CN105199384B - Fire-retardant benzoxazine nano composite material of transparent type and preparation method thereof - Google Patents
Fire-retardant benzoxazine nano composite material of transparent type and preparation method thereof Download PDFInfo
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- CN105199384B CN105199384B CN201510602647.6A CN201510602647A CN105199384B CN 105199384 B CN105199384 B CN 105199384B CN 201510602647 A CN201510602647 A CN 201510602647A CN 105199384 B CN105199384 B CN 105199384B
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- 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
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- 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
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- 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
- C08K2201/016—Additives defined by their aspect ratio
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses fire-retardant benzoxazine nano composite material of a kind of transparent type and preparation method thereof.The fire-retardant benzoxazine nano composite material of the transparent type is peeled off state layer shape α basic zirconium phosphates by 75~99 parts of benzoxazine colophonies and 1~25 part and constituted.Wherein, the lamella diameter and thickness proportion for peeling off state layer shape α basic zirconium phosphates are 50~1000.The fire-retardant benzoxazine nano composite material of transparent type that the present invention is provided, on the basis of the good combination property of material is ensured, reduce benzoxazine monomer ring-opening polymerisation temperature, the fire resistance of benzoxazine colophony is improved simultaneously, the optimization of thermosetting resin multiple performance is realized, is that thermosetting resin is modified the new Research Thinking of raising.The fire-retardant benzoxazine nano composite material of this kind of transparent type can be applied to require higher occasion to material transparent and fire resistance.
Description
Technical field
The present invention relates to fire-retardant benzoxazine nano composite material of a kind of transparent type and preparation method thereof, belong to new function
High polymer material and its preparation field.
Background technology
Benzoxazine (PBa) is a class novel hot setting resin, is heated through benzoxazine monomer (Ba) or catalyst action
Lower ring-opening polymerisation prepares (Journal of Polymer Science Part A:Polymer Chemistry,2011,49:
4213-4220；RSC Advances,2015,5:47284-47293.).Benzoxazine monomer is by phenols, primary amine and paraformaldehyde
Or formaldehyde reacts through Mannich and synthesized.By changing the structure of primary amine and phenolic compound, different types of Ben Bing Evil can be prepared
Piperazine monomer, and then obtain the benzoxazine colophony material (US7517925B2 of different performance feature；CN101578332A).Open loop
Discharged in polymerization process without small molecule, resin shrinkage rate is practically negligible, product size is stable.Benzoxazine colophony has thermally-stabilised
The advantage such as the good, intensity of property is high, modulus is big and dielectric constant is small, it is adaptable to engineering plastics and electrically insulating material (US2011/
0112235 A1).In numerous benzoxazine colophonies, bisphenol A-type benzoxazine has optimal combination property and low price,
Through obtaining market-oriented application.But bisphenol A-type benzoxazine is adjoint a large amount of black in incendivity, and combustion process in atmosphere
Dense smoke.As people are to demand of the numerous areas such as living environment safety and electronic apparatus to fire proofing, bisphenol type epoxy
The combustibility of resin seriously limits its application development.
At present, Dui benzoxazine colophonies, which carry out fire-retardant method, has：(1) the directly addition halogen system resistance into benzoxazine colophony
Fire agent, phosphonium flame retardant, containing phosphorus-nitrogen fire retardant or siliceous fire-retardant；(2) design and synthesize containing ignition-proof element (halogen, phosphorus, nitrogen or
Silicon) Xin type benzoxazine monomers (US8058362B2；).Halogenated flame retardant can discharge corrosivity toxic gas in combustion process,
There is great damage to human body and environment.The structure, relative polymerization such as-P-O- ,-P-C and-P=O in phosphorous and phosphorus-nitrogen combustion inhibitor
The groups, poor (the Journal of Applied Polymer of thermal stability such as-C-C- and-C-O in this body structure of thing
Science,2008,110:2413–2423).Therefore, material can be greatly lowered by phosphor-containing flame-proof structure being introduced into high polymer material
The thermal stability of material.The design and synthesis of Xin type benzoxazine monomers, can increase the production cycle of resin material, increase resin
The production cost of matrix.
Nano-particle will also tend to improve the thermal stability of material while high polymer material fire resistance is improved.
But the high interface of nano-particle can make it easily reunite, it is difficult to fine dispersion be reached in resin matrix, so as to influence material property.
To solve this problem, and in view of the raising of Flame Retardancy energy, generally had using phosphorus-containing compound to nano-particle
Machine is modified.It is modified through organic phosphorus compound, when nano-particle addition is larger, although make high polymer material fire resistance
It is improved, but thermal stability (the Materials Chemistry and Physics, 2014,146 of material can be reduced:
354-362)。
The present invention is overcomes organic phosphonium flame retardant to reduce the defect of high polymer material thermal stability, while considering benzo
The high limitation in the application of oxazine monomer polymerization temperature, is hindered using inorganic phosphorated laminar nano particle Dui benzoxazine colophonies
Combustion is modified, and reduces benzoxazine monomer curing reaction temperature.Inorganic phosphorated laminar nano particle can both keep the resistance of P elements
Performance is fired, there is good thermal stability again, while acidic-group can be catalyzed benzoxazine monomer ring-opening reaction.Party's legal system
Standby flame retardant type benzoxazine nano composite material has the good transparency, disclosure satisfy that electronic apparatus, space flight and aviation etc. are led
Requirement of the domain to flame retardant type benzoxazine performance and outward appearance.
