CN114702728A - Amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant and preparation method thereof - Google Patents

Amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant and preparation method thereof Download PDF

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CN114702728A
CN114702728A CN202210417101.3A CN202210417101A CN114702728A CN 114702728 A CN114702728 A CN 114702728A CN 202210417101 A CN202210417101 A CN 202210417101A CN 114702728 A CN114702728 A CN 114702728A
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hydrotalcite
amphoteric polymer
acrylic acid
flame
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秦子豪
马丽娜
杨毓恒
高翔
黄国波
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Taizhou University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

The invention provides an amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant and a preparation method thereof. The preparation method comprises the following steps of carrying out ion exchange reaction on hydrotalcite and acrylic acid; in-situ polymerization of acrylic acid modified hydrotalcite, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride; the amphoteric polymer in-situ intercalation hydrotalcite flame-retardant smoke suppressant is prepared by carrying out ion exchange on acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite and ammonium dihydrogen phosphate and ammonium octamolybdate in a water phase. The amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant can improve the flame-retardant and smoke-suppressant effects on polymers, improve the mechanical properties of a high-molecular composite material, reduce the harm of 'secondary pollution' in the use process, has a wide application range and meets the requirement of environmental protection.

Description

Amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant and preparation method thereof
Technical Field
The invention relates to a flame-retardant smoke suppressant, in particular to an amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant and a preparation method thereof.
Background
As the use of synthetic and natural polymer materials is spread in various fields of human life, the threat of fire due to their flammability has been on the spot. Experiments and facts prove that the flame-retardant treated high polymer material can effectively reduce the hidden danger of fire and reduce the risk of fire. However, the fact also shows that the flame retardant is not non-inflammable, the combustion is accompanied by smoke exhaust gas, and the smoke generation of some flame retardant plastics, especially halogen-antimony system flame retardant plastics, is even higher. In the 70's of the 20 th century, smoke was recognized as the leading risk factor for death in fires. Therefore, the flame retardance and smoke suppression research of the material is particularly important. The hydrotalcite has a special structure, and some water molecules exist in a hydroxide layer in the molecular structure, the water molecules can be removed under the condition of not damaging a layered structure, water removed from interlayer heating and water generated by hydroxyl decomposition can dilute oxygen in air and combustible gaseous products generated by polymer decomposition, and CO in the hydrotalcite structure3 2–Carbon dioxide released by thermal decomposition is beneficial to blocking oxygen and has flame retardant effect. However, hydrotalcite has the disadvantages of easy agglomeration and poor compatibility with polymers, and needs to be organically modified, and commonly used modifiers includeOrganic acid, various surfactants and coupling agents, but the common modifier improves the mechanical property of the matrix material, but reduces the flame-retardant and smoke-suppressing efficiency of the hydrotalcite, and the aims of high-efficiency flame-retardant and smoke-suppressing and effective enhancement modification of the flame retardant are difficult to realize.
Disclosure of Invention
Aiming at the technical problems, according to the requirements of flame retardance and smoke suppression modification, the phosphorus-nitrogen compound which is efficiently expanded into carbon and ammonium octamolybdate with the smoke suppression effect are loaded on the surface of hydrotalcite by a chemical modification method to obtain the hydrotalcite efficient flame-retardant smoke suppressant. The hydrotalcite flame-retardant smoke suppressant has a catalytic char formation-double-gas source expansion synergistic flame-retardant effect, and in the combustion process of a polymer, phosphoric acid, metal oxide, molybdate radical and the like which are thermal decomposition products of hydrotalcite are subjected to synergistic catalytic solid phase decomposition in a condensed phase to promote the formation of a carbon layer and simultaneously decompose NH generated3And H2O promotes the rapid expansion of the material, the material is rapidly expanded into carbon in a condensed phase, the release of combustible products is reduced, most of the base material is retained in the carbon layer, and the high-efficiency flame-retardant smoke-suppression effect is achieved.
The invention aims to provide amphoteric polymer in-situ intercalated hydrotalcite with flame-retardant and smoke-suppressing functions.
