CN113025079B - Modified hydrotalcite and preparation method and application thereof - Google Patents

Modified hydrotalcite and preparation method and application thereof Download PDF

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CN113025079B
CN113025079B CN202110213679.2A CN202110213679A CN113025079B CN 113025079 B CN113025079 B CN 113025079B CN 202110213679 A CN202110213679 A CN 202110213679A CN 113025079 B CN113025079 B CN 113025079B
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retardant
flame
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modified hydrotalcite
hydrotalcite
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CN113025079A (en
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温明宇
朱猛
朱嘉智
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Beihua University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a modified hydrotalcite and a preparation method and application thereof. The modified hydrotalcite is polyvinyl alcohol phosphate modified hydrotalcite or phosphorus-nitrogen flame retardant modified hydrotalcite, the compatibility of the hydrotalcite and a polymer is successfully improved by the polyvinyl alcohol phosphate or phosphorus-nitrogen flame retardant modified hydrotalcite, and the prepared modified hydrotalcite is applied to the preparation of a flame-retardant adhesive, a flame-retardant veneer and a flame-retardant plywood so as to successfully prepare two kinds of formaldehyde-free release plywood with good flame retardant property. The method provided by the invention is simple, stable in reaction and easy to control, and does not cause negative influence on the bonding strength of the adhesive, and the prepared flame-retardant plywood has a good flame-retardant effect.

Description

Modified hydrotalcite and preparation method and application thereof
Technical Field
The invention relates to the field of flame-retardant materials, and in particular relates to modified hydrotalcite as well as a preparation method and application thereof.
Background
Hydrotalcite is an inorganic flame retardant material, and has been drawing attention because of its excellent flame retardant properties. It has the characteristics of environmental protection, wide source, low price and the like, and has the defects that: OH contained in water in hydrotalcite laminate-Hydrogen bonds can be formed, and the condensation of the hydrogen bonds and coordinated water molecules can be aggregated, so that the dispersion of the hydrogen bonds in the polymer is influenced, various performance indexes of the material are reduced, and the requirement of actual use cannot be met. On the other hand, the interlayer spacing of the unmodified hydrotalcite is small, so that macromolecules are difficult to enter the interlayer, the compatibility with a high molecular polymer material is poor, and the actual use requirement cannot be met when the hydrotalcite is applied to the polymer material, so that how to modify the hydrotalcite to improve the compatibility of the hydrotalcite and the polymer improves the actual application effect of the hydrotalcite, thereby expanding the application range of the hydrotalcite, which is urgently solved in the fieldThe technical problem is solved.
Disclosure of Invention
The invention aims to provide a modified hydrotalcite, a preparation method and application thereof, so as to solve the technical problems.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is as follows: provides a modified hydrotalcite, and the modifier of the modified hydrotalcite is polyvinyl alcohol phosphate or a phosphorus-nitrogen flame retardant.
The second technical scheme of the invention is as follows: the preparation method of the modified hydrotalcite comprises the following steps:
adding the mixed metal ion solution and the mixed alkali solution into the modifier solution, aging after the reaction is finished, filtering, washing and precipitating until the pH value is neutral, and drying to obtain modified hydrotalcite; the modifier is polyvinyl alcohol phosphate or a phosphorus-nitrogen flame retardant.
Preferably, the mixed metal ion solution is a mixed solution of divalent metal ions and trivalent metal ions, wherein the concentration of the divalent metal ions is 1.2-2.4mol/L, the concentration of the trivalent metal ions is 0.6-1.2mol/L, and the molar ratio of the divalent metal ions to the trivalent metal ions is 2: 1; the mixed alkali solution is a mixed solution of sodium hydroxide and sodium carbonate, wherein the concentration of the sodium hydroxide is 3.6-7.2mol/L, and the concentration of the sodium carbonate is 0.37-0.74 mol/L; the reaction time is 2 h; the aging condition is aging at 80 ℃ for 30 min;
when the modifier is polyvinyl alcohol phosphate, the mass concentration of the modifier solution is 8-10%; the volume ratio of the mixed metal ion solution to the mixed alkali solution to the modifier solution is 1:1: 2;
when the modifier is a phosphorus-nitrogen flame retardant, the mass concentration of the modifier solution is 2-12%; the volume ratio of the mixed metal ion solution to the mixed alkali solution to the modifier solution is 1:1: 2.
