CN109096539A - A kind of fire retardant and preparation method thereof, polycarbonate composite material and preparation method thereof - Google Patents
A kind of fire retardant and preparation method thereof, polycarbonate composite material and preparation method thereof Download PDFInfo
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- CN109096539A CN109096539A CN201810746956.4A CN201810746956A CN109096539A CN 109096539 A CN109096539 A CN 109096539A CN 201810746956 A CN201810746956 A CN 201810746956A CN 109096539 A CN109096539 A CN 109096539A
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
- C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention belongs to technical field of polymer materials more particularly to a kind of fire retardant and preparation method thereof, polycarbonate composite material and preparation method thereof.The present invention provides a kind of fire retardant, the fire retardant is 1,3,5,7- to four benzsulfamide adamantane.Fire retardant of the present invention provides good fat-soluble, stability using adamantane as core, for flame retardant molecule；Four ends of the bridge of fire retardant replace the content that ignition-proof element can be improved, and element sulphur decomposes the SO generated2PC can be promoted to be crosslinked, played a role in condensed phase, nitrogen decomposes the non-flammable compressive gas generated and dilutes starvation, formation condensed phase working mechanism fire-retardant when gentle identical, so that fire retardant is high-efficient in the gas phase；Meanwhile the polarity of the amino of fire retardant can increase flame retardant molecule and the compatibility of PC.Also, fire retardant of the present invention, without compounding, additive amount is few when making an addition to improvement flame retardant property in PC, small to the Effect on Mechanical Properties of PC material；Compared with sulfonate salt flame, the hygroscopicity of the fire retardant is low.
Description
Technical field
The invention belongs to technical field of polymer materials more particularly to a kind of fire retardant and preparation method thereof, polycarbonate
Composite material and preparation method.
Background technique
The engineering plastics advantage easy to process by the performances such as itself high intensity, high temperature resistant, anticorrosive and material,
Certain application aspects can substitute metal material, have been widely used for aerospace, electrotechnical, electronic, Vehicle Engineering, office are set
There is the material Transformation Tendency to mould Dai Gang, to mould Dai Mu in the industries such as standby, energy saving building.Wherein, polycarbonate
(Polycarbonate, PC) has become one of fastest-rising engineering plastics of usage amount in the world by its excellent performance.So
And in terms of flame retardant property, although PC itself can reach the V-2 rank of fire rating UL-94 and limit oxygen index can reach
26%, but it is still unable to satisfy in the high requirement of certain application fields.Therefore efficient and environmentally friendly halogen-free flame retardants is developed
It is particularly important on the application bottleneck for breaking through PC material.
Currently used halogen-free flame retardants has nitrogenated flame retardant, phosphorus flame retardant, silicon-series five-retardant, sulfonate salt flame
Deng above-mentioned halogen-free flame retardants is added in PC, the flame retardant property of PC can be improved.But nitrogenated flame retardant and phosphorous flame-retardant
Additive amount of the agent in PC is big, influences on the performance of PC material itself big；Silicon-series five-retardant is at high cost, and generally requiring compounding makes
With；Sulfonate salt flame poor water resistance, process are easy to appear agglomeration.
Summary of the invention
In view of this, the present invention provides a kind of fire retardant and preparation method thereof, polycarbonate composite material and its preparations
Method, for solving in existing PC fire retardant, the additive amount of nitrogenated flame retardant and phosphorus flame retardant in PC is big, to PC material sheet
The performance of body influences big；Silicon-series five-retardant is at high cost, generally requires and is used in compounding；Sulfonate salt flame poor water resistance, it is processed
Journey is easy to appear the problem of agglomeration.
The specific technical solution of the present invention is as follows:
A kind of fire retardant, the fire retardant are 1,3,5,7- to four benzsulfamide adamantane；The 1,3,5,7- is to four benzene
Shown in the structural formula of sulfonamide adamantane such as formula (I)；
The present invention also provides a kind of preparation methods of fire retardant, comprising the following steps:
First is carried out with ammonium hydroxide to four benzene sulfonyl chloride adamantane by 1,3,5,7- to react, and obtains 1,3,5,7- to four benzene sulfonyls
Amine adamantane；
Wherein, shown in described 1,3,5, the 7- structural formula such as formula (I) to four benzsulfamide adamantane；
Preferably, described reacted with ammonium hydroxide progress first by 1,3,5,7- four benzene sulfonyl chloride adamantane specifically includes:
Described 1,3,5,7- is dissolved in after the first organic solvent four benzene sulfonyl chloride adamantane, ammonium hydroxide is added, under stiring into
Row first reacts.
Preferably, described 1,3,5,7- are prepared four benzene sulfonyl chloride adamantane in accordance with the following methods:
A) halogenated adamantane is carried out Friedel-Crafts with benzene to react, obtains 1,3,5,7- to tetraphenyl adamantane；
B) second is carried out to tetraphenyl adamantane and chlorosulfonic acid by described 1,3,5,7- to react, obtain described 1,3,5,7- pairs
Four benzene sulfonyl chloride adamantane.
Preferably, the step a) is specifically included:
The halogenated adamantane, the benzene, promotor and catalyst are mixed, Friedel-Crafts reaction is carried out, obtains 1,
3,5,7- is to tetraphenyl adamantane.
Preferably, the promotor is one of tert-butyl bromide, isobutyl bromide and benzyl bromine or a variety of；
The catalyst is one of aluminum trichloride (anhydrous), anhydrous ferric trichloride and anhydrous zinc chloride or a variety of.