The content of the invention
The application prepares the fire-retardant benzoxazine colophony material of transparent type, material tool by inorganic phosphorated laminar nano particle
There are good thermal stability, high intensity and Young's modulus and good fire resistance, disclosure satisfy that electronic apparatus and boat
Requirement of its aviation field to high performance resin material.Simultaneously in the present invention, inorganic phosphorated laminar nano particle can significantly drop
The solidification temperature of low benzoxazine monomer, and then material processing and forming temperature is reduced, the energy is saved, material production cost is reduced.
The main object of the present invention is to be received the problem of presence for prior art there is provided a kind of fire-retardant benzoxazine of transparent type
The preparation method of nano composite material and this material.
Specifically, the fire-retardant benzoxazine nano composite material of transparent type that the present invention is provided, by 75~99 parts of benzoxazines
Resin and 1~25 part of stripping state laminar alpha zirconium phosphate composition.Wherein, the lamella diameter and thickness proportion of alpha zirconium phosphate be 50~
1000.P elements in alpha zirconium phosphate structure can be effectively played during material combustion promotes into charcoal effect；Alpha zirconium phosphate is received
Rice layer structure can play physical barrier performance, delay or blocks air in oxygen and heat transmission effect, so as to play resistance
Fuel efficiency fruit；Acidic-group in alpha zirconium phosphate nanometer layer can be with benzoxazine monomer formation hydrogen bond action, Jiang Di oxazine ring electronics
Cloud density, and then reduce benzoxazine monomer solidification temperature.
In the preparation method for the fire-retardant benzoxazine nano composite material of transparent type that the present invention is provided, alpha zirconium phosphate knot is utilized
Structure feature, carries out nanometer stripping to it using polyetheramine, prepares alpha zirconium phosphate nanoscale twins；With reference to stripping state alpha zirconium phosphate nanometer
The performance characteristics of lamella and benzoxazine monomer, after the two in acetone ultrasound premix, then vacuum rotary steam removing solvent, are obtained
Benzoxazine monomer/stripping state alpha zirconium phosphate nanoscale twins mixture, benzoxazine monomer is in alpha zirconium phosphate nanoscale twins afterwards
Ring-opening polymerisation in situ, obtains the fire-retardant benzoxazine colophony material of transparent type in the presence of under conditions of.In alpha zirconium phosphate lamellar structure-
P-OH has faintly acid, while Zr4+Belong to lewis acid, both acid centres can Dui benzoxazine monomers ring-opening polymerisation
To catalytic action, so as to reduce benzoxazine monomer ring-opening polymerisation temperature.According to maximum energy criterion, benzoxazine monomer α-
After zirconium phosphate nano sheet interlayer in-situ polymerization, it is impossible to rotated by molecule segment and assemble nanoscale twins, and then ensure α-phosphorus
Sour zirconium lamella permanent nano-dispersed in benzoxazine colophony matrix, so as to ensure the fire-retardant persistence of material.
The purpose of the present invention, is implemented to realize by following technology.Wherein, described raw material number unless otherwise specified, is
Parts by weight.
First, the present invention provides a kind of fire-retardant benzoxazine nano composite material of transparent type, the fire-retardant Ben Bing Evil of the transparent type
Piperazine nano composite material is peeled off state laminar alpha zirconium phosphate by 75~99 parts of benzoxazine colophonies and 1~25 part and constituted.
Wherein, the lamella diameter and thickness proportion for peeling off state laminar alpha zirconium phosphate are 50~1000.
Secondly, the present invention also provides a kind of preparation method of the fire-retardant benzoxazine nano composite material of above-mentioned transparent type, should
Method comprises the following steps：
(1) state laminar alpha zirconium phosphate ultrasonic disperse is peeled off in 5~200 parts of acetone by 1~25 part；
(2) by 75~99 parts of benzoxazine monomer stirring and dissolvings in 50~100 parts of acetone；
(3) solution for obtaining step (2) is slowly added into the solution that step (1) is obtained, afterwards ultrasonic disperse 30~
120min obtains the mixture containing benzoxazine monomer/alpha zirconium phosphate；
(4) use Rotary Evaporators, 50~120 DEG C of gradient increased temperature removing steps (3) obtain containing benzoxazine monomer/α-
Acetone in the mixture of basic zirconium phosphate, and remove air therein；
(5) material for obtaining step (4) is added in the glass mold pre-processed using releasing agent, and 100~130
DEG C vacuum defoamation；
(6) that the material and mould after deaeration are transferred in temperature programming baking oven into 140~160 DEG C of solidifications 2~24 together is small
When, 180~200 DEG C solidify 0~4 hour；In the process, benzoxazine monomer is peeling off state laminar alpha zirconium phosphate catalytic action
Lower open loop cross-linking reaction, ultimately forms the transparent flame-retarding type nano composite material of benzoxazine colophony/alpha zirconium phosphate composition；Solidification
After the completion of process, after natural cooling, the described fire-retardant benzoxazine nano composite material of transparent type is obtained.
