CN115286726A - Flame-retardant modifier for plastics and preparation method thereof - Google Patents
Flame-retardant modifier for plastics and preparation method thereof Download PDFInfo
- Publication number
- CN115286726A CN115286726A CN202210927736.8A CN202210927736A CN115286726A CN 115286726 A CN115286726 A CN 115286726A CN 202210927736 A CN202210927736 A CN 202210927736A CN 115286726 A CN115286726 A CN 115286726A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- heating
- cyclodextrin
- solution
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame retardant modifier for plastics and a preparation method thereof; according to the invention, hexachlorocyclotriphosphazene is modified, and modified beta-cyclodextrin is introduced to the surface, so that when a thermal decomposition phenomenon occurs, non-combustible gases such as phosphoric acid, ammonia gas and nitrogen are generated, and meanwhile, the beta-cyclodextrin is thermally decomposed to release moisture, reduce the combustion surface temperature and promote the dehydration and carbonization of the flame retardant. Beta-cyclodextrin is modified by diphenylmethane diisocyanate, so that the surface energy of the beta-cyclodextrin is reduced, the prepared flame retardant has better compatibility in plastic polymers, the polymer interface gaps can be filled, and the mechanical property and the thermal stability of the polymer are enhanced. 1-4-oxyphosphate-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane is utilized to have high phosphorus content and a pentaerythritol molecular structure, so that plastics and a flame retardant can be promoted to form carbon in the combustion process, and the flame retardant performance of the flame retardant is enhanced.
Description
Technical Field
The invention relates to the technical field of flame retardant modifiers for plastics, in particular to a flame retardant modifier for plastics and a preparation method thereof.
Background
Polypropylene or polyethylene plastics are widely known for use in many fields such as containers, non-woven fabrics and electrical industries. Unfortunately, the development of plastic polymer articles in various fields is limited due to their poor flame retardant properties. With the understanding of fire hazard, research on flame retardants has been receiving more and more attention in recent decades. In the past, halogen-containing compounds have dominated the flame retardant industry. These materials have excellent properties in terms of effectiveness, price and compatibility. Unfortunately, the corrosive gases released by these flame retardants during combustion severely affect public safety. Nowadays, halogen-free flame retardants gradually come into the eye of people, whose dense carbon layer produced during combustion can expand under the inert gases released from the matrix. The expanded carbon layer can be used as a physical barrier to limit the heat and mass transfer and diffusion of the combustible gas, but the problems that the stability of the expandable carbon layer is insufficient, the carbon layer is not compact enough and the combustible gas cannot be prevented from escaping are also caused.
Therefore, the invention of the flame retardant modifier for plastics has important significance.
Disclosure of Invention
The invention aims to provide a flame retardant modifier for plastics and a preparation method thereof, which aim to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a flame retardant modifier for plastics is prepared according to the following steps:
adding the modified hexachlorocyclotriphosphazene and 1-4-oxyphosphate-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into an acetonitrile solution to obtain a mixed solution, and heating and stirring for reaction; and adding sodium hydroxide, heating for reflux reaction, evaporating, washing, performing suction filtration, and drying to obtain the flame retardant modifier for plastics.
Further, the modified hexachlorocyclotriphosphazene is prepared by the following method:
adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, and heating and stirring the solution to react under the argon atmosphere; cooling, filtering and washing; dialyzing, freezing and drying to obtain the modified hexachlorocyclotriphosphazene.
Further, the hexachlorocyclotriphosphazene solution is a tetrahydrofuran solution of hexachlorocyclotriphosphazene, wherein the weight ratio of hexachlorocyclotriphosphazene: the mass ratio of tetrahydrofuran is 1:4; the modified beta-cyclodextrin solution is a mixed solution of modified beta-cyclodextrin, potassium carbonate, tetrahydrofuran and N, N-dimethyl amide, wherein the modified beta-cyclodextrin: potassium carbonate: tetrahydrofuran: the mass ratio of the N, N-dimethyl amide is 1:1.1:2.5:3.5; phosphonitrilic chloride trimer: the mass ratio of the modified beta-cyclodextrin is 1: (1-1.2).
Further, the heating and stirring reaction temperature is 80-85 ℃, and the heating and stirring reaction time is 24 hours.
Further, the modified beta-cyclodextrin is prepared by the following method:
adding beta-cyclodextrin into ethyl acetate, stirring and heating; adding ethyl acetate solution of diphenylmethane diisocyanate, and stirring while keeping the temperature; vacuum filtering, washing and heating to obtain the modified beta-cyclodextrin.
