CN111548476A - Flame-retardant environment-friendly polyurethane material and preparation method thereof - Google Patents
Flame-retardant environment-friendly polyurethane material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant environment-friendly polyurethane material which comprises the following raw materials in parts by weight: 50-60 parts of diphenylmethane diisocyanate, 12-15 parts of polycaprolactone, 6-8 parts of a flame retardant and 1-2 parts of modified diatomite; the polyurethane material is prepared by the following method: firstly, preparing a polyurethane prepolymer; and secondly, reacting the prepolymer with a flame retardant to obtain the polyurethane material. According to the invention, a self-made flame retardant is used as one of polyurethane copolymerization raw materials, so that flame retardant molecules are grafted on a polyurethane molecular chain in a chemical bonding manner to form a part of a main chain structure; by adding the modified diatomite into the raw materials, the compatibility and the dispersibility of the diatomite in a polymer matrix are improved, and a reinforcing effect is better exerted; the diatomite can play a synergistic role in the flame retardant, so that the flame retardant property of the polyurethane material is further enhanced; the obtained polyurethane material not only has higher comprehensive mechanical property, but also greatly improves the flame retardant property.
Description
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to a flame-retardant environment-friendly polyurethane material and a preparation method thereof.
Background
Polyurethanes, which are polymers containing urethane groups in the main chain of a macromolecule, are called polyurethanes, and are classified into two major classes, polyester polyurethanes and polyether polyurethanes. Polyurethanes have many excellent properties and therefore have a wide range of uses. Polyurethane elastomers are used in many fields such as shoe materials, clothing, pipes, films and sheets, cables, automobiles, construction, medical and health, national defense, sports and leisure, and the like. The polyurethane material is flammable, often can produce toxic gas in the combustion process, causes the security of polyurethane to descend, especially in the building field, improves the flame retardant property of polyurethane and can obviously promote the application range of polyurethane, promotes the security in the use. Therefore, the flame retardant property of the polyurethane material is improved, and the method has important research significance.
Chinese patent No. CN201410316495.9 discloses a halogen-free flame-retardant thermoplastic polyurethane material, which is composed of the following raw materials in parts by weight: 70-80 parts of thermoplastic polyurethane elastomer, 5-20 parts of melamine cyanurate, 3-4 parts of antimony trioxide, 10100.1-1 parts of antioxidant, 1-2 parts of lithium silicate, 0.1-0.2 part of vanadium acetylacetonate, 2-3 parts of locust bean gum, 1-2 parts of tetrabutylammonium bromide, 1-2 parts of magnesium sulfate, 1-2 parts of 1, 2-dimethylimidazole, 1-2 parts of sodium gluconate and 1-2 parts of processing aid. However, the polyurethane material adopts inorganic flame retardants such as melamine cyanurate and antimony trioxide, and although the inorganic flame retardants are halogen-free, the inorganic flame retardants have poor compatibility with a polyurethane polymer matrix, so that the flame retardants and other additives are difficult to uniformly disperse in the polymer matrix, thereby affecting the flame retardance, mechanical properties and other properties of the polyurethane material.
Disclosure of Invention
The invention aims to provide a flame-retardant environment-friendly polyurethane material and a preparation method thereof, wherein a self-made flame retardant is used as one of polyurethane copolymerization raw materials, so that flame retardant molecules are grafted on a polyurethane molecular chain in a chemical bonding mode to form a part of a main chain structure, the flame retardant property of the polyurethane material can be effectively improved, and compared with the traditional blending mode, the problem of weakening the mechanical property of the material caused by migration and enrichment of the flame retardant can be avoided; by adding the modified diatomite into the raw materials, the diatomite can also participate in polyurethane copolymerization reaction after being modified, so that the compatibility and the dispersibility of the diatomite in a polymer matrix are improved, and the reinforcing effect is better played; in addition, the diatomite can play a synergistic role in a flame retardant, so that the flame retardant property of the polyurethane material is further enhanced; the obtained polyurethane material not only has higher comprehensive mechanical property, but also greatly improves the flame retardant property, and has wide application range.
