CN117384425A - Polyurethane hard bubble oxygen index chemical regulator and preparation method and application thereof - Google Patents

Polyurethane hard bubble oxygen index chemical regulator and preparation method and application thereof Download PDF

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Publication number
CN117384425A
CN117384425A CN202311695900.8A CN202311695900A CN117384425A CN 117384425 A CN117384425 A CN 117384425A CN 202311695900 A CN202311695900 A CN 202311695900A CN 117384425 A CN117384425 A CN 117384425A
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oxygen index
stirring
reduced pressure
reaction
compound
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朱国全
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Shandong University of Technology
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Shandong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6521—Six-membered rings
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5353—Esters of phosphonic acids containing also nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—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
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a polyurethane hard bubble oxygen index chemical regulator, and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) Adding a proteinogen compound, a polyalcohol, a formaldehyde compound and a first catalyst into a drying reactor containing a condensing tube, and stirring for reaction to obtain a first material; 2) Adding a second catalyst into the first material, stirring for reaction, and distilling under reduced pressure to obtain a second material; 3) And adding a carboxyl phosphate compound and a third catalyst into the second material, stirring for reaction, adding alkali liquor to adjust the pH value of the mixed material to 7-11, and performing reduced pressure distillation to obtain the polyurethane hard bubble oxygen index chemical regulator. The preparation method provided by the invention has the advantages that the process is simple, the operation is easy, the cost is low, the prepared oxygen index chemical regulator contains two flame retardant elements of nitrogen and phosphorus, and the two flame retardant elements can produce synergistic effect, so that the flame retardant and fireproof performance of the polyurethane rigid foam material can be effectively improved.

Description

Polyurethane hard bubble oxygen index chemical regulator and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a polyurethane hard bubble oxygen index chemical regulator, and a preparation method and application thereof.
Background
At present, the country is greatly popularizing building energy-saving materials, and the application market prospect of the polyurethane hard foam heat preservation material is very broad; the hard polyurethane foam material has very excellent physical and mechanical properties and chemical corrosion resistance, has low heat conductivity coefficient and good heat insulation performance, has very strong binding force with most materials, becomes an indispensable material in a plurality of fields, and is widely applied to building heat preservation, petrochemical pipeline heat preservation, solar heat preservation, transportation heat preservation, refrigerator and freezer heat preservation, heat insulation and the like; however, polyurethane rigid foam materials which are not subjected to flame retardant treatment belong to inflammable materials, have poor safety and fireproof performance, are easy to cause fire hazards, and are greatly limited in application.
Disclosure of Invention
In view of the above, the present invention aims to provide a chemical regulator for oxygen index of polyurethane hard foam, which aims to improve oxygen index of polyurethane hard foam material and further improve fireproof performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect, an embodiment of the present invention provides a method for preparing a chemical regulator for polyurethane hard foam oxygen index, including the following steps:
1) Adding a proteinogen compound, a polyalcohol, a formaldehyde compound and a first catalyst into a drying reactor containing a condensing tube, and stirring for reaction to obtain a first material;
2) Adding a second catalyst into the first material, stirring for reaction, and distilling under reduced pressure to obtain a second material;
3) And adding a carboxyl phosphate compound and a third catalyst into the second material, stirring for reaction, adding alkali liquor to adjust the pH value of the mixed material to 7-11, and performing reduced pressure distillation to obtain the polyurethane hard bubble oxygen index chemical regulator.
The preparation method provided by the embodiment of the invention has the advantages of simple synthesis process, easiness in operation, readily available raw materials and low price; the prepared polyurethane hard foam oxygen index chemical regulator contains two flame retardant elements of nitrogen and phosphorus, and the two flame retardant elements can generate mutual synergistic effect, so that the oxygen index of the polyurethane hard foam material is improved, and the flame retardant property is improved; the polyurethane hard bubble oxygen index chemical regulator does not contain halogen, is environment-friendly, and has wide industrial application prospect.