More preferably, the divalent metal ion is Mg2+、Zn2+Or Cu2+(ii) a The trivalent metal ion is Al3+、Fe3+Or Cr3+。
Preferably, the polyvinyl alcohol phosphate is prepared by a method comprising the following steps: adding polyvinyl alcohol (PVA) into water, heating to dissolve, adding urea, raising the temperature to 95 ℃, adding phosphoric acid, reacting for 3 hours, cooling to room temperature, precipitating with ethanol, washing the precipitate, and drying to obtain polyvinyl alcohol phosphate (PPVA);
more preferably, the phosphoric acid is 85% phosphoric acid, and the mass ratio of the added polyvinyl alcohol to the added urea to the 85% phosphoric acid is 1:2: 2.7.
Preferably, the phosphorus-nitrogen flame retardant solution is prepared by a method comprising the following steps: dissolving N-hydroxymethyl-3- (dimethoxyphosphono) propionamide, heating to 70-80 ℃, adding urea, reacting for 30-60 min, and cooling to room temperature to obtain phosphorus-nitrogen flame retardant solution.
More preferably, the mass ratio of the N-hydroxymethyl-3- (dimethoxyphosphono) propionamide to the urea is 16: 1.
The second technical scheme of the invention is as follows: provides an application of the modified hydrotalcite in flame-retardant materials.
Preferably, the flame retardant material comprises: the flame-retardant veneer comprises a flame-retardant adhesive, a flame-retardant veneer and a flame-retardant plate.
Preferably, when the modified hydrotalcite is applied to the flame-retardant adhesive, the flame-retardant adhesive is prepared by taking polyvinyl alcohol and ethylene-vinyl acetate copolymer or styrene as main agents and the modified hydrotalcite as a filler.
More preferably, the mass ratio of the polyvinyl alcohol to the ethylene-vinyl acetate copolymer (EVA) or Styrene (SBR) is 0.49: 3; the addition amount of the modified hydrotalcite is 10-20% of the mass of the main agent.
Preferably, when the modified hydrotalcite is applied to the flame-retardant veneer, the flame-retardant veneer is prepared by soaking the wood veneer in a modified hydrotalcite solution with the mass concentration of 5-10% for 24-48 h and then drying.
Preferably, when the modified hydrotalcite is applied to the flame-retardant plywood, an adhesive prepared by taking the modified hydrotalcite as a filler and a curing agent P-MDI are uniformly mixed, coated on a veneer, and subjected to hot pressing to obtain the flame-retardant plywood.
More preferably, the formulaThe addition amount of the curing agent P-MDI is 10 percent of the mass of the main agent; the hot pressing conditions are that the hot pressing temperature is 110 ℃, the hot pressing time is 1min/mm, the hot pressing pressure is 3.5MPa, and the glue coating amount is 220g/m2。
The chemical structural general formula of the hydrotalcite is [ M ]2+ 1-xM3+ x(OH)2]x+(An- x/n)·mH2O, wherein M2 +Represents a divalent metal cation, such as Mg2+、Zn2+、Cu2+Etc. M3+Representing a trivalent metal cation, e.g. Al3+、Fe3+、Cr3+And the like, octahedral voids located on the host laminate; a. then-Representing anions of valency-n exchangeable between layers, e.g. Cl-、CO3 2-Etc., x ═ M3+/(M2++M3+) M is the number of water of hydration.
The invention has the following beneficial technical effects:
according to the invention, the polyvinyl alcohol phosphate modified hydrotalcite with a complete structure and the phosphorus-nitrogen flame retardant modified hydrotalcite are prepared by reasonably proportioning the layered metal ions and the organic materials of the hydrotalcite, and the modified polyvinyl alcohol phosphate exists between layers of the hydrotalcite in an anion form, so that the compatibility of the hydrotalcite and the polymer is successfully improved.
The modified hydrotalcite can be used as a filler for preparing a flame-retardant adhesive with flame-retardant property, the bonding strength of the adhesive cannot be negatively influenced by the addition of the modified hydrotalcite, and the bonding strength after the addition still meets the bonding strength requirement (not less than 0.70MPa) of a class II plywood specified in GB/T9846-one 2015.
According to the invention, the polyvinyl alcohol phosphate modified hydrotalcite or the phosphorus-nitrogen flame retardant modified hydrotalcite is used as the flame-retardant adhesive filler, the limited oxygen index of the pressed plywood is 34.6%, and compared with the adhesive without the flame-retardant filler (the limited oxygen index is 26.4%), the flame retardant property is obviously improved, which shows that the polyvinyl alcohol phosphate modified hydrotalcite or the phosphorus-nitrogen flame retardant modified hydrotalcite enables the plywood pressed by the aldehyde-free API adhesive to have good flame retardant property.