In the above method, the ultrasound described in step (1) and step (3), its frequency is 20-40 hertz；
Benzoxazine monomer in step (2) is bisphenol-f type benzoxazine monomer (structure a), bisphenol A-type benzoxazine list
Body (structure b), phenolphthalein type benzoxazine monomer (structure c) or thiodiphenol type benzoxazine monomer (one kind in structure d)；
Temperature programming baking oven used in the present invention is conventional use of instrument, the temperature programming that in the market can be bought
Baking oven is used equally for the present invention.In the present invention, DHG-9075AD type temperature programming baking ovens are used.
In addition, in the preparation method of the fire-retardant benzoxazine nano composite material of above-mentioned transparent type, peeling off state layer shape α-phosphorus
Sour zirconium is carried out obtaining after intercalation is organically-modified to alpha zirconium phosphate in acetone by polyetheramine.Amido and alpha-phosphate in polyethers amine structure
Hydroxyl in zirconium lamellar structure can form very strong Hyarogen-bonding, so polyethers amine molecule enter alpha zirconium phosphate lamella it
Between, after ultrasonic disperse, it is in that state is completely exfoliated to make alpha zirconium phosphate lamella.
In the preparation method of the above-mentioned fire-retardant benzoxazine nano composite material of transparent type of the present invention, state layer shape alpha-phosphate is peeled off
The preparation method of zirconium comprises the following steps：
(1) by the alpha zirconium phosphate powder that 5~15 parts of lamella diameters and thickness proportion are 5~20, in 40~100 hertz of ultrasounds
Under the conditions of, it is distributed in 200~500 parts of acetone；
(2) 10-50 parts of simple function groups or difunctional polyetheramine are weighed, be dispersed in 20-60 parts of acetone obtain polyetheramine-
Acetone dispersion liquor；
(3) by polyetheramine-acetone dispersion liquor of step (2), in the range of 25-60 minutes step (1) is added drop-wise to obtain
Solution in；40~100 hertz of 1~3h of ultrasonic disperse after dripping, magnetic particle is stirred 6~24 hours, obtains alpha zirconium phosphate-poly-
Ether amines-acetone stripper；
(4) centrifugal treating is carried out to alpha zirconium phosphate-polyetheramine-acetone stripper of step (3) using supercentrifuge；
(5) by the upper liquid after step (4) centrifugal treating after 15000~25000 revs/min of high speed centrifugation processing, under
The stripping state laminar alpha zirconium phosphate that secondary precipitum is lamella diameter and thickness proportion is 50~1000.
Above-mentioned stripping state laminar alpha zirconium phosphate may be homogenously dispersed in acetone, absolute ethyl alcohol, toluene, benzene, N, N- after ultrasound
In dimethylformamide and NVP solvent.
In the preparation method step of above-mentioned stripping state laminar alpha zirconium phosphate, simple function group or double officials described in step (2)
The ether amines that can reunite are one kind in following structure (I), structure (II) or structure (III).
Wherein, in structure (I), x/y=0.1~9, molecular weight is 600~2000；In structure (II), x=2~35, molecule
Measure as 200~2000；In structure (III), x+z=1~6, y=2~40, molecular weight is 200~2000.
Centrifugation step speed described in step (4) is 5000-10000 revs/min；
The structure being related in the embodiment of the present invention is carried out by the following method with performance test：
(1) solidification temperature：Using U.S.'s TA companies Q20 types differential scanning calorimeter (DSC) test unit and monomer/α-phosphorus
The initial curing temperature and maximum cure rate corresponding temperature of sour zirconium mixture.
(2) microstructure：Analyzed using JEOL JSM-5900LV types ESEMs (SEM).By sample in vacuum coater
It is upper gold-plated, then observe, image, the micro-structure diagram of layer of charcoal after being burnt on SEM instrument.
(3) thermal stability：Surveyed respectively in air and nitrogen atmosphere using STA449F3 types thermal analyzer (NETZSCH)
Try the heat endurance of nano composite material.Range of measuring temp is room temperature~800 DEG C, and heating rate is 10 DEG C/min, gas stream
Speed is 60mL/min.
(4) fire resistance：The HRR of toughness reinforcing-fire proofing is determined using the technical standards of UK FTT ISO 5660
And smoke density, investigate the fire resistance of material.By toughening flame-proof type epoxy resin be made it is long it is generous be respectively 100mm,
100mm, 3.2mm model, are tested on cone calorimetry.
The present invention compared with the prior art, with following advantage：
(1) the fire-retardant benzoxazine nano composite material of transparent type that the present invention is provided, is ensureing the good combination property of material
On the basis of, benzoxazine monomer ring-opening polymerisation temperature is reduced, while improving the fire resistance of benzoxazine colophony, is realized
Thermosetting resin multiple performance optimizes, and is that thermosetting resin is modified the new Research Thinking of raising.
