CN110373024A - A kind of flame-resistant high-temperature-resistant composite polyimide material and preparation method thereof - Google Patents
A kind of flame-resistant high-temperature-resistant composite polyimide material and preparation method thereof Download PDFInfo
- Publication number
- CN110373024A CN110373024A CN201910648440.0A CN201910648440A CN110373024A CN 110373024 A CN110373024 A CN 110373024A CN 201910648440 A CN201910648440 A CN 201910648440A CN 110373024 A CN110373024 A CN 110373024A
- Authority
- CN
- China
- Prior art keywords
- parts
- flame
- alkali lignin
- retardant
- composite
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of flame-resistant high-temperature-resistant composite polyimide materials and preparation method thereof, belong to expansion flame-retardant material technical field.Comprising: by weight, 60 parts -90 parts of modified polyimide, 20 parts -40 parts of modified alkali lignin, 5 parts -25 parts of organic composite flame-retardant, 2 parts -5 parts of inorganic composite flame retardants, 3 parts -5 parts of poly silane coupling agent, 3 parts -5 parts of triphenyl phosphite, 3 parts -5 parts of maleic anhydride grafted polyethylene and hard 0.5 part -3 parts of zinc of cholic acid.Preparation method includes: that (1) mixes above-mentioned modified polyimide and modified alkali lignin, and stirs evenly；(2) organic composite flame-retardant, inorganic composite flame retardants, poly silane coupling agent, triphenyl phosphite, maleic anhydride grafted polyethylene and hard cholic acid zinc are added, continues to be stirred to react 1-2h, polyimides flame retardant composite material is made.Flame-resistant high-temperature-resistant composite polyimide material heat resistance of the invention is good, thermal stability is strong, good flame retardation effect.
Description
Technical field
The present invention relates to expansion flame-retardant material technical fields, and in particular to a kind of flame-resistant high-temperature-resistant composite polyimide material
And preparation method thereof.
Background technique
Polyimides is due to being widely used in Aeronautics and Astronautics with excellent thermal stability and good mechanical performance
With the industries such as electronics.In recent years, the fire-retardant fireproof of polymer is just being increasingly subject to the attention of people, and is often applied to high temperature ring
The polyimides of border or aviation field, anti-flammability are even more to receive much attention.But it is applied to high temperature protection textile and special type electricity
The special dimensions such as gas insulation film propose more stringent requirement to the performance especially temperature tolerance of fire proofing.
Summary of the invention
The object of the present invention is to provide a kind of flame-resistant high-temperature-resistant composite polyimide materials and preparation method thereof, to solve mesh
The preceding temperature tolerance high request to fire proofing the problem of.
The technical scheme to solve the above technical problems is that
A kind of polyimides flame retardant composite material comprising: by weight, 60 parts -90 parts of modified polyimide is modified
20 parts -40 parts of alkali lignin, 5 parts -25 parts of organic composite flame-retardant, 2 parts -5 parts of inorganic composite flame retardants, poly silane coupling agent
3 parts -5 parts, 3 parts -5 parts of triphenyl phosphite, 3 parts -5 parts of maleic anhydride grafted polyethylene and hard 0.5 part -3 parts of zinc of cholic acid.
Further, in preferred embodiments of the present invention, above-mentioned polyimides flame retardant composite material comprising: by weight
Measure part meter, 70 parts -80 parts of modified polyimide, 25 parts -35 parts of modified alkali lignin, 10 parts -20 parts of organic composite flame-retardant, nothing
2 parts -5 parts of machine composite flame-retardant agent, 3 parts -5 parts of poly silane coupling agent, 3 parts -5 parts of triphenyl phosphite, maleic anhydride grafting are poly-
0.5 part -3 parts of 3 parts -5 parts of ethylene and hard cholic acid zinc.
Further, in preferred embodiments of the present invention, above-mentioned polyimides flame retardant composite material comprising: by weight
Measure part meter, 75 parts of modified polyimide, 30 parts of modified alkali lignin, 15 parts of organic composite flame-retardant, inorganic composite flame retardants 2
Parts -5 parts, 3 parts -5 parts of poly silane coupling agent, 3 parts -5 parts of triphenyl phosphite, 3 parts -5 parts of maleic anhydride grafted polyethylene and
Hard 0.5 part -3 parts of zinc of cholic acid.