Drawings
Fig. 1 is an SEM image of the polyvinyl alcohol phosphate ester intercalated hydrotalcite prepared in example 1.
Fig. 2 is an SEM image of the unmodified magnesium aluminum hydrotalcite prepared in comparative example 2.
FIG. 3 is an FT-IR spectrum of polyvinyl alcohol phosphate prepared in example 1.
Figure 4 is a graph of the FT-IR spectra of the polyvinyl alcohol phosphate intercalated hydrotalcite prepared in example 1 and the unmodified magnesium aluminum hydrotalcite prepared in comparative example 2.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings, and this detailed description should not be taken to be limiting of the invention, but is rather a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Weighing PVA10g, dissolving in a three-neck flask containing 110mL deionized water, slowly stirring, heating in 80 ℃ water bath to completely dissolve, adding 20g urea after dissolving, raising the temperature of the water bath to 95 ℃, slowly dropwise adding phosphoric acid, slowly dropwise adding 27g phosphoric acid (85%) within 30min, and reacting at 95 ℃ for 3 h. After the reaction is finished, cooling to room temperature, pouring into a beaker, separating out the product polyvinyl alcohol phosphate (PPVA) by using a large amount of anhydrous ethanol, tearing the flocculent precipitate, and washing by using distilled water until the pH value is stabilized at neutral. Drying in vacuum drying oven at 60 deg.C to constant weight.
Adding 7.23g of anhydrous magnesium sulfate and 10g of aluminum sulfate octadecahydrate into 50ml of deionized water to prepare a salt solution; an alkali solution was prepared by adding 7.2g of sodium hydroxide and 1.91g of anhydrous sodium carbonate to 50mL of deionized water. Weighing 10g of PPVA, adding the PPVA into a flask filled with 100mL of deionized water, and stirring in a water bath at 85 ℃ until the PPVA is completely dissolved; adjusting to 80 ℃, stirring vigorously, simultaneously dripping the mixed salt solution and the mixed alkali solution into the flask, slowly and equivalently adding, continuing to stir for 2 hours after dripping, stopping stirring after the reaction is finished, aging at 80 ℃ for 30 minutes, carrying out suction filtration while hot, washing with distilled water until the pH value of the product is neutral, and drying at 80 ℃ to constant weight to obtain the polyvinyl alcohol phosphate intercalated hydrotalcite.
Soaking a wood veneer in a polyvinyl alcohol phosphate intercalated hydrotalcite solution with the mass concentration of 10% for 24 hours, and drying to prepare the flame-retardant veneer for preparing the plywood.
Preparing PVA solution with concentration of 7% (w 7%), adding certain amount of EVA (mPVA solution: mEVA 7:3) to the solution, wherein the total amount of the two is 100g, then using polyvinyl alcohol phosphate ester intercalated hydrotalcite as filler, adding 17%, and mixing uniformly for later use. Before preparing sizing, adding (omega 7 percent) curing agent P-MDI, wherein the adding amount of the P-MDI is 10 percent of the mass of the main agent, and uniformly mixing for use.
Hot pressing temperature is 110 ℃, hot pressing time is 180 seconds, hot pressing pressure is 3.5MPa, and the glue coating amount is 220g/m2And (5) manufacturing the three-layer plywood.
The wet bonding strength is determined to be 0.835MPa, and the limiting oxygen index LOI is 33.8%.
Example 2
Weighing 100g of N-hydroxymethyl-3- (dimethoxyphosphono) propionamide solution with the mass concentration of 80%, dissolving in a three-neck flask to prepare 65% of the mass concentration, slowly stirring, heating in a water bath to 75 ℃, adding 5g of urea, and rapidly stirring for 60 min. After the reaction is finished, cooling to room temperature to obtain phosphorus-nitrogen flame retardant liquid (mass concentration is 67%) for later use.
Adding 7.23g of anhydrous magnesium sulfate and 10g of aluminum sulfate octadecahydrate into 50ml of deionized water to prepare a salt solution; an alkali solution was prepared by adding 7.2g of sodium hydroxide and 1.91g of anhydrous sodium carbonate to 50mL of deionized water. Diluting 16g of phosphorus-nitrogen flame retardant liquid to 100ml, and placing the diluted liquid in a flask; and (2) violently stirring, simultaneously dropwise adding the mixed salt solution and the mixed alkali solution into the flask, slowly adding the mixed salt solution and the mixed alkali solution in equal amount, continuously stirring for 2 hours after dropwise adding is finished, stopping stirring after the reaction is finished, aging for 30 minutes at 80 ℃, performing suction filtration while the reaction is hot, washing with distilled water until the pH value of a product is neutral, and drying at 80 ℃ to constant weight to obtain the phosphorus-nitrogen flame retardant modified hydrotalcite.