(2) research method that the present invention is provided can save energy in benzoxazine colophony and its nano composite material preparation process
Source is consumed, and then reduces material production cost.Meanwhile, it is thermally-stabilised that the research method that the present invention is provided improves benzoxazine colophony
Performance, extends benzoxazine colophony burning time, reduce benzoxazine colophony in combustion HRR and
Carbon monoxide and carbon dioxide releasing amount, improve benzoxazine colophony safety in utilization.
(3) in the fire-retardant benzoxazine nano composite material of transparent type that the present invention is provided, reduction solidification temperature and raising are played
The nanometer alpha zirconium phosphate of fire resistance, is monolithic laminate, be may be homogenously dispersed in benzoxazine colophony matrix, and with
Benzoxazine colophony matrix has good interface compatibility, it is ensured that the fire-retardant persistence of material.
(4) the fire-retardant benzoxazine nano composite material of transparent type that the present invention is provided, preparation process is simple, it is easy to industrialize
Production.
Brief description of the drawings
Fig. 1 is pure bis-phenol described in bisphenol A-type benzoxazine monomer/alpha zirconium phosphate mixture described in embodiment 1 and comparative example 1
The DSC test curves of A type benzoxazine monomers；
Fig. 2 is thermogravimetric test (TGA) curve of material in air atmosphere after solidifying described in embodiment 1 and comparative example 1；
Fig. 3 is thermogravimetric test (TGA) curve of material in nitrogen atmosphere after solidifying described in embodiment 1 and comparative example 1；
Fig. 4 be obtained after solidifying described in embodiment 3 and comparative example 1 in material tapered calorimetric test HRR-when
Half interval contour；
Fig. 5 is that the carbon monoxide (CO) obtained after solidifying described in embodiment 3 and comparative example 1 in the tapered calorimetric test of material is total
Burst size-time graph；
Fig. 6 is layer of charcoal (a) outer surface and (b) internal structure scanning electron microscope (SEM) photograph after material combustion after solidifying described in embodiment 3.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that following examples are served only for
The invention will be further described, it is impossible to is interpreted as limiting the scope of the invention, person skilled in the art's root in the field
Some nonessential modifications and adaptations are made to the present invention according to the invention described above content, the scope of the present invention is still fallen within.
Embodiment 1
It is 20 alpha zirconium phosphate powder by 5 parts of lamella diameters and thickness proportion, under 40 hertz of ultrasound conditions, is distributed to
In 200 parts of acetone, alpha zirconium phosphate powder-acetone suspension is obtained.Weigh the type simple function group of structure I that 16 parts of molecular weight are 1000
Polyetheramine, is dispersed in 50 parts of acetone and obtains the type simple function group polyetheramine of structure I-acetone dispersion liquor.By the type simple function group of structure I
It is added drop-wise in polyetheramine-acetone dispersion liquor, 25 minutes in alpha zirconium phosphate powder-acetone suspension.40 hertz after dripping
Ultrasonic disperse 1h, magnetic particle is stirred 24 hours, obtains the type simple function group polyetheramine of alpha zirconium phosphate-structure I-acetone stripper.From
10000 revs/min of rotating speeds of scheming carry out centrifugal treating to the type simple function group polyetheramine of alpha zirconium phosphate-structure I-acetone stripper.
The type simple function group polyetheramine of alpha zirconium phosphate-structure I-acetone stripper is divided into clarification after 10000 revs/min of processing of centrifuge
Upper liquid and the centrifugation a small amount of precipitum of bottom of the tube.Upper liquid after centrifugal treating is handled in 20000 revs/min of high speed centrifugations
Afterwards, next precipitum is the laminar alpha zirconium phosphate for the type simple function group polyetheramine of structure I stripping that molecular weight is 1000.
3 parts of molecular weight exist for 40 hertz of ultrasonic disperses of alpha zirconium phosphate of the 1000 type simple function group polyetheramine of structure I stripping
In 15 parts of acetone.97 parts of bisphenol A-type benzoxazine monomers are dissolved in 100 parts of acetone.Then by the type simple function group of said structure I
Alpha zirconium phosphate/the acetone dispersion liquor and bisphenol A-type benzoxazine monomer that polyetheramine is peeled off/acetone soln are mixed, and 40 hertz super
Sound disperses 30min.Using Rotary Evaporators, acetone is removed under 50 DEG C, 80 DEG C and 120 DEG C three temperature stages, and remove bisphenol-A
Air in type benzoxazine monomer/stripping state alpha zirconium phosphate mixture.By bisphenol A-type benzoxazine monomer/stripping state α-phosphorus
Sour zirconium mixture is added in the glass mold pre-processed using releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, by mould
And bisphenol A-type benzoxazine monomer/stripping state alpha zirconium phosphate mixture is transferred in temperature programming baking oven.160 DEG C of solidifications 24 are small
When.In the process, bisphenol A-type benzoxazine monomer open loop cross-linking reaction under alpha zirconium phosphate catalytic action, forms bisphenol A-type
Benzoxazine colophony/alpha zirconium phosphate nano composite material.After the completion of solidification process, natural cooling obtains the fire-retardant bisphenol-A of transparent type
Type benzoxazine nano composite material.