The structure of the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant is shown in figure 3.
In FIG. 3, the bars represent hydrotalcite, and the amphoteric polymer inserted between the hydrotalcite layers is a copolymer of acrylic acid, N-dimethylacrylamide and methacryloyloxyethyltrimethylammonium chloride.
The amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant is characterized in that a terpolymer of acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride inserted between hydrotalcite layers is connected with hydrotalcite through ionic bonds, and octamolybdate radicals and dihydrogen phosphate radicals are connected with a copolymer of acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride through ionic bonds.
The second technical problem to be solved by the invention is to provide a preparation method of the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant.
The preparation method of the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant comprises the following steps:
(1) and carrying out ion exchange reaction on the hydrotalcite and acrylic acid to prepare the acrylic acid modified hydrotalcite.
(2) The acrylic acid modified hydrotalcite is subjected to in-situ polymerization with N, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride in a water phase under the action of an initiator to prepare the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite.
(3) The acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite is subjected to ion exchange with ammonium dihydrogen phosphate and ammonium octamolybdate in a water phase to prepare the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant.
The reaction principle of the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant is shown in figure 4.
The following describes the steps (1) to (3) in detail.
The reaction in step (1) of the present invention may be specifically carried out as follows: and (3) uniformly dispersing the hydrotalcite in a water phase, adding acrylic acid, stirring and reacting for 2-8 hours at 40-60 ℃, and separating to obtain the acrylic acid modified hydrotalcite.
In the step (1), the feeding mass ratio of the hydrotalcite to the acrylic acid is 1.0: 0.01 to 0.05.
After the reaction in the step (1), conventional separation methods such as filtration and the like can be adopted to separate and obtain the acrylic acid modified hydrotalcite.
The reaction in step (2) of the present invention may be specifically carried out as follows: uniformly dispersing acrylic acid modified hydrotalcite in a water phase, adding N, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride, uniformly mixing, adding an ammonium persulfate/sodium bisulfite initiation system, stirring and reacting for 4-10 hours at 45-80 ℃, and separating to obtain the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite.
In the step (2), the feeding mass ratio of the acrylic acid modified hydrotalcite to N, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride is 1.0: 0.03-0.15: 0.05 to 0.20.
In the step (2), the feeding mass ratio of the acrylic acid modified hydrotalcite to the ammonium persulfate/sodium bisulfite initiation system is 1.0: 0.01-0.03, wherein the mass ratio of ammonium persulfate to sodium bisulfite in the ammonium persulfate/sodium bisulfite initiation system is 3: 1.
after the reaction in the step (2), conventional separation methods such as filtration and the like can be adopted to separate and obtain the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite.
The reaction in step (3) of the present invention may be specifically carried out as follows: uniformly dispersing acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite in a water phase, adding ammonium dihydrogen phosphate and ammonium octamolybdate, stirring at normal temperature for reacting for 2-6 hours, and separating to obtain the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant.
In the step (3), the feeding mass ratio of the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite to ammonium dihydrogen phosphate and ammonium octamolybdate is 1.0: 0.05-0.15: 0.05 to 0.10.
After the reaction in the step (3), the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant can be obtained by adopting conventional separation methods such as filtration and the like.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
1. the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant prepared by the invention adopts a halogen-free flame-retardant system, and utilizes the synergistic flame-retardant and smoke-suppressing effects of the amino-containing amphoteric polymer, ammonium dihydrogen phosphate, ammonium octamolybdate and hydrotalcite, so that the flame-retardant and smoke-suppressing effects on the polymer are improved, the use amount of the flame-retardant smoke suppressant in the polymer is reduced, and the production cost of the flame-retardant material is reduced.
2. The amphoteric polymer in-situ intercalation hydrotalcite flame-retardant smoke suppressant prepared by the invention performs amphoteric polymer in-situ intercalation on hydrotalcite, is beneficial to the high molecular chain segment entering hydrotalcite interlamination in the melt blending process to form a nano composite material, improves the compatibility with a polymer matrix and improves the mechanical property of the high molecular composite material.