The wood veneer is soaked in 10 mass percent phosphorus-nitrogen flame retardant modified hydrotalcite solution for 24 hours and then dried to prepare the flame-retardant veneer for preparing the plywood.
Preparing PVA solution with concentration of 7% (omega 7%), adding a certain amount of EVA (mPVA solution: mEVA 7:3) to the PVA solution, wherein the total amount of the EVA and the mPVA solution is 100g, then taking phosphorus-nitrogen flame retardant modified hydrotalcite as filler, adding 17%, and uniformly mixing for later use. Before preparing sizing, adding (omega 7 percent) curing agent P-MDI, wherein the adding amount of the P-MDI is 10 percent of the mass of the main agent, and uniformly mixing for use.
Hot pressing temperature is 110 ℃, hot pressing time is 180 seconds, hot pressing pressure is 3.5MPa, and the glue coating amount is 220g/m2And (5) manufacturing the three-layer plywood.
The wet bonding strength is determined to be 0.82MPa, and the limiting oxygen index LOI is 34.6%.
Example 3
Weighing 100g of N-hydroxymethyl-3- (dimethoxyphosphono) propionamide solution with the mass concentration of 80%, dissolving in a three-neck flask to prepare 65% of solution with the mass concentration, slowly stirring, heating in a water bath to 70 ℃, adding 5g of urea, and rapidly stirring for 60 min. After the reaction is finished, cooling to room temperature to obtain phosphorus-nitrogen flame retardant liquid (mass concentration is 67%) for later use.
Adding 14.46g of anhydrous magnesium sulfate and 20g of aluminum sulfate octadecahydrate into 50ml of deionized water to prepare a salt solution; an alkali solution was prepared by adding 14.4g of sodium hydroxide and 3.82g of anhydrous sodium carbonate to 50mL of deionized water. Diluting 8g of phosphorus-nitrogen flame retardant liquid to 100ml, and placing the diluted liquid in a flask; and (2) violently stirring, simultaneously dropwise adding the mixed salt solution and the mixed alkali solution into the flask, slowly adding the mixed salt solution and the mixed alkali solution in equal amount, continuously stirring for 2 hours after dropwise adding is finished, stopping stirring after the reaction is finished, aging for 30 minutes at 80 ℃, performing suction filtration while the reaction is hot, washing with distilled water until the pH value of a product is neutral, and drying at 80 ℃ to constant weight to obtain the phosphorus-nitrogen flame retardant modified hydrotalcite.
The wood veneer is soaked in a phosphorus-nitrogen flame retardant modified hydrotalcite solution with the mass concentration of 5% for 48 hours and then dried to prepare the flame-retardant veneer for preparing the plywood.
Preparing PVA solution with concentration of 7% (omega 7%), adding a certain amount of EVA (mPVA solution: mEVA 7:3) into the PVA solution, wherein the total amount of the EVA and the mPVA solution is 100g, then taking phosphorus-nitrogen flame retardant modified hydrotalcite as filler, adding 10%, and uniformly mixing for later use. Before preparing sizing, adding (omega 7 percent) curing agent P-MDI, wherein the adding amount of the P-MDI is 10 percent of the mass of the main agent, and uniformly mixing for use.
Hot pressing temperature is 110 ℃, hot pressing time is 180 seconds, hot pressing pressure is 3.5MPa, and the glue coating amount is 220g/m2And (5) manufacturing the three-layer plywood.
The wet bond strength was determined to be 0.81MPa and the limiting oxygen index LOI was determined to be 33.1%.
Example 4
Weighing 100g of N-hydroxymethyl-3- (dimethoxyphosphono) propionamide solution with the mass concentration of 80%, dissolving in a three-neck flask to prepare 65% of the mass concentration, slowly stirring, heating in a water bath to 80 ℃, adding 5g of urea, and rapidly stirring for 60 min. After the reaction is finished, cooling to room temperature to obtain phosphorus-nitrogen flame retardant liquid (mass concentration is 67%) for later use.