Preferably, the step b) is specifically included:
Under condition of ice bath, it is added dropwise in described 1,3,5, the 7- mixed liquor to tetraphenyl adamantane and the second organic solvent
Chlorosulfonic acid, then 30 DEG C~50 DEG C are warming up to, the second reaction is carried out, obtains 1,3,5,7- to four benzene sulfonyl chloride adamantane.
The present invention also provides a kind of polycarbonate composite materials, comprising: polycarbonate and 1,3,5,7- to four benzsulfamides
Adamantane；
Shown in structural formula such as formula (I) of the 1,3,5,7- to four benzsulfamide adamantane；
Preferably, in parts by weight, 99.7~99.95 parts of the polycarbonate, described 1,3,5,7- to four benzsulfamides
0.05~0.3 part of adamantane.
The present invention also provides a kind of preparation methods of polycarbonate composite material, comprising:
Polycarbonate and 1,3,5,7- to four benzsulfamide adamantane melt blendings, are obtained into the polycarbonate composite wood
Material；
Shown in structural formula such as formula (I) of the 1,3,5,7- to four benzsulfamide adamantane；
In conclusion the fire retardant is 1,3,5,7- to four benzsulfamide Buddha's warrior attendants the present invention provides a kind of fire retardant
Alkane；Shown in structural formula such as formula (I) of the 1,3,5,7- to four benzsulfamide adamantane.Fire retardant of the present invention is using adamantane as core
The heart provides good fat-soluble, stability for flame retardant molecule；Containing for ignition-proof element can be improved in the four ends of the bridge substitution of fire retardant
Amount, for organic sulfonamide composite fire retardant containing two kinds of sulphur, nitrogen ignition-proof elements simultaneously, element sulphur decomposes the SO generated2It can
It to promote PC to be crosslinked, plays a role in condensed phase, nitrogen decomposes the non-flammable compressive gas generated and dilutes starvation, shape in the gas phase
At condensed phase working mechanism fire-retardant when gentle identical, so that fire retardant is high-efficient；Meanwhile the polarity of the amino of fire retardant
Flame retardant molecule and the compatibility of PC are can increase.Also, fire retardant of the present invention is without compounding, itself includes sulphur, two kinds of nitrogen resistances
Fire element；Introduce the rigidity of stablizing of adamantane, it is fat-soluble good, have the characteristics that can multidigit replace, ignition-proof element content height, sulphur
Element and the fire-retardant flame retardant property that can make PC material of nitrogen dual element effectively improve, and making an addition to improves anti-flammability in PC
Additive amount is few when energy, small to the Effect on Mechanical Properties of PC material；Compared with sulfonate salt flame, the hygroscopicity of the fire retardant is low,
It is less prone to agglomeration.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of fire retardant of the present invention；
Fig. 2 is the infrared spectrogram of fire retardant of the present invention；
Fig. 3 is the scanning electron microscope diagram of polycarbonate composite material 2 in the embodiment of the present invention；
Fig. 4 is that element sulphur is under a scanning electron microscope in polycarbonate composite material 2 in the embodiment of the present invention
Mapping figure；
Fig. 5 is the scanning electron microscope diagram of polycarbonate composite material 5 in comparative example of the present invention；
Fig. 6 is that element sulphur is under a scanning electron microscope in polycarbonate composite material 5 in comparative example of the present invention
Mapping figure.
Specific embodiment
The present invention provides a kind of fire retardants and preparation method thereof, polycarbonate composite material and preparation method thereof, are used for
It solves in existing PC fire retardant, the additive amount of nitrogenated flame retardant and phosphorus flame retardant in PC is big, to the performance of PC material itself
It influences big；Silicon-series five-retardant is at high cost, generally requires and is used in compounding；Sulfonate salt flame poor water resistance, process are easy
The problem of existing agglomeration.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
A kind of fire retardant, fire retardant 1,3,5,7- is to four benzsulfamide adamantane；1,3,5,7- is to four benzsulfamides gold
Shown in the structural formula such as formula (I) of rigid alkane；
Fire retardant of the present invention provides good fat-soluble, stability using adamantane as core, for flame retardant molecule；Fire retardant
Four ends of the bridge replace the content of ignition-proof element can be improved, it is multiple for organic sulfonamide simultaneously containing two kinds of sulphur, nitrogen ignition-proof elements
Mould assembly fire retardant, element sulphur, which decomposes the SO2 generated, to promote PC to be crosslinked, and play a role in condensed phase, and nitrogen, which is decomposed, to be generated
Non-flammable compressive gas dilute starvation in the gas phase, formed condensed phase it is gentle identical when fire-retardant working mechanism so that fire retardant
Flame retarding efficiency is high；Meanwhile the polarity of the amino of fire retardant can increase flame retardant molecule and the compatibility of PC.Also, the present invention
Fire retardant itself includes two kinds of sulphur, nitrogen ignition-proof elements without compounding；The rigidity of stablizing of adamantane is introduced, it is fat-soluble good, have
Can multidigit the characteristics of replacing, ignition-proof element content is high, element sulphur and the fire-retardant anti-flammability that can make PC material of nitrogen dual element
It can effectively improve, additive amount is few when making an addition to improvement flame retardant property in PC, small to the Effect on Mechanical Properties of PC material；With sulphur
Hydrochlorate fire retardant is compared, and the hygroscopicity of the fire retardant is low, is less prone to agglomeration.