Further, the beta-cyclodextrin: the mass ratio of the diphenylmethane diisocyanate is 4:1.
further, the stirring and heating temperature is 75-80 ℃, and the stirring and heating time is 2 hours; the heat preservation stirring temperature is 75-80 ℃, and the heat preservation stirring time is 3 hours; the heating temperature is 80 ℃, and the heating time is 24h.
Further, the modified hexachlorocyclotriphosphazene: 1-4-oxyphospho-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane: the mass ratio of the sodium hydroxide is (1-1.5): (6-9): 32, the concentration of the mixed solution is 0.014-0.016 mol/L.
Further, the heating and stirring reaction temperature is 60-65 ℃, the heating and stirring reaction time is 1h, the heating reflux reaction temperature is 80-85 ℃, and the heating reflux reaction time is 2h.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, hexachlorocyclotriphosphazene is modified, and the modified beta-cyclodextrin is introduced into the surface, when the thermal decomposition phenomenon occurs, the P-O-C bond and the P-N bond in the modified hexachlorotriphosphazene molecule are broken to generate phosphoric acid, ammonia gas, nitrogen gas and other non-flammable gases, and meanwhile, the beta-cyclodextrin is self-decomposed to release moisture, reduce the combustion surface temperature, absorb toxic gases and promote the dehydration of the flame retardant to form carbon.
Beta-cyclodextrin is modified by diphenylmethane diisocyanate, so that the surface energy of the beta-cyclodextrin is reduced, and the beta-cyclodextrin has hydrophobic property; on one hand, the dispersibility of the flame retardant in a reaction system is enhanced, and the agglomeration phenomenon is avoided, on the other hand, the prepared flame retardant has better compatibility in a plastic polymer, and can fill up polymer interface gaps and enhance the mechanical property and the thermal stability of the polymer.
The flame retardant is prepared by nucleophilic substitution of 1-4 oxyphosphate-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane and modified hexachlorocyclotriphosphazene, the flame retardant has high phosphorus content by utilizing the 1-4 oxyphosphate-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane and has a pentaerythritol molecular structure, can promote plastics and the flame retardant to form charcoal in the combustion process and enhance the flame retardant performance, and the addition of diphenylmethane diisocyanate and beta-cyclodextrin in the modified beta-cyclodextrin can help promote the flame retardant to generate a stable expandable carbon layer, so that the problem that the carbon layer is unstable and cannot hinder the escape of combustible gas due to the expansion of the 1-4 oxyphosphate-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
S1: adding 10g of beta-cyclodextrin into ethyl acetate, heating to 75 ℃, and stirring for 2 hours; adding 2.5g ethyl acetate solution of diphenylmethane diisocyanate, and stirring for 3h at 75 ℃; vacuum filtering, washing, and heating at 80 deg.C for 24 hr to obtain modified beta-cyclodextrin;
s2: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 10g of modified beta-cyclodextrin, 11g of potassium carbonate and 35gN, N-dimethyl amide into 25g of tetrahydrofuran solution to obtain modified beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s3: adding 10g of modified hexachlorocyclotriphosphazene and 60g of 1-4-oxyphosphate-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into the acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring to react for 1h; and adding 320g of sodium hydroxide, heating to 80 ℃, carrying out reflux reaction for 2h, evaporating, washing, carrying out suction filtration, and drying to obtain the flame retardant modifier for plastics.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Example 2
S1: adding 10g of beta-cyclodextrin into ethyl acetate, heating to 75 ℃, and stirring for 2h; adding 2.5g of ethyl acetate solution of diphenylmethane diisocyanate, and stirring for 3 hours at the temperature of 75 ℃; vacuum filtering, washing, and heating at 80 deg.C for 24 hr to obtain modified beta-cyclodextrin;
s2: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 11g of modified beta-cyclodextrin, 12.1g of potassium carbonate and 38.5g of N, N-dimethyl amide into 27.5g of tetrahydrofuran solution to obtain a modified beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s3: adding 12g of modified hexachlorocyclotriphosphazene and 68g of 1-4 oxyphosphate-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into the acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring for reaction for 1 hour; and adding 320g of sodium hydroxide, heating to 80 ℃, performing reflux reaction for 2 hours, evaporating, washing, performing suction filtration, and drying to obtain the flame retardant modifier for the plastic.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Example 3
