CN109735094A - A kind of nitrogen phosphorus silicon is grapheme modified/preparation method of selfreparing polyurethane flame-proof composite material - Google Patents
A kind of nitrogen phosphorus silicon is grapheme modified/preparation method of selfreparing polyurethane flame-proof composite material Download PDFInfo
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Abstract
The invention discloses a kind of nitrogen phosphorus silicon it is grapheme modified/preparation method of selfreparing polyurethane flame-proof composite material.The invention composite material be by the modification of nitrogen phosphorus silicon functionalization graphene with containing double selenium selfreparing polyurethane precursors by suspension polymerisation, wherein functionalization graphene be by graphene oxide and polyethyleneimine, phosphonium flame retardant, isocyanato silanes covalent modification and obtain.Composite material of the present invention can cooperate with the effect for playing graphene and its nitrogenous of surface, phosphorus, silicon polymer, assign the good anti-flammability of polyurethane material.Meanwhile polyurethane backbone under visible light can repair material disconnected section, scratch equivalent damage containing the double selenium keys of dynamic.Preparation method provided by the invention is easy to operate, environmental-friendly, and prepared composite material has excellent fire-retardant and self-repair function, can be applied to the fields such as smart coat and packaging.
Description
Technical field
The present invention relates to smart coat and packaging field, in particular to a kind of nitrogen phosphorus silicon is grapheme modified/the poly- ammonia of selfreparing
The preparation of ester flame retardant composite material.
Background technique
Polyurethane material is low in cost, the processing is simple, has excellent performance, and is widely used in intellectual material, optical material, life
The fields such as object medical material (Angewandte Chemie International Edition, 2013,52 (36): 9422-
9441).Due to the property of material itself, it is also easy to produce micro-crack, aging equivalent damage in machine-shaping and use process, greatly limits
Safety and the practicability (Polymer, 2015,69:369-383) of material are made.Therefore, how to extend polyurethane material
Service life make its own function obtain fully playing the research hotspot as materials science field.Self-repair material conduct
One newer field, by mechanism can be divided into foreign aid's type self-repair material and Intrinsical self-repair material (Nature, 2001,
409 (6822): 794-797).The wherein relatively easy design and implementation of Intrinsical self-repair material containing dynamic covalent bond,
Material itself is set to occur covalently or non-covalently to act on realization selfreparing under certain environmental stimuli (such as light, heat, electricity, magnetic)
(Progress in Polymer Science, 2008,33 (5): 479-522).Double selenium keys are because of its chemical bond energy low (172
KJ/mol), and there is visible light-inducing commutativity, can deduce double selenium bond energys it is enough it is mild under conditions of carry out dynamic exchange
(Progress in Polymer Science, 2016,52:107-135).There is document by aliphatic double selenium small molecule lists
Body, long-chain polytetrahydrofuran and diisocyanate carry out block polymerization, have obtained a kind of polyurethane bullet with self-repair function
Property body, strand containing double selenium keys can be induced to carry out dynamic exchange to realize self-healing (Advanced under visible light
Materials, 2015,27 (47): 7740-7745).
Since most of polyurethane materials lack flame-retardant composition, it is easy burning, production, the life of people are caused serious
Threat.Traditional fire retardant is well usually used in the preparation of flame retardant polyurethane material, but such flame retardant polyurethane because of flame retardant property
Not only dosage is big for material, but also generally requires to disperse by dispersing agent with polymeric matrix compound tense, seriously affects polymer matrix
The performance of body material, especially some halogen containing flame-retardants are heated to generate a large amount of dense smoke and toxic gas, easily cause serious
Secondary disaster (Progress in Organic Coatings, 2015,89:170-180).