Since sulfonate salt flame be as salt, there is very strong moisture pick-up properties, cause the water resistance of fire retardant poor,
And sulfonate salt flame disperses poor in PC material, is easy to happen agglomeration, influences fire retardant to the fire-retardant of PC material
Performance.Fire retardant of the present invention is sulphur nitrogen composite fire retardant, as organic based flame retardant, has certain hydrophobicity compared to salt
Can, while the amino group introduced, hydrogen bond can be formed with the ester group in PC material, it is compatible in PC material to reinforce fire retardant
Property, the adamantane core for being preferably dispersed among PC substrate, and containing is embedded in PC material molecule chain as non-polar group
In, certain plasticization can be played.Nitrogen can play fire retardation, in conjunction with sulphur as ignition-proof element in the gas phase simultaneously
Element plays fire retardation in condensed phase, while playing a role in two-phase, and flame retardant effect is more excellent.
Referring to Fig. 1, being the nucleus magnetic hydrogen spectrum figure of fire retardant of the present invention.It is environment phase at a on adamantane at 2.17 in Fig. 1
With 12 H, be 8 H of d on amino at 7.31, be 16 H at b+c on phenyl ring at 7.8.
Referring to Fig. 2, being the infrared spectrogram of fire retardant of the present invention.In Fig. 2,1334cm-1Peak be sulfuryl amine group in S
The asymmetric vibration peak of=O, 1163cm-1For the stretching vibration peak of S=O；And 3362cm-1、3258cm-1Peak be sulfoamido
The stretching vibration peak of N-H, 708cm in group-1For the asymmetric vibration peak of N-H；833cm-1Disubstituted feature is aligned for phenyl ring
Peak.
The present invention also provides a kind of preparation methods of fire retardant, comprising the following steps:
First is carried out with ammonium hydroxide to four benzene sulfonyl chloride adamantane by 1,3,5,7- to react, and obtains 1,3,5,7- to four benzene sulfonyls
Amine adamantane；
Wherein, shown in 1,3,5, the 7- structural formula such as formula (I) to four benzsulfamide adamantane；
In the present invention, 1,3,5,7- reacts four benzene sulfonyl chloride adamantane with ammonium hydroxide progress first and specifically includes:
1,3,5,7- is dissolved in after the first organic solvent four benzene sulfonyl chloride adamantane, ammonium hydroxide is added, carries out under stiring
One reaction.
1,3,5,7- is 1:10~100, preferably 1:10~70 to the mass ratioes of four benzene sulfonyl chloride adamantane and ammonium hydroxide, more
Preferably 1:10~50.
1,3,5,7- to the mass ratio of four benzene sulfonyl chloride adamantane, the first organic solvent and ammonium hydroxide be 1:1~20:10~
100, preferably 1:1~10:10~70, more preferably 1:2~7:10~50.
The temperature of first reaction is 10 DEG C~100 DEG C, preferably 10 DEG C~80 DEG C, more preferably 20 DEG C~50 DEG C.
The time of first reaction is 12h~for 24 hours, preferably 12h~20h, more preferably 12h~16h.
The revolving speed of stirring is 50rpm~150rpm.
First organic solvent includes one of tetrahydrofuran, methylene chloride, ethyl acetate, chloroform and benzene or a variety of.
In the present invention, first carried out to four benzene sulfonyl chloride adamantane and ammonium hydroxide by 1,3,5,7- react more specifically include:
1,3,5,7- is dissolved in the first organic solvent four benzene sulfonyl chloride adamantane, it, will be molten by constant pressure funnel
There are 1,3,5,7- slowly to instill the first organic solvent of four benzene sulfonyl chloride adamantane to fill in the three-necked flask of ammonium hydroxide, at room temperature
Stirring, carries out 12h~the first reaction for 24 hours, pours into separatory funnel stand after reaction, and solution layering goes to take upper layer organic
Layer, vacuum distillation obtain pale yellow powder, and 6h~for 24 hours is dried at 40 DEG C in a vacuum drying oven~80 DEG C.
In the present invention, 1,3,5,7- is prepared four benzene sulfonyl chloride adamantane in accordance with the following methods:
A) halogenated adamantane is carried out Friedel-Crafts with benzene to react, obtains 1,3,5,7- to tetraphenyl adamantane；
B) second is carried out with chlorosulfonic acid to tetraphenyl adamantane by 1,3,5,7- to react, obtain 1,3,5,7- to four benzene sulfonyls
Chlorine adamantane.
In the present invention, step a) is specifically included:
Halogenated adamantane, benzene, promotor and catalyst are mixed, Friedel-Crafts reaction is carried out, obtains 1,3,5,7- pairs
Tetraphenyl adamantane.
Halogenated adamantane includes one of monobromo adamantane, a chlorine adamantane and dibromodiamantane or a variety of.
Halogenated adamantane, benzene, promotor and catalyst molar ratio be 1:10~100:1~5:0.01~0.3, preferably
1:10~80:1~4:0.01~0.2, more preferably 1:20~60:1~3:0.05~0.2.
The temperature of Friedel-Crafts reaction is 30 DEG C~150 DEG C, preferably 40 DEG C~120 DEG C, more preferably 50 DEG C~100
℃。
The time of Friedel-Crafts reaction is 0.5h~5h, preferably 0.5h~3h, more preferably 0.5h~2h.