S1: adding 10g of beta-cyclodextrin into ethyl acetate, heating to 75 ℃, and stirring for 2h; adding 2.5g ethyl acetate solution of diphenylmethane diisocyanate, and stirring for 3h at 75 ℃; vacuum filtering, washing, and heating at 80 deg.C for 24 hr to obtain modified beta-cyclodextrin;
s2: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 12g of modified beta-cyclodextrin, 13.2g of potassium carbonate and 42gN, and adding N-dimethyl amide into 30g of tetrahydrofuran solution to obtain a modified beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s3: adding 13g of modified hexachlorocyclotriphosphazene and 72g of 1-4 oxyphosphide-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into an acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring for reacting for 1h; and adding 320g of sodium hydroxide, heating to 80 ℃, carrying out reflux reaction for 2h, evaporating, washing, carrying out suction filtration, and drying to obtain the flame retardant modifier for plastics.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Example 4
S1: adding 10g of beta-cyclodextrin into ethyl acetate, heating to 75 ℃, and stirring for 2 hours; adding 2.5g ethyl acetate solution of diphenylmethane diisocyanate, and stirring for 3h at 75 ℃; vacuum filtering, washing, and heating at 80 deg.C for 24 hr to obtain modified beta-cyclodextrin;
s2: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 12g of modified beta-cyclodextrin, 13.2g of potassium carbonate and 42gN, N-dimethyl amide into 30g of tetrahydrofuran solution to obtain a modified beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s3: adding 14g of modified hexachlorocyclotriphosphazene and 74g of 1-4 oxyphosphate-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into the acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring for reaction for 1 hour; and adding 320g of sodium hydroxide, heating to 80 ℃, performing reflux reaction for 2 hours, evaporating, washing, performing suction filtration, and drying to obtain the flame retardant modifier for the plastic.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Example 5
S1: adding 10g of beta-cyclodextrin into ethyl acetate, heating to 75 ℃, and stirring for 2h; adding 2.5g ethyl acetate solution of diphenylmethane diisocyanate, and stirring for 3h at 75 ℃; vacuum filtering, washing, and heating at 80 deg.C for 24 hr to obtain modified beta-cyclodextrin;
s2: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 12g of modified beta-cyclodextrin, 13.2g of potassium carbonate and 42gN, and adding N-dimethyl amide into 30g of tetrahydrofuran solution to obtain a modified beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s3: adding 15g of modified hexachlorocyclotriphosphazene and 82g of 1-4 oxyphosphide-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into an acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring for reacting for 1h; and adding 320g of sodium hydroxide, heating to 80 ℃, performing reflux reaction for 2 hours, evaporating, washing, performing suction filtration, and drying to obtain the flame retardant modifier for the plastic.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Example 6
S1: adding 10g of beta-cyclodextrin into ethyl acetate, heating to 75 ℃, and stirring for 2h; adding 2.5g of ethyl acetate solution of diphenylmethane diisocyanate, and stirring for 3 hours at the temperature of 75 ℃; vacuum filtering, washing, and heating at 80 deg.C for 24 hr to obtain modified beta-cyclodextrin;
s2: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 12g of modified beta-cyclodextrin, 13.2g of potassium carbonate and 42gN, N-dimethyl amide into 30g of tetrahydrofuran solution to obtain a modified beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s3: adding 15g of modified hexachlorocyclotriphosphazene and 90g of 1-4 oxyphosphide-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into an acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring for reacting for 1h; and adding 320g of sodium hydroxide, heating to 80 ℃, carrying out reflux reaction for 2h, evaporating, washing, carrying out suction filtration, and drying to obtain the flame retardant modifier for plastics.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Comparative example 1
S1: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 10g of modified beta-cyclodextrin, 11g of potassium carbonate and 35gN, N-dimethyl amide into 25g of tetrahydrofuran solution to obtain beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into a beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s2: adding 10g of modified hexachlorocyclotriphosphazene and 60g of 1-4 oxyphosphide-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into an acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring for reacting for 1h; and adding 320g of sodium hydroxide, heating to 80 ℃, carrying out reflux reaction for 2h, evaporating, washing, carrying out suction filtration, and drying to obtain the flame retardant modifier for plastics.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Comparative example 2