It is with going deep into for Organic/Inorganic Composite Nanomaterials research, the inorganic nano material with flame retarding function is compound
To polymeric matrix be expected to solve combustible polymers material safety problem, especially it is necessary to seek a kind of dosage it is few, point
Dissipate the novel nano-material (Polymer Chemistry, 2014,5 (4): 1145-1154) that property is good, flame retarding efficiency is high.Stone
Black alkene is a kind of carbon nanomaterial with bi-dimensional cellular shape lattice structure being made of carbon atom, has high-ratio surface, height resistance to
The features such as hot, high-intensitive, be widely used in polymer composites field (Nature Nanotechnology, 2008,3
(6): 327-331).Since graphene sheet layer has barrier property to gas, and the layer of charcoal that while burning generates can play physics resistance
Every effect, the excellent thermal stability of polymer material and flame retardant property (Industrial & Engineering can be assigned
Chemistry Research, 2011,50 (9): 5376-5383).However, there is stronger Van der Waals between graphene sheet layer
Power, it is easy to reunite in a polymer matrix, and graphene load capacity in a polymer matrix and to flame retardance of polymer performance
Raising it is all very limited, cannot be used separately as fire retardant (Journal of Materials Chemistry A,
2015,3 (15): 8034-8044).Therefore, a kind of environmental protection how is prepared, the functionalization graphene of highly effective flame-retardant is one urgently
It solves the problems, such as.A kind of important derivatives of the graphene oxide as graphene, it is at low cost, easily prepared, and its surface is rich
Containing a large amount of carboxyl, hydroxyl and epoxy group isoreactivity group, functionalization is carried out using the small organic molecule rich in nitrogen, phosphorus, silicon
Modification, it is grapheme modified to prepare a kind of novel nitrogen phosphorus silicon, and is further polymerize with containing double selenium selfreparing polyurethane precursors, no
It is only able to solve dispersion problem of the graphene in polyurethane matrix, while selfreparing compound polyurethane material can be significantly improved
Flame retardant property, thermal stability and mechanical property.
Chinese patent (CN108299653A) discloses a kind of Phosphorus-nitrogen flame retardant functionalization graphene and preparation method thereof,
It is by the branched polyethylene imine (BPEI) and 9 of nitrogenous P elements respectively, the miscellaneous -10- phospho hetero phenanthrene -10- oxygen of 10- dihydro-9-oxy
Compound (DOPO) modified graphene oxide and obtain, prepared functionalization graphene has fire retardation, with polycaprolactone (PLA) point
Subchain has stronger affinity, but the invention is only modified graphene oxide with the polymer of nitrogenous P elements, fire-retardant effect
Rate is general, and does not apply in polymeric matrix material, especially there is the polymer material of intelligent response.Chinese patent
(CN106117486A) dihydric alcohol, the dihydric alcohol of key containing acylhydrazone and cystine linkage, the poly- ammonia of selfreparing of a kind of key containing acylhydrazone are disclosed
Ester elastomer and preparation method thereof, it is the dihydric alcohol and polyurethane by the dihydric alcohol of the key containing acylhydrazone or key containing acylhydrazone and cystine linkage
Performed polymer is prepared, and has self-repair function, but do not have flame retarding function, there are security risks.
So far, both at home and abroad in relation to functionalization graphene/compound polyurethane material while in terms of fire-retardant and selfreparing
Research have not been reported.Therefore, by functionalization graphene with carried out containing double selenium selfreparing polyurethane precursors compound, be based on functionalization
The characteristics such as the heat-resisting of graphene, activeness and quietness can significantly improve flame retardant property, thermal stability and the mechanical property of composite material
Energy.Meanwhile polyurethane backbone under visible light can repair material disconnected section, scratch equivalent damage containing the double selenium keys of dynamic.
Preparation method provided by the invention is easy to operate, environmental-friendly, and prepared composite material has excellent fire-retardant and selfreparing
Function.
Summary of the invention
The invention patent relates to a kind of nitrogen phosphorus silicon it is grapheme modified/selfreparing polyurethane flame-proof composite material, the invention institute
Stating composite material is obtained with containing double selenium selfreparing polyurethane precursors by suspension polymerisation by nitrogen phosphorus silicon is grapheme modified.
Nitrogen phosphorus silicon provided by the present invention is grapheme modified/and selfreparing polyurethane flame-proof composite material is characterized in that:
(1) nitrogen phosphorus silicon provided by the present invention it is grapheme modified/selfreparing polyurethane flame-proof composite material be based on functionalization graphite
The characteristics such as the heat-resisting of alkene, activeness and quietness, while the graphene after the modification of nitrogen phosphorus silicon can significantly improve the fire-retardant of composite material
Performance, thermal stability and mechanical property.(2) nitrogen phosphorus silicon provided by the present invention it is grapheme modified/selfreparing polyurethane flame-proof is multiple
The polyurethane backbone of condensation material under visible light can repair material disconnected section, scratch equivalent damage containing the double selenium keys of dynamic.
Preparation method provided by the invention is easy to operate, environmental-friendly, and prepared composite material has excellent fire-retardant and selfreparing
Function can be applied to the fields such as smart coat and packaging.