It is pure double described in bisphenol A-type benzoxazine monomer described in embodiment 1/stripping state alpha zirconium phosphate mixture and comparative example 1
The DSC test curves of phenol A type benzoxazine monomers are shown in accompanying drawing 1.Accompanying drawing 2 and accompanying drawing 3 are respectively that transparent type described in embodiment 1 is fire-retardant
Bisphenol A-type benzoxazine colophony is in air and nitrogen atmosphere described in bisphenol A-type benzoxazine nano composite material and comparative example 1
Thermogravimetric test (TGA) curve.It can see from accompanying drawing 1, alpha zirconium phosphate can be greatly lowered benzoxazine Open loop temperature,
And substantially reduce maximum cure rate corresponding temperature.Thermogravimetric curve shows in accompanying drawing 2 and accompanying drawing 3, in air atmosphere and blanket of nitrogen
The thermal stability and high-temperature residual amount of benzoxazine colophony can be improved by enclosing middle alpha zirconium phosphate.
Embodiment 2
It is 5 alpha zirconium phosphate powder by 15 parts of lamella diameters and thickness proportion, under 100 hertz of ultrasound conditions, is distributed to
In 500 parts of acetone, alpha zirconium phosphate powder-acetone suspension is obtained.Weigh the type difunctional of structure III that 50 parts of molecular weight are 600
Polyetheramine, is dispersed in 60 parts of acetone and obtains the type difunctional polyetheramine of structure III-acetone dispersion liquor.By the type difunctionality of structure III
It is added drop-wise in reunion ether amines-acetone dispersion liquor, 60 minutes in alpha zirconium phosphate powder-acetone suspension.100 hertz after dripping
Hereby ultrasonic disperse 1h, magnetic particle stirring 12 hours, obtain the type difunctional polyetheramine of alpha zirconium phosphate-structure III-acetone stripper.
5000 revs/min of rotating speeds of centrifuge are carried out at centrifugation to the type simple function group polyetheramine of alpha zirconium phosphate-structure III-acetone stripper
Reason.The type simple function group polyetheramine of alpha zirconium phosphate-structure III-acetone stripper is divided into clear after 5000 revs/min of processing of centrifuge
Clear upper liquid and the centrifugation a small amount of precipitum of bottom of the tube.Upper liquid after centrifugal treating is handled in 15000 revs/min of high speed centrifugations
Afterwards, next precipitum is the laminar alpha zirconium phosphate for the type difunctional polyetheramine of structure III stripping that molecular weight is 600.
40 hertz of ultrasonic disperses of alpha zirconium phosphate that 15 parts of type difunctional polyetheramines of said structure III are peeled off are in 40 parts of acetone
In.85 parts of bisphenol-f type benzoxazine monomers are dissolved in 90 parts of acetone.Then by above-mentioned alpha zirconium phosphate/acetone dispersion liquor and benzene
Bing oxazines monomer/40 hertz of acetone soln ultrasonic disperse 30min.Using Rotary Evaporators, under 50 and 100 DEG C of two temperature stages
Acetone is removed, and removes the air in benzoxazine monomer/alpha zirconium phosphate mixture.By bisphenol-f type benzoxazine monomer/α-phosphorus
Sour zirconium mixture is added in the glass mold pre-processed using releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, by mould
And benzoxazine monomer/alpha zirconium phosphate mixture is transferred in temperature programming baking oven.140 DEG C solidify 4 hours, and 200 DEG C of solidifications 4 are small
When.In the process, bisphenol-f type benzoxazine monomer open loop cross-linking reaction under alpha zirconium phosphate catalytic action, forms bisphenol-f type
Benzoxazine/alpha zirconium phosphate nano composite material.After the completion of solidification process, natural cooling obtains the fire-retardant benzoxazine of transparent type
Nano composite material.
Embodiment 3
It is 20 alpha zirconium phosphate powder by 5 parts of lamella diameters and thickness proportion, under 40 hertz of ultrasound conditions, is distributed to
In 250 parts of acetone, alpha zirconium phosphate powder-acetone suspension is obtained.Weigh the type simple function group of structure I that 16 parts of molecular weight are 1000
Polyetheramine, is dispersed in 50 parts of acetone and obtains the type simple function group polyetheramine of structure I-acetone dispersion liquor.By the type simple function group of structure I
It is added drop-wise in polyetheramine-acetone dispersion liquor, 25 minutes in alpha zirconium phosphate powder-acetone suspension.40 hertz after dripping
Ultrasonic disperse 1h, magnetic particle is stirred 18 hours, obtains the type simple function group polyetheramine of alpha zirconium phosphate-structure I-acetone stripper.From
10000 revs/min of rotating speeds of scheming carry out centrifugal treating to the type simple function group polyetheramine of alpha zirconium phosphate-structure I-acetone stripper.
The type simple function group polyetheramine of alpha zirconium phosphate-structure I-acetone stripper is divided into clarification after 10000 revs/min of processing of centrifuge
Upper liquid and the centrifugation a small amount of precipitum of bottom of the tube.By the upper liquid after above-mentioned centrifugal treating at 20000 revs/min of high speed centrifugations
After reason, next precipitum is the laminar alpha zirconium phosphate that the type simple function group polyetheramine of structure I that molecular weight is 1000 is peeled off.