S1: adding 10g of beta-cyclodextrin into ethyl acetate, heating to 75 ℃, and stirring for 2h; adding 2.5g ethyl acetate solution of diphenylmethane diisocyanate, and stirring for 3h at 75 ℃; vacuum filtering, washing, and heating at 80 deg.C for 24 hr to obtain modified beta-cyclodextrin;
s2: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 10g of modified beta-cyclodextrin, 11g of potassium carbonate and 35gN, N-dimethyl amide into 25g of tetrahydrofuran solution to obtain a modified beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s3: adding 10g of modified hexachlorocyclotriphosphazene and 60g of pentaerythritol into an acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring for reacting for 1h; and adding 320g of sodium hydroxide, heating to 80 ℃, carrying out reflux reaction for 2h, evaporating, washing, carrying out suction filtration, and drying to obtain the flame retardant modifier for plastics.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Comparative example 3
S1: adding 10g of beta-cyclodextrin into ethyl acetate, heating to 75 ℃, and stirring for 2 hours; adding 2.5g of ethyl acetate solution of diphenylmethane diisocyanate, and stirring for 3 hours at the temperature of 75 ℃; vacuum filtering, washing, and heating at 80 deg.C for 24 hr to obtain modified beta-cyclodextrin;
s2: dissolving 10g of hexachlorocyclotriphosphazene in 40g of tetrahydrofuran solution to obtain hexachlorocyclotriphosphazene solution; adding 10g of modified beta-cyclodextrin, 11g of potassium carbonate and 35gN, N-dimethyl amide into 25g of tetrahydrofuran solution to obtain a modified beta-cyclodextrin solution; adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, heating to 80 ℃ in an argon atmosphere, and stirring for reacting for 24 hours; cooling, filtering and washing; dialyzing, freezing and drying to obtain modified hexachlorocyclotriphosphazene;
s3: adding 10g of modified hexachlorocyclotriphosphazene and 150g of 1-4 oxyphosphate-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into the acetonitrile solution to obtain a mixed solution, heating to 60 ℃, and stirring for reaction for 1 hour; and adding 320g of sodium hydroxide, heating to 80 ℃, carrying out reflux reaction for 2h, evaporating, washing, carrying out suction filtration, and drying to obtain the flame retardant modifier for plastics.
And (3) testing: and (3) testing the combustion performance: the limiting oxygen index is tested according to GB/T2046-1993, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm;
the vertical burning performance is tested according to the entry of GB/T2048-1996, and the size of a sample is 120mm multiplied by 10mm multiplied by 4mm.
Examples 1 to 6 show the reactivity of hexachlorocyclotriphosphazene: 1-4-oxyphospho-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane: the mass ratio of the sodium hydroxide is 1.5:9: and 32, the prepared flame retardant has the best flame retardant effect.
In comparative example 1, the thermal stability of the prepared flame retardant is poor due to no modification of beta-cyclodextrin, and agglomeration easily occurs in a reaction system, so that the modification grafting rate is reduced and the flame retardant performance is reduced.
In comparative example 2, the flame retardant was prepared by using pentaerythritol instead of 1-4 oxyphos-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane, resulting in a decrease in flame retardant properties because 1-4 oxyphos-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane has a high phosphorus content and a molecular structure of pentaerythritol capable of promoting char formation of the plastic and the flame retardant during combustion.
In comparative example 3, the content of 1-4 oxyphos-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane was too large, resulting in a decrease in the stability of the produced expandable carbon layer, and failure to isolate the escape of combustible gas, resulting in a decrease in flame retardancy.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a flame retardant modifier for plastics is characterized by comprising the following steps: the preparation method comprises the following steps:
adding modified hexachlorocyclotriphosphazene and 1-4 oxyphosphate-4 hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane into an acetonitrile solution to obtain a mixed solution, and heating and stirring for reaction; and adding sodium hydroxide, heating for reflux reaction, evaporating, washing, performing suction filtration, and drying to obtain the flame retardant modifier for plastics.
2. The method for preparing a flame retardant modifier for plastics according to claim 1, wherein: the modified hexachlorocyclotriphosphazene is prepared by the following method:
adding a hexachlorocyclotriphosphazene solution into the modified beta-cyclodextrin solution, and heating and stirring the solution to react under the argon atmosphere; cooling, filtering and washing; dialyzing, freezing and drying to obtain the modified hexachlorocyclotriphosphazene.
