CN109651800A - A kind of nitrogen phosphorus silicon is grapheme modified/preparation method of shape memory polyurethane flame retardant composite material - Google Patents
A kind of nitrogen phosphorus silicon is grapheme modified/preparation method of shape memory polyurethane flame retardant composite material Download PDFInfo
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- CN109651800A CN109651800A CN201910026502.4A CN201910026502A CN109651800A CN 109651800 A CN109651800 A CN 109651800A CN 201910026502 A CN201910026502 A CN 201910026502A CN 109651800 A CN109651800 A CN 109651800A
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08L2201/12—Shape memory
Abstract
The invention discloses a kind of nitrogen phosphorus silicon it is grapheme modified/preparation method of shape memory polyurethane flame retardant composite material.The invention composite material is by the functionalization graphene and polyurethane precursor of nitrogen phosphorus silicon modification 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 and shape memory function.In addition, the shape memory function of the composite material can not only be realized by traditional outside heating method, while also remote control can be realized by the photo-thermal effect of graphene.Preparation method provided by the invention is easy to operate, environmental-friendly, and prepared composite material has excellent fire-retardant and shape memory 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/and shape memory is poly-
The preparation of urethane flame retardant composite material.
Background technique
In recent years, thermal shape memory polymer is by common concern and research, the poly- ammonia of more blocks with Typical Representative
Ester material because the advantages that its mechanical performance is excellent, chemical property is stable, process is easy in scientific research circle and engineering circles by
Generally favor, and be widely used in the fields such as smart coat and packaging (Progress in Polymer Science,
2015,49-50:3-33.).But most of polyurethane material be it is flammable or inflammable, strongly limit material safety and
Practicability.Therefore, the excellent flame-retarding characteristic of shape memory polyurethane how is assigned as polymer science and materials science field
Research hotspot.
It is with going deep into for Organic/Inorganic Composite Nanomaterials research, the inorganic nano material with flame retarding function is compound
It is expected to solve the problems, such as inflammable (the Polymer Degradation and of shape-memory polymer to polymeric matrix
Stability, 2009,94 (6): 971-979).Traditional fire retardant is well usually used in flame retardant composite material because of flame retardant property
Preparation, but not only dosage is big for such fire proofing, but also generally requires to disperse by dispersing agent with polymeric matrix compound tense,
The performance of polymeric matrix material is seriously affected, especially some halogen containing flame-retardants, the heated a large amount of dense smoke and toxic of generating
Gas, easily cause serious secondary disaster (Journal of Colloid and Interface Science, 2018,
521:160-171).Therefore, it is necessary to seek the novel nano-material that a kind of dosage is few, dispersibility is good, flame retarding efficiency is high.
Graphene is a kind of carbon nanomaterial with bi-dimensional cellular shape lattice structure being made of carbon atom, has high ratio
The features such as surface, high-fire resistance, high intensity, be widely used in polymer composites field (Carbon, 2011,49 (1):
198-205).Since graphene sheet layer has barrier property to gas, and the layer of charcoal that while burning generates can play physical barrier work
With the excellent thermal stability of polymer material and flame retardant property can be assigned.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 (Composites Science and Technology,
2018,165:161-167).Therefore, how to prepare it is a kind of environmental protection, highly effective flame-retardant functionalization graphene be one urgently to be resolved
The problem of.A kind of important derivatives of the graphene oxide as graphene, it is at low cost, easily prepared, and its surface is rich in big
Carboxyl, hydroxyl and the epoxy group isoreactivity group of amount carry out functional modification using the small organic molecule rich in nitrogen, phosphorus, silicon,
It is grapheme modified to prepare a kind of novel nitrogen phosphorus silicon, and is further polymerize with shape memory polyurethane precursor, can not only solve
Certainly dispersion problem of the graphene in polyurethane matrix, while the flame retardant property of composite material, thermal stability can be significantly improved
And mechanical property.
