CN107254141A - Fire retardant and terylene and fire retarding epoxide resin solidfied material and preparation method thereof - Google Patents
Fire retardant and terylene and fire retarding epoxide resin solidfied material and preparation method thereof Download PDFInfo
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- CN107254141A CN107254141A CN201710505140.8A CN201710505140A CN107254141A CN 107254141 A CN107254141 A CN 107254141A CN 201710505140 A CN201710505140 A CN 201710505140A CN 107254141 A CN107254141 A CN 107254141A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5093—Complexes of amines
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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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
Abstract
The present invention relates to field of flame retardant products, and more particularly to a kind of fire retardant and terylene and fire retarding epoxide resin solidfied material and preparation method thereof.The fire retardant obtains good fire resistance by the synergy of nitrogen phosphorus, and passes through the amino in molecule and the strength of hydroxyl reinforced epoxy.The fire retarding epoxide resin solidfied material not only has good fire resistance, also with preferable mechanical performance.
Description
Technical field
The present invention relates to field of flame retardant products, and more particularly to a kind of fire retardant and terylene and fire retarding epoxide resin solidification
Thing and preparation method thereof.
Background technology
Terylene, epoxy resin etc. can introduce the mode containing flame-retardant monomer by using additive flame retardant or in the molecule
Carry out fire-retardant processing.Additive flame retardant directly with resin mixture, it is easy to process, adapt to it is wide, be the main body of fire retardant；Reaction
Type fire retardant frequently as bonding monomeis into polymer chain, it is small and flame retardant effect is lasting on product properties influence；Conventional is fire-retardant
Agent is divided into halogenated flame retardant, nitrogenated flame retardant, phosphorus flame retardant, silicon-series five-retardant, expansion type flame retardant, inorganic filler etc..Mesh
Before, using it is more be organic phosphorus flame retardant, wherein with phosphate ester flame retardants and phosphorous oxide-based being most widely used.
For the preferable flame retardant effect of acquisition, the addition of phosphate ester flame retardants and phosphorous oxide-based fire retardant is larger, and addition is needed
15-40% or so are reached, and it is big to products machinery performance impact, it can typically reduce tensile strength.
The content of the invention
It is an object of the invention to provide a kind of fire retardant, the fire retardant is obtained well by the synergy of nitrogen-phosphorus
Fire resistance, and pass through the amino in molecule and the strength of hydroxyl reinforced epoxy.
Another object of the present invention is to provide a kind of fire retarding epoxide resin solidfied material, the fire retarding epoxide resin solidfied material is not
Only there is good fire resistance, also with preferable mechanical performance.
Another object of the present invention is to provide a kind of method for preparing fire retarding epoxide resin solidfied material, this method operation letter
Single, reaction condition is easily achieved.
Another object of the present invention is to provide a kind of terylene, the terylene has good fire resistance.
The present invention is solved its technical problem and realized using following technical scheme：
The present invention provides a kind of fire retardant, and its structural formula is：
The present invention also provides a kind of fire retarding epoxide resin solidfied material, and it is mainly prepared by above-mentioned fire retardant.
The present invention also provides a kind of method for preparing fire retarding epoxide resin solidfied material, by above-mentioned fire retardant and epoxy resin and
Be heating and curing shaping after curing agent mixing.
The present invention also provides a kind of terylene, and it is mainly prepared by above-mentioned fire retardant.
The beneficial effect of fire retardant and terylene and fire retarding epoxide resin solidfied material of the present invention and preparation method thereof is：With showing
There is technology to compare, the new fire retardant that provides of the present invention for existing fire retardant its efficiently, it is Halogen, environment-friendly, can
It is used as the permanent sex flame retardant of thermosetting resin.Terylene has good fire resistance, and fire retarding epoxide resin solidfied material not only has
There is good fire resistance, its mechanical strength also obtains lifting by a relatively large margin.And prepare the fire retarding epoxide resin solidfied material
Process, simple to operate, condition is easily achieved, can industrialized production.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to institute in embodiment
The accompanying drawing needed to use is briefly described.