In the present invention, the promotor is one of tert-butyl bromide, isobutyl bromide and benzyl bromine or a variety of；
The catalyst is one of aluminum trichloride (anhydrous), anhydrous ferric trichloride and anhydrous zinc chloride or a variety of.
In the present invention, step a) more specifically includes:
1- bromine adamantane is placed in condensation reflux unit and CaCl2In the three-necked flask of drying tube, then successively add
Enter benzene and promotor, be slowly stirred down and be slowly added into catalyst, heat up 60 DEG C~80 DEG C, keeps fierce reflux state, carry out Fu
Gram alkylated reaction stops reaction after reacting 30min~80min, mixture is poured into suitable mixture of ice and water, is added
Suitable ether, after being sufficiently stirred, filtering, gained filter residue is placed at 40 DEG C~60 DEG C dry 12h~for 24 hours, then with chloroform is molten
Agent carries out Soxhlet extraction, and remaining solid is placed under room temperature after extraction 12h~36h and is dried, and obtains 1,3,5,7- to tetraphenyl gold
Rigid alkane.
In the present invention, step b) is specifically included:
Under condition of ice bath, chlorine sulphur is added dropwise in 1,3,5, the 7- mixed liquor to tetraphenyl adamantane and the second organic solvent
Acid, then 30 DEG C~50 DEG C are warming up to, the second reaction is carried out, obtains 1,3,5,7- to four benzene sulfonyl chloride adamantane.
The time of second reaction is 1h~2h, preferably 60min~100min, more preferably 60min~80min.
1,3,5,7- is 1:5~50, preferably 1:5~35 to the molar ratio of tetraphenyl adamantane and chlorosulfonic acid, more preferably
For 1:10~20.
1,3,5,7- is 1:1~100:5~50 to the molar ratio of tetraphenyl adamantane, the second organic solvent and chlorosulfonic acid,
Preferably 1:20~70:5~35, more preferably 1:30~60:10~20.
Second organic solvent includes one of methylene chloride, chloroform, toluene, dioxane and benzene or a variety of.
In the present invention, step b) more specifically includes:
Second organic solvent is added to condensation reflux unit, device for absorbing tail gas and CaCl2Three mouthfuls of drying tube
In flask, then 1,3,5,7- is suspended in methylene chloride tetraphenyl adamantane, chlorine sulphur is slowly added dropwise under conditions of ice bath
Acid is added dropwise, and 10min~30min is stirred under condition of ice bath, is then to slowly warm up to 25 DEG C~50 DEG C, and it is anti-to carry out second
It answers, reacts 30min~90min, stand be cooled to room temperature after completion of the reaction, gained mixture is centrifugated, it is clear to pour out upper layer
Liquid removes solvent by vacuum distillation, obtains clear yellow viscous oily object, and water-washing oscillation has white solid precipitation, washes, filtering,
12h~for 24 hours is dried at 30 DEG C in a vacuum drying oven~60 DEG C, obtains 1,3,5,7- to four benzene sulfonyl chloride adamantane.
The present invention also provides a kind of polycarbonate composite materials, comprising: polycarbonate and 1,3,5,7- to four benzsulfamides
Adamantane；
Shown in structural formula such as formula (I) of the 1,3,5,7- to four benzsulfamide adamantane；
In the present invention, in parts by weight, 99.7~99.95 parts of polycarbonate, 1,3,5,7- to four benzsulfamide adamantane
0.05~0.3 part.
It is furthermore preferred that in parts by weight, 99.8~99.95 parts of polycarbonate, 1,3,5,7- to four benzsulfamide adamantane
0.05~0.2 part.
The present invention also provides a kind of preparation methods of polycarbonate composite material, comprising:
Polycarbonate and 1,3,5,7- to four benzsulfamide adamantane melt blendings, are obtained into polycarbonate composite material；
Shown in 1,3,5, the 7- structural formula such as formula (I) to four benzsulfamide adamantane；
For a further understanding of the present invention, the present invention will be described in detail combined with specific embodiments below.
Embodiment 1
1) dry 1- bromine adamantane 20g (0.093mol) is placed in condensation reflux unit and CaCl2Drying tube
In 500mL three-necked flask, 100mL (1.12mol) benzene is then sequentially added, 26g (95mmol) tert-butyl bromide is slowly stirred lower slow
It is slow that 2.4g (9.04mmol) aluminum trichloride (anhydrous) is added, 70 DEG C are warming up to, fierce reflux state is kept, it is anti-to carry out Friedel-Crafts
It answers, stops reaction after reacting 30min, mixture is poured into suitable mixture of ice and water, suitable ether is added, sufficiently stirs
After mixing, filtering, gained filter residue is placed at 75 DEG C dry 12h, then with chloroform is that solvent carries out Soxhlet extraction, and extraction will remain after one day
Remaining solid, which is placed under room temperature, to be dried, and obtains white powder to get 1,3,5,7- to tetraphenyl adamantane.
2) 50mL (0.39mol) methylene chloride is added to condensation reflux unit, device for absorbing tail gas and CaCl2It is dry
In the 150mL three-necked flask of dry pipe, then 3.26g (7.41mmol) 1,3,5,7- is suspended in methylene chloride to tetraphenyl adamantane
In, 3mL (75.2mmol) chlorosulfonic acid is slowly added dropwise under conditions of ice bath, is added dropwise, stirs 10min under condition of ice bath,
Then 30 DEG C are to slowly warm up to, the second reaction is carried out, reacts 60min, stand be cooled to room temperature after completion of the reaction, gained is mixed
Object centrifuge separation, pours out supernatant liquor, removes solvent by vacuum distillation, obtains clear yellow viscous oily object, water-washing oscillation has white
Color solid is precipitated, and three times, filtering dries 12h at 45 DEG C in a vacuum drying oven to get 1,3,5,7- to four benzene sulfonyl chlorides for washing
Adamantane.