The purpose of the present invention is what is be achieved through the following technical solutions:
Nitrogen phosphorus silicon of the present invention is grapheme modified/and selfreparing polyurethane flame-proof composite material is grapheme modified by nitrogen phosphorus silicon
It is obtained with containing double selenium selfreparing polyurethane precursors by suspension polymerisation.
The nitrogen phosphorus silicon is grapheme modified/and selfreparing polyurethane flame-proof composite material synthesizes by following special process:
(1) the grapheme modified preparation of nitrogen phosphorus silicon: graphene oxide water solution (1 mg/mL) is placed in equipped with magnetic stir bar
In single-necked flask, the polyethyleneimine that mass concentration is 0.1% ~ 1.5% is added, nitrogen protection reacts at room temperature 24 ~ 48 h, be centrifuged,
It is dry that nitrogen is grapheme modified；It is scattered in nitrogen is grapheme modified in organic solvent, the phosphonium flame retardant of 1 ~ 5 mmol is added, urges
Agent, nitrogen protection react at room temperature 24 ~ 48 h, are centrifuged, are dry that nitrogen phosphorus is grapheme modified；By the grapheme modified dispersion of nitrogen phosphorus
In organic solvent, the isocyanato silanes of 1 ~ 5 mmol, nitrogen protection, 60 ~ 80 DEG C of 24 ~ 36 h of reaction, after centrifugation are added
It is grapheme modified to obtain nitrogen phosphorus silicon, it is spare；(2) preparation containing double selenium selfreparing polyurethane precursors: by mole percent by 1 ~ 50 part
Polyetherdiol, 3 ~ 150 parts of isocyanate group monomer, 2 ~ 100 parts of chain extender, 1 ~ 3 times of solid content of organic solvent,
0.001 ~ 0.01 part of organic bismuth catalyst is placed in the three-necked flask with agitating device, nitrogen protection, and 50 ~ 80 DEG C, reaction
2 ~ 6 h are obtained containing double selenium selfreparing polyurethane precursors, spare；(3) nitrogen phosphorus silicon it is grapheme modified/selfreparing polyurethane flame-proof is multiple
The preparation of condensation material: suspension in situ is carried out with polyurethane precursor for 1.0 ~ 5.0% by mass percentage by nitrogen phosphorus silicon is grapheme modified
Polymerization, nitrogen protection, 60 ~ 80 DEG C, react 2 ~ 6 h, obtain nitrogen phosphorus silicon it is grapheme modified/selfreparing polyurethane flame-proof composite wood
Material.
Wherein, the number average molecular weight of polyethyleneimine used is one of 600,2000,4000；Phosphorous resistance used
Firing agent is one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its derivative；Used catalyst is three second
Amine；Isocyanato silanes used are one of isocyanatopropyl trimethoxy silane, isocyanatopropyl triethoxysilane；
Polyetherdiol used is one of polytetrahydrofuran diol, polyoxypropyleneglycol；The quantity average mark of polyetherdiol used
Son amount is one of 1000,2000,4000；Diisocyanate used is isophorone diisocyanate, toluene diisocynate
One of ester, hexamethylene diisocyanate；Chain extender used is double selenium glycol；Organic solvent used is acetone, butanone, four
One of hydrogen furans.
The present invention has the advantages that nitrogen phosphorus silicon of the present invention it is grapheme modified/selfreparing polyurethane flame-proof composite material be by
Functionalization graphene is obtained with containing double selenium selfreparing polyurethane precursors by suspension polymerisation, which can cooperate with performance stone
The effect of black alkene and its nitrogenous of surface, phosphorus, silicon polymer assigns the good anti-flammability of polyurethane material.In addition, the composite wood
The polyurethane backbone of material under visible light can repair material disconnected section, scratch equivalent damage containing the double selenium keys of dynamic.This hair
The preparation method of bright offer is easy to operate, environmental-friendly, and prepared composite material has excellent fire-retardant and self-repair function,
It can be applied to the fields such as smart coat and packaging.
