MDI-ATT containing isocyanate groups; then reacting 4,4' -diaminodiphenylmethane MDA with MDI-ATT to prepare attapulgite MDA-ATT containing amino; finally, the spiro pentaerythritol diphosphoric acid diphosphoryl chloride PDD reacts with amino on MDA-ATT, so that the attapulgite-based composite flame retardant PDATT modified by nitrogen-phosphorus containing organic matters is obtained; wherein, PDD is obtained by the reaction of phosphorus oxychloride and pentaerythritol; when PDD is synthesized, the mass ratio of phosphorus oxychloride to pentaerythritol is 12.5: 1; when MDI-ATT is synthesized, the mass ratio of MDI to ATT is 1: 2; when the MDA-ATT is synthesized, the mass ratio of MDI-ATT to MDA is 2: 1; when PDATT is synthesized, the mass ratio of MDA-ATT to PDD is 2: 1;
the preparation method comprises the following steps:
step 1, grafting MDI to ATT by using MDI to prepare MDI-ATT
Adding ATT into a three-neck flask, adding anhydrous DMF, and performing ultrasonic treatment to uniformly disperse ATT; introducing nitrogen to remove air in the three-neck flask, adding MDI, heating the oil bath kettle to 80 ℃ under the protection of nitrogen, and carrying out magnetic stirring reaction for 1 h; after the reaction is finished, washing unreacted MDI with anhydrous DMF, and then drying and grinding to prepare MDI-ATT;
step 2, grafting the MDA to the MDI-ATT to prepare the MDA-ATT
Adding MDI-ATT and MDA into a three-neck flask, and adding anhydrous DMF for dispersion; introducing nitrogen to remove air in the three-neck flask, heating the oil bath kettle to 55 ℃ under the protection of the nitrogen, and carrying out magnetic stirring reaction for 12 hours; after the reaction is finished, sequentially washing with anhydrous DMF and acetone, drying and grinding to obtain MDA-ATT;
step 3, preparing PDATT
3a Synthesis of PDD by Oxidation
Taking pentaerythritol particles and phosphorus oxychloride liquid, adding the pentaerythritol particles and the phosphorus oxychloride liquid into a three-neck flask, and mixing; gradually heating the mixture to 110 ℃, magnetically stirring the mixture to react for 12 hours under the protection of nitrogen, and absorbing HCl gas generated by the reaction by using NaOH aqueous solution; after the reaction is finished, obtaining a product through suction filtration, sequentially washing the product with carbon tetrachloride and ethanol, drying the product to constant weight, and grinding the product to obtain PDD;
3b, adding MDA-ATT and PDD into a three-neck flask, and then adding acetonitrile for dispersion; and introducing nitrogen to remove air in the three-neck flask, under the protection of nitrogen, heating the oil bath kettle to 80 ℃, carrying out reflux reaction for 2 hours, dropwise adding a drop of pyridine, reacting for 3 hours, stopping the reaction, cooling to room temperature, repeatedly washing, drying and grinding the product by using ethanol to obtain the PDATT.
2. The attapulgite-based composite flame retardant modified by nitrogen-phosphorus-containing organic matter, which is prepared by the preparation method of claim 1.
3. The use of the attapulgite-based composite flame retardant according to claim 2, characterized in that: the polylactic acid material is used as a flame retardant; in the process of inflaming retarding of the polylactic acid material, the spiro pentaerythritol diphosphoric acid dichloride and the 4,4' -diaminodiphenylmethane which are grafted on the attapulgite-based composite flame retardant contain nitrogen and phosphorus elements, so the attapulgite-based composite flame retardant is a nitrogen-phosphorus synergistic flame retardant; in the combustion process of the polylactic acid, the attapulgite-based composite flame retardant is decomposed into phosphoric acid or polyphosphoric acid to promote the surface of the polylactic acid to be rapidly dehydrated and carbonized to form a carbonized layer, the flame retardant is decomposed into nonvolatile glass materials, and meanwhile, nitrogen elements are decomposed to absorb heat and generate non-combustible gas to reduce the oxygen concentration at the flame in the combustion process, thereby playing a flame retardant role.
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| CN110387065B (en) * | 2019-07-29 | 2021-04-06 | 江苏点金石凹土矿业有限公司 | Preparation method of superfine high-purity sodium-based attapulgite clay flame-retardant auxiliary |
| CN111995988A (en) * | 2020-09-22 | 2020-11-27 | 武汉科技大学 | Composite core-shell structure phase-change heat storage material and preparation method thereof |
| CN114230962B (en) * | 2021-12-18 | 2024-09-06 | 江苏立汉科技有限公司 | Preparation method and application of attapulgite modified ABS plastic flame-retardant composite material |
| CN114456548B (en) * | 2022-03-14 | 2023-09-12 | 湖北中烟工业有限责任公司 | Organic/inorganic hybrid flame retardant, preparation method thereof and flame-retardant HDPE composite material |
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