3) 2g (2.4mmol) 1,3,5,7- is dissolved in 20mL tetrahydrofuran four benzene sulfonyl chloride adamantane, passes through constant pressure
Dropping funel will slowly instill the tetrahydrofuran of tetraphenyl sulfonic acid chloride and fill 20mL ammonium hydroxide dissolved with adamantyl -1,3,5,7-
In the three-necked flask of (25wt%), 12h is stirred at room temperature, is carried out the first reaction, is poured into separatory funnel stand after reaction,
Solution layering removes to take upper organic layer, and vacuum distillation obtains pale yellow powder, dries 12h at 45 DEG C in a vacuum drying oven, i.e.,
1,3,5,7- is obtained to four benzsulfamide adamantane.
Embodiment 2
1) dry 1- bromine adamantane 20g (0.093mol) is placed in condensation reflux unit and CaCl2Drying tube
In 500mL three-necked flask, 150mL (1.12mol) benzene is then sequentially added, 26g (95mmol) tert-butyl bromide is slowly stirred lower slow
It is slow that 2.4g (9.04mmol) aluminum trichloride (anhydrous) is added, 90 DEG C are warming up to, fierce reflux state is kept, it is anti-to carry out Friedel-Crafts
It answers, stops reaction after reacting 30min, mixture is poured into suitable mixture of ice and water, suitable ether is added, sufficiently stirs
After mixing, filtering, gained filter residue is placed at 75 DEG C dry 12h, then with chloroform is that solvent carries out Soxhlet extraction, and extraction will remain after one day
Remaining solid, which is placed under room temperature, to be dried, and obtains white powder to get 1,3,5,7- to tetraphenyl adamantane.
2) with the step 2) of embodiment 1.
3) with the step 3) of embodiment 1.
Embodiment 3
1) dry 1- bromine adamantane 20g (0.093mol) is placed in condensation reflux unit and CaCl2Drying tube
In 500mL three-necked flask, 200mL (1.12mol) benzene is then sequentially added, 26g (95mmol) tert-butyl bromide is slowly stirred lower slow
It is slow that 2.4g (9.04mmol) aluminum trichloride (anhydrous) is added, 80 DEG C are warming up to, fierce reflux state is kept, it is anti-to carry out Friedel-Crafts
It answers, stops reaction after reacting 45min, mixture is poured into suitable mixture of ice and water, suitable ether is added, sufficiently stirs
After mixing, filtering, gained filter residue is placed at 75 DEG C dry 12h, then with chloroform is that solvent carries out Soxhlet extraction, and extraction will remain after one day
Remaining solid, which is placed under room temperature, to be dried, and obtains white powder to get 1,3,5,7- to tetraphenyl adamantane.
2) with the step 2) of embodiment 1.
3) with the step 3) of embodiment 1.
Embodiment 4
1) dry 1- bromine adamantane 20g (0.093mol) is placed in condensation reflux unit and CaCl2Drying tube
In 500mL three-necked flask, 200mL (1.12mol) benzene is then sequentially added, 26g (95mmol) tert-butyl bromide is slowly stirred lower slow
It is slow that 1.2g (9.04mmol) aluminum trichloride (anhydrous) is added, 80 DEG C are warming up to, fierce reflux state is kept, it is anti-to carry out Friedel-Crafts
It answers, stops reaction after reacting 45min, mixture is poured into suitable mixture of ice and water, suitable ether is added, sufficiently stirs
After mixing, filtering, gained filter residue is placed at 75 DEG C dry 12h, then with chloroform is that solvent carries out Soxhlet extraction, and extraction will remain after one day
Remaining solid, which is placed under room temperature, to be dried, and obtains white powder to get 1,3,5,7- to tetraphenyl adamantane.
2) with the step 2) of embodiment 1.
3) with the step 3) of embodiment 1.
Embodiment 5
1) dry 1- bromine adamantane 20g (0.093mol) is placed in condensation reflux unit and CaCl2Drying tube
In 500mL three-necked flask, 200mL (1.12mol) benzene is then sequentially added, 26g (95mmol) tert-butyl bromide is slowly stirred lower slow
It is slow that 1.2g (9.04mmol) aluminum trichloride (anhydrous) is added, 90 DEG C are warming up to, fierce reflux state is kept, it is anti-to carry out Friedel-Crafts
It answers, stops reaction after reacting 45min, mixture is poured into suitable mixture of ice and water, suitable ether is added, sufficiently stirs
After mixing, filtering, gained filter residue is placed at 75 DEG C dry 12h, then with chloroform is that solvent carries out Soxhlet extraction, and extraction will remain after one day
Remaining solid, which is placed under room temperature, to be dried, and obtains white powder to get 1,3,5,7- to tetraphenyl adamantane.
2) with the step 2) of embodiment 1.
3) with the step 3) of embodiment 1.