Chinese patent (CN108314787A) disclose a kind of phosphorus-nitrogen containing silicon polymer modified graphene oxide fire retardant and
Preparation method, it is monomer modified by MAdiDOPO, MAPOSS and GMA of phosphorus-nitrogen containing element silicon by free radical polymerisation process
Graphene oxide and obtain, prepared functionalization graphene has fire retardation, but is only capable of dispersion in organic solvent, exists certain
Limitation, in addition the invention with polymeric matrix material carry out it is compound, especially with intelligent response polymer
Basis material.Chinese patent (CN107163211A) discloses a kind of preparation method of shape memory polyurethane, it is by Buddha's warrior attendant
The star-like poly-epsilon-caprolactone of alkyl and long chain diol, isocyanates is aggregated and obtains, and has shape memory function, but without fire-retardant
Ingredient does not also have flame retarding function, and there are security risks.It is fire-retardant that Chinese patent (CN108192485A) discloses a kind of thermostabilization
The preparation method of graphene oxide polyurethane coating, it be by surface of graphene oxide grafted maleic anhydride and polyolefin,
And be applied in coating, graphene oxide polyurethane prepared by the invention has certain flame-retarding characteristic, but graphite oxide after modification
Effective flame-retardant composition on alkene surface is single, and needs outer adding assistant in application process, and forms a film and do not have shape memory
Function.
So far, both at home and abroad in relation to functionalization graphene/shape memory polyurethane composite material simultaneously in shape memory
Research with dissipation capacity has not been reported.Therefore, functionalization graphene and the progress of shape memory polyurethane precursor is compound, it is based on
The characteristics such as the heat-resisting of functionalization graphene, activeness and quietness, photo-thermal effect can not only significantly improve the anti-flammability of composite material
Energy, thermal stability and mechanical property, and it is different from traditional thermal shape memory polymer material, it is answered prepared by the present invention
The shape memory function of condensation material can not only be realized by traditional outside heating method, can also pass through the photo-thermal effect reality of graphene
Existing remote control.Preparation method provided by the invention is easy to operate, environmental-friendly, and prepared composite material has excellent resistance
Combustion and shape memory function.
Summary of the invention
The invention patent relates to a kind of nitrogen phosphorus silicon it is grapheme modified/the preparation side of shape memory polyurethane flame retardant composite material
Method, the invention composite material are to pass through suspension polymerisation with shape memory polyurethane precursor by nitrogen phosphorus silicon is grapheme modified
?.
Nitrogen phosphorus silicon provided by the present invention is grapheme modified/and shape memory polyurethane flame retardant composite material is characterized in that:
(1) nitrogen phosphorus silicon provided by the present invention it is grapheme modified/shape memory polyurethane flame retardant composite material be based on function fossil
The characteristics such as the heat-resisting of black alkene, activeness and quietness, photo-thermal effect, while the graphene after the modification of nitrogen phosphorus silicon can significantly improve composite wood
Flame retardant property, thermal stability and the mechanical property of material.(2) nitrogen phosphorus silicon provided by the present invention it is grapheme modified/shape memory is poly-
The shape memory function of urethane flame retardant composite material is by the thermal reversibility and hard section or crosslinking points of crystallinity soft segment come real
Existing, the shape memory function of composite material prepared by the present invention can not only be realized by traditional outside heating method, may be used also
Remote control is realized by the photo-thermal effect of graphene.Preparation method provided by the invention is easy to operate, environmental-friendly, prepared
Composite material have excellent fire-retardant and shape memory function, can be applied to smart coat and packaging etc. fields.
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 shape memory polyurethane flame retardant composite material is to modify graphite by nitrogen phosphorus silicon
Alkene and shape memory polyurethane precursor are obtained by suspension polymerisation.
The nitrogen phosphorus silicon is grapheme modified/and shape memory polyurethane flame retardant 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 of shape memory polyurethane precursor: poly- by 1 ~ 50 part by mole percent
Esterdiol, 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, 50 ~ 80 DEG C, reacts 2 ~ 6 h,
Polyurethane precursor is obtained, it is spare；(3) nitrogen phosphorus silicon it is grapheme modified/preparation of shape memory polyurethane flame retardant composite material: by nitrogen
Grapheme modified phosphorus silicon is by mass percentage 1.0 ~ 5.0% and polyurethane precursor progress in-situ suspension polymerization, nitrogen protection, 60 ~
80 DEG C, react 2 ~ 6 h, obtain nitrogen phosphorus silicon it is grapheme modified/shape memory polyurethane flame retardant composite 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；
Polyester-diol used is one of polycaprolactone, poly adipate succinic acid ester, polyethylene glycol adipate；Polyester-diol used
Number average molecular weight be one of 1000,2000,4000；Diisocyanate used be isophorone diisocyanate,
One of toluene di-isocyanate(TDI), hexamethylene diisocyanate；Chain extender used be ethylene glycol, Isosorbide-5-Nitrae butanediol, 1,6- oneself
One of glycol；Organic solvent used is one of acetone, butanone, tetrahydrofuran.
