CN105778110B - A kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement - Google Patents
A kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement Download PDFInfo
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- CN105778110B CN105778110B CN201610152259.7A CN201610152259A CN105778110B CN 105778110 B CN105778110 B CN 105778110B CN 201610152259 A CN201610152259 A CN 201610152259A CN 105778110 B CN105778110 B CN 105778110B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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Abstract
The invention discloses a kind of preparation methods of flame-proof heat-resistant polyphosphazene insulating cement, including polychloride phosphonitrile is added in tetrahydrofuran solution, obtain solution A；2,6- difluorophenols are reacted to fluorine-containing phenol oxygroup sodium for 40 DEG C with sodium hydroxide, obtain B solution；Carborane bisphenol-A and bromo alkyl are put into reaction kettle, are heated to 60~70 DEG C, is stirred to react to homogeneous, obtains polydichlorophosphazenes solution；Solution A point is added dropwise in polydichlorophosphazenes solution, B solution is added after reaction, the reaction was continued to completely to get to flame-proof heat-resistant electrical cable insulating cement.The electrical cable insulating cement that the present invention is gone out by the way that the material preparations such as 2,6- difluorophenols and the monoalky lether of bis-phenol containing carborane are added has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
Description
Technical field
The present invention relates to electric wire and cable material, more particularly to a kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement.
Background technology
With the raising of the development and electrical equipment and electrical technology of electric cause, high-power electrical, electronic product it is contour
The extensive use of the sci-tech product of performance, a kind of cable compound that can meet cable requirement while there is flame-proof heat-resistant
Seem particularly important.With the development of science and technology and social progress, because the cable of polyvinyl chloride and halogen containing flame-retardant is burning
When producible smog it is harmful, cause so many people in fire to be choked to death, precision equipment paralysis, halogen CABLE MATERIALS will
Gradually it is eliminated.Thus design and prepare it is harmless to humans, environmentally protective, while but also with excellent flame retardant property and insulation performance
Cable be of great significance.
Chlorine atom has very strong activity in polydichlorophosphazenes structure, can be replaced by nucleopilic reagent, obtain the poly- phosphorus of no chlorine
Carbonitrile derivatives.Polyphosphazene derivatives are that be alternately arranged a kind of novel inorganic one as backbone structure using P, N atom organic high poly-
Object, with the characteristic that traditional organic polymer and inorganic matter hardly match, phosphorus and nitrogen in main chain impart its good resistance
Fire performance, the organic component on side chain impart with the good compatibility of polyolefin, and polyphosphazene is environmentally protective.Pass through organic group
The selection of group and side chain, can assign polyphosphazene a variety of excellent performances, such as poly-alkoxyl phosphonitrile, poly- aryloxy group phosphonitrile material
Use temperature range at -70 DEG C~300 DEG C, it has been found that poly- aryloxy group phosphonitrile elastomer be used for combustion safety require very
High electrical isolation occasion has very ideal performance.The fluorine-containing poly- aryloxy group phosphonitrile sizing material of side group designed at present has very high
Tearing strength upholds performance and excellent electrical property, is a kind of excellent electrical cable insulating materials.The material is high-content
Nitrogen and P elements, the collaboration system constituted have good flame retardant property.
Chinese patent CN102682870A discloses a kind of the third glue of rail traffic second insulation termite-resistant rodent-resistant low smoke and zero halogen resistance
Fire direct current high voltage cable Insulation Material.The insulating material for cable following raw materials according is made, and the weight proportion of material component is：The third rubber of second
100 parts of glue, 2.3~3.2 parts of vulcanizing agent, 0.3~1.2 part of co-curing agent, 50~67 parts of reinforcing agent, 5~7 parts of microcrystalline wax, ring
5~7 parts of oxygen soybean oil, 0.8~1.2 part of coupling agent, 8~10 parts of low density polyethylene (LDPE), 5~8 parts of zinc oxide nano, anti-aging agent
1.2~1.6 parts, 5~7 parts of red lead, 1.0~5 parts of bitter earth nano powder, 15~25 parts of White Carbon black.The cable insulating material uses oxygen
Change the inorganic anti-flaming materials such as magnesium, zinc oxide, the compatibility between inorganic matter and organic polymer is poor, often reduces cable material
The mechanical property and processing performance of material, it is also possible to change the heatproof rank of polymer.