Specific embodiment:
Embodiment one: (1 mg/mL) is dispersed in deionized water in single-necked flask by 500 g graphene oxides, is stirred in magnetic force
It mixes down and 1 g polyethyleneimine (M is slowly added dropwisen≈ 600), nitrogen protection reacts at room temperature 24 h, is centrifuged, is dry that nitrogen modifies stone
Black alkene；It being scattered in 250 mg nitrogen are grapheme modified in butanone (3 mg/mL), 9, the 10- dihydro-9-oxy for being added 1.08 g is miscellaneous-
10- phospho hetero phenanthrene -10- oxide, 0.53 g triethylamine and 0.77 g carbon tetrachloride, nitrogen protection react at room temperature 24 h, be centrifuged,
It is dry that nitrogen phosphorus is grapheme modified；It is scattered in 200 g nitrogen phosphorus are grapheme modified in butanone (3 mg/mL), 2 g isocyanic acids is added
Propyl trimethoxy silicane, nitrogen protection, 80 DEG C of 24 h of reaction, after centrifugation nitrogen phosphorus silicon it is grapheme modified, it is spare.By 10 g
Polytetrahydrofuran diol (Mn=1000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit, at 110 DEG C,
Vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；Sequentially add 6.44 g in sequence in three-necked flask
Isophorone diisocyanate, 30 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection heats up under mechanical stirring
To 80 °C of 2 h of reaction；The bis- selenium glycol of 4.48 g are added, in 60 °C of 6 h of reaction, are obtained containing before double selenium selfreparing polyurethane
Body, it is spare.100 mg nitrogen phosphorus silicon are grapheme modified compound containing double selenium selfreparing polyurethane precursors progress with 10 g, at 60 DEG C
The reaction was continued 5 h, are cooled to room temperature, pour mask, can be obtained after dry 48 h at 30 ~ 60 DEG C nitrogen phosphorus silicon it is grapheme modified from
Repair polyurethane flame-proof composite material.
Embodiment two: (1 mg/mL) is dispersed in deionized water in single-necked flask by 500 g graphene oxides, in magnetic
1 g polyethyleneimine (M is slowly added dropwise under power stirringn≈ 600), nitrogen protection reacts at room temperature 24 h, is centrifuged, is dry that nitrogen is repaired
Adorn graphene；It is scattered in 250 mg nitrogen are grapheme modified in butanone (3 mg/mL), 9, the 10- dihydro-9-oxy of 1.08 g is added
Miscellaneous -10- phospho hetero phenanthrene -10- oxide, 0.53 g triethylamine and 0.77 g carbon tetrachloride, nitrogen protection react at room temperature 24 h, from
It is the heart, dry that nitrogen phosphorus is grapheme modified；It is scattered in 200 g nitrogen phosphorus are grapheme modified in butanone (3 mg/mL), it is different that 2 g is added
Cyanic acid propyl trimethoxy silicane, nitrogen protection, 80 DEG C of 24 h of reaction, after centrifugation nitrogen phosphorus silicon it is grapheme modified, it is spare.It will
10 g polytetrahydrofuran diol (Mn=1000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit, 110
DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；Sequentially add 6.44 in sequence in three-necked flask
G isophorone diisocyanate, 30 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection heats up under mechanical stirring
To 80 °C of 2 h of reaction；The bis- selenium glycol of 4.48 g are added, in 60 °C of 6 h of reaction, are obtained containing before double selenium selfreparing polyurethane
Body, it is spare.300 mg nitrogen phosphorus silicon are grapheme modified compound containing double selenium selfreparing polyurethane precursors progress with 10 g, at 60 DEG C
The reaction was continued 5 h, are cooled to room temperature, pour mask, can be obtained after dry 48 h at 30 ~ 60 DEG C nitrogen phosphorus silicon it is grapheme modified from
Repair polyurethane flame-proof composite material.
Embodiment three: (1 mg/mL) is dispersed in deionized water in single-necked flask by 500 g graphene oxides, in magnetic
1 g polyethyleneimine (M is slowly added dropwise under power stirringn≈ 600), nitrogen protection reacts at room temperature 24 h, is centrifuged, is dry that nitrogen is repaired
Adorn graphene；It is scattered in 250 mg nitrogen are grapheme modified in butanone (3 mg/mL), 9, the 10- dihydro-9-oxy of 1.08 g is added
Miscellaneous -10- phospho hetero phenanthrene -10- oxide, 0.53 g triethylamine and 0.77 g carbon tetrachloride, nitrogen protection react at room temperature 24 h, from
It is the heart, dry that nitrogen phosphorus is grapheme modified；It is scattered in 200 g nitrogen phosphorus are grapheme modified in butanone (3 mg/mL), it is different that 2 g is added
Cyanic acid propyl trimethoxy silicane, nitrogen protection, 80 DEG C of 24 h of reaction, after centrifugation nitrogen phosphorus silicon it is grapheme modified, it is spare.It will
10 g polytetrahydrofuran diol (Mn=1000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit, 110
DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；Sequentially add 6.44 in sequence in three-necked flask
G isophorone diisocyanate, 30 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection heats up under mechanical stirring
To 80 °C of 2 h of reaction；The bis- selenium glycol of 4.48 g are added, in 60 °C of 6 h of reaction, are obtained containing before double selenium selfreparing polyurethane
Body, it is spare.500 mg nitrogen phosphorus silicon are grapheme modified compound containing double selenium selfreparing polyurethane precursors progress with 10 g, at 60 DEG C
The reaction was continued 5 h, are cooled to room temperature, pour mask, can be obtained after dry 48 h at 30 ~ 60 DEG C nitrogen phosphorus silicon it is grapheme modified from
Repair polyurethane flame-proof composite material.