40 hertz of ultrasonic disperses of alpha zirconium phosphate that 10 parts of type simple function group polyetheramines of said structure I are peeled off are in 40 parts of acetone
In.90 parts of bisphenol A-type benzoxazine monomers are dissolved in 90 parts of acetone.Then by above-mentioned alpha zirconium phosphate/acetone dispersion liquor and benzene
Bing oxazines monomer/40 hertz of acetone soln ultrasonic disperse 30min.Using Rotary Evaporators, under 50 and 110 DEG C of two temperature stages
Acetone is removed, and removes the air in benzoxazine monomer/alpha zirconium phosphate mixture.By bisphenol A-type benzoxazine monomer/α-phosphorus
Sour zirconium mixture is added in the glass mold pre-processed using releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, by mould
And benzoxazine monomer/alpha zirconium phosphate mixture is transferred in temperature programming baking oven.160 DEG C solidify 24 hours.In the process,
Bisphenol A-type benzoxazine monomer open loop cross-linking reaction under alpha zirconium phosphate catalytic action, formation bisphenol A-type benzoxazine colophony/
Alpha zirconium phosphate nano composite material.After the completion of solidification process, natural cooling obtains the fire-retardant bisphenol A-type benzoxazine of transparent type and received
Nano composite material.
Accompanying drawing 4 and accompanying drawing 5 are to be obtained after solidifying described in embodiment 3 and comparative example 1 in the tapered calorimetric test of resin material respectively
Total burst size-the time graph of HRR-time graph and carbon monoxide (CO) arrived.Comparing result shows, alpha zirconium phosphate
HRR and peak value in benzoxazine colophony combustion process can be effectively reduced, is people while the duration of ignition can be extended
Escape provides the more time in a fire.As long as CO is one of lethal reason in fire.Compared with pure benzoxazine colophony, benzene
CO burst sizes are greatly lowered in Bing oxazines resin/alpha zirconium phosphate nano composite material combustion process.Accompanying drawing 6 is the institute of embodiment 3
State after solidification layer of charcoal (a) outer surface and (b) internal structure scanning electron microscope (SEM) photograph after resin material burning.From the figure, it can be seen that benzene
Bing oxazines resin/alpha zirconium phosphate nano composite material can form outer surface densification, the layer of charcoal of internal porous in combustion.
This layer of charcoal can effectively play the effect of barrier Mass and heat transfer, and then reduce HRR, so as to play fire retardation.
Embodiment 4
It is 10 alpha zirconium phosphate powder by 10 parts of lamella diameters and thickness proportion, under 40 hertz of ultrasound conditions, is distributed to
In 300 parts of acetone, alpha zirconium phosphate powder-acetone suspension is obtained.Weigh the type difunctional of structure II that 25 parts of molecular weight are 200
Polyetheramine, is dispersed in 40 parts of acetone and obtains the type difunctional polyetheramine of structure II-acetone dispersion liquor.By the type difunctionality of structure II
It is added drop-wise in reunion ether amines-acetone dispersion liquor, 35 minutes in alpha zirconium phosphate powder-acetone suspension.60 hertz after dripping
Hereby ultrasonic disperse 1.5h, magnetic particle stirring 16 hours, obtain the type difunctional polyetheramine of alpha zirconium phosphate-structure II-acetone and peel off
Liquid.10000 revs/min of rotating speeds of centrifuge are centrifuged to the type difunctional polyetheramine of alpha zirconium phosphate-structure II-acetone stripper
Processing.The type difunctional polyetheramine of alpha zirconium phosphate-structure II-acetone stripper divides after 10000 revs/min of processing of centrifuge
For clarification upper liquid and the centrifugation a small amount of precipitum of bottom of the tube.By the upper liquid after above-mentioned centrifugal treating in 25000 revs/min of high speeds
After centrifugal treating, next precipitum is that molecular weight is the laminar alpha zirconium phosphate that the type difunctional polyetheramine of 200 structure II is peeled off.
40 hertz of ultrasonic disperses of alpha zirconium phosphate that 25 parts of type difunctional polyetheramines of said structure II are peeled off are in 100 parts of acetone
In.75 parts of phenolphthalein type benzoxazine monomers are dissolved in 50 parts of acetone.Then by above-mentioned alpha zirconium phosphate/acetone dispersion liquor and benzo
Oxazine monomer/30 hertz of acetone soln ultrasonic disperse 120min.Using Rotary Evaporators, under 60 and 120 DEG C of two temperature stages
Acetone is removed, and removes the air in benzoxazine monomer/alpha zirconium phosphate mixture.By phenolphthalein type benzoxazine monomer/α-phosphorus
Sour zirconium mixture is added in the glass mold pre-processed using releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, by mould
And benzoxazine monomer/alpha zirconium phosphate mixture is transferred in temperature programming baking oven.160 DEG C solidify 2 hours, and 200 DEG C of solidifications 4 are small
When.In the process, phenolphthalein type benzoxazine monomer open loop cross-linking reaction under alpha zirconium phosphate catalytic action, forms phenolphthalein type benzene
Bing oxazines resin/alpha zirconium phosphate nano composite material.After the completion of solidification process, natural cooling obtains the fire-retardant Ben Bing Evil of transparent type
Piperazine nano composite material.