In some embodiments, in step 1), the proteinogenic compound comprises at least one of melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine; the polyalcohol comprises at least one of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, polyethylene glycol (molecular weight 200-300), polypropylene glycol (molecular weight 200-300) and polytetrahydrofuran ether glycol (molecular weight 200-300); the formaldehyde compound comprises at least one of an industrial formaldehyde solution with 37-40% of formaldehyde solid content and a paraformaldehyde solution with 30-40% of water; the first catalyst comprises at least one of ammonia water, hexamethylenetetramine, triethylamine, propylamine and butylamine.
In some embodiments, in the step 1), the molar ratio of solid formaldehyde in the formaldehyde compound to the proteinoid compound is (3.5-6): 1; the molar ratio of the polyol to the proteinogenic compound is (3.5-6) 1; the amount of the first catalyst is 3-4 per mill of the weight of the proteinogenic compound.
In some embodiments, in the step 1), the reaction temperature of the stirring reaction is 40-95 ℃ and the reaction time is 10-40 min.
In some embodiments, in the step 2), the second catalyst includes at least one of formic acid, acetic acid, propionic acid, malonic acid, succinic acid, oxalic acid, phosphoric acid, phosphorous acid; the dosage of the second catalyst accounts for 4-8 per mill of the weight of the proteinogenic compounds.
In some embodiments, in the step 2), the reaction temperature of the stirring reaction is 40-95 ℃ and the reaction time is 10-40 min;
and/or the reduced pressure distillation is carried out at the temperature of 80-95 ℃, the pressure of-0.1 to-0.095 MPa and the time of 1-2 h.
In some embodiments, in the step 3), the carboxyl phosphate compound comprises at least one of carboxyl dimethyl phosphate, carboxyl diethyl phosphate, carboxyl dipropyl phosphate, carboxyl dibutyl phosphate, carboxyl methyl phosphite, carboxyl ethyl phosphite, carboxyl propyl phosphite, carboxyl butyl phosphite; the third catalyst comprises at least one of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid; the dosage of the third catalyst accounts for 3 to 6 per mill of the weight of the proteinogen compound, and the mol ratio of the carboxyl phosphate group compound to the proteinogen compound is (1 to 2): 1;
and/or the alkali liquor is sodium hydroxide solution with the mass concentration of 10-20%.
In some embodiments, in the step 3), the reaction temperature of the stirring reaction is 80-95 ℃ and the reaction time is 1.5-2.5 h;
and/or the reduced pressure distillation is carried out at the temperature of 80-95 ℃, the pressure of-0.1 to-0.095 MPa and the time of 1-2 h.
In a second aspect, embodiments of the present invention also provide a polyurethane hard foam oxygen index chemical modifier, which is prepared by the preparation method according to the first aspect.
In a third aspect, the embodiment of the invention also provides an application of the polyurethane hard bubble oxygen index chemical modifier in a building thermal insulation material.
Detailed Description
In a first aspect, an embodiment of the present invention provides a method for preparing a chemical regulator for polyurethane hard foam oxygen index, including the following steps:
1) Adding a proteinogen compound, a polyalcohol, a formaldehyde compound and a first catalyst into a drying reactor containing a condensing tube, and stirring for reaction to obtain a first material;
2) Adding a second catalyst into the first material, stirring for reaction, and distilling under reduced pressure to obtain a second material;
3) And adding a carboxyl phosphate compound and a third catalyst into the second material, stirring for reaction, adding alkali liquor to adjust the pH value of the mixed material to 7-11, and performing reduced pressure distillation to obtain the polyurethane hard bubble oxygen index chemical regulator.