It has been reported in relation to the halogen-free environment-friendly flame-proof containing polyphosphazene：Chinese Patent Application No. CN201210113112,
A kind of preparation method of the halogen-free environment-friendly flame-proof cable material of polyolefin system containing polyphosphazene is disclosed, is primarily characterized in that：Poly- phosphorus
Nitrile is added into 10~35 parts in CABLE MATERIALS, is total to fire retardants such as 5~25 parts of tricresyl phosphates, poly-metaphosphoric acid or ammonium polyphosphate
The halogen-free environment-friendly flame-proof cable material of polyolefin containing polyphosphazene has been made in same-action.Polyphosphazene used herein is poly-alkoxyl phosphorus
Nitrile or polyphosphazene maleic amide, thermal stability is not good enough, and high temperature resistance still has larger limitation.
Invention content
The present invention provides that a kind of good flame resistance, heat resistance are high, make simple flame-proof heat-resistant to solve above-mentioned technical problem
The preparation method of polyphosphazene insulating cement.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement, includes the following steps：
S1, the polychloride phosphonitriles of 58g being taken, be added in 400mL tetrahydrofuran solutions, stirring to polychloride phosphonitrile is completely dissolved,
Polychloride phosphonitrile tetrahydrofuran solution is obtained, it is spare；
S2, it takes 130.1g 2,6- difluorophenols to be dissolved in 150mL tetrahydrofuran solutions, 40g is slowly added to by blender
The temperature of solution is adjusted to 40 DEG C of constant temperature by sodium hydroxide, and it is two that reaction is reacted for 1 hour completely to 2,6- difluorophenols under stiring
Until fluorine phenol oxygroup sodium, intermediate product solution (I) is obtained, it is spare；
S3, the 1000mL three-necked flasks equipped with blender, condenser pipe and constant pressure funnel are taken, the 1,7- of 33.2g is added
Two (4- hydroxy phenyls)-carboranes, 4g sodium hydroxides are slowly added to by blender, add 150mL tetrahydrofuran solutions and
In 21.2g bromooctanes to three-necked flask, and lead to nitrogen into reaction solution, after 2 hours are stirred to react at 65 DEG C, by temperature
50 DEG C are down to, the three-necked flask after being reacted；
S4, respectively by the obtained polychloride phosphonitrile tetrahydrofuran solution and intermediate product solution in step S1 and step S2
(I), it is reacted in the three-necked flask slowly instilled by constant pressure funnel after step S3 reactions, obtains reaction solution；
S5, it reaction solution is poured into the beaker for fill tap water is stirred, after stirring 10min, obtain agglomerating in solution
Rubbery solid, the rubbery solid of cohesion and solution are detached, by tetrahydrofuran solution to rubber-like after separation
Solid is dissolved, then solution is poured into and repeats this step in the beaker for fill tap water, until washing away in rubbery solid
Salinity, finally obtained rubbery solid are difluoro phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene.
Present invention has the advantages that：The chlorine atom that polydichlorophosphazenes polymer is replaced by using alkoxy, improves poly- phosphorus
The water resistance of nitrile, but thermal stability is not good enough, and carborane is added in substituent group then improves polyphosphazene polymer stability, resistance to
It is hot.The electrical cable insulation gone out by the way that the material preparations such as 2,6- difluorophenols and the monoalky lether of bis-phenol containing carborane are added
Glue has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
Further, above-mentioned steps S4 is specially：
First by polychloride phosphonitrile tetrahydrofuran solution, three mouthfuls after step S3 reactions are slowly instilled by constant pressure funnel
In flask, after being added dropwise, continue stirring 1~2 hour；
Again by intermediate product solution (I), is slowly instilled in the solution after stirring, be added dropwise by constant pressure funnel
Afterwards, continue stirring 2~3 hours, obtain reaction solution.In this way, more refining its reaction process, keep reaction more complete.