Further, in preferred embodiments of the present invention, the preparation step of above-mentioned modified polyimide includes: poly- to shell
Acetic acid is added in sugar to be dissolved, chitosan solution is obtained；By the methylvinylcyclosiloxane pre-polymerization through naoh treatment
Body, benzophenone tetracarboxylic dianhydride, methylene dianiline (MDA) are added in o-dichlorohenzene solvent, and chitosan solution is added and first stirs
It is gradually warming up to 250 DEG C -350 DEG C again after reaction 10h-15h, after removing solvent and the water of reaction generation, it is sub- to obtain modified polyamides
Amine, and chitosan content is the 10wt%-15wt% of modified polyimide；Wherein, methylvinylcyclosiloxane performed polymer, two
Benzophenonetetracarboxylic dianhydride and methylene dianiline (MDA) the mass ratio of the material are 1:(1-3): (1.5-4.5)；The concentration of chitosan solution
For 2wt%-5wt%.
Methylvinylcyclosiloxane performed polymer through naoh treatment of the invention be use concentration for 10% hydrogen
What sodium oxide molybdena obtained after handling methylvinylcyclosiloxane performed polymer immersion 20min.
Further, in preferred embodiments of the present invention, the preparation method of above-mentioned modified alkali lignin includes:
(1) mix reagent that alkali lignin is added to chloroacetic chloride and pyridine is handled；
(2) alkali lignin will be obtained after processing to be dissolved in the aqueous solution of ethyl alcohol, and be added to calcium and magnesium complex solid alkali and benzene
Phenol stirring, obtains alkali lignin powder by revolving after fully reacting；
(3) after alkali lignin powder being configured to solution, 10wt%-20wt% dilute hydrochloric acid is added and adjusts PH to 2-3, through clear
Wash isolated modified alkali lignin；
Wherein, the mass ratio of chloroacetic chloride and pyridine is (1.5-2) in step (1): 1；Alkali lignin, calcium and magnesium in step (2)
Complex solid alkali, phenol additional amount mass ratio be (0.6-0.8): 1:(0.1-0.2).
Further, in preferred embodiments of the present invention, above-mentioned organic composite flame-retardant includes: phosphoric acid tert-butyl benzene two
Benzene rouge, hypo-aluminum orthophosphate and melamine isocyanates, wherein phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine are different
The mass ratio of cyanate is 25:(1-5): (1-5).
Further, in preferred embodiments of the present invention, above-mentioned inorganic composite flame retardants include: nano-sized magnesium hydroxide and
Nano-aluminum hydroxide, wherein the mass ratio of nano-sized magnesium hydroxide and nano-aluminum hydroxide is 1:3-4.
The preparation method of above-mentioned flame-resistant high-temperature-resistant composite polyimide material, comprising:
(1) above-mentioned modified polyimide and modified alkali lignin are mixed, and stirred evenly；
(2) organic composite flame-retardant, inorganic composite flame retardants, poly silane coupling agent, triphenyl phosphite, horse are added
Maleic anhydride grafted polyethylene and hard cholic acid zinc, continue to be stirred to react 1-2h, and polyimides flame retardant composite material is made.
The invention has the following advantages:
1, the present invention is that flexible, asymmetry poly- silicon is introduced in polyimide backbone structure using modified polyimide
The polymer of oxygen alkane chain link can reduce the interface energy of system, improve the toughness of material, widen the use temperature range of material,
Have the characteristics that anti-flammability, heat resistance, nonflammable, raw smoke of burning is few.And also it is modified by chitosan, is had
The case where strength and stiffness for avoiding to cause because of the introducing of polysiloxanes Polyimidesiloxane of effect reduce.Simultaneously as
Polyfunctional group (hydroxyl and amino) on chitosan can form cross-linked network structure with alkali lignin, improve the close structure of material
Degree, to improve the flame retardant effect of material, draw high intensity and impact strength.
2, the present invention is by greatly improving hydroxyl in alkali lignin molecular structure to alkali lignin modified amination treatment
Content and activity, so that the validity of alkali lignin is also improved, so that it is guaranteed that it can be before itself be decomposed at a lower temperature
It reacts and is decomposed to form coke and water, and then increase coke residue output, play fire-retardant effect.