Fig. 1 is the infrared spectrum for the fire retardant that the embodiment of the present invention 1 is prepared；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram for the fire retardant that the embodiment of the present invention 1 is prepared.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
In the description of the invention, it is necessary to which explanation, term " first ", " second " etc. are only used for distinguishing description, without
It is understood that to indicate or imply relative importance.
Below to resistance fire retardant and terylene and fire retarding epoxide resin solidfied material of the embodiment of the present invention and preparation method thereof
It is specifically described.
A kind of fire retardant provided in an embodiment of the present invention, its structural formula is：
The molecular formula of the fire retardant is C50H38N2O8P2S, its physical parameter is：It is white powder under normal temperature, it is water insoluble.
The embodiment of the present invention also provides a kind of preparation method of fire retarding epoxide resin solidfied material, comprises the following steps：
S1, intermediate synthesis；
Catalytic reaction, addition accelerator and 2- are occurred into the presence of catalyst for addition accelerator and Benzaldehyde,2-hydroxy
What hydroxy benzaldehyde was actually occurred is condensation reaction.Reaction mechanism is：The carbonyl of Benzaldehyde,2-hydroxy carries out parent with amino first
Core addition reaction, forms the secondary amine with hydroxyl, in the presence of catalyst, sloughs one's share of expenses for a joint undertaking water formation imines.
Further specifically operating process is, addition accelerator and solvent mixed under the atmosphere of protection gas after again with 2- hydroxyls
Benzaldehyde and catalyst hybrid concurrency life catalytic reaction.Using protection gas be in order to prevent the oxygen in air to addition promote
Agent and the reaction of Benzaldehyde,2-hydroxy produce influence, prevent the generation of accessory substance, it is ensured that the yield and purity of intermediate, reduce
The operation of subsequent purification.
Further, catalytic reaction is by the mixture back flow reaction of addition accelerator, Benzaldehyde,2-hydroxy and catalyst
5-8 hours.Catalytic reaction is at reflux, it is ensured that dissolving of the solution to each reactant reaches maximum, promotes reactant
Between reaction progress, while backflow is reacted for addition accelerator and Benzaldehyde,2-hydroxy provides necessary reaction environment.And
The reaction time of 5-8 hours, it can either ensure that addition accelerator and Benzaldehyde,2-hydroxy fully carry out catalytic reaction, can guarantee that again
The yield and purity for the intermediate that catalytic reaction is obtained.Specific reflux temperature is the boiling point progress according to used reaction dissolvent
It is determined that.
Further, the mol ratio of addition accelerator and Benzaldehyde,2-hydroxy is 1:2-3, the usage amount of solvent is every mole
Addition accelerator uses 100-450ml solvents, and the consumption of catalyst uses 0.1-0.5g catalyst for every mole of addition accelerator.
Using above-mentioned ratio addition addition accelerator, Benzaldehyde,2-hydroxy, solvent and catalyst, it is ensured that the ratio of reactant in solvent
Example is suitable, and catalyst can effectively act on reactant, promotes the progress of reaction.If above-mentioned reactant does not use above-mentioned ratio
Example then can cause intermediate normally to generate, and then cause fire retardant normally to generate, or containing a large amount of in intermediate
Impurity, and the species of impurity is various, it is impossible to by impurity and the separation of intermediate well, then influence the life of follow-up fire retardant
Into.
Preferably, the mol ratio of addition accelerator and Benzaldehyde,2-hydroxy is 1:2.2-2.5, the usage amount of solvent is often to rub
Your addition accelerator uses 100-300ml solvents, and the consumption of catalyst is catalyzed for every mole of addition accelerator using 0.2-0.4g
Agent.
Further, addition accelerator is 4,4'- diaminobenzene sulfones.4,4'- diaminobenzene sulfone Chinese nickname DDS, are used
In treatment Various Types of Leprosy disease.Industrial curing agent as epoxy resin etc..Its effect is for imines in embodiments of the present invention
Generation provide amido, provide necessary parent nucleus skeleton for fire retardant.