The purpose of the invention can be realized by the following technical scheme:
the flame-retardant environment-friendly polyurethane material comprises the following raw materials in parts by weight: 50-60 parts of diphenylmethane diisocyanate, 12-15 parts of polycaprolactone, 6-8 parts of a flame retardant and 1-2 parts of modified diatomite;
the polyurethane material is prepared by the following method:
firstly, placing modified diatomite in a beaker, sequentially adding diphenylmethane diisocyanate and polycaprolactone, heating to 75-80 ℃, and reacting at constant temperature for 120-150min to obtain a prepolymer terminated by isocyanate groups;
and secondly, weighing the prepolymer, preheating to 65-70 ℃, performing vacuum defoaming, quickly pouring the flame retardant into the prepolymer after the prepolymer is free of bubbles, placing the prepolymer in a water bath at 75-80 ℃, mechanically stirring for 2-3min, pouring the prepolymer into a mold, performing vacuum defoaming for 70-80s, and finally placing the prepolymer in a 120 ℃ oven to react for 10-12h to obtain the polyurethane material.
Further, the flame retardant is prepared by the following method:
(1) adding 17.4g of hexachlorocyclotriphosphazene and 150mL of toluene into a three-neck flask, stirring and dissolving completely, cooling to 0 ℃ by using an ice salt water bath, keeping an ice bath, introducing ammonia gas for reaction under uniform stirring at 150r/min, performing suction filtration after reaction for 4-5h, collecting a filter cake, and drying to obtain an intermediate;
(2) weighing 33.5g of intermediate, 60mL of formaldehyde aqueous solution and 0.14g of hexamethylenetetramine in a flask, stirring in a constant-temperature water bath at 80 ℃, reacting for 160min at 150 ℃, adding 12.5g of triethanolamine, controlling the pH value of the solution to be 8-9, continuously reacting for 2h, centrifugally collecting a product, washing with distilled water for 3-4 times, and drying in vacuum to obtain the flame retardant.
Further, the mass fraction of the aqueous formaldehyde solution in the step (2) is 40%.
Further, the modified diatomite is prepared by the following method:
s1, placing diatomite in a three-neck flask, slowly adding mixed acid liquor, performing ultrasonic dispersion for 70-80min while stirring, performing condensation reflux reaction for 3h in a water bath at 60 ℃, naturally cooling the reaction liquid to room temperature, performing suction filtration, washing a product with deionized water until the washing liquid is neutral, placing the product in a drying box, drying to constant weight, grinding, and sieving with a 100-mesh sieve to obtain acidified diatomite;
s2, weighing 2.8g of the acidified diatomaceous earth prepared above and 150mL of toluene in a three-neck flask, N2Under protection, ultrasonically dispersing for 30-40min while stirring, heating to 60 ℃ in an oil bath, adding 23-25g of toluene diisocyanate and 3-4 drops of dibutyltin dilaurate, stirring for reaction for 9-10h, performing suction filtration, washing with toluene for 5-6 times, drying a filter cake in a vacuum drying oven at 50 ℃ for 10-12h, grinding, and sieving with a 100-mesh sieve to obtain the modified diatomite.
Further, in the step S1, the mixed acid solution is a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, and the amount ratio of the diatomite to the mixed acid solution is 1g:40-50 mL.
A preparation method of a flame-retardant environment-friendly polyurethane material comprises the following steps:
firstly, placing modified diatomite in a beaker, sequentially adding diphenylmethane diisocyanate and polycaprolactone, heating to 75-80 ℃, and reacting at constant temperature for 120-150min to obtain a prepolymer terminated by isocyanate groups;
and secondly, weighing the prepolymer, preheating to 65-70 ℃, performing vacuum defoaming, quickly pouring the flame retardant into the prepolymer after the prepolymer is free of bubbles, placing the prepolymer in a water bath at 75-80 ℃, mechanically stirring for 2-3min, pouring the prepolymer into a mold, performing vacuum defoaming for 70-80s, and finally placing the prepolymer in a 120 ℃ oven to react for 10-12h to obtain the polyurethane composite material.