3, the present invention is compounded using organic composite flame-retardant and inorganic composite flame retardants, is wherein adopted in organic composite flame-retardant
Melamine isocyanates can promote phosphoric acid tert-butyl benzene hexichol rouge and hypo-aluminum orthophosphate and lignin that phosphorus acylation reaction occurs
Phosphamide is generated, the phosphamide of generation is easy to alkali lignin and occurs to react at rouge and be conducive to thermal stability.And organic composite hinders
Combustion agent phosphorus-nitrogen flame-retardant system can promote chitosan and modified alkali lignin to be decomposed to form coke and water at a lower temperature, and increase
Add coke residue output, to improve flame retardant effect.And organic composite flame-retardant forms dilatancy coke at high temperature
Layer, plays a part of heat-insulated resistance oxygen protective layer.
And nano-aluminum hydroxide and nano-sized magnesium hydroxide are used, filler while and excellent inorganic had both been played the role of
Fire retardant advantageously forms continuous, anti-oxidant inorganic matter protective layer, hinders with organic composite with biggish surface energy
Combustion agent can play the role of cooperative flame retardant.A large amount of heat can be absorbed in burning initial stage inorganic composite flame retardants, is reduced organic
The flue gas that composite flame-retardant agent burning generates, and dense and uniform filling can be caused in intumescent char layer, it is not easily to fall off, to improve resistance
Fuel efficiency fruit.
Specific embodiment
Principles and features of the present invention are described with reference to embodiments, the given examples are served only to explain the present invention,
It is not intended to limit the scope of the present invention.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer suggests
Condition carries out.Reagents or instruments used without specified manufacturer is the conventional products that can be obtained by commercially available purchase.
Embodiment 1:
The flame-resistant high-temperature-resistant composite polyimide material of the present embodiment include: by weight, 60 parts of modified polyimide,
20 parts of modified alkali lignin, 5 parts of organic composite flame-retardant, 2 parts of inorganic composite flame retardants, 3 parts of poly silane coupling agent, phosphorous acid
3 parts of triphenylmethyl methacrylate, 3 parts of maleic anhydride grafted polyethylene and hard 0.5 part of zinc of cholic acid.
Wherein, the preparation step of modified polyimide includes: and acetic acid is added into chitosan to be dissolved, and obtains chitosan
Solution；By methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride, methylene hexichol through naoh treatment
Amine is added in o-dichlorohenzene solvent, and chitosan solution is added first is stirred to react after 10h and be gradually warming up to 250 DEG C again, is removed
After the water that solvent and reaction generate, modified polyimide is obtained, and chitosan content is the 10wt% of modified polyimide；Its
In, methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride and methylene dianiline (MDA) the mass ratio of the material are 1:1:
1.5；The concentration of chitosan solution is 2wt%.
The preparation method of modified alkali lignin includes:
(1) mix reagent that alkali lignin is added to chloroacetic chloride and pyridine is handled；
(2) alkali lignin will be obtained after processing to be dissolved in the aqueous solution of ethyl alcohol, and be added to calcium and magnesium complex solid alkali and benzene
Phenol stirring, obtains alkali lignin powder by revolving after fully reacting；
(3) after alkali lignin powder being configured to solution, 10wt% dilute hydrochloric acid is added and adjusts PH to 2-3, cleaned separation
Obtain modified alkali lignin；
Wherein, the mass ratio of chloroacetic chloride and pyridine is 1.5:1 in step (1)；Alkali lignin, calcium and magnesium are compound in step (2)
Solid base, phenol additional amount mass ratio be 0.6:1:0.1.
Organic composite flame-retardant includes: phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates,
In, the mass ratio of phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates is 25:1:1.
Inorganic composite flame retardants include: nano-sized magnesium hydroxide and nano-aluminum hydroxide, wherein nano-sized magnesium hydroxide and nanometer
The mass ratio of aluminium hydroxide is 1:3.
The preparation method of the flame-resistant high-temperature-resistant composite polyimide material of the present embodiment, comprising:
(1) above-mentioned modified polyimide and modified alkali lignin are mixed, and stirred evenly；
(2) organic composite flame-retardant, inorganic composite flame retardants, poly silane coupling agent, triphenyl phosphite, horse are added
Maleic anhydride grafted polyethylene and hard cholic acid zinc, continue to be stirred to react 1h, and polyimides flame retardant composite material is made.