In some embodiments, in step 1), the proteinogenic compound comprises at least one of melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine; the polyalcohol comprises at least one of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, polyethylene glycol (molecular weight 200-300), polypropylene glycol (molecular weight 200-300) and polytetrahydrofuran ether glycol (molecular weight 200-300); the formaldehyde compound comprises at least one of an industrial formaldehyde solution with 37-40% of formaldehyde solid content and a paraformaldehyde solution with 30-40% of water; the first catalyst comprises at least one of ammonia water, hexamethylenetetramine, triethylamine, propylamine and butylamine;
further, the molar ratio of solid formaldehyde to proteinic compounds in the formaldehyde compound is (3.5-6): 1, non-limiting examples are: 3.5:1, 4:1, 4.5:1, 5:1, 5.8:1, 6:1, etc.;
the molar ratio of polyol to proteinogenic compound is (3.5-6): 1, non-limiting examples are: 3.5:1, 4:1, 4.5:1, 5:1, 5.2:1, 6:1, etc.;
the amount of the first catalyst is 3 to 4% by weight of the proteinogenic compound, such as, without limitation: 3 permillage, 3.2 permillage, 3.5 permillage, 3.8 permillage, 4 permillage, etc.
In some embodiments, in step 1), the reaction temperature of the stirred reaction is 40 to 95 ℃, non-limiting examples are: 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 95 ℃ and the like; the reaction time is 10 to 40 minutes, such as, without limitation: 10min, 20min, 25min, 30min, 35min, 40min, etc.
In some embodiments, in step 2), the second catalyst comprises at least one of formic acid, acetic acid, propionic acid, malonic acid, succinic acid, oxalic acid, phosphoric acid, phosphorous acid; and the amount of the second catalyst is 4 to 8% by weight of the proteinogenic compound, such as, but not limited to: 4 permillage, 4.5 permillage, 5 permillage, 6 permillage, 6.8 permillage, 7 permillage, 8 permillage, etc.
In some embodiments, in step 2), the reaction temperature of the stirred reaction is 40 to 95 ℃, non-limiting examples are: 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 95 ℃ and the like; the reaction time is 10 to 40 minutes, such as, without limitation: 10min, 20min, 25min, 30min, 35min, 40min, etc.;
and/or, the temperature of the reduced pressure distillation is 80 to 95 ℃, non-limiting examples being: 80 ℃, 85 ℃, 88 ℃, 90 ℃, 95 ℃ and the like; the pressure is-0.1 to-0.095 MPa, non-limiting examples being: -0.1MPa, -0.098MPa, -0.096MPa, -0.095MPa, etc.; the time is 1-2 hours, non-limiting examples are: 1h, 1.5h, 1.8h, 2h, etc.
In some embodiments, in step 3), the carboxyphosphate compound comprises at least one of dimethyl carboxyphosphate, diethyl carboxyphosphate, dipropyl carboxyphosphate, dibutyl carboxyphosphate, methyl carboxyphosphite, ethyl carboxyphosphite, propyl carboxyphosphite, butyl carboxyphosphite; the third catalyst comprises at least one of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid; and the amount of the third catalyst is 3 to 6% by weight of the proteinogenic compound, such as, but not limited to: 3 permillage, 3.5 permillage, 4 permillage, 5 permillage, 5.5 permillage, 6 permillage, etc.; the molar ratio of carboxyl phosphate compound to proteinogenic compound is (1-2): 1, non-limiting examples are: 1:1, 1.5:1, 2:1, etc.;
and/or the alkali liquor is sodium hydroxide solution with the mass concentration of 10-20%.
In some embodiments, in step 3), the reaction temperature of the stirred reaction is 80 to 95 ℃, non-limiting examples are: 80 ℃, 85 ℃, 90 ℃, 92 ℃, 95 ℃ and the like; the reaction time is 1.5 to 2.5 hours, non-limiting examples are: 1.5h, 1.8h, 2h, 2.5h, etc.;
and/or, the temperature of the reduced pressure distillation is 80 to 95 ℃, non-limiting examples being: 80 ℃, 85 ℃, 88 ℃, 90 ℃, 95 ℃ and the like; the pressure is-0.1 to-0.095 MPa, non-limiting examples being: -0.1MPa, -0.098MPa, -0.095MPa, etc.; the time is 1-2 hours, non-limiting examples are: 1h, 1.5h, 1.8h, 2h, etc.