In order to solve the above technical problems, the another technical solution that uses of the present invention for：
A kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement, includes the following steps：
S1, the polychloride phosphonitriles of 58g being taken, be added in 400mL tetrahydrofuran solutions, stirring to polychloride phosphonitrile is completely dissolved,
Polychloride phosphonitrile tetrahydrofuran solution is obtained, it is spare；
S2, it takes 162.1g p-trifluoromethyl-phenols to be dissolved in 150mL tetrahydrofuran solutions, is slowly added to by blender
The temperature of solution is adjusted to 40 DEG C of constant temperature by 40g sodium hydroxides, under stiring react 1 hour it is completely anti-to p-trifluoromethyl-phenol
Until should be to trifluoromethyl phenol oxygroup sodium, intermediate product solution (II) is obtained, it is spare；
S3, the 1000mL three-necked flasks equipped with blender, condenser pipe and constant pressure funnel are taken, the 1,7- of 33.2g is added
Two (4- hydroxy phenyls)-carboranes, 4g sodium hydroxides are slowly added to by blender, add 150mL tetrahydrofuran solutions and
In 21.2g bromooctanes to three-necked flask, and leading to nitrogen into reaction solution will be warm after being stirred to react 2 hours at 100 DEG C
Degree is down to 50 DEG C, the three-necked flask after being reacted；
S4, respectively by the obtained polychloride phosphonitrile tetrahydrofuran solution and intermediate product solution in step S1 and step S2
(II), it is reacted in the three-necked flask slowly instilled by constant pressure funnel after step S3 reactions, obtains reaction solution；
S5, it reaction solution is poured into the beaker for fill tap water is stirred, after stirring 10min, obtain agglomerating in solution
Rubbery solid, the rubbery solid of cohesion and solution are detached, by tetrahydrofuran solution to rubber-like after separation
Solid is dissolved, then solution is poured into and repeats this step in the beaker for fill tap water, until washing away in rubbery solid
Salinity, finally obtained rubbery solid are trifluoromethyl phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene.
Present invention has the advantages that：The chlorine atom that polydichlorophosphazenes polymer is replaced by using alkoxy, improves poly- phosphorus
The water resistance of nitrile, but thermal stability is not good enough, and carborane is added in substituent group then improves polyphosphazene polymer stability, resistance to
It is hot.The electrical cable insulation gone out by the way that the material preparations such as p-trifluoromethyl-phenol and the monoalky lether of bis-phenol containing carborane are added
Glue has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
Further, above-mentioned steps S4 is specially：
First by polychloride phosphonitrile tetrahydrofuran solution, three mouthfuls after step S3 reactions are slowly instilled by constant pressure funnel
In flask, after being added dropwise, continue stirring 1~2 hour；
Again by intermediate product solution (II), is slowly instilled in the solution after stirring, be added dropwise by constant pressure funnel
Afterwards, continue stirring 2~3 hours, obtain reaction solution.In this way, more refining its reaction process, keep reaction more complete.
In order to solve the above technical problems, the another technical solution that uses of the present invention for：
A kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement, which is characterized in that include the following steps：
S1, the polychloride phosphonitriles of 58g being taken, be added in 400mL tetrahydrofuran solutions, stirring to polychloride phosphonitrile is completely dissolved,
Polychloride phosphonitrile tetrahydrofuran solution is obtained, it is spare；
S2, it takes 178.1g to be dissolved in 150mL tetrahydrofuran solutions trifluoro-methoxy-phenol, is slowly added to by blender
The temperature of solution is adjusted to 40 DEG C of constant temperature by 40g sodium hydroxides, reacts 1 hour under stiring to complete to trifluoro-methoxy-phenol
Reaction is spare until to trifluoromethyl phenol oxygroup sodium, to obtain intermediate product solution (III)；
S3, the 1000mL three-necked flasks equipped with blender, condenser pipe and constant pressure funnel are taken, the 1,7- of 33.2g is added
Two (4- hydroxy phenyls)-carboranes, 4g sodium hydroxides are slowly added to by blender, add 150mL tetrahydrofuran solutions and
In 21.2g bromooctanes to three-necked flask, and leading to nitrogen into reaction solution will be warm after being stirred to react 2 hours at 100 DEG C
Degree is down to 50 DEG C, the three-necked flask after being reacted；
S4, respectively by the obtained polychloride phosphonitrile tetrahydrofuran solution and intermediate product solution in step S1 and step S2
(III), it is reacted in the three-necked flask slowly instilled by constant pressure funnel after step S3 reactions, obtains reaction solution；
S5, it reaction solution is poured into the beaker for fill tap water is stirred, after stirring 10min, obtain agglomerating in solution
Rubbery solid, the rubbery solid of cohesion and solution are detached, by tetrahydrofuran solution to rubber-like after separation
Solid is dissolved, then solution is poured into and repeats this step in the beaker for fill tap water, until washing away in rubbery solid
Salinity, finally obtained rubbery solid are trifluoromethoxy phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene.