Embodiment 6
1) dry 1- bromine adamantane 20g (0.093mol) is placed in condensation reflux unit and CaCl2Drying tube
In 500mL three-necked flask, 200mL (1.12mol) benzene is then sequentially added, 26g (95mmol) tert-butyl bromide is slowly stirred lower slow
It is slow that 2.4g (9.04mmol) aluminum trichloride (anhydrous) is added, 90 DEG C are warming up to, fierce reflux state is kept, it is anti-to carry out Friedel-Crafts
It answers, stops reaction after reacting 1h, mixture is poured into suitable mixture of ice and water, suitable ether is added, is sufficiently stirred
Afterwards, it filters, gained filter residue is placed at 75 DEG C dry 12h, then with chloroform is that solvent carries out Soxhlet extraction, will be remaining after extraction one day
Solid, which is placed under room temperature, to be dried, and obtains white powder to get 1,3,5,7- to tetraphenyl adamantane.
2) with the step 2) of embodiment 1.
3) with the step 3) of embodiment 1.
Embodiment 7
1) with the step 1) of embodiment 6.
2) 50mL (0.39mol) methylene chloride is added to condensation reflux unit, device for absorbing tail gas and CaCl2It is dry
In the 150mL three-necked flask of dry pipe, then 3.26g (7.41mmol) 1,3,5,7- is suspended in methylene chloride to tetraphenyl adamantane
In, 3mL (75.2mmol) chlorosulfonic acid is slowly added dropwise under conditions of ice bath, is added dropwise, stirs 10min under condition of ice bath,
Then 35 DEG C are to slowly warm up to, the second reaction is carried out, reacts 45min, stand be cooled to room temperature after completion of the reaction, gained is mixed
Object centrifuge separation, pours out supernatant liquor, removes solvent by vacuum distillation, obtains clear yellow viscous oily object, water-washing oscillation has white
Color solid is precipitated, and three times, filtering dries 12h at 45 DEG C in a vacuum drying oven to get 1,3,5,7- to four benzene sulfonyl chlorides for washing
Adamantane.
3) with the step 3) of embodiment 1.
Embodiment 8
1) with the step 1) of embodiment 6.
2) 50mL (0.39mol) methylene chloride is added to condensation reflux unit, device for absorbing tail gas and CaCl2It is dry
In the 150mL three-necked flask of dry pipe, then 3.26g (7.41mmol) 1,3,5,7- is suspended in methylene chloride to tetraphenyl adamantane
In, 3mL (75.2mmol) chlorosulfonic acid is slowly added dropwise under conditions of ice bath, is added dropwise, stirs 10min under condition of ice bath,
Then 35 DEG C are to slowly warm up to, the second reaction is carried out, reacts 60min, stand be cooled to room temperature after completion of the reaction, gained is mixed
Object centrifuge separation, pours out supernatant liquor, removes solvent by vacuum distillation, obtains clear yellow viscous oily object, water-washing oscillation has white
Color solid is precipitated, and three times, filtering dries 12h at 45 DEG C in a vacuum drying oven to get 1,3,5,7- to four benzene sulfonyl chlorides for washing
Adamantane.
3) with the step 3) of embodiment 1.
Embodiment 9
1) with the step 1) of embodiment 6.
2) 50mL (0.39mol) methylene chloride is added to condensation reflux unit, device for absorbing tail gas and CaCl2It is dry
In the 150mL three-necked flask of dry pipe, then 3.26g (7.41mmol) 1,3,5,7- is suspended in methylene chloride to tetraphenyl adamantane
In, 4mL (75.2mmol) chlorosulfonic acid is slowly added dropwise under conditions of ice bath, is added dropwise, stirs 10min under condition of ice bath,
Then 35 DEG C are to slowly warm up to, the second reaction is carried out, reacts 75min, stand be cooled to room temperature after completion of the reaction, gained is mixed
Object centrifuge separation, pours out supernatant liquor, removes solvent by vacuum distillation, obtains clear yellow viscous oily object, water-washing oscillation has white
Color solid is precipitated, and three times, filtering dries 12h at 45 DEG C in a vacuum drying oven to get 1,3,5,7- to four benzene sulfonyl chlorides for washing
Adamantane.
3) with the step 3) of embodiment 1.
Embodiment 10
1) with the step 1) of embodiment 6.
2) with the step 2) of embodiment 9.
3) with the step 3) of embodiment 1.
Embodiment 11
1) with the step 1) of embodiment 6.
2) with the step 2) of embodiment 6.
3) 2g (2.4mmol) 1,3,5,7- is dissolved in 20mL tetrahydrofuran four benzene sulfonyl chloride adamantane, passes through constant pressure
Dropping funel will slowly instill the tetrahydrofuran of tetraphenyl sulfonic acid chloride and fill 30mL ammonium hydroxide dissolved with adamantyl -1,3,5,7-
In the three-necked flask of (25wt%), 12h is stirred at room temperature, is carried out the first reaction, is poured into separatory funnel stand after reaction,
Solution layering removes to take upper organic layer, and vacuum distillation obtains pale yellow powder, dries 12h at 45 DEG C in a vacuum drying oven, i.e.,
1,3,5,7- is obtained to four benzsulfamide adamantane.
Embodiment 12
1) with the step 1) of embodiment 3.
2) with the step 2) of embodiment 9.
3) 2g (2.4mmol) 1,3,5,7- is dissolved in 20mL tetrahydrofuran four benzene sulfonyl chloride adamantane, passes through constant pressure
Dropping funel will slowly instill the tetrahydrofuran of tetraphenyl sulfonic acid chloride and fill 40mL ammonium hydroxide dissolved with adamantyl -1,3,5,7-
It in the three-necked flask of (25wt%), stirs at room temperature for 24 hours, carries out the first reaction, pour into separatory funnel stand after reaction,
Solution layering removes to take upper organic layer, and vacuum distillation obtains pale yellow powder, dries 12h at 45 DEG C in a vacuum drying oven, i.e.,
1,3,5,7- is obtained to four benzsulfamide adamantane.