The present invention has the advantages that nitrogen phosphorus silicon of the present invention it is grapheme modified/shape memory polyurethane flame retardant composite material is
It is obtained by functionalization graphene and polyurethane precursor by suspension polymerisation, which, which can cooperate with, plays graphene and its table
The effect of the nitrogenous of face, phosphorus, silicon polymer assigns the good anti-flammability of polyurethane material and shape memory function.In addition, this is multiple
The shape memory function of condensation material can not only be realized by traditional outside heating method, while can also be imitated by the photo-thermal of graphene
It should realize remote control.Preparation method provided by the invention is easy to operate, environmental-friendly, and prepared composite material has excellent
Fire-retardant and shape memory function, can be applied to smart coat and packaging etc. fields.
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
Polycaprolactone (Mn=1000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit, at 110 DEG C, vacuum degree
To carry out decompression water removal under conditions of 0.09 MPa, cool down；Sequentially add the different Fo Er of 6.44 g in sequence in three-necked flask
Ketone diisocyanate, 30 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection are warming up to 80 °C under mechanical stirring
React 2 h；1.80 g 1,4-butanediol are added, in 70 °C of 3 h of reaction, obtain shape memory polyurethane precursor, it is spare.It will
200 mg nitrogen phosphorus silicon are grapheme modified to carry out compound, the reaction was continued at 60 DEG C 5 h with 10 g shape memory polyurethane precursors, cold
But to room temperature, pour mask can be obtained the grapheme modified shape memory polyurethane of nitrogen phosphorus silicon after dry 48 h at 30 ~ 60 DEG C and answer
Condensation material.
Embodiment two: (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 poly adipate succinic acid ester (Mn=1000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit
In, at 110 DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；In three-necked flask in sequence according to
6.44 g isophorone diisocyanate of secondary addition, 30 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection, in machine
80 °C of 2 h of reaction are warming up under tool stirring；1.80 g 1,4-butanediol are added, in 70 °C of 3 h of reaction, obtain shape note
Recall polyurethane precursor, it is spare.200 mg nitrogen phosphorus silicon are grapheme modified compound with the progress of 10 g shape memory polyurethane precursors,
60 DEG C of the reaction was continued 5 h, are cooled to room temperature, pour mask, and nitrogen phosphorus silicon modification graphite can be obtained after dry 48 h at 30 ~ 60 DEG C
Alkene shape memory polyurethane composite material.
Embodiment three: (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 poly adipate succinic acid ester (Mn=2000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit
In, at 110 DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；In three-necked flask in sequence according to
3.22 g isophorone diisocyanate of secondary addition, 20 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection, in machine
80 °C of 2 h of reaction are warming up under tool stirring；0.90 g 1,4-butanediol is added, in 70 °C of 3 h of reaction, obtains shape note
Recall polyurethane precursor, it is spare.200 mg nitrogen phosphorus silicon are grapheme modified compound with the progress of 10 g shape memory polyurethane precursors,
60 DEG C of the reaction was continued 5 h, are cooled to room temperature, pour mask, and nitrogen phosphorus silicon modification graphite can be obtained after dry 48 h at 30 ~ 60 DEG C
Alkene shape memory polyurethane 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 poly adipate succinic acid ester (Mn=2000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit
In, at 110 DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；In three-necked flask in sequence according to
3.22 g isophorone diisocyanate of secondary addition, 20 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection, in machine
80 °C of 2 h of reaction are warming up under tool stirring；0.90 g 1,4-butanediol is added, in 70 °C of 3 h of reaction, obtains shape note
Recall polyurethane precursor, it is spare.200 mg nitrogen phosphorus silicon are grapheme modified compound with the progress of 10 g shape memory polyurethane precursors,
60 DEG C of the reaction was continued 5 h, are cooled to room temperature, pour mask, and nitrogen phosphorus silicon modification graphite can be obtained after dry 48 h at 30 ~ 60 DEG C
Alkene shape memory polyurethane 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 polyethylene glycol adipate (Mn=4000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit
In, at 110 DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；In three-necked flask in sequence according to
1.61 g isophorone diisocyanate of secondary addition, 20 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection, in machine
80 °C of 2 h of reaction are warming up under tool stirring；0.45 g 1,4-butanediol is added, in 70 °C of 3 h of reaction, obtains shape note
Recall polyurethane precursor, it is spare.100 mg nitrogen phosphorus silicon are grapheme modified compound with the progress of 10 g shape memory polyurethane precursors,
60 DEG C of the reaction was continued 5 h, are cooled to room temperature, pour mask, and nitrogen phosphorus silicon modification graphite can be obtained after dry 48 h at 30 ~ 60 DEG C
Alkene shape memory polyurethane composite material.