Embodiment 2:
The flame-resistant high-temperature-resistant composite polyimide material of the present embodiment include: by weight, 70 parts of modified polyimide,
25 parts of modified alkali lignin, 10 parts of organic composite flame-retardant, 3 parts of inorganic composite flame retardants, 3 parts of poly silane coupling agent, phosphorous
3 parts of triphenyl phosphate ester, 3 parts of maleic anhydride grafted polyethylene and hard 1 part of zinc of cholic acid
Wherein, the preparation step of modified polyimide includes: and acetic acid is added into chitosan to be dissolved, and obtains chitosan
Solution；By methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride, methylene hexichol through naoh treatment
Amine is added in o-dichlorohenzene solvent, and chitosan solution is added first is stirred to react after 12h and be gradually warming up to 270 DEG C again, is removed
After the water that solvent and reaction generate, modified polyimide is obtained, and chitosan content is the 12wt% of modified polyimide；Its
In, methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride and methylene dianiline (MDA) the mass ratio of the material are 1:
1.5:2.5；The concentration of chitosan solution is 3wt%.
The preparation method of modified alkali lignin includes:
(1) mix reagent that alkali lignin is added to chloroacetic chloride and pyridine is handled；
(2) alkali lignin will be obtained after processing to be dissolved in the aqueous solution of ethyl alcohol, and be added to calcium and magnesium complex solid alkali and benzene
Phenol stirring, obtains alkali lignin powder by revolving after fully reacting；
(3) after alkali lignin powder being configured to solution, 12wt% dilute hydrochloric acid is added and adjusts PH to 2-3, cleaned separation
Obtain modified alkali lignin；
Wherein, the mass ratio of chloroacetic chloride and pyridine is 1.7:1 in step (1)；Alkali lignin, calcium and magnesium are compound in step (2)
Solid base, phenol additional amount mass ratio be 0.65:1:0.15.
Organic composite flame-retardant includes: phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates,
In, the mass ratio of phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates is 25:2:2.
Inorganic composite flame retardants include: nano-sized magnesium hydroxide and nano-aluminum hydroxide, wherein nano-sized magnesium hydroxide and nanometer
The mass ratio of aluminium hydroxide is 1:3.
The preparation method of the flame-resistant high-temperature-resistant composite polyimide material of the present embodiment, comprising:
(1) above-mentioned modified polyimide and modified alkali lignin are mixed, and stirred evenly；
(2) organic composite flame-retardant, inorganic composite flame retardants, poly silane coupling agent, triphenyl phosphite, horse are added
Maleic anhydride grafted polyethylene and hard cholic acid zinc, continue to be stirred to react 1h, and polyimides flame retardant composite material is made.
Embodiment 3:
The flame-resistant high-temperature-resistant composite polyimide material of the present embodiment include: by weight, 70 parts of modified polyimide,
30 parts of modified alkali lignin, 15 parts of organic composite flame-retardant, 4 parts of inorganic composite flame retardants, 4 parts of poly silane coupling agent, phosphorous
4 parts of triphenyl phosphate ester, 4 parts of maleic anhydride grafted polyethylene and hard 1.5 parts of zinc of cholic acid.
Wherein, the preparation step of modified polyimide includes: and acetic acid is added into chitosan to be dissolved, and obtains chitosan
Solution；By methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride, methylene hexichol through naoh treatment
Amine is added in o-dichlorohenzene solvent, and chitosan solution is added first is stirred to react after 13h and be gradually warming up to 300 DEG C again, is removed
After the water that solvent and reaction generate, modified polyimide is obtained, and chitosan content is the 13wt% of modified polyimide；Its
In, methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride and methylene dianiline (MDA) the mass ratio of the material are 1:2:
3；The concentration of chitosan solution is 3.5wt%.
The preparation method of modified alkali lignin includes:
(1) mix reagent that alkali lignin is added to chloroacetic chloride and pyridine is handled；
(2) alkali lignin will be obtained after processing to be dissolved in the aqueous solution of ethyl alcohol, and be added to calcium and magnesium complex solid alkali and benzene
Phenol stirring, obtains alkali lignin powder by revolving after fully reacting；
(3) after alkali lignin powder being configured to solution, 15wt% dilute hydrochloric acid is added and adjusts PH to 2-3, cleaned separation
Obtain modified alkali lignin；
Wherein, the mass ratio of chloroacetic chloride and pyridine is 1.7:1 in step (1)；Alkali lignin, calcium and magnesium are compound in step (2)
Solid base, phenol additional amount mass ratio be 0.7:1:0.15.