Embodiment 13
By polycarbonate (PC), for 24 hours, 1, the 3,5,7- of the preparation of embodiment 1 are to four benzsulfamide Buddha's warrior attendants for drying at 100 DEG C
After alkane is dried in vacuo 12h at 80 DEG C, by 1, the 3,5,7- of the PC of 99.94 mass parts after drying and 0.06 mass parts to four benzene
The mixing of sulfonamide adamantane, is added into 230 DEG C of mixer, the shear melting under the revolving speed of 70rpm, mixing 10min is obtained
Composite material, composite material is after broken crusher machine, then polycarbonate is prepared through compression molding instrument hot press forming technology and answers
Condensation material 1.
Embodiment 14
By polycarbonate (PC), for 24 hours, 1, the 3,5,7- of the preparation of embodiment 1 are to four benzene sulfonyls for drying under conditions of 100 DEG C
After amine adamantane is dried in vacuo 12h at 80 DEG C, by the 1,3,5,7- of the PC of 99.92 mass parts after drying and 0.08 mass parts
Four benzsulfamide adamantane are mixed, are added into 230 DEG C of mixer, the shear melting under the revolving speed of 70rpm, mixing
10min, obtains composite material, and composite material is prepared after broken crusher machine, then through compression molding instrument hot press forming technology
Polycarbonate composite material 2.
Embodiment 15
By polycarbonate (PC), for 24 hours, 1, the 3,5,7- of the preparation of embodiment 1 are to four benzene sulfonyls for drying under conditions of 100 DEG C
After amine adamantane is dried in vacuo 12h at 80 DEG C, by the 1,3,5,7- of the PC of 99.90 mass parts after drying and 0.10 mass parts
Four benzsulfamide adamantane are mixed, are added into 230 DEG C of mixer, the shear melting under the revolving speed of 70rpm, mixing
10min, obtains composite material, and composite material is prepared after broken crusher machine, then through compression molding instrument hot press forming technology
Polycarbonate composite material 3.
Comparative example 1
By polycarbonate (PC), for 24 hours, triphenyl phosphate (TPP) is dried in vacuo at 40 DEG C for drying under conditions of 100 DEG C
After 12h, the PC of 90 mass parts after the drying and TPP of 10 mass parts is mixed, is added into 230 DEG C of mixer, in 70rpm
Revolving speed under shear melting, mixing 10min obtains composite material, and composite material is after broken crusher machine, then through compression molding instrument
Polycarbonate composite material 4 is prepared in hot press forming technology.
Comparative example 2
By polycarbonate (PC), for 24 hours, adamantyl -1,3,5,7- to four benzene melamines for drying under conditions of 100 DEG C
After sulfonate (ASN) is dried in vacuo 12h at 80 DEG C, the KSS of the PC of 99.92 mass parts after drying and 0.08 mass parts are mixed
It closes, is added into 230 DEG C of mixer, the shear melting under the revolving speed of 70rpm, mixing 10min obtains composite material, compound
Polycarbonate composite material 5 is prepared after broken crusher machine, then through compression molding instrument hot press forming technology in material.
Comparative example 3
By polycarbonate (PC), for 24 hours, the PC after drying is added to 230 DEG C of mixer for drying under conditions of 100 DEG C
In, the shear melting under the revolving speed of 70rpm, mixing 10min obtains material, and material is after broken crusher machine, then through compression molding
Instrument hot press forming technology is prepared into makrolon material.
Embodiment 19
The present embodiment uses vertical combustion and oxygen index (OI) test method to the poly- carbon of embodiment 13~15 and comparative example 1~3
Acid esters composite material or makrolon material carry out combustibility test, and test result is shown in Table 1.Table 1 shows that polycarbonate is compound
Material 1 to 3 does not drip in testing, cotton of not igniting, and flame retardant rating and oxygen index (OI) are higher than polycarbonate composite material 4, gather
Carbonic ester composite material 5 and makrolon material illustrate resistance of the fire retardant 1,3,5,7- of the present invention to four benzsulfamide adamantane
Fuel efficiency rate is high compared with triphenyl phosphate and potassium phenylsulphonyl benzene sulfonate.
Wherein, vertical burn test is according to " measurement-Horizontal Bridgman Method and normal beam technique of Plastics Combustion performance " GB/T 2408-
2008 standards are carried out in CZF-5 type horizontal vertical burning tester, and oxygen index (OI) test is according to " measurement-water of Plastics Combustion performance
Flat method and normal beam technique " GB/T 2406-93 standard, it is carried out in JF-3 type oxygen index (OI) tester.
1 combustibility test result of table
Embodiment 20
After 14 polycarbonate composite material 2 of embodiment is impregnated 72h in water with 2 polycarbonate composite material 5 of comparative example,
It takes out, after drying 12h at 110 DEG C, according to " measurement-Horizontal Bridgman Method and normal beam technique of Plastics Combustion performance " GB/T 2408-2008
Standard carries out vertical burn test in CZF-5 type horizontal vertical burning tester, and test result is shown in Table 2.Table 2 shows embodiment
It is also able to maintain excellent flame retardant property after 14 polycarbonate composite materials 2 are soaked, flame retardant rating is constant, and oxygen index (OI) variation relatively compares
2 polycarbonate composite material 5 of example is small, illustrates that fire retardant 1,3,5,7- of the present invention is low to four benzsulfamide adamantane hygroscopicity, tool
There is excellent water resistance.