Present invention has the advantages that：The chlorine atom that polydichlorophosphazenes polymer is replaced by using alkoxy, improves poly- phosphorus
The water resistance of nitrile, but thermal stability is not good enough, and carborane is added in substituent group then improves polyphosphazene polymer stability, resistance to
It is hot.It is exhausted by the way that the electrical cable gone out to the material preparations such as trifluoro-methoxy-phenol and the monoalky lether of bis-phenol containing carborane is added
Edge glue has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
Further, above-mentioned steps S4 is specially：
First by polychloride phosphonitrile tetrahydrofuran solution, three mouthfuls after step S3 reactions are slowly instilled by constant pressure funnel
In flask, after being added dropwise, continue stirring 1~2 hour；
Again by intermediate product solution (III), is slowly instilled in the solution after stirring, be added dropwise by constant pressure funnel
Afterwards, continue stirring 2~3 hours, obtain reaction solution.In this way, more refining its reaction process, keep reaction more complete.
In order to solve the above technical problems, the another technical solution that uses of the present invention for：
A kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement, which is characterized in that include the following steps：
S1, the polychloride phosphonitriles of 58g being taken, be added in 400mL tetrahydrofuran solutions, stirring to polychloride phosphonitrile is completely dissolved,
Polychloride phosphonitrile tetrahydrofuran solution is obtained, it is spare；
S2, it takes 212.1g to be dissolved in 150mL tetrahydrofuran solutions pentafluoroethyl group phenol, is slowly added to by blender
The temperature of solution is adjusted to 40 DEG C of constant temperature by 40g sodium hydroxides, reacts 1 hour under stiring to completely anti-to pentafluoroethyl group phenol
Until should be to pentafluoroethyl group phenol oxygroup sodium, intermediate product solution (IV) is obtained, it is spare；
S3, the 1000mL three-necked flasks equipped with blender, condenser pipe and constant pressure funnel are taken, the 1,7- of 33.2g is added
Two (4- hydroxy phenyls)-carboranes, 4g sodium hydroxides are slowly added to by blender, add 150mL tetrahydrofuran solutions and
In 21.2g bromooctanes to three-necked flask, and leading to nitrogen into reaction solution will be warm after being stirred to react 2 hours at 100 DEG C
Degree is down to 50 DEG C, the three-necked flask after being reacted；
S4, respectively by the obtained polychloride phosphonitrile tetrahydrofuran solution and intermediate product solution in step S1 and step S2
(IV), it is reacted in the three-necked flask slowly instilled by constant pressure funnel after step S3 reactions, obtains reaction solution；
S5, it reaction solution is poured into the beaker for fill tap water is stirred, after stirring 10min, obtain agglomerating in solution
Rubbery solid, the rubbery solid of cohesion and solution are detached, by tetrahydrofuran solution to rubber-like after separation
Solid is dissolved, then solution is poured into and repeats this step in the beaker for fill tap water, until washing away in rubbery solid
Salinity, finally obtained rubbery solid are pentafluoroethyl group phenol oxygroup list decyl ethers carborane bis-phenol oxygroup polyphosphazene.
Present invention has the advantages that：The chlorine atom that polydichlorophosphazenes polymer is replaced by using alkoxy, improves poly- phosphorus
The water resistance of nitrile, but thermal stability is not good enough, and carborane is added in substituent group then improves polyphosphazene polymer stability, resistance to
It is hot.It is insulated to the electrical cable that the material preparations such as pentafluoroethyl group phenol and the monoalky lether of bis-phenol containing carborane go out by being added
Glue has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
Further, above-mentioned steps S4 is specially：
First by polychloride phosphonitrile tetrahydrofuran solution, three mouthfuls after step S3 reactions are slowly instilled by constant pressure funnel
In flask, after being added dropwise, continue stirring 1~2 hour；
Again by intermediate product solution (IV), is slowly instilled in the solution after stirring, be added dropwise by constant pressure funnel
Afterwards, continue stirring 2~3 hours, obtain reaction solution.In this way, more refining its reaction process, keep reaction more complete.