3. According to the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant, ammonium dihydrogen phosphate and ammonium octamolybdate are anchored on the surface of hydrotalcite through chemical bonds, so that the problem of mobility of an organic small-molecule flame retardant is solved, and the harm of secondary pollution in the using process is reduced.
4. The amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant disclosed by the invention does not contain halogen, has a good flame-retardant smoke suppressant effect and a wide application range, and meets the environmental protection requirement.
Drawings
FIG. 1 is an infrared spectrum of an amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant;
FIG. 2 is a scanning electron microscope image of an amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant;
FIG. 3 is a schematic structural diagram of an amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant;
FIG. 4 is the reaction principle of amphoteric polymer in-situ intercalated hydrotalcite fire retardant smoke suppressant preparation.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
Adding 1L of distilled water and 100g of hydrotalcite into a stainless steel reaction kettle, carrying out ultrasonic dispersion for 30 minutes, adding 5g of acrylic acid, stirring and reacting for 2 hours at 60 ℃, washing a product obtained by filtering for multiple times by using distilled water, and drying the obtained solid by blowing air to constant weight to obtain the acrylic acid modified hydrotalcite.
Adding 100g of the acrylic acid modified hydrotalcite into 1L of distilled water, performing ultrasonic dispersion for 30 minutes, transferring the mixture into a three-neck flask provided with a mechanical stirrer, a thermometer and a reflux condenser, adding 15g N, N-dimethylacrylamide and 20g of methacryloyloxyethyl trimethyl ammonium chloride, uniformly mixing, adding 3g of ammonium sulfate/sodium bisulfite initiation system (the mass ratio of ammonium persulfate to sodium bisulfite is 3: 1), stirring and reacting for 4 hours at 80 ℃, filtering the suspension obtained by the reaction, washing with distilled water for three times, and drying in an oven at 100 ℃ for 24 hours to obtain the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite.
Adding 100g of the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite into 1L of distilled water, ultrasonically dispersing for 30 minutes, transferring into a three-neck flask provided with a mechanical stirrer, a thermometer and a reflux condenser, adding 15g of ammonium dihydrogen phosphate and 10g of ammonium octamolybdate, stirring at normal temperature for reacting for 6 hours, washing a product obtained by filtering with distilled water for multiple times, and drying the obtained solid by blowing to constant weight to obtain the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant, wherein an infrared spectrogram is shown in figure 1.
Example 2
Adding 1L of distilled water and 100g of hydrotalcite into a stainless steel reaction kettle, carrying out ultrasonic dispersion for 30 minutes, adding 1g of acrylic acid, stirring and reacting for 8 hours at 40 ℃, washing a product obtained by filtering with distilled water for multiple times, and drying the obtained solid by air blowing until the weight is constant to obtain the acrylic acid modified hydrotalcite.
Adding 100g of the acrylic acid modified hydrotalcite into 1L of distilled water, carrying out ultrasonic dispersion for 30 minutes, transferring the mixture into a three-neck flask provided with a mechanical stirrer, a thermometer and a reflux condenser, adding 5g N, N-dimethylacrylamide and 5g of methacryloyloxyethyl trimethyl ammonium chloride, uniformly mixing, adding 1g of ammonium sulfate/sodium bisulfite initiation system (the mass ratio of ammonium persulfate to sodium bisulfite is 3: 1), carrying out stirring reaction for 10 hours at 45 ℃, filtering the suspension obtained by the reaction, washing the suspension with distilled water for three times, and drying the suspension in an oven at 100 ℃ for 24 hours to obtain the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite.
Adding 100g of the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite into 1L of distilled water, ultrasonically dispersing for 30 minutes, transferring into a three-neck flask provided with a mechanical stirrer, a thermometer and a reflux condenser, adding 5g of ammonium dihydrogen phosphate and 5g of ammonium octamolybdate, stirring at normal temperature for reaction for 2 hours, washing a product obtained by filtering with distilled water for multiple times, and drying the obtained solid by blowing to constant weight to obtain the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant.