Table 2 impregnates after-combustion the performance test results
Embodiment 21
By 14 polycarbonate composite material 2 of embodiment with 2 polycarbonate composite material 5 of comparative example according to " plastics cantilever beam
The measurement of impact strength " GB/T 1843-2008 standard, it is strong that notch shock is carried out by XJU-22 type radial-boom impact tester
The test of degree, test result are shown in Table 3.The notch impact strength of makrolon material is 16.3kJ/m-2, polycarbonate composite material
2 notch impact strength is 16.83kJ/m-2, and the notch impact strength of polycarbonate composite material 5 is 13.62kJ/m-2, say
Bright fire retardant of the present invention is small to the Effect on Mechanical Properties of PC material.
3 notch impact strength test result of table
Embodiment 22
14 polycarbonate composite material 2 of embodiment is led to after notch shock with 2 polycarbonate composite material 5 of comparative example
Overscanning electron microscopy detects the surface of section, and passes through the distribution situation of mapping map analysis element sulphur.
Fig. 3 to Fig. 6 is please referred to, Fig. 3 and Fig. 5 are respectively polycarbonate composite material 2 and the present invention in the embodiment of the present invention
The scanning electron microscope diagram of polycarbonate composite material 5 in comparative example.Fig. 4 and Fig. 6 is respectively poly- carbon in the embodiment of the present invention
Element sulphur in acid esters composite material 2 and comparative example of the present invention in polycarbonate composite material 5 is under scanning electron microscope diagram
Mapping figure.Fig. 3 to Fig. 6 shows that the fire retardant after notch shock of polycarbonate composite material 2 is evenly distributed, and poly- carbon
The fire retardant after notch shock of acid esters composite material 5 is unevenly distributed, and illustrates the fire retardant 1,3,5,7- of the present invention to four benzene sulphurs
Amidoadamantane is uniformly distributed in polycarbonate composite material 2, and the compatibility of fire retardant and PC of the present invention is good.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of fire retardant, which is characterized in that the fire retardant is 1,3,5,7- to four benzsulfamide adamantane；Described 1,3,5,
Shown in structural formula such as formula (I) of the 7- to four benzsulfamide adamantane；
2. a kind of preparation method of fire retardant, which comprises the following steps:
First is carried out with ammonium hydroxide to four benzene sulfonyl chloride adamantane by 1,3,5,7- to react, and obtains 1,3,5,7- to four benzsulfamides gold
Rigid alkane；
Wherein, shown in described 1,3,5, the 7- structural formula such as formula (I) to four benzsulfamide adamantane；
3. preparation method according to claim 2, which is characterized in that it is described by 1,3,5,7- to four benzene sulfonyl chloride adamantane
It reacts and specifically includes with ammonium hydroxide progress first:
Described 1,3,5,7- is dissolved in after the first organic solvent four benzene sulfonyl chloride adamantane, ammonium hydroxide is added, carries out under stiring
One reaction.
4. preparation method according to claim 2, which is characterized in that described 1,3,5,7- press four benzene sulfonyl chloride adamantane
It is prepared according to following methods:
A) halogenated adamantane is carried out Friedel-Crafts with benzene to react, obtains 1,3,5,7- to tetraphenyl adamantane；
B) second is carried out with chlorosulfonic acid to tetraphenyl adamantane by described 1,3,5,7- to react, obtain described 1,3,5,7- to four benzene
Sulfonic acid chloride adamantane.
5. the preparation method according to claim 4, which is characterized in that the step a) is specifically included:
The halogenated adamantane, the benzene, promotor and catalyst are mixed, Friedel-Crafts reaction is carried out, obtains 1,3,5,
7- is to tetraphenyl adamantane.
6. preparation method according to claim 5, which is characterized in that the promotor be tert-butyl bromide, isobutyl bromide and
One of benzyl bromine is a variety of；
The catalyst is one of aluminum trichloride (anhydrous), anhydrous ferric trichloride and anhydrous zinc chloride or a variety of.
7. the preparation method according to claim 4, which is characterized in that the step b) is specifically included:
Under condition of ice bath, chlorine sulphur is added dropwise in described 1,3,5, the 7- mixed liquor to tetraphenyl adamantane and the second organic solvent
Acid, then 30 DEG C~50 DEG C are warming up to, the second reaction is carried out, obtains 1,3,5,7- to four benzene sulfonyl chloride adamantane.
8. a kind of polycarbonate composite material characterized by comprising polycarbonate and 1,3,5,7- to four benzsulfamide Buddha's warrior attendants
Alkane；
Shown in described 1,3,5, the 7- structural formula such as formula (I) to four benzsulfamide adamantane；
9. polycarbonate composite material according to claim 8, which is characterized in that in parts by weight, the polycarbonate
99.7~99.95 parts, described 1,3,5,7- to 0.05~0.3 part of four benzsulfamide adamantane.
10. a kind of preparation method of polycarbonate composite material characterized by comprising
Polycarbonate and 1,3,5,7- to four benzsulfamide adamantane melt blendings, are obtained into the polycarbonate composite material；
Shown in structural formula such as formula (I) of the 1,3,5,7- to four benzsulfamide adamantane；
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