Further, solvent is one kind in tetrahydrofuran, chloroform, ethanol or its combination.Tetrahydrofuran is a class
Heterocyclic organic compounds.It is one of most strong polarity ethers, and a kind of the non-of middle polarity is used as in chemical reaction and extraction
Proton solvent.Tetrahydrofuran easily becomes peroxide in storage.Chloroform colourless transparent liquid.There is special odor.Taste
Sweet tea.High refractive power, non-ignitable, matter weight is volatile.Sterling is to photaesthesia, and meeting illumination can act on the oxygen in air, gradually decompose and give birth to
Into the phosgene (phosgene) and hydrogen chloride of severe toxicity.In embodiments of the present invention tetrahydrofuran, chloroform, ethanol or its combine
To solvent main function be dissolving reaction product, provide necessary reaction environment for the reaction between reaction product.Meanwhile,
Carried out towards the positive direction beneficial to reaction, reduce the generation of back reaction.
Further, catalyst is organic monoacid, and organic acid is as catalyst, and catalytic effect is good, and its acid intensity is fitted
Preferably, changed as reaction type caused by can preventing acidity of catalyst too strong during catalyst, and then ensure intermediate
Can normally it generate.Preferably, organic monoacid is one kind in acetic acid p-methyl benzenesulfonic acid or its combination.
Further, forbid have water during the course of the reaction, water can cause condensation reaction to be normally carried out, promote condensation anti-
The back reaction answered occurs, and then causes intermediate to generate.
Back flow reaction is handled reaction solution after terminating, and specific operation is that the solution reacted progress cooling is cold
But so that the intermediate that reaction is obtained is separated out from reaction solution, then filtered, washed and dried and obtained in fire retardant
Mesosome, intermediate is orange red.
S2, fire retardant synthesis；
The intermediate that above-mentioned catalytic reaction is obtained reacts with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
Specifically, reaction is addition reaction.Intermediate contains carbon-to-nitrogen double bon for electrophilic reagent during addition reaction, and 9,10- bis-
Hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides are then nucleopilic reagent, and nucleopilic reagent attack electrophilic reagent then occurs nucleophilic and added
Into.
Further, addition reaction is back flow reaction 10-14 hours under protective gas atmosphere.Protective gas is to prevent sky
Gas and oxygen enter reaction system, prevent the generation of side reaction, it is ensured that the purity of fire retardant and the performance of fire retardant.Backflow
Reaction 10-14 hours, it is ensured that necleophilic reaction is fully completed, it is ensured that each reactant is fully contacted and reacted.Specific backflow
Temperature is that the boiling point of the reaction dissolvent according to used in is determined.
Further, addition reaction solvent be tetrahydrofuran, chloroform, ethanol in one kind or its combination.And in
The mol ratio of mesosome and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1.3-1.5:1.Using aforementioned proportion energy
Enough ensure that 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide obtains fire retardant by whole additions.
Further, reaction solution is post-processed after addition reaction terminates, the high fire retardant of purity is obtained, specifically
Ground, is that reaction solution is naturally cooled into room temperature, fire retardant is separated out from reaction solution, is then filtered, washed and is dried
It is dry to obtain white solid, i.e. fire retardant.Further, the temperature of drying is 60-80 DEG C.
It should be noted that the fire retardant that the embodiment of the present invention is obtained passes through infrared detection, elementary analysis and nuclear-magnetism hydrogen
Analysis of spectrum carries out structure determination.
S3, prepare fire retarding epoxide resin solidfied material；
Be heating and curing shaping after above-mentioned fire retardant is mixed with epoxy resin and curing agent.It is fire-retardant in a heated condition
Curing reaction, which occurs, for agent, curing agent and epoxy resin can quickly generate fire retarding epoxide resin solidfied material.
Specifically being again heated to 85-105 DEG C after 45-70 parts of fire retardants are mixed with 10-20 parts of curing agent, then again
Add 650-750 part bisphenol A type epoxy resins, and at 110-120 DEG C dry 2-3 hours after, then at 160-170 DEG C drying
2-3 hours, produce fire retarding epoxide resin solidfied material.