Example 3
Adding 1L of distilled water and 100g of hydrotalcite into a stainless steel reaction kettle, carrying out ultrasonic dispersion for 30 minutes, adding 2.5g of acrylic acid, stirring and reacting for 6 hours at 50v, washing a product obtained by filtering with distilled water for multiple times, and drying the obtained solid by blowing air to constant weight to obtain the acrylic acid modified hydrotalcite.
Adding 100g of the acrylic acid modified hydrotalcite into 1L of distilled water, carrying out ultrasonic dispersion for 30 minutes, transferring the mixture into a three-neck flask provided with a mechanical stirrer, a thermometer and a reflux condenser, adding 7.5g N, N-dimethylacrylamide and 10g of methacryloyloxyethyl trimethyl ammonium chloride, uniformly mixing, adding 1.5g of ammonium sulfate/sodium bisulfite initiation system (the mass ratio of ammonium persulfate to sodium bisulfite is 3: 1), stirring and reacting at 55 ℃ for 7 hours, filtering the suspension obtained by the reaction, washing with distilled water for three times, and drying in an oven at 100 ℃ for 24 hours to obtain the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite.
Adding 100g of the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite into 1L of distilled water, ultrasonically dispersing for 30 minutes, transferring into a three-neck flask provided with a mechanical stirrer, a thermometer and a reflux condenser, adding 7.5g of ammonium dihydrogen phosphate and 10g of ammonium octamolybdate, stirring at normal temperature for reaction for 4 hours, washing a product obtained by filtering with distilled water for multiple times, and drying the obtained solid by blast to constant weight to obtain the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant.
Example 4: application of amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant
The preparation operation of the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant is the same as that in example 1. 100 parts of Ethylene Propylene Diene Monomer (EPDM), 20 parts of filling oil, 20 parts of amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant, 15 parts of white carbon black, 6 parts of sulfur, 3 parts of vulcanization accelerator dipentamethylenethiuram tetrasulfide (DPTT), 1 part of vulcanization accelerator 2-Mercaptobenzothiazole (MBT), 2 parts of nano zinc oxide, 1 part of stearic acid and 1 part of antioxidant 1010 are premixed, added into an internal mixer for full mixing and uniform discharging, and are discharged through a double-roller open mill, and placed into a flat-plate vulcanizing machine at 180 ℃ for compression molding for 8 minutes to prepare an amphoteric polymer in-situ intercalated hydrotalcite/EPDM composite material sample, and the measured limit oxygen index of the intercalated hydrotalcite/EPDM composite material is 33.7 percent, the flame retardant grade is UL-94V-0, the smoke density grade is 28, the tensile strength is 8.67MPa, and the elongation at break is 572 percent.
For comparison, the amphoteric polymer in-situ intercalation hydrotalcite flame-retardant smoke-suppressing agent in the formula of the amphoteric polymer in-situ intercalation hydrotalcite/EPDM composite material of example 4 is replaced by the same amount of the conventional dodecylsulfonic acid organic modified hydrotalcite, and the performance test results of the obtained organic modified hydrotalcite/EPDM composite material are as follows:
Figure BDA0003605258210000061
Figure BDA0003605258210000071
the formula of the organic modified hydrotalcite/EPDM composite material comprises the following components: 100 parts of EPDM, 20 parts of filling oil, 20 parts of organic modified hydrotalcite, 15 parts of white carbon black, 6 parts of sulfur, 3 parts of DPTT, 1 part of MBT, 2 parts of nano zinc oxide, 1 part of stearic acid and 1 part of antioxidant 1010, wherein the preparation process is the same as that of example 4; the formula and preparation process of the amphoteric polymer in-situ intercalation hydroplaning/EPDM composite material are the same as those in example 4.