Embodiment six: (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 polyethylene glycol adipate (Mn=4000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit
In, at 110 DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；In three-necked flask in sequence according to
1.61 g isophorone diisocyanate of secondary addition, 20 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection, in machine
80 °C of 2 h of reaction are warming up under tool stirring；0.45 g 1,4-butanediol is added, in 70 °C of 3 h of reaction, obtains shape note
Recall polyurethane precursor, it is spare.300 mg nitrogen phosphorus silicon are grapheme modified compound with the progress of 10 g shape memory polyurethane precursors,
60 DEG C of the reaction was continued 5 h, are cooled to room temperature, pour mask, and nitrogen phosphorus silicon modification graphite can be obtained after dry 48 h at 30 ~ 60 DEG C
Alkene shape memory polyurethane composite material.
Embodiment seven: (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 polyethylene glycol adipate (Mn=4000) it is placed in the three-necked flask equipped with blender, thermometer and condensing unit
In, at 110 DEG C, vacuum degree carries out decompression water removal under conditions of being 0.09 MPa, cools down；In three-necked flask in sequence according to
1.61 g isophorone diisocyanate of secondary addition, 20 mL butanone, 20 μ L organic bismuth catalysts 8108, nitrogen protection, in machine
80 °C of 2 h of reaction are warming up under tool stirring；0.45 g 1,4-butanediol is added, in 70 °C of 3 h of reaction, obtains shape note
Recall polyurethane precursor, it is spare.500 mg nitrogen phosphorus silicon are grapheme modified compound with the progress of 10 g shape memory polyurethane precursors,
60 DEG C of the reaction was continued 5 h, are cooled to room temperature, pour mask, and nitrogen phosphorus silicon modification graphite can be obtained after dry 48 h at 30 ~ 60 DEG C
Alkene shape memory polyurethane composite material.
Claims (2)
1. the invention patent relates to a kind of nitrogen phosphorus silicon it is grapheme modified/the preparation side of shape memory polyurethane flame retardant composite material
Method, it is characterised 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 of shape memory polyurethane precursor: poly- by 1 ~ 50 part by mole percent
Esterdiol, 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, 50 ~ 80 DEG C, reacts 2 ~ 6 h,
Polyurethane precursor is obtained, it is spare；(3) nitrogen phosphorus silicon it is grapheme modified/preparation of shape memory polyurethane flame retardant composite material: by nitrogen
Grapheme modified phosphorus silicon is by mass percentage 1.0 ~ 5.0% and polyurethane precursor progress in-situ suspension polymerization, nitrogen protection, 60 ~
80 DEG C, react 2 ~ 6 h, obtain nitrogen phosphorus silicon it is grapheme modified/shape memory polyurethane flame retardant composite material.
2. nitrogen phosphorus silicon according to claim 1 is grapheme modified/the preparation side of shape memory polyurethane flame retardant composite material
Method, it is characterised in that 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；
Polyester-diol used is one of polycaprolactone, poly adipate succinic acid ester, polyethylene glycol adipate；Polyester-diol used
Number average molecular weight be one of 1000,2000,4000；Diisocyanate used be isophorone diisocyanate,
One of toluene di-isocyanate(TDI), hexamethylene diisocyanate；Chain extender used be ethylene glycol, Isosorbide-5-Nitrae butanediol, 1,6- oneself
One of glycol；Organic solvent used is one of acetone, butanone, tetrahydrofuran.
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