3. The method for preparing a flame retardant modifier for plastics according to claim 2, characterized in that: the hexachlorocyclotriphosphazene solution is a tetrahydrofuran solution of hexachlorocyclotriphosphazene, wherein the weight ratio of hexachlorocyclotriphosphazene: the mass ratio of tetrahydrofuran is 1:4; the modified beta-cyclodextrin solution is a mixed solution of modified beta-cyclodextrin, potassium carbonate, tetrahydrofuran and N, N-dimethyl amide, wherein the modified beta-cyclodextrin: potassium carbonate: tetrahydrofuran: the mass ratio of the N, N-dimethyl amide is 1:1.1:2.5:3.5; phosphonitrilic chloride trimer: the mass ratio of the modified beta-cyclodextrin is 1: (1-1.2).
4. The preparation method of the flame retardant modifier for plastics as claimed in claim 2, wherein: the heating and stirring reaction temperature is 80-85 ℃, and the heating and stirring reaction time is 24h.
5. The method for preparing a flame retardant modifier for plastics according to claim 3, wherein: the modified beta-cyclodextrin is prepared by the following method:
adding beta-cyclodextrin into ethyl acetate, stirring and heating; adding ethyl acetate solution of diphenylmethane diisocyanate, and stirring while keeping the temperature; vacuum filtering, washing and heating to obtain the modified beta-cyclodextrin.
6. The preparation method of the flame retardant modifier for plastics as claimed in claim 5, wherein: beta-cyclodextrin: the mass ratio of the diphenylmethane diisocyanate is 4:1.
7. the preparation method of the flame retardant modifier for plastics as claimed in claim 5, wherein: stirring and heating at 75-80 deg.c for 2 hr; the stirring temperature is kept at 75-80 ℃, and the stirring time is kept at 3h; the heating temperature is 80 ℃, and the heating time is 24h.
8. The method for preparing a flame retardant modifier for plastics according to claim 1, wherein: modified hexachlorocyclotriphosphazene: 1-4-oxyphospho-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane: the mass ratio of the sodium hydroxide is (1-1.5): (6-9): 32, the concentration of the mixed solution is 0.014-0.016 mol/L.
9. The method for preparing a flame retardant modifier for plastics according to claim 1, wherein: the heating and stirring reaction temperature is 60-65 ℃, the heating and stirring reaction time is 1h, the heating reflux reaction temperature is 80-85 ℃, and the heating reflux reaction time is 2h.
10. The flame retardant modifier for plastics, which is obtained by the method for preparing a flame retardant modifier for plastics according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210927736.8A CN115286726B (en) | 2022-08-03 | 2022-08-03 | Flame retardant modifier for plastics and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210927736.8A CN115286726B (en) | 2022-08-03 | 2022-08-03 | Flame retardant modifier for plastics and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115286726A true CN115286726A (en) | 2022-11-04 |
| CN115286726B CN115286726B (en) | 2023-08-11 |
Family
ID=83825944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210927736.8A Active CN115286726B (en) | 2022-08-03 | 2022-08-03 | Flame retardant modifier for plastics and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115286726B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117124666A (en) * | 2023-09-20 | 2023-11-28 | 江苏耀鸿电子有限公司 | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof |
| CN117442921A (en) * | 2023-11-01 | 2024-01-26 | 四川峰邦消防科技有限公司 | Novel polymer gel fire-extinguishing flame retardant and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342482A (en) * | 2002-03-19 | 2003-12-03 | Polyplastics Co | Flame-resistant resin composition |
| CN105348326A (en) * | 2015-12-15 | 2016-02-24 | 湖南工程学院 | N-P flameresistant material and preparation method thereof and application in textiles |
| CN105859915A (en) * | 2016-06-12 | 2016-08-17 | 沈阳化工大学 | Preparation method of environment-friendly biobase three-source-integrated fire retardant |
| CN109806851A (en) * | 2019-03-25 | 2019-05-28 | 东华大学 | A kind of cyclodextrin porous material and preparation method thereof |
| CN114702891A (en) * | 2022-04-11 | 2022-07-05 | 国网浙江省电力有限公司营销服务中心 | Flame-retardant hydrophobic coating for electric energy metering box and preparation method thereof |
-
2022
- 2022-08-03 CN CN202210927736.8A patent/CN115286726B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342482A (en) * | 2002-03-19 | 2003-12-03 | Polyplastics Co | Flame-resistant resin composition |