Organic composite flame-retardant includes: phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates,
In, the mass ratio of phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates is 25:3:3.
Inorganic composite flame retardants include: nano-sized magnesium hydroxide and nano-aluminum hydroxide, wherein nano-sized magnesium hydroxide and nanometer
The mass ratio of aluminium hydroxide is 1:3.5.
The preparation method of the flame-resistant high-temperature-resistant composite polyimide material of the present embodiment, comprising:
(1) above-mentioned modified polyimide and modified alkali lignin are mixed, and stirred evenly；
(2) organic composite flame-retardant, inorganic composite flame retardants, poly silane coupling agent, triphenyl phosphite, horse are added
Maleic anhydride grafted polyethylene and hard cholic acid zinc, continue to be stirred to react 1.5h, and polyimides flame retardant composite material is made.
Embodiment 4:
The flame-resistant high-temperature-resistant composite polyimide material of the present embodiment include: by weight, 80 parts of modified polyimide,
35 parts of modified alkali lignin, 20 parts of organic composite flame-retardant, 4 parts of inorganic composite flame retardants, 4 parts of poly silane coupling agent, phosphorous
4 parts of triphenyl phosphate ester, 4 parts of maleic anhydride grafted polyethylene and hard 2 parts of zinc of cholic acid.
Wherein, the preparation step of modified polyimide includes: and acetic acid is added into chitosan to be dissolved, and obtains chitosan
Solution；By methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride, methylene hexichol through naoh treatment
Amine is added in o-dichlorohenzene solvent, and chitosan solution is added first is stirred to react after 14h and be gradually warming up to 320 DEG C again, is removed
After the water that solvent and reaction generate, modified polyimide is obtained, and chitosan content is the 14wt% of modified polyimide；Its
In, methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride and methylene dianiline (MDA) the mass ratio of the material are 1:
2.5:4；The concentration of chitosan solution is 4wt%.
The preparation method of modified alkali lignin includes:
(1) mix reagent that alkali lignin is added to chloroacetic chloride and pyridine is handled；
(2) alkali lignin will be obtained after processing to be dissolved in the aqueous solution of ethyl alcohol, and be added to calcium and magnesium complex solid alkali and benzene
Phenol stirring, obtains alkali lignin powder by revolving after fully reacting；
(3) after alkali lignin powder being configured to solution, 17wt% dilute hydrochloric acid is added and adjusts PH to 2-3, cleaned separation
Obtain modified alkali lignin；
Wherein, the mass ratio of chloroacetic chloride and pyridine is 1.9:1 in step (1)；Alkali lignin, calcium and magnesium are compound in step (2)
Solid base, phenol additional amount mass ratio be 0.75:1:0.2.
Organic composite flame-retardant includes: phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates,
In, the mass ratio of phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates is 25:4:4.
Inorganic composite flame retardants include: nano-sized magnesium hydroxide and nano-aluminum hydroxide, wherein nano-sized magnesium hydroxide and nanometer
The mass ratio of aluminium hydroxide is 1:3-4.
The preparation method of the flame-resistant high-temperature-resistant composite polyimide material of the present embodiment, comprising:
(1) above-mentioned modified polyimide and modified alkali lignin are mixed, and stirred evenly；
(2) organic composite flame-retardant, inorganic composite flame retardants, poly silane coupling agent, triphenyl phosphite, horse are added
Maleic anhydride grafted polyethylene and hard cholic acid zinc, continue to be stirred to react 2h, and polyimides flame retardant composite material is made.
Embodiment 5:
The flame-resistant high-temperature-resistant composite polyimide material of the present embodiment include: by weight, 90 parts of modified polyimide,
40 parts of modified alkali lignin, 25 parts of organic composite flame-retardant, 5 parts of inorganic composite flame retardants, 5 parts of poly silane coupling agent, phosphorous
5 parts of triphenyl phosphate ester, 5 parts of maleic anhydride grafted polyethylene and hard 3 parts of zinc of cholic acid.