The invention has the beneficial effects that:
the invention adds a special flame retardant in the polyurethane polymerization process, the prepared flame retardant is of a polyol structure, and the formed polyol is a P-N type compound which takes cyclotriphosphazene as a matrix and is a P-N type flame retardant molecule; the polyol can participate in copolymerization reaction of polyurethane, is grafted on a polyurethane molecular chain in a chemical bonding mode to form a part of a main chain structure, and can effectively improve the flame retardant property of a polyurethane material; compared with a mode of adding a flame retardant in a blending mode (the flame retardant is easy to migrate and locally enrich in a composite material matrix, and the mechanical property and the flame retardant property of the material are influenced), the mode of forming a part of a polyurethane main chain in a chemical bonding mode can effectively avoid the migration and enrichment conditions, so that the flame retardant effective components are uniformly distributed in the polyurethane material, the mechanical property is not influenced, and the flame retardant property is improved;
according to the invention, modified diatomite is added into the material, and after the diatomite is acidified, more-COOH groups are formed on the surface of the diatomite, and the-COOH reacts with-NCO groups on TDI molecules to form-CONH-groups, so that the TDI molecules are grafted on the surface of the diatomite molecules; because two-NCO groups exist at the benzene ring meta-position of TDI, the reaction activities of the two-NCO groups are different, only the-NCO groups on the methyl para-position react with the-COOH under the influence of the control of reaction conditions and steric hindrance, and the bare-NCO groups are introduced on the surface of the diatomite, so that the diatomite can participate in the copolymerization reaction of polyurethane and is combined with a polyurethane matrix in a chemical bonding manner, and the compatibility and the dispersibility of the diatomite in the polymer matrix are further improved; in the system, the-NCO on the reactive diatomite participates in the polymerization reaction of a polyurethane matrix to generate a composite material with a micro-crosslinking network structure, so that the movement of a high molecular chain segment is limited, and higher energy is needed for conformation change, so that the heat deformation resistance of the composite material is improved, and the heat resistance is improved; the diatomite is used as an inorganic filler, and can effectively transfer the load from the polymer matrix to the inorganic filler under the action of external force, so that the reinforcing effect of the diatomite is exerted, and the composite material has higher comprehensive mechanical property; in addition, the diatomite has the advantages of large porosity, low density, good heat resistance and the like, can play a synergistic effect with a flame retardant, and improves the flame retardant property of the composite material;
according to the invention, the self-made flame retardant is used as one of polyurethane copolymerization raw materials, so that flame retardant molecules are grafted on a polyurethane molecular chain in a chemical bonding mode to form a part of a main chain structure, the flame retardant property of the polyurethane material can be effectively improved, and compared with the traditional blending mode, the problem of weakening the mechanical property of the material caused by migration and enrichment of the flame retardant can be avoided; by adding the modified diatomite into the raw materials, the diatomite can also participate in polyurethane copolymerization reaction after being modified, so that the compatibility and the dispersibility of the diatomite in a polymer matrix are improved, and the reinforcing effect is better played; in addition, the diatomite can play a synergistic role in a flame retardant, so that the flame retardant property of the polyurethane material is further enhanced; the obtained polyurethane material not only has higher comprehensive mechanical property, but also greatly improves the flame retardant property, avoids the use of halogen-containing flame retardant, meets the requirement of environmental protection, and has wide application range.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The flame-retardant environment-friendly polyurethane material comprises the following raw materials in parts by weight: 50-60 parts of diphenylmethane diisocyanate (MDI), 12-15 parts of polycaprolactone, 6-8 parts of a flame retardant and 1-2 parts of modified diatomite;