Specific implementation mode
In order to describe the technical content, the structural feature, the achieved object and the effect of this invention in detail, below in conjunction with embodiment
It is explained in detail.
Definition：Polychloride phosphonitrile is phosphonitrilic chloride polymer；
Chinese:Phosphonitrilic chloride polymer；English name:Poly(phosphonitrilic chloride)；
Alias:cyclo-Dibromodi-μ-methylene[μ-(tetrahydrofuran)]trizinc；
More titles:Monosodiumtaurocholicacid；
No. CAS:31550-05-7；Molecular formula:Cl18N4P6；Molecular weight:880.023366.
The preparation method of flame-proof heat-resistant polyphosphazene insulating cement of the present invention has synthesized a kind of novel fluorine phenol oxygroup and carborane
Polyphosphazene polymer insulating cement.The main chain of the polymer architecture is made of phosphorus, nitrogen, and side group is by fluorine-containing phenol oxygroup and carborane
Bis-phenol monoalky lether form, fluorine-containing phenol oxygroup include 2,6- difluorophenols, p-trifluoromethyl-phenol, to trifluoro-methoxy-phenol with
And to pentafluoroethyl group phenol.Polydichlorophosphazenes are easy to obtain part with carborane bis-phenol monoalky lether generation nucleophilic substitution
Substituted polyphosphazene polymer, the polyphosphazene polymer are further reacted with fluorine-containing phenol oxygroup, and there is no need to complicated group guarantors
Shield reaction, it will be able to substitution reaction occur on the phosphorus atom.Carborane is introduced into as substituent group in polyphosphazene side chain, does not destroy carbon
The cage structure of borine synthesizes polyphosphazene polymer of the side chain with carborane structure.The polymer that invention makes is a kind of with resistance
Heat-resistant insulator material is fired, is a kind of ideal material of electrical isolation occasion exigent to combustion safety.
Embodiment one
A kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement, includes the following steps：
Step 1: taking the polychloride phosphonitriles of 58g, it is added in 400mL tetrahydrofuran solutions, stirring is completely molten to polychloride phosphonitrile
Solution, obtains polychloride phosphonitrile tetrahydrofuran solution, spare；
Step 2: taking 130.1g 2,6- difluorophenols are dissolved in 150mL tetrahydrofuran solutions, are slowly added by blender
Enter 40g sodium hydroxides, the temperature of solution be adjusted to 40 DEG C of constant temperature, under stiring react 1 hour it is completely anti-to 2,6- difluorophenols
Until should be difluoro phenol oxygroup sodium, intermediate product solution (I) is obtained, it is spare；
Step 3: taking the 1000mL three-necked flasks equipped with blender, condenser pipe and constant pressure funnel, it is added 33.2g's
1,7- bis- (4- hydroxy phenyls)-carborane, is slowly added to 4g sodium hydroxides by blender, it is molten to add 150mL tetrahydrofurans
In liquid and 21.2g bromooctanes to three-necked flask, and lead to nitrogen into reaction solution, it, will after 2 hours are stirred to react at 65 DEG C
Temperature is down to 50 DEG C, the three-necked flask after being reacted；
Step 4: polychloride phosphonitrile tetrahydrofuran solution is slowly first instilled step step 3 by constant pressure funnel
In three-necked flask after reaction, after being added dropwise, continue stirring 1~2 hour；
Again by intermediate product solution (I), is slowly instilled in the solution after stirring, be added dropwise by constant pressure funnel
Afterwards, continue stirring 2~3 hours, obtain reaction solution.
It is stirred Step 5: reaction solution is poured into the beaker for fill tap water, after stirring 10min, obtains in solution
The rubbery solid of cohesion detaches the rubbery solid of cohesion and solution, by tetrahydrofuran solution to rubber after separation
Colloidal solid is dissolved, then solution is poured into and repeats this step in the beaker for fill tap water, until washing away rubbery solid
In salinity, finally obtained rubbery solid be difluoro phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene.