Wherein, the preparation step of modified polyimide includes: and acetic acid is added into chitosan to be dissolved, and obtains chitosan
Solution；By methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride, methylene hexichol through naoh treatment
Amine is added in o-dichlorohenzene solvent, and chitosan solution is added first is stirred to react after 15h and be gradually warming up to 350 DEG C again, is removed
After the water that solvent and reaction generate, modified polyimide is obtained, and chitosan content is the 15wt% of modified polyimide；Its
In, methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride and methylene dianiline (MDA) the mass ratio of the material are 1:3:
4.5；The concentration of chitosan solution is 5wt%.
The preparation method of modified alkali lignin includes:
(1) mix reagent that alkali lignin is added to chloroacetic chloride and pyridine is handled；
(2) alkali lignin will be obtained after processing to be dissolved in the aqueous solution of ethyl alcohol, and be added to calcium and magnesium complex solid alkali and benzene
Phenol stirring, obtains alkali lignin powder by revolving after fully reacting；
(3) after alkali lignin powder being configured to solution, 20wt% dilute hydrochloric acid is added and adjusts PH to 2-3, cleaned separation
Obtain modified alkali lignin；
Wherein, the mass ratio of chloroacetic chloride and pyridine is 2:1 in step (1)；Alkali lignin, calcium and magnesium composite solid in step (2)
Body alkali, phenol additional amount mass ratio be 0.8:1:0.2.
Organic composite flame-retardant includes: phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates,
In, the mass ratio of phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates is 25:5:5.
Inorganic composite flame retardants include: nano-sized magnesium hydroxide and nano-aluminum hydroxide, wherein nano-sized magnesium hydroxide and nanometer
The mass ratio of aluminium hydroxide is 1:4.
The preparation method of the flame-resistant high-temperature-resistant composite polyimide material of the present embodiment, comprising:
(1) above-mentioned modified polyimide and modified alkali lignin are mixed, and stirred evenly；
(2) organic composite flame-retardant, inorganic composite flame retardants, poly silane coupling agent, triphenyl phosphite, horse are added
Maleic anhydride grafted polyethylene and hard cholic acid zinc, continue to be stirred to react 2h, and polyimides flame retardant composite material is made.
Reference examples 1
This reference examples difference from Example 3 is that, using unmodified polyimides, remaining is same as Example 3.
Reference examples 2
This reference examples difference from Example 3 is that, using unmodified alkali lignin, remaining is same as Example 3.
The effect of the embodiment 1-5 and comparative example 1-2 fire-retardant performance of composite material prepared is measured, according to GB/T
8924 standards carry out the test of oxygen index (OI), carry out vertical burn test by ASTM standard, test result see the table below.
The performance test table of table 1 embodiment 1-5 and comparative example 1-2
It can be seen from Table 1 that the limit oxygen index of embodiment 1-5 is all larger than 27, it is nonflammable to meet open fire, or after burning
Leaving flame can extinguish rapidly, can be resistant to 300 DEG C or more of high temperature, and the flame retardant rating of embodiment is said also superior to reference examples
Bright flame-resistant high-temperature-resistant polyimides flame retardant composite material of the invention has good flame-retardance energy.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of flame-resistant high-temperature-resistant composite polyimide material, characterized in that it comprises: by weight, modified polyamides is sub-
60 parts -90 parts of amine, 20 parts -40 parts of modified alkali lignin, 5 parts -25 parts of organic composite flame-retardant, 2 part -5 of inorganic composite flame retardants
Part, 3 parts -5 parts of poly silane coupling agent, 3 parts -5 parts of triphenyl phosphite, 3 parts -5 parts of maleic anhydride grafted polyethylene and hard gallbladder
0.5 part -3 parts of sour zinc.
2. polyimides flame retardant composite material according to claim 1, characterized in that it comprises: by weight, change
Property 70 parts -80 parts of polyimides, 25 parts -35 parts of modified alkali lignin, 10 parts -20 parts of organic composite flame-retardant, inorganic compounding resistance
Fire 2 parts -5 parts of agent, 3 parts -5 parts of poly silane coupling agent, 3 parts -5 parts of triphenyl phosphite, 3 part -5 of maleic anhydride grafted polyethylene
0.5 part -3 parts of part and hard cholic acid zinc.