the flame retardant is prepared by the following method:
(1) adding 17.4g of hexachlorocyclotriphosphazene and 150mL of toluene into a three-neck flask, stirring and dissolving completely, cooling to 0 ℃ by using an ice salt water bath, keeping an ice bath, introducing ammonia gas for reaction under uniform stirring at 150r/min, performing suction filtration after reaction for 4-5h, collecting a filter cake, and drying to obtain an intermediate;
reacting-Cl group on hexachlorocyclotriphosphazene with ammonia gas under ice bath condition to enable-Cl group on hexachlorocyclotriphosphazene to be-NH2Substitution to form an aminated cyclotriphosphazene;
(2) weighing 33.5g of intermediate, 60mL of formaldehyde aqueous solution (the mass fraction of formaldehyde is 40%) and 0.14g of hexamethylenetetramine in a flask, stirring in a constant-temperature water bath at 80 ℃, reacting for 160min at 150 ℃, adding 12.5g of triethanolamine, controlling the pH value of the solution to be 8-9, continuing to react for 2h, centrifugally collecting a product, washing with distilled water for 3-4 times, and performing vacuum drying to obtain the flame retardant;
-NH on an intermediate molecule2Nucleophilic addition reaction is carried out on formaldehyde molecules under the catalytic action of hexamethylenetetramine to form-NH-CH2OH, hydrogen on imino (-NH-) and-CH on triethanolamine molecule2Substitution reaction of-OH to form-N- (CH)2-OH)2Obtaining a polyol structure, namely the formed flame retardant is of the polyol structure; the formed polyol is a P-N type compound which takes cyclotriphosphazene as a matrix and is a P-N type flame retardant molecule; the polyol can participate in copolymerization reaction of polyurethane, is grafted on a polyurethane molecular chain in a chemical bonding mode to form a part of a main chain structure, and can effectively improve the flame retardant property of a polyurethane material; compared with a mode of adding a flame retardant in a blending mode (the flame retardant is easy to migrate and locally enrich in a composite material matrix, and the mechanical property and the flame retardant property of the material are influenced), the mode of forming a part of a polyurethane main chain in a chemical bonding mode can effectively avoid the migration and enrichment conditions, so that the flame retardant effective components are uniformly distributed in the polyurethane material, the mechanical property is not influenced, and the flame retardant property is improved;
the modified diatomite is prepared by the following method:
s1, placing diatomite in a three-neck flask, slowly adding mixed acid liquor (the mixed acid liquor is mixed liquor of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3: 1), stirring and ultrasonically dispersing for 70-80min, then carrying out condensation reflux reaction for 3h in a water bath at 60 ℃, naturally cooling the reaction liquid to room temperature, carrying out suction filtration, washing a product with deionized water until a washing liquid is neutral, placing the washing liquid in a drying box to dry to constant weight, grinding, and sieving with a 100-mesh sieve to obtain acidified diatomite;
wherein the dosage ratio of the diatomite to the mixed acid liquid is 1g:40-50 mL;
s2, weighing 2.8g of the acidified diatomaceous earth prepared above and 150mL of toluene in a three-neck flask, N2Under protection, ultrasonic dispersion is carried out for 30-40min while stirring, oil bath heating is carried out to 60 ℃, 23-25g of Toluene Diisocyanate (TDI) and 3-4 drops of dibutyltin dilaurate (catalyst) are stirred and react for 9-10h, the mixture is filtered, washed for 5-6 times by toluene, a filter cake is placed in a vacuum drying oven at 50 ℃ for drying for 10-12h, and the filter cake is ground and sieved by a 100-mesh sieve to obtain modified diatomite;