Curing agent and fire retardant are mixed first be in order to prevent after addition epoxy resin, epoxy resin at once with curing agent
Reaction, so cause production epoxy resin cured product in composition it is inconsistent, then reduce its flame retardant effect.Meanwhile, it will hinder
It is to lift the reactivity of fire retardant and curing agent that combustion agent carries out heating again after mixing with curing agent, it is ensured that epoxy resin adds
Plus after can be reacted at once with curing agent and fire retardant.Using being heated stage by stage, prevent the rate of heat addition too fast, prevent fire-retardant
Local reaction occurs for agent, curing agent and epoxy resin, it is ensured that the uniformity of reaction, it is ensured that the homogeneity of generation product.
Further, during curing agent is 4,4'- MDAs (DDM), 4,4'- diaminodiphenylsulfones (DDS)
A kind of or its combination.4,4'- MDAs are white or Light yellow crystals powder, as the resistance to of epoxy resin adhesive
High-temperature curing agent, referring generally to 26~30 parts of consumption, 28 parts of optimum amount.4,4' diaminodiphenyl sulfone (DDS) is tied for white
Crystalline substance, or slightly yellow crystalline powder, odorlessness, bitter, for synthesizing polysulfonamides resin and other polymers.
The embodiment of the present invention also provides a kind of fire retarding epoxide resin solidfied material, the fire retarding epoxide resin solidfied material mainly by
Above-mentioned fire retardant is prepared.
It should be noted that testing its limited oxygen index using oxygen index instrument and universal material tester tests its stretching
Intensity.
The embodiment of the present invention also provides a kind of terylene, and it is mainly prepared by above-mentioned fire retardant.Specifically prepare
Method is that fire retardant is with terylene using mass ratio as 1：8-10 ratio be added to after being well mixed in double screw extruder and squeezed
Go out, produce the terylene with fire resistance.Then its limited oxygen index is tested using oxygen index instrument.
New fire retardant provided in an embodiment of the present invention for existing fire retardant its efficiently, it is Halogen, environment-friendly,
The permanent sex flame retardant of thermosetting resin can be used as.Meanwhile, the epoxy resin being modified using the fire retardant not only has good resistance
Performance is fired, while also having good mechanical performance.And the method for preparing fire retarding epoxide resin solidfied material is simple to operate, bar is reacted
Part is easily achieved.And modified terylene also has good fire resistance.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of fire retardant that the present embodiment is provided, its structural formula is as follows.
The embodiment of the present invention also provides a kind of method for preparing fire retardant：
S1, intermediate synthesis：After 1mol 4,4'- diaminobenzene sulfone and the mixing of 100ml tetrahydrofurans, in nitrogen protection
Under, tetrahydrofuran reflux temperature is heated to, 2mol Benzaldehyde,2-hydroxies and 0.2g acetic acid is then added, and react 6 hours.Instead
Drying obtains orange red intermediate 0.96mol, i.e. intermediate after being washed 3 times using tetrahydrofuran after cooling, filtering after should terminating
Yield be 96.5%.
S2, fire retardant synthesis：By 1.3mol intermediates and 1mol 9, the miscellaneous -10- phospho hetero phenanthrenes -10- oxygen of 10- dihydro-9-oxies
After compound mixing, tetrahydrofuran is added as reaction dissolvent, and is reacted 12 hours under the reflux temperature of tetrahydrofuran.Reaction
After end, reaction solution is naturally cooled into room temperature, fire retardant is separated out from reaction solution, then filtered and utilize tetrahydrochysene
Furans is washed 3 times, then obtains 0.95mol white solids, i.e. fire retardant in 60 DEG C of drying.Fire retardant yield is 95.5%.
Infrared detection, elementary analysis and nucleus magnetic hydrogen spectrum analysis are carried out to fire retardant, its result is referring to Fig. 1-Fig. 2.Wherein,
Infrared detection is referring to Fig. 1, it is known that in 3269cm-1, 1590cm-1, 1507cm-1, 1334cm-1, 1233cm-1, 921cm-1, 747cm-1
Etc. occur in that characteristic peak.Elementary analysis (%)：C is 66.29% (67.56%)；H is 4.60% (H, 4.31%)；N is
3.08% (3.15%).It is theoretical value in 7.01% (6.97%), its bracket that P, which is, it was demonstrated that above-mentioned reaction product is fire retardant
DSD.Nucleus magnetic hydrogen spectrum is analyzed referring to Fig. 2, it is known that1H NMR(400MHz,Methanol-d4)δ9.47(s,1H),9.72(s,1H),
(m, the H) of 6.49-8.21 (m, Ar-H), 5.56 (m, H), 5.27
The present embodiment also provides a kind of fire retarding epoxide resin solidfied material, and the fire retarding epoxide resin solidfied material is mainly by above-mentioned
Fire retardant prepare.