3. flame-resistant high-temperature-resistant composite polyimide material according to claim 2, characterized in that it comprises: by weight
Part meter, 75 parts of modified polyimide, 30 parts of modified alkali lignin, 15 parts of organic composite flame-retardant, 2 part -5 of inorganic composite flame retardants
Part, 3 parts -5 parts of poly silane coupling agent, 3 parts -5 parts of triphenyl phosphite, 3 parts -5 parts of maleic anhydride grafted polyethylene and hard gallbladder
0.5 part -3 parts of sour zinc.
4. flame-resistant high-temperature-resistant composite polyimide material according to claim 1-3, which is characterized in that described to change
Property polyimides preparation step include: into chitosan be added acetic acid dissolved, obtain chitosan solution；It will be through hydroxide
Methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride, the methylene dianiline (MDA) of sodium processing are added to adjacent dichloro
It in benzene solvent, and chitosan solution is added first is stirred to react after 10h-15h and be gradually warming up to 250 DEG C -350 DEG C again, remove solvent
After the water generated with reaction, modified polyimide is obtained, and chitosan content is the 10wt%-15wt% of modified polyimide；
Wherein, methylvinylcyclosiloxane performed polymer, benzophenone tetracarboxylic dianhydride and methylene dianiline (MDA) the mass ratio of the material are 1:
(1-3): (1.5-4.5)；The concentration of chitosan solution is 2wt%-5wt%.
5. flame-resistant high-temperature-resistant composite polyimide material according to claim 1-3, which is characterized in that described to change
The preparation method of property alkali lignin includes:
(1) mix reagent that alkali lignin is added to chloroacetic chloride and pyridine is handled；
(2) alkali lignin will be obtained after processing to be dissolved in the aqueous solution of ethyl alcohol, and be added to calcium and magnesium complex solid alkali and phenol stirs
It mixes, obtains alkali lignin powder by revolving after fully reacting；
(3) after alkali lignin powder being configured to solution, be added 10wt%-20wt% dilute hydrochloric acid adjust PH to 2-3, cleaned point
From obtaining modified alkali lignin；
Wherein, the mass ratio of chloroacetic chloride and pyridine is (1.5-2) in step (1): 1；Alkali lignin, calcium and magnesium are compound in step (2)
Solid base, phenol additional amount mass ratio be (0.6-0.8): 1:(0.1-0.2).
6. flame-resistant high-temperature-resistant composite polyimide material according to claim 1-3, which is characterized in that described to have
Machine composite flame-retardant agent includes: phosphoric acid tert-butyl benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates, wherein the tertiary fourth of phosphoric acid
The mass ratio of base benzene hexichol rouge, hypo-aluminum orthophosphate and melamine isocyanates is 25:(1-5): (1-5).
7. flame-resistant high-temperature-resistant composite polyimide material according to claim 1-3, which is characterized in that the nothing
Machine composite flame-retardant agent includes: nano-sized magnesium hydroxide and nano-aluminum hydroxide, wherein nano-sized magnesium hydroxide and nano-aluminum hydroxide
Mass ratio is 1:3-4.
8. the preparation method of the described in any item flame-resistant high-temperature-resistant composite polyimide materials of claim 1-7, which is characterized in that
Include:
(1) modified polyimide and modified alkali lignin are mixed, and stirred evenly；
(2) organic composite flame-retardant, inorganic composite flame retardants, poly silane coupling agent, triphenyl phosphite, maleic acid are added
Acid anhydride grafted polyethylene and hard cholic acid zinc, continue to be stirred to react 1h-2h, and polyimides flame retardant composite material is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910648440.0A CN110373024A (en) | 2019-07-18 | 2019-07-18 | A kind of flame-resistant high-temperature-resistant composite polyimide material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910648440.0A CN110373024A (en) | 2019-07-18 | 2019-07-18 | A kind of flame-resistant high-temperature-resistant composite polyimide material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110373024A true CN110373024A (en) | 2019-10-25 |
Family
ID=68253801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910648440.0A Pending CN110373024A (en) | 2019-07-18 | 2019-07-18 | A kind of flame-resistant high-temperature-resistant composite polyimide material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110373024A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117005199A (en) * | 2023-08-07 | 2023-11-07 | 烟台大学 | Preparation of MOFs modified nitrogen-phosphorus-silicon flame retardant and application of MOFs modified nitrogen-phosphorus-silicon flame retardant in cotton fabric |