after the diatomite is acidified, more-COOH groups are formed on the surface, the-COOH reacts with-NCO groups on TDI molecules to form-CONH-groups, and the TDI molecules are grafted on the surface of the diatomite molecules; because two-NCO groups exist at the benzene ring meta-position of TDI, the reaction activities of the two-NCO groups are different, only the-NCO groups on the methyl para-position react with the-COOH under the influence of the control of reaction conditions and steric hindrance, and the bare-NCO groups are introduced on the surface of the diatomite, so that the diatomite can participate in the copolymerization reaction of polyurethane and is combined with a polyurethane matrix in a chemical bonding manner, and the compatibility and the dispersibility of the diatomite in the polymer matrix are further improved; in the system, the-NCO on the reactive diatomite participates in the polymerization reaction of a polyurethane matrix to generate a composite material with a micro-crosslinking network structure, so that the movement of a high molecular chain segment is limited, and higher energy is needed for conformation change, so that the heat deformation resistance of the composite material is improved, and the heat resistance is improved; the diatomite is used as an inorganic filler, and can effectively transfer the load from the polymer matrix to the inorganic filler under the action of external force, so that the reinforcing effect of the diatomite is exerted, and the composite material has higher comprehensive mechanical property; in addition, the diatomite has the advantages of large porosity, low density, good heat resistance and the like, can play a synergistic effect with a flame retardant, and improves the flame retardant property of the composite material;
the polyurethane material is prepared by the following method:
firstly, placing modified diatomite in a beaker, sequentially adding diphenylmethane diisocyanate (MDI) and polycaprolactone, heating to 75-80 ℃, and reacting at constant temperature for 120-150min to obtain a prepolymer blocked by an isocyanate group;
and secondly, weighing the prepolymer, preheating to 65-70 ℃, performing vacuum defoaming, quickly pouring the flame retardant into the prepolymer after the prepolymer is free of bubbles, placing the prepolymer in a water bath at 75-80 ℃, mechanically stirring for 2-3min, pouring the prepolymer into a mold, performing vacuum defoaming for 70-80s, and finally placing the prepolymer in a 120 ℃ oven to react for 10-12h to obtain the polyurethane composite material.
Example 1
The flame-retardant environment-friendly polyurethane material comprises the following raw materials in parts by weight: 50 parts of diphenylmethane diisocyanate, 12 parts of polycaprolactone, 6 parts of a flame retardant and 1 part of modified diatomite;
the polyurethane material is prepared by the following method:
firstly, placing modified diatomite in a beaker, sequentially adding diphenylmethane diisocyanate and polycaprolactone, heating to 75 ℃, and reacting at constant temperature for 120min to obtain a prepolymer terminated by an isocyanate group;
and secondly, weighing the prepolymer, preheating to 65 ℃, performing vacuum defoaming, quickly pouring the flame retardant into the prepolymer after the prepolymer is free of bubbles, mechanically stirring for 2min in a 75 ℃ water bath, pouring into a mold, performing vacuum defoaming for 70s, and finally putting into a 120 ℃ oven for reaction for 10h to obtain the polyurethane material.
Example 2
The flame-retardant environment-friendly polyurethane material comprises the following raw materials in parts by weight: 55 parts of diphenylmethane diisocyanate, 13 parts of polycaprolactone, 7 parts of a flame retardant and 1.5 parts of modified diatomite;
the polyurethane material is prepared by the following method:
firstly, placing modified diatomite in a beaker, sequentially adding diphenylmethane diisocyanate and polycaprolactone, heating to 78 ℃, and reacting at constant temperature for 135min to obtain a prepolymer terminated by an isocyanate group;
and secondly, weighing the prepolymer, preheating to 68 ℃, performing vacuum defoaming, quickly pouring the flame retardant into the prepolymer after the prepolymer is free of bubbles, placing the prepolymer in a 78 ℃ water bath, mechanically stirring for 2.5min, pouring the prepolymer into a mold, performing vacuum defoaming for 75s, and finally placing the prepolymer in a 120 ℃ oven to react for 11h to obtain the polyurethane material.