The preparation method provided by the embodiment of the invention has the advantages of simple synthesis process, easiness in operation, low cost and convenience in purchase, and raw materials are all reagents well known in the industry, so that the method is very beneficial to industrialization. Because the preparation method involves multi-functional group reaction, the reaction failure is caused by the fact that the reaction is influenced by more factors and the control is poor, the reaction is carried out by adopting a step method, the catalyst is added in batches, the dosage of the catalyst and the proportion relation among the raw materials are strictly controlled, and meanwhile, the temperature and the time of each step of reaction are controlled within a reasonable range, so that the reaction accuracy is ensured. Therefore, the prepared chemical regulator for the oxygen index of the polyurethane hard foam can effectively improve the flame retardance and fire resistance of the polyurethane hard foam material.
In a second aspect, embodiments of the present invention also provide a polyurethane hard bubble oxygen index chemical modifier prepared by the preparation method as described in the first aspect.
The chemical regulator for the oxygen index of the polyurethane hard foam contains two flame retardant elements of nitrogen and phosphorus at the same time, and the two flame retardant elements can generate a synergistic effect, so that the oxygen index of the polyurethane hard foam material is improved, the flame retardant and fireproof performance of the polyurethane hard foam material is further improved, and the chemical regulator has higher application value.
In a third aspect, the embodiment of the invention also provides an application of the polyurethane hard bubble oxygen index chemical modifier in a building thermal insulation material.
Example 1
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine cyanurate, 4mol of ethylene glycol and an industrial formaldehyde solution (37%) containing 4mol of solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 35min at 45 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 4 per mill of melamine cyanurate into the first material, and stirring and reacting for 35min at 45 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dimethyl phosphate and 3 per mill of concentrated sulfuric acid with the weight of melamine cyanurate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 8; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5h, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 2
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine cyanurate, 4.5mol of ethylene glycol, an industrial formaldehyde solution (37%) containing 4.5mol of solid formaldehyde and hexamethylenetetramine with the weight of 4 per mill of melamine cyanurate into a drying reactor containing a condensing tube, and stirring and reacting for 35min at 45 ℃ to obtain a first material;
2) Adding 5%o acetic acid with the weight of melamine cyanurate into the first material, and stirring and reacting for 35min at 45 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dimethyl phosphate and 3 per mill of concentrated sulfuric acid with the weight of melamine cyanurate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 8; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5h, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 3
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine cyanurate, 5mol of ethylene glycol and an industrial formaldehyde solution (38%) containing 5mol of solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 35min at 50 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 5 per mill melamine cyanurate into the first material, and stirring and reacting for 35min at 50 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dimethyl phosphate and 3 per mill of concentrated sulfuric acid with the weight of melamine cyanurate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; then adding sodium hydroxide solution with the mass concentration of 12%, and adjusting the pH value of the mixed material to 8; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 4
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine cyanurate, 6mol of ethylene glycol and 6mol of industrial formaldehyde solution (38%) containing solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 35min at 45 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 4 per mill of melamine cyanurate into the first material, and stirring and reacting for 35min at 45 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dimethyl phosphate and 3 per mill of concentrated hydrochloric acid with the weight of melamine cyanurate into the second material, and stirring at 80 ℃ for reaction for 2 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 8; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 5
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) 1mol of melamine phosphate, 4mol of diethylene glycol and an industrial formaldehyde solution (37%) containing 4mol of solid formaldehyde are added into a drying reactor containing a condensing tube, and hexamethylene tetramine with the weight of 3 per mill of melamine phosphate is stirred and reacted for 35min at 50 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 4 per mill of melamine phosphate into the first material, and stirring and reacting for 35min at 50 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of diethyl carboxyphosphate and 3 per mill of concentrated hydrochloric acid with the weight of melamine phosphate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5h, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 6
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine phosphate, 4.5mol of diethylene glycol and an industrial formaldehyde solution (38%) containing 4.5mol of solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 30min at 50 ℃ to obtain a first material;