Present invention has the advantages that：The chlorine atom that polydichlorophosphazenes polymer is replaced by using alkoxy, improves poly- phosphorus
The water resistance of nitrile, but thermal stability is not good enough, and carborane is added in substituent group then improves polyphosphazene polymer stability, resistance to
It is hot.The electrical cable insulation gone out by the way that the material preparations such as 2,6- difluorophenols and the monoalky lether of bis-phenol containing carborane are added
Glue has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
Embodiment two
Embodiment two and embodiment one difference lies in：
In step 2, takes 162.1g p-trifluoromethyl-phenols to be dissolved in 150mL tetrahydrofuran solutions, react 1 under stiring
Hour until p-trifluoromethyl-phenol is reacted completely for trifluoromethyl phenol oxygroup sodium, obtains intermediate product solution (II), spare；
In step 3, when leading to nitrogen into reaction solution, reaction 2 hours is stirred at a temperature of 100 DEG C；
In step 4, reacted using intermediate product solution (II).
Present invention has the advantages that：The chlorine atom that polydichlorophosphazenes polymer is replaced by using alkoxy, improves poly- phosphorus
The water resistance of nitrile, but thermal stability is not good enough, and carborane is added in substituent group then improves polyphosphazene polymer stability, resistance to
It is hot.The electrical cable insulation gone out by the way that the material preparations such as p-trifluoromethyl-phenol and the monoalky lether of bis-phenol containing carborane are added
Glue has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
Embodiment three
Embodiment three and embodiment one difference lies in：
In step 2, takes 178.1g to be dissolved in 150mL tetrahydrofuran solutions trifluoro-methoxy-phenol, react under stiring
Until being reacted completely trifluoro-methoxy-phenol for trifluoromethyl phenol oxygroup sodium, intermediate product solution (III) is obtained within 1 hour, it is standby
With；
In step 3, when leading to nitrogen into reaction solution, reaction 2 hours is stirred at a temperature of 100 DEG C；
In step 4, reacted using intermediate product solution (III).
Present invention has the advantages that：The chlorine atom that polydichlorophosphazenes polymer is replaced by using alkoxy, improves poly- phosphorus
The water resistance of nitrile, but thermal stability is not good enough, and carborane is added in substituent group then improves polyphosphazene polymer stability, resistance to
It is hot.It is exhausted by the way that the electrical cable gone out to the material preparations such as trifluoro-methoxy-phenol and the monoalky lether of bis-phenol containing carborane is added
Edge glue has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
Example IV
Example IV and embodiment one difference lies in：
In step 2, takes 212.1g to be dissolved in 150mL tetrahydrofuran solutions pentafluoroethyl group phenol, react 1 under stiring
Hour until reaction is to pentafluoroethyl group phenol oxygroup sodium completely to pentafluoroethyl group phenol, obtains intermediate product solution (IV), spare；
In step 3, when leading to nitrogen into reaction solution, reaction 2 hours is stirred at a temperature of 100 DEG C；
In step 4, reacted using intermediate product solution (IV).
Present invention has the advantages that：The chlorine atom that polydichlorophosphazenes polymer is replaced by using alkoxy, improves poly- phosphorus
The water resistance of nitrile, but thermal stability is not good enough, and carborane is added in substituent group then improves polyphosphazene polymer stability, resistance to
It is hot.It is insulated to the electrical cable that the material preparations such as pentafluoroethyl group phenol and the monoalky lether of bis-phenol containing carborane go out by being added
Glue has excellent electrical insulation properties, while heat resistance is high, flame retardant property is good, preparation method is simple.