Example 3
The flame-retardant environment-friendly polyurethane material comprises the following raw materials in parts by weight: 60 parts of diphenylmethane diisocyanate, 15 parts of polycaprolactone, 8 parts of a flame retardant and 2 parts of modified diatomite;
the polyurethane material is prepared by the following method:
firstly, placing modified diatomite in a beaker, sequentially adding diphenylmethane diisocyanate and polycaprolactone, heating to 80 ℃, and reacting at constant temperature for 150min to obtain a prepolymer terminated by isocyanate groups;
and secondly, weighing the prepolymer, preheating to 70 ℃, performing vacuum defoaming, quickly pouring the flame retardant into the prepolymer after the prepolymer is free of bubbles, mechanically stirring for 3min in a water bath at 80 ℃, pouring into a mold, performing vacuum defoaming for 80s, and finally putting into a 120 ℃ oven for reaction for 12h to obtain the polyurethane material.
Comparative example 1
The flame retardant in example 1 was replaced with a conventional P-N flame retardant, and the remaining raw materials and preparation process were not changed.
Comparative example 2
The modified diatomite in example 1 was replaced with ordinary diatomite, and the remaining raw materials and preparation process were unchanged.
Comparative example 3
The modified diatomaceous earth used in example 1 was removed, and the remaining raw materials and preparation were unchanged.
The following property tests were carried out on the polyurethane materials obtained in examples 1 to 3 and comparative examples 1 to 3: cutting the polyurethane material into test samples, and testing the mechanical properties according to GB/T528-; the limit oxygen index LOI and UL94 combustion rating of the test material combustion; the test results are shown in the following table:
as can be seen from the above table, the tensile strength of the polyurethane materials prepared in examples 1-3 is 28.6-28.9MPa, and the elongation at break is 490-495%, which indicates that the polyurethane materials prepared by the invention have good comprehensive mechanical properties; it can be known that the limit oxygen index of the polyurethane material prepared in examples 1-3 is 28.3-28.6%, and the UL94 combustion grade reaches V-1 grade, which indicates that the polyurethane material prepared by the invention has good flame retardant property; the invention is described by combining with comparative example 1, the self-made flame retardant is adopted, the flame retardant can participate in the polyurethane copolymerization reaction, and is combined on a polyurethane molecular chain in a chemical bonding mode, so that the problems of reduced mechanical property and flame retardant property caused by migration and enrichment of the flame retardant can be avoided; compared with comparative example 2 and comparative example 3, the modified diatomite can participate in the copolymerization reaction of polyurethane, the compatibility of the diatomite and the polymer matrix is improved, the uniform dispersion of the diatomite in the polymer matrix is promoted, the uniformly dispersed diatomite can fully play a role in reinforcing the filler, and in addition, the diatomite can also synergize a flame retardant to further enhance the flame retardant performance.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. The flame-retardant environment-friendly polyurethane material is characterized by comprising the following raw materials in parts by weight: 50-60 parts of diphenylmethane diisocyanate, 12-15 parts of polycaprolactone, 6-8 parts of a flame retardant and 1-2 parts of modified diatomite;
the polyurethane material is prepared by the following method:
firstly, placing modified diatomite in a beaker, sequentially adding diphenylmethane diisocyanate and polycaprolactone, heating to 75-80 ℃, and reacting at constant temperature for 120-150min to obtain a prepolymer terminated by isocyanate groups;
and secondly, weighing the prepolymer, preheating to 65-70 ℃, performing vacuum defoaming, quickly pouring the flame retardant into the prepolymer after the prepolymer is free of bubbles, placing the prepolymer in a water bath at 75-80 ℃, mechanically stirring for 2-3min, pouring the prepolymer into a mold, performing vacuum defoaming for 70-80s, and finally placing the prepolymer in a 120 ℃ oven to react for 10-12h to obtain the polyurethane material.