As can be seen from the limit oxygen index value, the flame retardant level and the smoke density level, compared with the conventional organic modified hydrotalcite, the amphoteric polymer in-situ intercalated hydrotalcite flame retardant smoke suppressant used in the invention can effectively improve the flame retardant and smoke suppressant performance of EPDM, and the mechanical property modification effect of the amphoteric polymer in-situ intercalated hydrotalcite on EPDM is better than that of the organic modified hydrotalcite. The intercalated hydrotalcite/EPDM composite material prepared by the invention has good compatibility of the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant and the matrix material, has multiple functions of flame retardance, smoke suppression and reinforcement, and can improve the mechanical strength of the matrix material while modifying the flame retardance and the smoke suppression of the matrix material.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (10)

1. The flame-retardant smoke suppressant of the amphoteric polymer in-situ intercalated hydrotalcite is characterized by comprising the hydrotalcite and the amphoteric polymer inserted between hydrotalcite layers, wherein the amphoteric polymer is a terpolymer of acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride.
2. The amphoteric polymer in-situ intercalated hydrotalcite flame retardant and smoke suppressant according to claim 1, wherein the hydrotalcite interlayer further contains octamolybdate radical and dihydrogen phosphate radical; the amphoteric polymer is connected with the hydrotalcite through an ionic bond, and the octamolybdate radical and the dihydrogen phosphate radical are connected with the amphoteric polymer through an ionic bond.
3. The method for preparing the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant according to claim 1, characterized by comprising the following steps:
(1) mixing hydrotalcite and acrylic acid in a water phase, and carrying out an ion exchange reaction to prepare acrylic acid modified hydrotalcite;
(2) carrying out in-situ polymerization on the acrylic acid modified hydrotalcite, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride in a water phase under the action of an initiator to prepare acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite;
(3) and (3) in a water phase, the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite is subjected to ion exchange with ammonium dihydrogen phosphate and ammonium octamolybdate to prepare the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant.
4. The method for preparing the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant according to claim 3, wherein the step (1) is specifically as follows: uniformly dispersing hydrotalcite powder in a water phase, adding acrylic acid, stirring and reacting for 2-8 hours at 40-60 ℃, and separating to obtain the acrylic acid modified hydrotalcite.
5. The method for preparing the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant according to claim 4, wherein the feeding mass ratio of the hydrotalcite to the acrylic acid is 1.0: 0.01 to 0.05.
6. The method for preparing the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant according to claim 3, wherein the step (2) is specifically as follows: uniformly dispersing acrylic acid modified hydrotalcite in a water phase, adding N, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride, uniformly mixing, adding an initiator, stirring and reacting at 45-80 ℃ for 4-10 hours, and separating to obtain acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite.
7. The method for preparing the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke-suppressant agent according to claim 6, wherein the initiator is prepared from ammonium persulfate and sodium bisulfite according to a mass ratio of 3: 1 are mixed to obtain the product.
8. The method for preparing the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant according to claim 6, wherein the feeding mass ratio of the acrylic acid modified hydrotalcite to N, N-dimethylacrylamide to methacryloyloxyethyl trimethylammonium chloride is 1.0: 0.03 to 0.15: 0.05 to 0.20; the feeding mass ratio of the acrylic acid modified hydrotalcite to the initiator is 1.0: 0.01 to 0.03.
9. The method for preparing the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant according to claim 3, wherein the step (3) is specifically as follows: uniformly dispersing acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethyl ammonium chloride terpolymer modified hydrotalcite in a water phase, adding ammonium dihydrogen phosphate and ammonium octamolybdate, stirring at normal temperature for reacting for 2-6 hours, and separating to obtain the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant.
10. The method for preparing the amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant according to claim 9, wherein the feeding mass ratio of the acrylic acid, N-dimethylacrylamide and methacryloyloxyethyl trimethylammonium chloride terpolymer modified hydrotalcite to ammonium dihydrogen phosphate and ammonium octamolybdate is 1.0: 0.05-0.15: 0.05 to 0.10.
CN202210417101.3A 2022-04-20 2022-04-20 Amphoteric polymer in-situ intercalated hydrotalcite flame-retardant smoke suppressant and preparation method thereof Withdrawn CN114702728A (en)

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