Adding 7.23g of anhydrous magnesium sulfate and 10g of aluminum sulfate octadecahydrate into 50ml of deionized water to prepare a salt solution; an alkali solution was prepared by adding 7.2g of sodium hydroxide and 1.91g of anhydrous sodium carbonate to 50mL of deionized water. Diluting 4g of phosphorus-nitrogen flame retardant liquid to 100ml, and placing the diluted liquid in a flask; and (2) violently stirring, simultaneously dropwise adding the mixed salt solution and the mixed alkali solution into the flask, slowly adding the mixed salt solution and the mixed alkali solution in equal amount, continuously stirring for 2 hours after dropwise adding is finished, stopping stirring after the reaction is finished, aging for 30 minutes at 80 ℃, performing suction filtration while the reaction is hot, washing with distilled water until the pH value of a product is neutral, and drying at 80 ℃ to constant weight to obtain the phosphorus-nitrogen flame retardant modified hydrotalcite.
The wood veneer is soaked in a phosphorus-nitrogen flame retardant modified hydrotalcite solution with the mass concentration of 8% for 36 hours and then dried to prepare the flame-retardant veneer for preparing the plywood.
Preparing PVA solution with concentration of 7% (omega 7%), adding a certain amount of EVA (mPVA solution: mEVA 7:3) into the PVA solution, wherein the total amount of the EVA and the mPVA solution is 100g, then taking phosphorus-nitrogen flame retardant modified hydrotalcite as a filler, adding the phosphorus-nitrogen flame retardant modified hydrotalcite with the amount of 20%, and uniformly mixing the mixture for later use. Before preparing sizing, adding (omega 7 percent) curing agent P-MDI, wherein the adding amount of the P-MDI is 10 percent of the mass of the main agent, and uniformly mixing for use.
Hot pressing temperature is 110 ℃, hot pressing time is 180 seconds, hot pressing pressure is 3.5MPa, and the glue coating amount is 220g/m2And (5) manufacturing the three-layer plywood.
The wet bonding strength was determined to be 0.82MPa and the limiting oxygen index LOI was determined to be 32.6%.
Comparative example 1
The wood veneer is impregnated with the phosphorus-nitrogen flame retardant modified hydrotalcite prepared in example 2: the wood veneer is soaked in 10 mass percent phosphorus-nitrogen flame retardant modified hydrotalcite solution for 24 hours and then dried to prepare the flame-retardant veneer for preparing the plywood.
A PVA solution with a concentration of 7% (ω ═ 7%) was prepared, and a certain amount of EVA (mPVA solution: mEVA ═ 7:3) was added thereto, and a total of 100g of the two was mixed uniformly for use. Before preparing sizing, adding (omega 7 percent) curing agent P-MDI, wherein the adding amount of the P-MDI is 10 percent of the mass of the main agent, and uniformly mixing for use.
Hot pressing temperature is 110 ℃, hot pressing time is 180 seconds, hot pressing pressure is 3.5MPa, and the glue coating amount is 220g/m2And (5) manufacturing the three-layer plywood.
The wet bonding strength is 0.88MPa, and the limiting oxygen index LOI is 26.4%.
Comparative example 2
Adding 7.23g of anhydrous magnesium sulfate and 10g of aluminum sulfate octadecahydrate into 50ml of deionized water to prepare a salt solution; an alkali solution was prepared by adding 7.2g of sodium hydroxide and 1.91g of anhydrous sodium carbonate to 50mL of deionized water. And after the temperature of the water bath is raised to 80 ℃, simultaneously dripping the mixed salt solution and the mixed alkali solution into a three-neck flask, slowly and equivalently adding, continuously stirring for 2 hours after dripping, stopping stirring after the reaction is finished, aging for 30 minutes at 80 ℃, performing suction filtration while the reaction is hot, washing with distilled water until the pH value of the product is neutral, and drying at 80 ℃ to constant weight to obtain the unmodified product, namely the magnesium-aluminum hydrotalcite.
Soaking the wood veneer in 10% mass concentration unmodified magnesium aluminum hydrotalcite solution for 24h, and drying to obtain the flame-retardant veneer for preparing the plywood.
Preparing PVA solution with concentration of 7% (omega 7%), adding a certain amount of EVA (mPVA solution: mEVA 7:3) to the PVA solution, wherein the total amount of the EVA and the mPVA is 100g, then taking unmodified magnesium-aluminum hydrotalcite as a filler, adding 17%, and uniformly mixing for later use. Before preparing sizing, adding (omega 7 percent) curing agent P-MDI, wherein the adding amount of the P-MDI is 10 percent of the mass of the main agent, and uniformly mixing for use.