The present embodiment also provides a kind of preparation method of fire retarding epoxide resin solidfied material：
100 DEG C are again heated to after 45g fire retardants and 20g4,4'- MDA are mixed, 700g is then added
Bisphenol A type epoxy resin, and at 120 DEG C dry 3 hours after, then at 160 DEG C dry 2 hours, produce fire retarding epoxide resin
Solidfied material.
The present embodiment also provides a kind of terylene, and it is mainly prepared by above-mentioned fire retardant.Specifically preparation method
It is that fire retardant is with terylene using mass ratio as 1：8 ratio be added to after being well mixed in double screw extruder and extruded, and is produced
Terylene with fire resistance.
Embodiment 2
The embodiment of the present invention provides a kind of method for preparing fire retardant：
S1, intermediate synthesis：After 1mol 4,4'- diaminobenzene sulfone and the mixing of 200ml chloroforms, in nitrogen protection
Under, chloroform reflux temperature is heated to, 2.5mol Benzaldehyde,2-hydroxies and 0.1g p-methyl benzenesulfonic acids is then added, and instead
Answer 8 hours.Drying obtains orange red intermediate after being washed 3 times using chloroform after cooling, filtering after reaction terminates
0.97mol, i.e. intermediate yield are 97.1%.
S2, fire retardant synthesis：By 1.4mol intermediates and 1mol 9, the miscellaneous -10- phospho hetero phenanthrenes -10- oxygen of 10- dihydro-9-oxies
After compound mixing, chloroform is added as reaction dissolvent, and is reacted 10 hours under the reflux temperature of chloroform.Reaction
After end, reaction solution is naturally cooled into room temperature, fire retardant is separated out from reaction solution, then filtered and utilize trichlorine
Methane wash 3 times, then obtain 0.96mol white solids, i.e. fire retardant in 70 DEG C of drying.Fire retardant yield is 96.4%.
The present embodiment also provides a kind of preparation method of fire retarding epoxide resin solidfied material：
85 DEG C are again heated to after 60g fire retardants and 15g4,4'- diaminodiphenylsulfone are mixed, 750g is then added double
Phenol A type epoxy resin, and at 110 DEG C dry 2.5 hours after, then at 170 DEG C dry 3 hours, produce fire retarding epoxide resin
Solidfied material.
The present embodiment also provides a kind of terylene, and it is mainly prepared by above-mentioned fire retardant.Specifically preparation method
It is that fire retardant is with terylene using mass ratio as 1：9 ratio be added to after being well mixed in double screw extruder and extruded, and is produced
Terylene with fire resistance.
Embodiment 3
The embodiment of the present invention also provides a kind of method for preparing fire retardant：
S1, intermediate synthesis：After 1mol 4,4'- diaminobenzene sulfone and the mixing of 300ml ethanol, under nitrogen protection, plus
Heat then adds 3mol Benzaldehyde,2-hydroxies and 0.5g acetic acid, and react 5 hours to alcohol reflux temperature.Reaction terminates rear cold
But it is 96.3% that drying, which obtains orange red intermediate 0.96mol, the i.e. yield of intermediate, after being washed 3 times using ethanol after, filtering.
S2, fire retardant synthesis：By 1.5mol intermediates and 1mol 9, the miscellaneous -10- phospho hetero phenanthrenes -10- oxygen of 10- dihydro-9-oxies
After compound mixing, ethanol is added as reaction dissolvent, and is reacted 14 hours under the reflux temperature of ethanol.After reaction terminates,
Reaction solution is naturally cooled into room temperature, fire retardant is separated out from reaction solution, then filtered and utilize ethanol washing 3
It is secondary, then obtain 0.95mol white solids, i.e. fire retardant in 80 DEG C of drying.Fire retardant yield is 94.9%.