2) Adding 5%o acetic acid by weight of melamine phosphate into the first material, and stirring and reacting for 35min at 50 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of diethyl carboxyphosphate and 3 per mill of concentrated hydrochloric acid with the weight of melamine phosphate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 8; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5h, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 7
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine phosphate, 5mol of diethylene glycol and 5mol of industrial formaldehyde solution (37%) containing solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 35min at 50 ℃ to obtain a first material;
2) Adding 5%o acetic acid by weight of melamine phosphate into the first material, and stirring and reacting for 35min at 50 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of diethyl carboxyphosphate and 3 per mill of concentrated hydrochloric acid with the weight of melamine phosphate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 8
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) 1mol of melamine phosphate, 6mol of diethylene glycol and 6mol of industrial formaldehyde solution (37%) containing solid formaldehyde are added into a drying reactor containing a condensing tube, and hexamethylenetetramine with the weight of 4 per mill of melamine phosphate is stirred and reacted for 35min at 55 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 5 per mill of melamine phosphate into the first material, and stirring and reacting for 35min at 55 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of diethyl carboxyphosphate and 3 per mill of concentrated hydrochloric acid with the weight of melamine phosphate into the second material, and stirring at 85 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5h, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 9
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine, 4mol of propylene glycol, an industrial formaldehyde solution (38%) containing 4mol of solid formaldehyde and 3%o of hexamethylenetetramine by weight of melamine into a drying reactor containing a condensing tube, and stirring and reacting for 30min at 55 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 4 per mill of melamine into the first material, and stirring and reacting for 30min at 55 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dipropyl phosphate and 3 per mill of concentrated sulfuric acid with the weight of melamine into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH to 10; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5h, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 10
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine, 4.5mol of propylene glycol, an industrial formaldehyde solution (37%) containing 4.5mol of solid formaldehyde and 3 per mill of hexamethylenetetramine by weight of melamine into a drying reactor containing a condensing tube, and stirring and reacting for 35min at 55 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 4 per mill of melamine into the first material, and stirring and reacting for 35min at 55 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dipropyl phosphate and 3 per mill of concentrated sulfuric acid with the weight of melamine into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH to 10; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5h, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 11
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine, 5mol of propylene glycol, industrial formaldehyde solution (37%) containing 5mol of solid formaldehyde and 3%o of hexamethylenetetramine by weight of melamine into a drying reactor containing a condensing tube, and stirring and reacting for 30min at 60 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 4 per mill of melamine into the first material, and stirring and reacting for 30min at 60 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dipropyl phosphate and 3 per mill of concentrated sulfuric acid with the weight of melamine into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH to 10; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 12
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine, 6mol of propylene glycol, 6mol of industrial formaldehyde solution containing solid formaldehyde (37%) and 4%o hexamethylenetetramine by weight of melamine into a drying reactor containing a condensing tube, and stirring and reacting for 35min at 55 ℃ to obtain a first material;
2) Adding 5%o acetic acid with the weight of melamine into the first material, and stirring and reacting for 35min at 55 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dipropyl phosphate and 4 per mill of concentrated sulfuric acid with the weight of melamine into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; then adding a sodium hydroxide solution with the mass concentration of 13%, and adjusting the pH value of the mixed material to be 10; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 13
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine pyrophosphate, 4mol of glycerol, 4mol of industrial formaldehyde solution (37%) containing solid formaldehyde and 4%o of hexamethylenetetramine by weight of melamine pyrophosphate into a drying reactor containing a condensing tube, and stirring and reacting for 30min at 65 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 5 per mill melamine pyrophosphate into the first material, and stirring and reacting for 30min at 65 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dipropyl phosphate and 4 per mill of concentrated sulfuric acid with the weight of melamine pyrophosphate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 14