Embodiment 5
It is 15 alpha zirconium phosphate powder by 5 parts of lamella diameters and thickness proportion, under 40 hertz of ultrasound conditions, is distributed to
In 200 parts of acetone, alpha zirconium phosphate powder-acetone suspension is obtained.Weigh the type difunctionality of structure II that 10 parts of molecular weight are 2000
Reunion ether amines, are dispersed in 20 parts of acetone and obtain the type difunctional polyetheramine of structure II-acetone dispersion liquor.By the double officials of the type of structure II
Can be reunited ether amines-acetone dispersion liquor, be added drop-wise in 25 minutes in alpha zirconium phosphate powder-acetone suspension.40 after dripping
Hertz ultrasonic disperse 1h, magnetic particle is stirred 6 hours, is obtained the type difunctional polyetheramine of alpha zirconium phosphate-structure II-acetone and is peeled off
Liquid.10000 revs/min of rotating speeds of centrifuge are centrifuged to the type difunctional polyetheramine of alpha zirconium phosphate-structure II-acetone stripper
Processing.The type difunctional polyetheramine of alpha zirconium phosphate-structure II-acetone stripper divides after 10000 revs/min of processing of centrifuge
For clarification upper liquid and the centrifugation a small amount of precipitum of bottom of the tube.By the upper liquid after above-mentioned centrifugal treating in 25000 revs/min of high speeds
After centrifugal treating, next precipitum is the stratiform alpha-phosphate that the type difunctional polyetheramine of structure II that molecular weight is 2000 is peeled off
Zirconium.
40 hertz of ultrasonic disperses of alpha zirconium phosphate that 1 part of type difunctional polyetheramine of said structure II is peeled off are in 5 parts of acetone.
99 parts of polyethers amine type benzoxazine monomers are dissolved in 100 parts of acetone.Then by above-mentioned alpha zirconium phosphate/acetone dispersion liquor and benzo
Oxazine monomer/20 hertz of acetone soln ultrasonic disperse 100min.Using Rotary Evaporators, under 50 and 110 DEG C of two temperature stages
Acetone is removed, and removes the air in benzoxazine monomer/alpha zirconium phosphate mixture.By polyethers amine type benzoxazine monomer/α-
Basic zirconium phosphate mixture is added in the glass mold pre-processed using releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, by mould
Tool and benzoxazine monomer/alpha zirconium phosphate mixture are transferred in temperature programming baking oven.160 DEG C solidify 12 hours, 180 DEG C of solidifications
4 hours.In the process, polyethers amine type benzoxazine monomer open loop cross-linking reaction under alpha zirconium phosphate catalytic action, forms poly-
Ether amines type benzoxazine colophony/alpha zirconium phosphate nano composite material.After the completion of solidification process, natural cooling obtains transparent type resistance
Fire benzoxazine nano composite material.
Comparative example 1
After 100 parts of bisphenol A-type benzoxazine monomers, 120 DEG C of meltings, the glass pre-processed using releasing agent is added to
In mould, in 120 DEG C of vacuum drying ovens after deaeration, mould and benzoxazine monomer are transferred in temperature programming baking oven.160 DEG C solid
Change 12 hours.In this solidification process, bisphenol A-type benzoxazine monomer open loop cross-linking reaction forms bisphenol A-type benzoxazine tree
Fat.After the completion of solidification process, natural cooling obtains pure benzoxazine material.
Application Example 1
The toughening flame-proof type epoxy resin that embodiment 4 is formulated is applied to steel structure fireproofing coating.Concrete application implements step
It is rapid as follows, state alpha zirconium phosphate will be completely exfoliated first and weighed in benzoxazine monomer in number ratio described in embodiment 4, and press
It is uniform that the step of embodiment 4 carries out ultrasonic mixing；Afterwards, by its high pressure painting on 200mm × 200mm × 3mm steel plates, thickness is applied
2mm is spent, after solidifying by the condition of embodiment 4, the flameproof effect of testing coating.As a result show, be formulated using comparative example 1 prepared
Blank coating, without any flame retardant effect, the 1min steel plates back side just reaches 350 DEG C, and surface of steel plate is generated without layer of charcoal.By implementation
Coating fire resistance period prepared by the formula of example 4 is up to 10min, and in the expansion of the fine and close consistent internal structure in Surface Creation outer surface
Layer of charcoal, layer of charcoal highest thickness has 13mm.It is not in come off in steel construction BENDING PROCESS that the coating prepared is formulated by embodiment 4
With obvious crack, toughness is preferable.Wherein, flameproof effect intends combustion method test, flameproof effect using vertical combustion-big template die
Using fire resistance period as foundation, the longer flameproof effect of fire resistance period is better.Steel construction loses the critical-temperature of static balancing stability
For 500 DEG C or so, lost at 350 DEG C or so thirdly point one intensity, therefore steel plate back temperature will be worked as and reached needed for 350 DEG C
The time wanted is designated as the fire resistance period of coating.Bend test is tested on WDW-5 type microcomputer controlled electronic universal testing machines.