The present embodiment also provides a kind of preparation method of fire retarding epoxide resin solidfied material：
The mixture of 70g fire retardants and 10g4,4'- diaminodiphenylsulfones and 4,4'- MDAs is mixed
105 DEG C are again heated to after conjunction, 650g bisphenol A type epoxy resins are then added, and after being dried 2 hours at 115 DEG C, then
Dried 2.5 hours at 165 DEG C, produce fire retarding epoxide resin solidfied material.
The present embodiment also provides a kind of terylene, and it is mainly prepared by above-mentioned fire retardant.Specifically preparation method
It is that fire retardant is with terylene using mass ratio as 1：10 ratio be added to after being well mixed in double screw extruder and extruded, i.e.,
There must be the terylene of fire resistance.
Embodiment 4
The embodiment of the present invention also provides a kind of method for preparing fire retardant：
S1, intermediate synthesis：The mixed solvent of 1mol 4,4'- diaminobenzenes sulfones and 450ml ethanol and tetrahydrofuran is mixed
After conjunction, under nitrogen protection, the reflux temperature of the mixed solvent of ethanol and tetrahydrofuran is heated to, then adds 2.3mol 2-
Hydroxy benzaldehyde and 0.4g p-methyl benzenesulfonic acids, and react 7 hours.After reaction terminates ethanol and tetrahydrochysene are used after cooling, filtering
It is 95.4% that drying, which obtains orange red intermediate 0.95mol, the i.e. yield of intermediate, after the mixed solvent of furans is washed 3 times.
S2, fire retardant synthesis：By 1.4mol intermediates and 1mol 9, the miscellaneous -10- phospho hetero phenanthrenes -10- oxygen of 10- dihydro-9-oxies
After compound mixing, the mixed solvent of ethanol and tetrahydrofuran is added as reaction dissolvent, and in the mixed of ethanol and tetrahydrofuran
Reacted 13 hours under the reflux temperature of bonding solvent.After reaction terminates, reaction solution is naturally cooled into room temperature, fire retardant is from reaction
Separated out in solution, then filtered and washed 3 times using the mixed solvent of ethanol and tetrahydrofuran, then obtained in 75 DEG C of drying
0.95mol white solids, i.e. fire retardant.Fire retardant yield is 95.1%.
The present embodiment also provides a kind of preparation method of fire retarding epoxide resin solidfied material：
95 DEG C are again heated to after 55g fire retardants and 12g4,4'- diaminodiphenylsulfone are mixed, 720g is then added double
Phenol A type epoxy resin, and at 117 DEG C dry 2 hours after, then at 167 DEG C dry 3 hours, produce fire retarding epoxide resin consolidate
Compound.
The present embodiment also provides a kind of terylene, and it is mainly prepared by above-mentioned fire retardant.Specifically preparation method
It is that fire retardant is with terylene using mass ratio as 1：9.5 ratio be added to after being well mixed in double screw extruder and extruded, i.e.,
There must be the terylene of fire resistance.
Experimental example
Experimental example 1
Comparative example 1 is not added with the epoxy resin cured product of fire retardant
Comparative example 2 is not added with the terylene of fire retardant
The fire retarding epoxide resin solidfied material and the epoxy resin cured product of comparative example 1 prepared respectively to embodiment 1-4
Its limited oxygen index is tested using oxygen index instrument and universal material tester tests its tensile strength.Specific testing result is shown in Table
1。
Limited oxygen index and tensile strength testing result
| LOI values | Tensile strength | |
| Embodiment 1 | 38 | 94.27 |
| Embodiment 2 | 41 | 93.16 |
| Embodiment 3 | 39 | 92.86 |
| Embodiment 4 | 37 | 94.39 |
| Comparative example 1 | 17 | 79.15 |
It can be seen from table 1, the mechanical strength increase that with the addition of the oxireme resin of fire retardant is obvious, meanwhile, anti-flammability
Can also it be improved significantly.