Hot pressing temperature is 110 ℃, hot pressing time is 180 seconds, hot pressing pressure is 3.5MPa, and the glue coating amount is 220g/m2And (5) manufacturing the three-layer plywood.
The wet bonding strength is 0.74MPa, and the limiting oxygen index LOI is 25%.
FIG. 1 is an SEM image of a polyvinyl alcohol phosphate intercalated hydrotalcite prepared in example 1; from fig. 1, it can be seen that the introduction of PPVA did not change the properties of the hydrotalcite, and PPVA-LDH still maintains the layered structure of the magnesium-aluminum hydrotalcite itself.
FIG. 2 is an SEM image of an unmodified magnesium-aluminum hydrotalcite prepared in comparative example 2; as can be seen from FIG. 2, the self-made hydrotalcite has a good morphology and a layered structure.
FIG. 3 is an FT-IR spectrum of polyvinyl alcohol phosphate prepared in example 1; from FIG. 3, 1293cm in IR spectrum-1An absorption peak of P ═ O bond appears, which indicates that hydroxyl of PVA introduces phosphoric acid to carry out esterification reaction to form phosphoric acid group, wherein 1090cm is-1The absorption peak is the coincidence of the-P-O-C absorption peak and the lipid C-O stretching vibration absorption peak.The presence of P-O-C and P ═ O bonds combined confirms that the esterification reaction did occur.
FIG. 4 is an FT-IR spectra of a polyvinyl alcohol phosphate intercalated hydrotalcite prepared in example 1 and an unmodified magnesium aluminum hydrotalcite prepared in comparative example 2; from FIG. 4, it can be seen that the modified hydrotalcite is at 1336cm-1An absorption peak of P ═ O bond appears at 1111cm-1An absorption peak of the P-O-C bond appeared, indicating that PPVA was incorporated into hydrotalcite.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (5)

1. The preparation method of the modified hydrotalcite is characterized by comprising the following steps: adding the mixed metal ion solution and the mixed alkali solution into the modifier solution, aging after the reaction is finished, filtering, washing and precipitating until the pH value is neutral, and drying to obtain modified hydrotalcite; the modifier is a phosphorus-nitrogen flame retardant;
the mass concentration of the modifier solution is 2-12%; the volume ratio of the mixed metal ion solution to the mixed alkali solution to the modifier solution is 1:1: 2;
the phosphorus-nitrogen flame retardant solution is prepared by a method comprising the following steps: dissolving N-hydroxymethyl-3- (dimethoxyphosphono) propionamide, heating to 70-80 ℃, adding urea, reacting for 30-60 min, and cooling to room temperature to obtain phosphorus-nitrogen flame retardant solution;
the mass ratio of the N-hydroxymethyl-3- (dimethoxyphosphono) propionamide to the urea is 16: 1.
2. The process for producing modified hydrotalcite according to claim 1, wherein the mixed metal ion solution is a mixed solution of divalent metal ions and trivalent metal ions, wherein the concentration of divalent metal ions is 1.2 to 2.4mol/L, the concentration of trivalent metal ions is 0.6 to 1.2mol/L, and the molar ratio of divalent metal ions to trivalent metal ions is 2: 1; the mixed alkali solution is a mixed solution of sodium hydroxide and sodium carbonate, wherein the concentration of the sodium hydroxide is 3.6-7.2mol/L, and the concentration of the sodium carbonate is 0.37-0.74 mol/L; the reaction time is 2 h; the aging condition is aging at 80 ℃ for 30 min.
3. The use of the modified hydrotalcite prepared by the preparation method of claim 1 in flame retardant materials.
4. Use according to claim 3, wherein the flame retardant material comprises: flame-retardant adhesive, flame-retardant veneer and flame-retardant plywood.
5. The application of the modified hydrotalcite as claimed in claim 3, wherein when the modified hydrotalcite is applied to a flame-retardant adhesive, the flame-retardant adhesive is prepared by taking polyvinyl alcohol and ethylene-vinyl acetate copolymer or styrene as main agents and the modified hydrotalcite as a filler;
when the modified hydrotalcite is applied to the flame-retardant veneer, the wood veneer is soaked in a modified hydrotalcite solution with the mass concentration of 5-10% for 24-48 h and then dried to prepare the flame-retardant veneer;
when the modified hydrotalcite is applied to the flame-retardant plywood, an adhesive prepared by taking the modified hydrotalcite as a filler and a curing agent P-MDI are uniformly mixed, coated on a veneer, and hot-pressed to prepare the flame-retardant plywood.
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