| CN117005199B (en) * | 2023-08-07 | 2024-07-05 | 烟台大学 | Preparation of MOFs modified nitrogen-phosphorus-silicon flame retardant and application of MOFs modified nitrogen-phosphorus-silicon flame retardant in cotton fabric |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299778A (en) * | 2018-03-01 | 2018-07-20 | 合肥峰腾节能科技有限公司 | A kind of Environment-friendlywear-resistant wear-resistant strong-toughness fire-resisting plastic material and preparation method thereof |
-
2019
- 2019-07-18 CN CN201910648440.0A patent/CN110373024A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299778A (en) * | 2018-03-01 | 2018-07-20 | 合肥峰腾节能科技有限公司 | A kind of Environment-friendlywear-resistant wear-resistant strong-toughness fire-resisting plastic material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王研等: "CaO/MgO复合固体碱催化剂催化降解木质素的研究", 《林产化学与工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117005199A (en) * | 2023-08-07 | 2023-11-07 | 烟台大学 | Preparation of MOFs modified nitrogen-phosphorus-silicon flame retardant and application of MOFs modified nitrogen-phosphorus-silicon flame retardant in cotton fabric |
| CN117005199B (en) * | 2023-08-07 | 2024-07-05 | 烟台大学 | Preparation of MOFs modified nitrogen-phosphorus-silicon flame retardant and application of MOFs modified nitrogen-phosphorus-silicon flame retardant in cotton fabric |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | A bio-based ionic complex with different oxidation states of phosphorus for reducing flammability and smoke release of epoxy resins | |
| Rao et al. | Highly efficient, transparent, and environment-friendly flame-retardant coating for cotton fabric | |
| Zhang et al. | A novel organic-inorganic hybrid K-HBPE@ APP performing excellent flame retardancy and smoke suppression for polypropylene | |
| Wang et al. | High-efficiency phosphorus/nitrogen-containing flame retardant on epoxy resin | |
| Wang et al. | Metal compound-enhanced flame retardancy of intumescent epoxy resins containing ammonium polyphosphate | |
| Bao et al. | Epoxy resin flame retarded and toughed via flexible siloxane chain containing phosphaphenanthrene | |
| CN113667277B (en) | Low-heat-release, low-smoke and high-flame-retardance epoxy resin material and preparation method thereof | |
| TWI352114B (en) | ||
| CN109762115A (en) | A kind of resin combination and its application | |
| Fang et al. | A bio-based intumescent flame retardant with biomolecules functionalized ammonium polyphosphate enables polylactic acid with excellent flame retardancy | |
| Liu et al. | Cross-linkable phosphorus/nitrogen-containing aromatic ethylenediamine endowing epoxy resin with excellent flame retardancy and mechanical properties | |
| Yue et al. | Study on the performance of flame‐retardant esterified starch‐modified cassava dregs‐PBS composites | |
| CN109206665B (en) | A kind of hybrid modification hypo-aluminum orthophosphate and preparation method thereof | |
| CN112250985B (en) | Halogen-free flame-retardant ABS composition and preparation method and application thereof | |
| Ma et al. | Polyhydric SiO2 coating assistant to graft organophosphorus onto glass fabric for simultaneously improving flame retardancy and mechanical properties of epoxy resin composites | |
| Zhang et al. | A novel P‐S‐Si‐based cage‐structural monomer for flame‐retardant modification of unsaturated polyester resin | |
| Wang et al. | A novel DOPO‐containing HTBN endowing waterborne polyurethane with excellent flame retardance and mechanical properties | |
| Yu et al. | Cyclotriphosphazene hyperbranched P/N/Si prepared flame retardants improve mechanical properties and flame retardancy of epoxy resins | |
| Guo et al. | AP/N-containing hardener endowing bio-based epoxy thermosets with excellent thermal, mechanical and intrinsically flame-retardant performances | |
| Shen et al. | Study on preparation and properties of agricultural waste bagasse eco-type bio-flame-retardant/epoxy composites | |
| CN114806322B (en) | Bio-based flexible epoxy fireproof coating and preparation method and application thereof | |
| CN110373024A (en) | A kind of flame-resistant high-temperature-resistant composite polyimide material and preparation method thereof | |
| CN115613358B (en) | Compound plant fiber flame retardant modifier and application thereof | |
| CN112094502A (en) | High-temperature-resistant mixed silicone rubber and preparation method thereof | |
| CN114891272B (en) | Melamine formaldehyde resin microencapsulated flame retardant and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191025 |