Example IV: (1 mg/mL) is dispersed in deionized water in single-necked flask by 500 g graphene oxides, in magnetic
3.33 g polyethyleneimine (M are slowly added dropwise under power stirringn≈ 2000), nitrogen protection reacts at room temperature 24 h, centrifugation, dry
Nitrogen is grapheme modified；It is scattered in 250 mg nitrogen are grapheme modified in butanone (3 mg/mL), 9, the 10- dihydro-of 1.08 g is added
9- oxa- -10- phospho hetero phenanthrene -10- oxide, 0.53 g triethylamine and 0.77 g carbon tetrachloride, nitrogen protection, room temperature reaction 24
H is centrifuged, is dry that nitrogen phosphorus is grapheme modified；It is scattered in 200 g nitrogen phosphorus are grapheme modified in butanone (3 mg/mL), is added 2
G isocyanatopropyl triethoxysilane, nitrogen protection, 80 DEG C of 24 h of reaction, after centrifugation nitrogen phosphorus silicon it is grapheme modified, it is standby
With.By 10 g polyoxypropyleneglycol (Mn=1000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit,
At 110 DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；Successively add in sequence in three-necked flask
Enter 6.44 g isophorone diisocyanate, 30 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection is stirred in machinery
It mixes down and is warming up to 80 °C of 2 h of reaction；The bis- selenium glycol of 4.48 g are added, in 60 °C of 6 h of reaction, are obtained containing double selenium selfreparings
Polyurethane precursor, it is spare.300 mg nitrogen phosphorus silicon are grapheme modified compound containing double selenium selfreparing polyurethane precursors progress with 10 g,
The reaction was continued at 50 DEG C 5 h, are cooled to room temperature, pour mask, and nitrogen phosphorus silicon modification stone can be obtained after dry 48 h at 30 ~ 60 DEG C
Black alkene selfreparing polyurethane flame-proof composite material.
Embodiment five: (1 mg/mL) is dispersed in deionized water in single-necked flask by 500 g graphene oxides, in magnetic
6.66 g polyethyleneimine (M are slowly added dropwise under power stirringn≈ 4000), nitrogen protection reacts at room temperature 24 h, centrifugation, dry
Nitrogen is grapheme modified；It is scattered in 250 mg nitrogen are grapheme modified in butanone (3 mg/mL), 9, the 10- dihydro-of 1.08 g is added
9- oxa- -10- phospho hetero phenanthrene -10- oxide, 0.53 g triethylamine and 0.77 g carbon tetrachloride, nitrogen protection, room temperature reaction 24
H is centrifuged, is dry that nitrogen phosphorus is grapheme modified；It is scattered in 200 g nitrogen phosphorus are grapheme modified in butanone (3 mg/mL), is added 2
G isocyanatopropyl triethoxysilane, nitrogen protection, 80 DEG C of 24 h of reaction, after centrifugation nitrogen phosphorus silicon it is grapheme modified, it is standby
With.By 10 g polytetrahydrofuran diol (Mn=4000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit,
At 110 DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；Successively add in sequence in three-necked flask
Enter 1.61 g isophorone diisocyanate, 20 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection is stirred in machinery
It mixes down and is warming up to 80 °C of 2 h of reaction；The bis- selenium glycol of 1.12 g are added, in 60 °C of 6 h of reaction, are obtained containing double selenium selfreparings
Polyurethane precursor, it is spare.300 mg nitrogen phosphorus silicon are grapheme modified compound containing double selenium selfreparing polyurethane precursors progress with 10 g,
The reaction was continued at 50 DEG C 5 h, are cooled to room temperature, pour mask, and nitrogen phosphorus silicon modification stone can be obtained after dry 48 h at 30 ~ 60 DEG C
Black alkene selfreparing polyurethane flame-proof composite material.