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine pyrophosphate, 4.5mol of glycerol, an industrial formaldehyde solution (38%) containing 4.5mol of solid formaldehyde and 4 per mill of hexamethylenetetramine by weight of melamine pyrophosphate into a drying reactor containing a condensing tube, and stirring and reacting for 30min at 65 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 5 per mill melamine pyrophosphate into the first material, and stirring and reacting for 30min at 65 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dipropyl phosphate and 4 per mill of concentrated sulfuric acid with the weight of melamine pyrophosphate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 15
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine pyrophosphate, 5mol of glycerol and 5mol of industrial formaldehyde solution (38%) containing solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 30min at 70 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 5 per mill melamine pyrophosphate into the first material, and stirring and reacting for 30min at 70 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 80 ℃, the pressure to be-0.1 MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dipropyl phosphate and 4 per mill of concentrated sulfuric acid with the weight of melamine pyrophosphate into the second material, and stirring at 80 ℃ for reaction for 2.5 hours; then adding sodium hydroxide solution with the mass concentration of 15%, and adjusting the pH value of the mixed material to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 16
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine pyrophosphate, 6mol of glycerol and 6mol of industrial formaldehyde solution (38%) containing solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 25min at 70 ℃ to obtain a first material;
2) Adding oxalic acid with the weight of 5 per mill melamine pyrophosphate into the first material, and stirring and reacting for 25min at 70 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl dipropyl phosphate and 4 per mill of concentrated sulfuric acid with the weight of melamine pyrophosphate into the second material, and stirring at 85 ℃ for reaction for 2.5 hours; adding 10% sodium hydroxide solution, and adjusting pH value of the mixture to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 17
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine, 4mol of dipropylene glycol, an industrial formaldehyde solution (38%) containing 4mol of solid formaldehyde and 4%o hexamethylenetetramine by weight of melamine into a drying reactor containing a condensing tube, and stirring and reacting for 25min at 75 ℃ to obtain a first material;
2) Adding propionic acid with the weight of 5 per mill of melamine into the first material, and stirring and reacting for 25min at 75 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl propylene phosphite and 4 per mill of concentrated sulfuric acid with the weight of melamine into the second material, and stirring at 85 ℃ for reaction for 2.5 hours; then adding sodium hydroxide solution with the mass concentration of 15%, and adjusting the pH value of the mixed material to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 18
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine, 4.5mol of dipropylene glycol, an industrial formaldehyde solution (38%) containing 4.5mol of solid formaldehyde and hexamethylenetetramine with the weight of 4 per mill of melamine into a drying reactor containing a condensing tube, and stirring and reacting for 25min at 75 ℃ to obtain a first material;
2) Adding propionic acid with the weight of 5 per mill of melamine into the first material, and stirring and reacting for 25min at 75 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl propylene phosphite and 4 per mill of concentrated sulfuric acid with the weight of melamine into the second material, and stirring at 85 ℃ for reaction for 2.5 hours; then adding sodium hydroxide solution with the mass concentration of 15%, and adjusting the pH value of the mixed material to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 19
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine phosphate, 5mol of dipropylene glycol and 5mol of industrial formaldehyde solution (38%) containing solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 25min at 75 ℃ to obtain a first material;
2) Adding propionic acid with the weight of 5 per mill of melamine phosphate into the first material, and stirring and reacting for 25min at 75 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl propylene phosphite and 4 per mill of concentrated sulfuric acid with the weight of melamine phosphate into the second material, and stirring at 85 ℃ for reaction for 2.5 hours; then adding sodium hydroxide solution with the mass concentration of 15%, and adjusting the pH value of the mixed material to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Example 20
The embodiment provides a preparation method of a polyurethane hard foam oxygen index chemical regulator, which comprises the following steps:
1) Adding 1mol of melamine, 6mol of dipropylene glycol, 6mol of industrial formaldehyde solution containing solid formaldehyde (38%), 4%o of hexamethylenetetramine by weight of melamine into a drying reactor containing a condensing tube, and stirring and reacting for 25min at 75 ℃ to obtain a first material;
2) Adding propionic acid with the weight of 5 per mill of melamine into the first material, and stirring and reacting for 25min at 75 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 1.5 hours, and obtaining a second material;
3) Adding 1mol of carboxyl propylene phosphite and 4 per mill of concentrated sulfuric acid with the weight of melamine into the second material, and stirring at 85 ℃ for reaction for 2.5 hours; then adding sodium hydroxide solution with the mass concentration of 15%, and adjusting the pH value of the mixed material to 9; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 85 ℃, the pressure to be minus 0.1MPa and the time to be 2 hours, and obtaining the polyurethane hard bubble oxygen index chemical regulator.