It is above-mentioned, difluoro phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene, trifluoromethyl phenol oxygroup list Octyl Ether carbon
Borine bis-phenol oxygroup polyphosphazene, trifluoromethoxy phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene and pentafluoroethyl group phenol
Oxygroup list decyl ethers carborane bis-phenol oxygroup polyphosphazene, is polyphosphazene insulating cement.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement, which is characterized in that include the following steps：
S1, the polychloride phosphonitriles of 58g are taken, be added in 400mL tetrahydrofuran solutions, stirring is completely dissolved to polychloride phosphonitrile, is obtained
Polychloride phosphonitrile tetrahydrofuran solution, it is spare；
S2, it takes 130.1g 2,6- difluorophenols to be dissolved in 150mL tetrahydrofuran solutions, 40g hydrogen-oxygens is slowly added to by blender
Change sodium, the temperature of solution is adjusted to 40 DEG C of constant temperature, reacts 1 hour and reacted completely for difluoro phenol to 2,6- difluorophenols under stiring
Until oxygroup sodium, the first solution of intermediate product is obtained, it is spare；
S3, the 1000mL three-necked flasks equipped with blender, condenser pipe and constant pressure funnel are taken, 1,7-, the bis- (4- of 33.2g is added
Hydroxy phenyl)-carborane, 4g sodium hydroxides are slowly added to by blender, add 150mL tetrahydrofuran solutions and 21.2g
In bromooctane to three-necked flask, and leads to nitrogen into reaction solution and cooled the temperature to after being stirred to react 2 hours at 65 DEG C
50 DEG C, the three-necked flask after being reacted；
S4, respectively by step S1 and step S2 obtained polychloride phosphonitrile tetrahydrofuran solution and intermediate product first it is molten
Liquid is slowly instilled in the three-necked flask after step S3 reacts by constant pressure funnel and is reacted, obtains reaction solution；
S5, it reaction solution is poured into the beaker for fill tap water is stirred, after stirring 10min, obtain the rubber agglomerated in solution
Colloidal solid detaches the rubbery solid of cohesion and solution, by tetrahydrofuran solution to rubbery solid after separation
It is dissolved, then solution is poured into and repeats this step in the beaker for fill tap water, until the salinity in rubbery solid is washed away,
Finally obtained rubbery solid is difluoro phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene.
2. the preparation method of flame-proof heat-resistant polyphosphazene insulating cement according to claim 1, which is characterized in that above-mentioned steps S4
Specially：
First by polychloride phosphonitrile tetrahydrofuran solution, the three-necked flask after step S3 reactions is slowly instilled by constant pressure funnel
In, after being added dropwise, continue stirring 1~2 hour；
Again by the first solution of intermediate product, slowly instilled by constant pressure funnel in the solution after stirring, after being added dropwise, after
Continuous stirring 2~3 hours, obtains reaction solution.
3. a kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement, which is characterized in that include the following steps：
S1, the polychloride phosphonitriles of 58g are taken, be added in 400mL tetrahydrofuran solutions, stirring is completely dissolved to polychloride phosphonitrile, is obtained
Polychloride phosphonitrile tetrahydrofuran solution, it is spare；
S2, it takes 162.1g p-trifluoromethyl-phenols to be dissolved in 150mL tetrahydrofuran solutions, 40g hydrogen is slowly added to by blender
The temperature of solution is adjusted to 40 DEG C of constant temperature by sodium oxide molybdena, and it is pair that reaction is reacted for 1 hour completely to p-trifluoromethyl-phenol under stiring
Until trifluoromethyl phenol oxygroup sodium, the second solution of intermediate product is obtained, it is spare；
S3, the 1000mL three-necked flasks equipped with blender, condenser pipe and constant pressure funnel are taken, 1,7-, the bis- (4- of 33.2g is added
Hydroxy phenyl)-carborane, 4g sodium hydroxides are slowly added to by blender, add 150mL tetrahydrofuran solutions and 21.2g
In bromooctane to three-necked flask, and leads to nitrogen into reaction solution and cooled the temperature to after being stirred to react 2 hours at 100 DEG C
50 DEG C, the three-necked flask after being reacted；
S4, respectively by step S1 and step S2 obtained polychloride phosphonitrile tetrahydrofuran solution and intermediate product second it is molten
Liquid is slowly instilled in the three-necked flask after step S3 reacts by constant pressure funnel and is reacted, obtains reaction solution；
S5, it reaction solution is poured into the beaker for fill tap water is stirred, after stirring 10min, obtain the rubber agglomerated in solution
Colloidal solid detaches the rubbery solid of cohesion and solution, by tetrahydrofuran solution to rubbery solid after separation
It is dissolved, then solution is poured into and repeats this step in the beaker for fill tap water, until the salinity in rubbery solid is washed away,
Finally obtained rubbery solid is trifluoromethyl phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene.