Claims (6)
1. a kind of preparation method of the fire-retardant benzoxazine nano composite material of transparent type, it is characterised in that this method includes following
Step：
(1) state laminar alpha zirconium phosphate ultrasonic disperse is peeled off in 5~200 parts of acetone by 1~25 part；
(2) by 75~99 parts of benzoxazine monomer stirring and dissolvings in 50~100 parts of acetone；
(3) solution for obtaining step (2) is slowly added into the solution that step (1) is obtained, afterwards ultrasonic disperse 30~
120min obtains the mixture containing benzoxazine monomer/alpha zirconium phosphate；
(4) Rotary Evaporators are used, what 50~120 DEG C of gradient increased temperature removing steps (3) obtained contains benzoxazine monomer/alpha-phosphate
Acetone in the mixture of zirconium, and remove air therein；
(5) material for obtaining step (4) is added in the glass mold pre-processed using releasing agent, and 100~130 DEG C true
Empty deaeration；
(6) material and mould after deaeration are transferred in temperature programming baking oven into 140~160 DEG C together to solidify 2~24 hours,
180~200 DEG C solidify 0~4 hour；In the process, benzoxazine monomer is in the case where peeling off state laminar alpha zirconium phosphate catalytic action
Open loop cross-linking reaction, ultimately forms the transparent flame-retarding type nano composite material of benzoxazine colophony/alpha zirconium phosphate composition；Solidified
After the completion of journey, after natural cooling, the described fire-retardant benzoxazine nano composite material of transparent type is obtained；
Wherein, the preparation method of the stripping state laminar alpha zirconium phosphate in step (1) comprises the following steps：
1. by the alpha zirconium phosphate powder that 5~15 parts of lamella diameters and thickness proportion are 5~20, in 40~100 hertz of ultrasound conditions
Under, it is distributed in 200~500 parts of acetone；
2. 10-50 parts of simple function groups or difunctional polyetheramine are weighed, is dispersed in 20-60 parts of acetone and obtains polyetheramine-acetone
Dispersion liquid；
3. the solution that 1. step obtains is added drop-wise in the range of polyetheramine-acetone dispersion liquor by step 2., 25-60 minutes
In；40~100 hertz of 1~3h of ultrasonic disperse after dripping, magnetic particle is stirred 6~24 hours, obtain alpha zirconium phosphate-polyetheramine-
Acetone stripper；
4. centrifugal treating is carried out to the alpha zirconium phosphate-polyetheramine-acetone stripper of step 3. using supercentrifuge；
5. by the upper liquid after step 4. centrifugal treating after 15000~25000 revs/min of high speed centrifugation processing, sedimentation next time
The stripping state laminar alpha zirconium phosphate that thing is lamella diameter and thickness proportion is 50~1000.
2. the preparation method of the fire-retardant benzoxazine nano composite material of transparent type according to claim 1, it is characterised in that
Ultrasound described in step (1) and step (3), its frequency is 20-40 hertz.
3. the preparation method of the fire-retardant benzoxazine nano composite material of transparent type according to claim 1 or 2, its feature exists
In the benzoxazine monomer in step (2) is shown in the bisphenol-f type benzoxazine monomer shown in following structure a, following structure b
Bisphenol A-type benzoxazine monomer, the phenolphthalein type benzoxazine monomer shown in following structure c or following structure d shown in it is thio
One kind in hexichol phenolic benzoxazine monomer；
4. the preparation method of the fire-retardant benzoxazine nano composite material of transparent type according to claim 1, it is characterised in that
Peel off state laminar alpha zirconium phosphate preparation method the step of 2. described in simple function group or difunctional polyetheramine be following knot
One kind in structure I, structure II or structure III：
Wherein, in structure I, x/y=0.1~9, molecular weight is 600~2000；In structure II, x=2~35, molecular weight is 200
~2000；In structure III, x+z=1~6, y=2~40, molecular weight is 200~2000.
5. the preparation method of the fire-retardant benzoxazine nano composite material of transparent type according to claim 1 or 4, its feature exists
In, peel off state laminar alpha zirconium phosphate preparation method the step of 4. described in centrifugation step speed be 5000-10000 revs/min
Clock.
6. a kind of fire-retardant benzoxazine nano composite material of transparent type, it is characterised in that the fire-retardant benzoxazine of transparent type is received
Nano composite material is by stripping state that 75~99 parts of benzoxazine colophonies and 1~25 part of lamella diameter and thickness proportion are 50~1000
Laminar alpha zirconium phosphate is constituted；And the fire-retardant benzoxazine nano composite material of the transparent type is by any one of claim 1-5 kinds side
What method was prepared.
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| CN107474208B (en) * | 2017-08-01 | 2019-10-22 | 四川天策聚材科技有限公司 | A kind of multi-functional benzoxazine composite material and preparation method |
| CN112980135B (en) * | 2021-02-24 | 2022-06-10 | 西南石油大学 | Flame-retardant and toughened benzoxazine/bio-based phosphide composite material and preparation method thereof |
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| CN1515357A (en) * | 2003-01-08 | 2004-07-28 | 中国科学院大连化学物理研究所 | Lamellar zirconium phosphate crystal containing organic diamine, its preparation method and application |
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