Comparative example 1
The comparative example provides a preparation method of melamine nitrogen flame retardant polyether, which comprises the following steps:
1) Adding 1mol of melamine, 3mol of dipropylene glycol and 3mol of industrial formaldehyde solution (36%) containing solid formaldehyde into a drying reactor containing a condensing tube, and stirring and reacting for 45min at 35 ℃ to obtain a first material;
2) Adding 3%o of propionic acid with the weight of melamine into the first material, and stirring and reacting for 45min at 35 ℃; then carrying out reduced pressure distillation, controlling the temperature of the reduced pressure distillation to be 75 ℃, the pressure to be-0.093 MPa and the time to be 0.8h, and obtaining the melamine nitrogen flame-retardant polyether.
And (3) detecting products:
polyurethane rigid foam thermal insulation boards (8 cm thick) prepared by the chemical regulator for oxygen index of polyurethane rigid foam prepared in examples 17-19 and melamine nitrogen flame retardant polyether prepared in comparative example 1 according to the same method are respectively subjected to physical properties by an oxygen index tester, a thermal conductivity tester and a compressive strength tester, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the polyurethane rigid foam insulation board prepared from the polyurethane rigid foam oxygen index chemical modifier in the embodiment of the invention has an improved oxygen index, a reduced heat conductivity, and an improved compressive strength, and exhibits better comprehensive performance than the polyurethane rigid foam insulation board prepared from the melamine nitrogen flame retardant polyether containing only nitrogen.

Claims (10)

1. The preparation method of the polyurethane hard bubble oxygen index chemical regulator is characterized by comprising the following steps:
1) Adding a proteinogen compound, a polyalcohol, a formaldehyde compound and a first catalyst into a drying reactor containing a condensing tube, and stirring for reaction to obtain a first material;
2) Adding a second catalyst into the first material, stirring for reaction, and distilling under reduced pressure to obtain a second material;
3) And adding a carboxyl phosphate compound and a third catalyst into the second material, stirring for reaction, adding alkali liquor to adjust the pH value of the mixed material to 7-11, and performing reduced pressure distillation to obtain the polyurethane hard bubble oxygen index chemical regulator.
2. The method for preparing a chemical regulator for polyurethane hard bubble oxygen index according to claim 1, wherein in the step 1), the proteinogenic compound comprises at least one of melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine; the polyalcohol comprises at least one of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol; the formaldehyde compound comprises at least one of an industrial formaldehyde solution with 37-40% of formaldehyde solid content and a paraformaldehyde solution with 30-40% of water; the first catalyst comprises at least one of ammonia water, hexamethylenetetramine, triethylamine, propylamine and butylamine.
3. The method for preparing a chemical regulator for polyurethane hard bubble oxygen index according to claim 2, wherein in said step 1), the molar ratio of solid formaldehyde in said formaldehyde compound to said proteinic compound is (3.5-6): 1; the molar ratio of the polyol to the proteinogenic compound is (3.5-6) 1; the amount of the first catalyst is 3-4 per mill of the weight of the proteinogenic compound.