2. The flame-retardant environment-friendly polyurethane material as claimed in claim 1, wherein the flame retardant is prepared by the following method:
(1) adding 17.4g of hexachlorocyclotriphosphazene and 150mL of toluene into a three-neck flask, stirring and dissolving completely, cooling to 0 ℃ by using an ice salt water bath, keeping an ice bath, introducing ammonia gas for reaction under uniform stirring at 150r/min, performing suction filtration after reaction for 4-5h, collecting a filter cake, and drying to obtain an intermediate;
(2) weighing 33.5g of intermediate, 60mL of formaldehyde aqueous solution and 0.14g of hexamethylenetetramine in a flask, stirring in a constant-temperature water bath at 80 ℃, reacting for 160min at 150 ℃, adding 12.5g of triethanolamine, controlling the pH value of the solution to be 8-9, continuously reacting for 2h, centrifugally collecting a product, washing with distilled water for 3-4 times, and drying in vacuum to obtain the flame retardant.
3. The flame-retardant environment-friendly polyurethane material as claimed in claim 2, wherein the mass fraction of the aqueous formaldehyde solution in the step (2) is 40%.
4. The flame-retardant environment-friendly polyurethane material as claimed in claim 1, wherein the modified diatomite is prepared by the following method:
s1, placing diatomite in a three-neck flask, slowly adding mixed acid liquor, performing ultrasonic dispersion for 70-80min while stirring, performing condensation reflux reaction for 3h in a water bath at 60 ℃, naturally cooling the reaction liquid to room temperature, performing suction filtration, washing a product with deionized water until the washing liquid is neutral, placing the product in a drying box, drying to constant weight, grinding, and sieving with a 100-mesh sieve to obtain acidified diatomite;
s2, weighing 2.8g of the acidified diatomaceous earth prepared above and 150mL of toluene in a three-neck flask, N2Under protection, ultrasonically dispersing for 30-40min while stirring, heating to 60 ℃ in an oil bath, adding 23-25g of toluene diisocyanate and 3-4 drops of dibutyltin dilaurate, stirring for reaction for 9-10h, performing suction filtration, washing with toluene for 5-6 times, drying a filter cake in a vacuum drying oven at 50 ℃ for 10-12h, grinding, and sieving with a 100-mesh sieve to obtain the modified diatomite.
5. The flame-retardant environment-friendly polyurethane material as claimed in claim 4, wherein the mixed acid solution in the step S1 is a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, and the dosage ratio of the diatomite to the mixed acid solution is 1g:40-50 mL.
6. The preparation method of the flame-retardant environment-friendly polyurethane material as claimed in claim 1, characterized by comprising the following steps:
firstly, placing modified diatomite in a beaker, sequentially adding diphenylmethane diisocyanate and polycaprolactone, heating to 75-80 ℃, and reacting at constant temperature for 120-150min to obtain a prepolymer terminated by isocyanate groups;
and secondly, weighing the prepolymer, preheating to 65-70 ℃, performing vacuum defoaming, quickly pouring the flame retardant into the prepolymer after the prepolymer is free of bubbles, placing the prepolymer in a water bath at 75-80 ℃, mechanically stirring for 2-3min, pouring the prepolymer into a mold, performing vacuum defoaming for 70-80s, and finally placing the prepolymer in a 120 ℃ oven to react for 10-12h to obtain the polyurethane composite material.
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| CN112827367A (en) * | 2021-01-22 | 2021-05-25 | 武汉钜能科技有限责任公司 | Diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and preparation method thereof |
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| CN115873547A (en) * | 2022-10-15 | 2023-03-31 | 福州大学 | Solvent-free flame-retardant polyurethane adhesive and preparation method thereof |
| CN115873547B (en) * | 2022-10-15 | 2024-09-24 | 福州大学 | Solvent-free flame-retardant polyurethane adhesive and preparation method thereof |
| CN115490825A (en) * | 2022-10-20 | 2022-12-20 | 扬州工业职业技术学院 | Flame-retardant soft polyurethane material and preparation method thereof |
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