Experimental example 2
Its limit oxygen is tested using oxygen index instrument to the embodiment 1-4 terylene prepared and the terylene of comparative example 2 respectively
Index.Specific testing result is shown in Table 2.
Limited oxygen index testing result
| LOI values | |
| Embodiment 1 | 37 |
| Embodiment 2 | 39 |
| Embodiment 3 | 42 |
| Embodiment 4 | 40 |
| Comparative example 2 | 25 |
It can be seen from table 2, the fire resistance that with the addition of the terylene of fire retardant is improved significantly.
To sum up, new fire retardant provided in an embodiment of the present invention its efficient, Halogen, environment for existing fire retardant
Close friend, can be used as the permanent sex flame retardant of thermosetting resin.Meanwhile, the intramolecular of the fire retardant contains nitrogen and P elements, leads to
The synergy for crossing nitrogen-phosphorus obtains good fire resistance, and passes through the strong of the amino in molecule and hydroxyl reinforced epoxy
Power.The preparation method is simple to operate simultaneously, and reaction condition is gentle.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of fire retardant, it is characterised in that the structural formula of the fire retardant is：
2. a kind of fire retarding epoxide resin solidfied material, it is characterised in that the fire retarding epoxide resin solidfied material mainly will by right
The fire retardant described in 1 is asked to prepare.
3. a kind of method for preparing fire retarding epoxide resin solidfied material, it is characterised in that by the fire retardant and ring described in claim 1
Be heating and curing shaping after oxygen tree fat and curing agent mixing.
4. the method according to claim 3 for preparing fire retarding epoxide resin solidfied material, it is characterised in that the fire retardant is
By after 4,4'- diaminobenzenes sulfone, Benzaldehyde,2-hydroxy, solvent and catalyst reaction again with the miscellaneous -10- phosphas of 9,10- dihydro-9-oxies
The material prepared after the reaction of phenanthrene -10- oxides.
5. the method according to claim 4 for preparing fire retarding epoxide resin solidfied material, it is characterised in that 4, the 4'- bis-
Aminobenzene sulfone, the Benzaldehyde,2-hydroxy and the catalyst reaction are by the 4,4'- diaminobenzenes sulfone, the 2- hydroxy benzenes
The mixture back flow reaction of formaldehyde and catalyst 5-8 hours.
6. the method according to claim 4 for preparing fire retarding epoxide resin solidfied material, it is characterised in that 4, the 4'- bis-
The mol ratio of aminobenzene sulfone and the Benzaldehyde,2-hydroxy is 1:2-3, the usage amount of the solvent is every mole of 4,4'- bis-
Aminobenzene sulfone uses solvent described in 100-450ml, and the consumption of the catalyst uses for every mole of 4,4'- diaminobenzenes sulfone
Catalyst described in 0.1-0.5g.
7. the method according to claim 4 for preparing fire retarding epoxide resin solidfied material, it is characterised in that the solvent is four
Any one in hydrogen furans, chloroform, ethanol.
8. the method according to claim 4 for preparing fire retarding epoxide resin solidfied material, it is characterised in that the catalyst is
One kind in acetic acid, p-methyl benzenesulfonic acid.
9. the method according to claim 4 for preparing fire retarding epoxide resin solidfied material, it is characterised in that 4, the 4'- bis-
Aminobenzene sulfone, the Benzaldehyde,2-hydroxy, the catalyst and the miscellaneous -10- phospho hetero phenanthrenes -10- oxidations of 9, the 10- dihydro-9-oxies
Thing reaction is the intermediate that will be obtained after the 4,4'- diaminobenzenes sulfone, the Benzaldehyde,2-hydroxy and the catalyst reaction
After being mixed with the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide under protective gas atmosphere back flow reaction 10-14
Hour.
10. a kind of terylene, it is characterised in that the terylene is mainly prepared as the fire retardant described in claim 1.
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| CN112480373A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Flame-retardant epoxy resin composition and preparation method and application thereof |
| CN115141465A (en) * | 2022-06-13 | 2022-10-04 | 北京理工大学 | Epoxy resin system compatible with liquid oxygen and preparation method thereof |
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Application publication date: 20171017 |