4. The method for preparing a chemical regulator for polyurethane hard bubble oxygen index according to claim 1, wherein in the step 1), the reaction temperature of the stirring reaction is 40-95 ℃ and the reaction time is 10-40 min.
5. The method for preparing the chemical modifier for polyurethane hard bubble oxygen index according to claim 1, wherein in the step 2), the second catalyst comprises at least one of formic acid, acetic acid, propionic acid, malonic acid, succinic acid, oxalic acid, phosphoric acid and phosphorous acid; the dosage of the second catalyst accounts for 4-8 per mill of the weight of the proteinogenic compounds.
6. The method for preparing the chemical regulator for the oxygen index of polyurethane rigid foam according to claim 1, wherein in the step 2), the reaction temperature of the stirring reaction is 40-95 ℃ and the reaction time is 10-40 min; the temperature of the reduced pressure distillation is 80-95 ℃, the pressure is minus 0.1-minus 0.095MPa, and the time is 1-2 h.
7. The method for preparing a chemical regulator for polyurethane hard bubble oxygen index according to claim 1, wherein in the step 3), the carboxyl phosphate group compound comprises at least one of carboxyl dimethyl phosphate, carboxyl diethyl phosphate, carboxyl dipropyl phosphate, carboxyl dibutyl phosphate, carboxyl methyl phosphite, carboxyl ethyl phosphite, carboxyl propyl phosphite and carboxyl butyl phosphite; the third catalyst comprises at least one of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid; the dosage of the third catalyst accounts for 3 to 6 per mill of the weight of the proteinogen compound, and the mol ratio of the carboxyl phosphate group compound to the proteinogen compound is (1 to 2): 1; the alkali liquor is sodium hydroxide solution with the mass concentration of 10-20%.
8. The method for preparing the chemical regulator for the oxygen index of polyurethane rigid foam according to claim 1, wherein in the step 3), the reaction temperature of the stirring reaction is 80-95 ℃ and the reaction time is 1.5-2.5 h; the temperature of the reduced pressure distillation is 80-95 ℃, the pressure is minus 0.1-minus 0.095MPa, and the time is 1-2 h.
9. A polyurethane hard bubble oxygen index chemical modifier, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. Use of the polyurethane hard bubble oxygen index chemical modifier according to claim 9 in building insulation materials.
CN202311695900.8A 2023-12-12 2023-12-12 Polyurethane hard bubble oxygen index chemical regulator and preparation method and application thereof Pending CN117384425A (en)

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Publication number Priority date Publication date Assignee Title
CN105199096A (en) * 2015-11-11 2015-12-30 江苏钟山化工有限公司 Preparation and application of nitrogen and phosphorus structured flame-retardant polyether polyol
US20190112475A1 (en) * 2018-09-29 2019-04-18 Nanjing Tech University Polyurethane Polyol, and Preparation Method and Application Thereof
CN115677957A (en) * 2021-07-23 2023-02-03 江苏长顺高分子材料研究院有限公司 Preparation method of reactive phosphorus-nitrogen flame-retardant melamine hard foam polyol
CN116874701A (en) * 2022-09-23 2023-10-13 江苏长顺高分子材料研究院有限公司 Preparation method of reactive melamine resin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199096A (en) * 2015-11-11 2015-12-30 江苏钟山化工有限公司 Preparation and application of nitrogen and phosphorus structured flame-retardant polyether polyol
US20190112475A1 (en) * 2018-09-29 2019-04-18 Nanjing Tech University Polyurethane Polyol, and Preparation Method and Application Thereof
CN115677957A (en) * 2021-07-23 2023-02-03 江苏长顺高分子材料研究院有限公司 Preparation method of reactive phosphorus-nitrogen flame-retardant melamine hard foam polyol
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