4. the preparation method of flame-proof heat-resistant polyphosphazene insulating cement according to claim 3, which is characterized in that above-mentioned steps S4
Specially：
First by polychloride phosphonitrile tetrahydrofuran solution, the three-necked flask after step S3 reactions is slowly instilled by constant pressure funnel
In, after being added dropwise, continue stirring 1~2 hour；
Again by the second solution of intermediate product, slowly instilled by constant pressure funnel in the solution after stirring, after being added dropwise, after
Continuous stirring 2~3 hours, obtains reaction solution.
5. a kind of preparation method of flame-proof heat-resistant polyphosphazene insulating cement, which is characterized in that include the following steps：
S1, the polychloride phosphonitriles of 58g are taken, be added in 400mL tetrahydrofuran solutions, stirring is completely dissolved to polychloride phosphonitrile, is obtained
Polychloride phosphonitrile tetrahydrofuran solution, it is spare；
S2, it takes 178.1g to be dissolved in 150mL tetrahydrofuran solutions trifluoro-methoxy-phenol, 40g is slowly added to by blender
The temperature of solution is adjusted to 40 DEG C of constant temperature by sodium hydroxide, reacts 1 hour reacted completely to trifluoro-methoxy-phenol under stiring
Until to trifluoromethoxy phenol oxygroup sodium, intermediate product third solution is obtained, it is spare；
S3, the 1000mL three-necked flasks equipped with blender, condenser pipe and constant pressure funnel are taken, 1,7-, the bis- (4- of 33.2g is added
Hydroxy phenyl)-carborane, 4g sodium hydroxides are slowly added to by blender, add 150mL tetrahydrofuran solutions and 21.2g
In bromooctane to three-necked flask, and leads to nitrogen into reaction solution and cooled the temperature to after being stirred to react 2 hours at 100 DEG C
50 DEG C, the three-necked flask after being reacted；
S4, respectively by step S1 and step S2 obtained polychloride phosphonitrile tetrahydrofuran solution and intermediate product third it is molten
Liquid is slowly instilled in the three-necked flask after step S3 reacts by constant pressure funnel and is reacted, obtains reaction solution；
S5, it reaction solution is poured into the beaker for fill tap water is stirred, after stirring 10min, obtain the rubber agglomerated in solution
Colloidal solid detaches the rubbery solid of cohesion and solution, by tetrahydrofuran solution to rubbery solid after separation
It is dissolved, then solution is poured into and repeats this step in the beaker for fill tap water, until the salinity in rubbery solid is washed away,
Finally obtained rubbery solid is trifluoromethoxy phenol oxygroup list Octyl Ether carborane bis-phenol oxygroup polyphosphazene.
6. the preparation method of flame-proof heat-resistant polyphosphazene insulating cement according to claim 5, which is characterized in that above-mentioned steps S4
Specially：
First by polychloride phosphonitrile tetrahydrofuran solution, the three-necked flask after step S3 reactions is slowly instilled by constant pressure funnel
In, after being added dropwise, continue stirring 1~2 hour；
Again by intermediate product third solution, slowly instilled by constant pressure funnel in the solution after stirring, after being added dropwise, after
Continuous stirring 2~3 hours, obtains reaction solution.
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Effective date of registration: 20220413 Address after: 365400 No. 37, Gongye South Road, Chengnan Town, Ninghua County, Sanming City, Fujian Province Patentee after: Fujian Chaoyang wire and cable Co.,Ltd. Address before: 350200 Liyushan Industrial Zone, Heshang Town, Changle City, Fuzhou City, Fujian Province Patentee before: FUZHOU TONGERDA ELECTRIC WIRE & CABLE Co.,Ltd. |
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Denomination of invention: Preparation method of flame retardant and heat resistant polyphosphazene insulation adhesive Effective date of registration: 20230908 Granted publication date: 20181023 Pledgee: Agricultural Bank of China Limited Ninghua County Branch Pledgor: Fujian Chaoyang wire and cable Co.,Ltd. Registration number: Y2023350000200 |