Claims (2)
1. the invention patent relates to a kind of nitrogen phosphorus silicon it is grapheme modified/preparation method of selfreparing polyurethane flame-proof composite material,
It is characterized in that this method includes following particular step:
(1) the grapheme modified preparation of nitrogen phosphorus silicon: graphene oxide water solution (1 mg/mL) is placed in equipped with magnetic stir bar
In single-necked flask, the polyethyleneimine that mass concentration is 0.1% ~ 1.5% is added, nitrogen protection reacts at room temperature 24 ~ 48 h, be centrifuged,
It is dry that nitrogen is grapheme modified；It is scattered in nitrogen is grapheme modified in organic solvent, the phosphonium flame retardant of 1 ~ 5 mmol is added, urges
Agent, nitrogen protection react at room temperature 24 ~ 48 h, are centrifuged, are dry that nitrogen phosphorus is grapheme modified；By the grapheme modified dispersion of nitrogen phosphorus
In organic solvent, the isocyanato silanes of 1 ~ 5 mmol, nitrogen protection, 60 ~ 80 DEG C of 24 ~ 36 h of reaction, after centrifugation are added
It is grapheme modified to obtain nitrogen phosphorus silicon, it is spare；(2) preparation containing double selenium selfreparing polyurethane precursors: by mole percent by 1 ~ 50 part
Polyetherdiol, 3 ~ 150 parts of isocyanate group monomer, 2 ~ 100 parts of chain extender, 1 ~ 3 times of solid content of organic solvent,
0.001 ~ 0.01 part of organic bismuth catalyst is placed in the three-necked flask with agitating device, nitrogen protection, and 50 ~ 80 DEG C, reaction
2 ~ 6 h are obtained containing double selenium selfreparing polyurethane precursors, spare；(3) nitrogen phosphorus silicon it is grapheme modified/selfreparing polyurethane flame-proof is multiple
The preparation of condensation material: suspension in situ is carried out with polyurethane precursor for 1.0 ~ 5.0% by mass percentage by nitrogen phosphorus silicon is grapheme modified
Polymerization, nitrogen protection, 60 ~ 80 DEG C, react 2 ~ 6 h, obtain nitrogen phosphorus silicon it is grapheme modified/selfreparing polyurethane flame-proof composite wood
Material.
2. nitrogen phosphorus silicon according to claim 1 is grapheme modified/preparation method of selfreparing polyurethane flame-proof composite material,
It is characterized in that the number average molecular weight of polyethyleneimine used is one of 600,2000,4000；Phosphor-containing flame-proof used
Agent is one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its derivative；Used catalyst is three second
Amine；Isocyanato silanes used are one of isocyanatopropyl trimethoxy silane, isocyanatopropyl triethoxysilane；
Polyetherdiol used is one of polytetrahydrofuran diol, polyoxypropyleneglycol；The quantity average mark of polyetherdiol used
Son amount is one of 1000,2000,4000；Diisocyanate used is isophorone diisocyanate, toluene diisocynate
One of ester, hexamethylene diisocyanate；Chain extender used is double selenium glycol；Organic solvent used is acetone, butanone, four
One of hydrogen furans.
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| CN110330882A (en) * | 2019-07-30 | 2019-10-15 | 刘军 | A kind of selfreparing anti-corrosion polyurethane coating and preparation method |
| CN110423331A (en) * | 2019-08-05 | 2019-11-08 | 中电保力（北京）科技有限公司 | A kind of water-swellable flexible flame retardant foamed plastics and preparation method thereof |
| CN110655634A (en) * | 2019-11-13 | 2020-01-07 | 万华化学集团股份有限公司 | High flame-retardant polyurethane foam composite material and high flame-retardant polyurethane foam prepared from same |
| CN111187507A (en) * | 2020-01-14 | 2020-05-22 | 四川大学 | Preparation method of graphene-based hybrid flame retardant/self-repairing polyurethane flame-retardant composite material |
| CN112724358A (en) * | 2021-01-22 | 2021-04-30 | 四川大学 | Preparation method of waterborne flame-retardant self-repairing polyurethane based on modified graphene |
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| CN110655634A (en) * | 2019-11-13 | 2020-01-07 | 万华化学集团股份有限公司 | High flame-retardant polyurethane foam composite material and high flame-retardant polyurethane foam prepared from same |
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