| CN105348326A (en) * | 2015-12-15 | 2016-02-24 | 湖南工程学院 | N-P flameresistant material and preparation method thereof and application in textiles |
| CN105859915A (en) * | 2016-06-12 | 2016-08-17 | 沈阳化工大学 | Preparation method of environment-friendly biobase three-source-integrated fire retardant |
| CN109806851A (en) * | 2019-03-25 | 2019-05-28 | 东华大学 | A kind of cyclodextrin porous material and preparation method thereof |
| CN114702891A (en) * | 2022-04-11 | 2022-07-05 | 国网浙江省电力有限公司营销服务中心 | Flame-retardant hydrophobic coating for electric energy metering box and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| CHONG ZHANG等: "Synthesis of a novel branched cyclophosphazene-PEPA flame retardant and its application on polypropylene" * |
| YINLI LIU等: "One-pot fabrication of antibacterial b-cyclodextrin-based nanoparticles and their superfast, broad-spectrum adsorption towards pollutants" * |
| 马海云等: "磷睛衍生物大分子阻燃剂的合成及在聚丙烯中的应用" * |
| 黄娟等: "二苯基甲烷二异氰酸酯改性β-环糊精吸附性能" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117124666A (en) * | 2023-09-20 | 2023-11-28 | 江苏耀鸿电子有限公司 | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof |
| CN117124666B (en) * | 2023-09-20 | 2024-02-02 | 江苏耀鸿电子有限公司 | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof |
| CN117442921A (en) * | 2023-11-01 | 2024-01-26 | 四川峰邦消防科技有限公司 | Novel polymer gel fire-extinguishing flame retardant and preparation method thereof |
| CN117442921B (en) * | 2023-11-01 | 2024-05-24 | 四川峰邦消防科技有限公司 | Polymer gel fire-extinguishing flame retardant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115286726B (en) | 2023-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115286726A (en) | Flame-retardant modifier for plastics and preparation method thereof | |
| CN101921599B (en) | Bicyclic phosphate-based triazine derivative flame retardant and preparation method thereof | |
| CN101838538B (en) | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof | |
| CN104211954B (en) | A kind of preparation method of halogen-free flame-proof nylon 66 having polymer | |
| CN101613374B (en) | Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof | |
| CN110527053B (en) | Low-smoke flame-retardant rigid polyurethane foam material and preparation method thereof | |
| CN107474247B (en) | Preparation method of phosphorus-nitrogen synergistic water-soluble polymer flame retardant | |
| CN105348326A (en) | N-P flameresistant material and preparation method thereof and application in textiles | |
| CN105175735A (en) | Branched phosphorus-nitrogen type flame retardant and preparation method therefor | |
| CN104817685A (en) | Reactive epoxy resin flame-retardant curing agent containing phosphorus and nitrogen and preparation method thereof | |
| CN105924645A (en) | Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant | |
| CN104592297A (en) | Flame-retardant glycol containing phenyl phosphate-based symmetrical structure and preparation method thereof | |
| CN105481899A (en) | Novel halogen-free cyclotriphosphazene compound and its preparation method and use | |
| CN102702521B (en) | Macromolecule triazine charring agent with main chain containing piperazidine structure, and preparation method thereof | |
| CN101570518B (en) | Preparation method for expansion type melamine hypophosphite fire retardant | |
| CN111848893A (en) | Phosphorus-nitrogen intumescent flame retardant, preparation thereof and application thereof in polylactic acid | |
| CN107955155B (en) | Nitrogen-boron structure type flame-retardant polyether polyol and preparation method and application thereof | |
| CN105801624A (en) | Intumescent flame retardant containing phosphorus, nitrogen and sulfur and preparation method of intumescent flame retardant | |
| CN105348505A (en) | Preparation method for o-diaminobenzene phosphoryl chloride 3-butylene-1-amide polycarbonate | |
| Lee et al. | Single‐catalyst reactions from depolymerization to repolymerization: Transformation of polyethylene terephthalate to polyisocyanurate foam with deep eutectic solvents | |
| CN101831082B (en) | Method for preparing reactive phosphorus-nitrogen series intumescent flame retardant | |
| CN106349178A (en) | Preparation method of macromolecular three-element-integrated low-smoke halogen-free intumescent flame retardant | |
| CN106892943B (en) | A kind of compound in triazine class, preparation method and applications | |
| CN106986896B (en) | Star-like boron phosphazene derivative expansion type flame retardant and preparation method thereof | |
| CN106045928A (en) | Method for preparing triazine ring carbon-forming agent containing polyhydroxyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |