CN107868255A - The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification - Google Patents
The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses the preparation method and applications of the POSS DOPO triazine derivative flame retardants with self assembly humidification, the molecular structural formula of the fire retardant are as follows：Wherein R is The present invention improves the heat endurance and anti-flammability of epoxy resin-base on the basis of matrix mechanical property is ensured, has the advantages that good flame retardation effect, applied widely.
Description
Technical field
The invention belongs to technical field of flame retardant, and in particular to a kind of POSS-DOPO- tri- with self assembly humidification
The preparation method and applications of oxazine derivatives fire retardant.
Background technology
Epoxy resin has good physical and chemical performance, heat resistance, solvent resistance, excellent electrical insulation capability and machine
Tool performance, so as in electronic instrument, adhesive, building etc. extensive application.As epoxy resin is increasingly subject to people
Pay attention to, the requirement to its security is also gradually stepping up.Epoxy resin is 3 D stereo network structure, has higher planted agent
Power and surface energy, and it is inflammable, therefore also need to ensure its mechanical performance etc. on the basis of its anti-flammability is modified.
Phosphorus, nitrogen, silicon are effective ignition-proof elements.Wherein organophosphor can promote polymer carbon-coating is in burning into charcoal
Matrix can be protected from the erosion of heat and oxygen, so as to improve anti-flammability and heat endurance.9,10- dihydro-9-oxies are miscellaneous-
10- phospho hetero phenanthrene -10- oxides (DOPO) have excellent anti-flammability, and it has the uht-stable P-O-C protected by phenyl ring
Key and O=P-O groups, and DOPO is inexpensive and waterproof, the O-P-H keys in DOPO cause it to have very high reactivity, so as to
It is next polymer-modified to synthesize a series of derivative.
Nitrogen-containing group can discharge non-flammable gases, can with dilution oxygen, absorbed when burning surface decomposes heat or
Taking away heat reduces pyrolysis temperature, reaches fire-retardant effect.Existing many document reports cross the polymer that triazine is base, because
It has high nitrogen content, has well into charcoal effect.Triazine structure is not only fire-retardant nitrogen source, can also be hard by providing
Structure improve heat endurance.Meng Fanyi (a kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound, CN106009037A)
The fire-retardant carbon forming agent of triazine system macromolecular is prepared using isocyanuric acid three-glycidyl ester and hydramine reaction, had antidrip into charcoal
Fall effect.
Silicon-containing compound can promote to form the protection charcoal of thermal insulation, and this heat-staple carbon-coating can protect matrix, subtract
The generation of few imflammable gas product.Wherein POSS is that one kind has nanostructured, caged, has high content silicon element
Three-dimensional structure, there is excellent anti-flammability and polymeric matrix other performances can be improved.A kind of Dai Lizong (phosphorous pasc reactions
Type macromolecular fire retardant and preparation method and application, Chinese patent, publication number CN104262538A) it is by 4- metering systems
Amide groups aniline, phosphorous-containing monomers and the isobutyl group POSS of methacryloxypropyl seven are obtained by the preparation method of radical polymerization
To containing phosphorus silicon response type macromolecular fire retardant, can be applied in fire-retarded epoxy resin is prepared.
Existing various phosphorus systems, nitrogen system and silicon-series five-retardant at present, but the fire retardant of every kind of element has
Defect, for example addition is big in the polymer, compatibility is bad, reduces the problems such as mechanical performance of matrix.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of POSS- with self assembly humidification
DOPO- triazine derivative flame retardants.
Another object of the present invention is to provide the above-mentioned POSS-DOPO- pyrrolotriazine derivatives with self assembly humidification
The preparation method of fire retardant.
It is still another object of the present invention to provide a kind of based on the fire-retardant of above-mentioned POSS-DOPO- triazine derivative flame retardants
The preparation method of property epoxy resin.
Technical scheme is as follows：
POSS-DOPO- triazine derivative flame retardants with self assembly humidification, its molecular structural formula are as follows：
Wherein R is
R1For
The above-mentioned specific synthesis step of POSS-DOPO- triazine derivative flame retardants with self assembly humidification is as follows：
(1) Cyanuric Chloride and aminopropyl oligomeric silsesquioxane (POSS-NH are weighed2), it is organic molten that first is dissolved in respectively
In agent, stirring is dissolved at -5~0 DEG C, the first solution and the second solution is obtained, the second solution is added drop-wise in the first solution, together
The acid binding agents of Shi Tianjia first maintain the pH value of material, when the ratio of Cyanuric Chloride and aminopropyl oligomeric silsesquioxane is 1: 1
When~1.2, temperature maintains -5~10 DEG C；When the ratio of Cyanuric Chloride and aminopropyl oligomeric silsesquioxane is 1: 2~2.5
When, reaction temperature is slowly increased to room temperature, reacts 2~8h, then removes first organic solvent and obtains middle production after purifying
Thing；
(2) above-mentioned intermediate product and BisDOPO-OH are dissolved separately in the second organic solvent (see CN104262398A)
In, respectively obtain the 3rd solution and the 4th solution, intermediate product and BisDOPO-OH mol ratio are 1: 2~2.5 or 1: 1
~1.2, the 4th solution is slowly dropped in 1h in the 3rd solution, stirred at 60~80 DEG C, while adds second and ties up acid
Agent, 12~24h of reaction time, is then purified using distilled water and acetonitrile, is obtained described with self assembly humidification
POSS-DOPO- triazine derivative flame retardants.
In a preferred embodiment of the invention, the first organic solvent includes dichloromethane, chlorine in the step (1)
Imitative, ether and tetrahydrofuran, it is water-soluble that first acid binding agent includes aqueous sodium carbonate, sodium bicarbonate aqueous solution and calcium carbonate
Liquid.
In a preferred embodiment of the invention, the second organic solvent in the step (2) is dichloromethane, two
Two kinds of mixing with 1: 1 volume ratio in the ring of oxygen six and dimethyl sulfoxide, second acid binding agent include triethylamine, ethylenediamine
And isopropylamine.
In a preferred embodiment of the invention, the purification in the step (1) and (2) include precipitation, centrifugation and
It is lyophilized.
Another technical scheme of the present invention is as follows：
A kind of preparation method of fire-retarded epoxy resin, above-mentioned POSS-DOPO- triazine derivative flame retardants are in stirring and admittedly
Nano-particle is self-assembled into during change in the epoxy, is specifically comprised the following steps：
(1) glycidyl ether type epoxy resin is weighed in reaction vessel, being heated to 65~130 DEG C, according to 1~30wt%
Ratio add the POSS-DOPO- triazine derivative flame retardants with self assembly humidification, stirring and dissolving is to homogeneous
State, curing agent is added, is stirred until homogeneous dissolved state, then be quickly poured into warmed-up mould, be put into baking oven,
Setting heating schedule is solidified, and then Temperature fall, obtains the fire-retarded epoxy resin；The heating schedule is： 115
~125 DEG C of solidifications 4~6h, 135~145 DEG C of solidifications 1.8~2.2h, 175~185 DEG C of 1.8~2.2h of solidification.
In a preferred embodiment of the invention, the epoxy resin is bisphenol A type epoxy resin.
In a preferred embodiment of the invention, the curing agent includes aliphatic amine curing agent, aromatic amines
Curing agent, amide groups amine curing agent, latent solidification amine curing agent and urea substitute curing agent.
In a preferred embodiment of the invention, the heating schedule is：120 DEG C of solidifications 5h, 140 DEG C of solidification 2h,
180 DEG C of solidification 2h.
The beneficial effects of the invention are as follows：
1st, the present invention improves the heat endurance of epoxy resin-base and fire-retardant on the basis of matrix mechanical property is ensured
Property, there is good flame retardation effect, applied widely.
2nd, POSS-DOPO- triazine derivative flame retardant raw materials of the invention are easy to get, and cost is cheap, novel in design.
3rd, three kinds of phosphorus, nitrogen, silicon ignition-proof elements are designed into by POSS-DOPO- triazine derivative flame retardants of the invention simultaneously
In one molecule, phosphorus can promote into charcoal, and POSS can be increased the stability of carbon-coating by thermal decomposition, and it is dilute that nitrogen can generate gas
Oxygen release gas, and with phosphoric acid product organic reaction can occur for product, increase the thermal insulation of carbon-coating, there is three collaboration to hinder
Fuel efficiency fruit, single ignition-proof element can be overcome the shortcomings of.
4th, the present invention uses connection matrix of the Cyanuric Chloride as POSS-DOPO- triazine derivative flame retardants, and it is not only carried
For nitrogen, its triazine structure can also form rock-steady structure in combustion, increase the stability of carbon-coating.
5th, POSS-DOPO- triazine derivative flame retardants of the invention are applied in modified epoxy, are occurred in the base
Self assembly, nano particle is formed, play a part of strengthening mechanical property.
Brief description of the drawings
Fig. 1 is the synthetic route chart of the POSS-DOPO- triazine derivative flame retardants of the present invention.
Fig. 2 is the intermediate product and POSS-DOPO- triazine derivative flame retardants being prepared in the embodiment of the present invention 1
Infrared spectrum (FT-IR).
Fig. 3 is the intermediate product and POSS-DOPO- triazine derivative flame retardants being prepared in the embodiment of the present invention 1
Proton nmr spectra (1H-NMR)。
Fig. 4 is that the self assembly being prepared in the embodiment of the present invention 1 strengthens the electron-microscope scanning figure of modified epoxy
(SEM)。
Embodiment
Technical scheme is further detailed and described below by way of embodiment combination accompanying drawing.
The synthetic route of POSS-DOPO- triazine derivative flame retardants in the following embodiments of the present invention is as shown in Figure 1.
Embodiment 1
(1) synthesis of intermediate product
1.84g (0.01mo1) Cyanuric Chloride and 50mL tetrahydrofurans are added in 250mL three neck round bottom flask,
Again by 4.372g (0.005mo1) POSS-NH2It is dissolved in 50mL tetrahydrofuran, stirring is dissolved at -5~0 DEG C of difference, is obtained
To the first solution and the second solution, the second solution is added drop-wise in the first solution, low temperature, is slowly increased to room temperature, simultaneously
Add the NaHCO of the first acid binding agent 10%3Solution, pH value being kept as neutrality, reacting 6h, reaction terminates rear rotary evaporation concentration
Solvent, the first acid binding agent salt is removed using distillation water washing, intermediate product is further obtained using acetonitrile precipitation, yield is about
For 83%.(2) preparation of POSS-DOPO- triazine derivative flame retardants
The dimethyl sulfoxide of 100mL dioxane and 100mL is mixed into obtain the second organic solvent, takes 2.55g
The intermediate product of (0.0025mol) and 100mL the second organic solvent are added in 500mL three neck round bottom flask and dissolved
To the 3rd solution, then 2.82g (0.005mol) BisDOPO-OH is dissolved in 10mL the second solvent and obtains the 4th solution,
4th solution is slowly dropped in 1h in the 3rd solution, temperature rises to 80 DEG C, and the second acid binding agent triethylamine of addition maintains thing
The pH value of material is neutrality, reacts 24h.Reaction removes the second acid binding agent salt of generation using distilled water after terminating, then uses acetonitrile
Precipitation obtains the POSS-DOPO- triazine derivative flame retardants, and yield was about 70% (as shown in Figures 2 and 3).
(3) 20g bisphenol A type epoxy resin is weighed in single-necked flask, and heating-up temperature is raised to 85 DEG C, adds 0.25g's
POSS-DOPO- triazine derivative flame retardants, it is stirred for being dissolved to uniform state, weighs 5g curing agent 4,4- diaminourea two
Phenylmethane adds, and is stirred until homogeneous dissolved state, then is quickly poured into the special die heated, is put into baking oven, if
Determine heating schedule (120 DEG C of solidifications 5h, 140 DEG C of solidifications 2h, 180 DEG C of solidification 2h) to be solidified, Temperature fall after a period of time,
It can obtain fire-retarded epoxy resin (as shown in Figure 4).
The oxygen index (OI) of fire-retarded epoxy resin according to made from GB/T 2406-2009 measure the present embodiment is 26.6%.
The bending modulus that the fire-retarded epoxy resin of the present embodiment is measured according to three-point bending is shown in Table 1.
Embodiment 2
(1) synthesis of intermediate product
1.84g (0.01mol) Cyanuric Chloride and 50mL tetrahydrofurans are added in 250mL three neck round bottom flask,
Again by 4.372g (0.005mol) POSS-NH2It is dissolved in 50mL tetrahydrofuran, stirring is dissolved at -5~0 DEG C of difference, is obtained
To the first solution and the second solution, the second solution is added drop-wise in the first solution, low temperature, room temperature is slowly increased to, together
When add the NaHCO of the first acid binding agent 10%3Solution, pH value is kept to react 6h for neutrality.It is dense that reaction terminates rear rotary evaporation
Contracting solvent, the first acid binding agent salt is removed using distillation water washing, intermediate product, yield are further obtained using acetonitrile precipitation
About 83%.
(2) preparation of POSS-DOPO- triazine derivative flame retardants
The dimethyl sulfoxide of 100mL dioxane and 100mL is mixed into obtain the second organic solvent, takes 2.55g
The intermediate product of (0.0025mol) and 100mL the second organic solvent are added in 500mL three neck round bottom flask and dissolved
To the 3rd solution, then 2.82g (0.005mol) BisDOPO-OH is dissolved in 10mL the second organic solvent to obtain the 4th molten
Liquid, the 4th solution is slowly dropped in 1h in the 3rd solution, temperature rises to 80 DEG C, addition the second acid binding agent triethylamine dimension
The pH value for holding material is neutrality, reacts 24h.Reaction removes the second acid binding agent salt of generation using distilled water after terminating, then uses
Acetonitrile precipitation obtains the POSS-DOPO- triazine derivative flame retardants, and yield is about 70% (using proton nmr spectra, carbon
The method of spectrum and phosphorus spectrum characterizes final product).
(3) 20g bisphenol A type epoxy resin is weighed in single-necked flask, and heating-up temperature is raised to 85 DEG C, adds 0.773g
POSS-DOPO- triazine derivative flame retardants, be stirred for being dissolved to uniform state, weigh 5g 4,4- diaminourea hexichol first
Alkane adds, and is stirred until homogeneous dissolved state, then is quickly poured into the special die heated, is put into baking oven, and setting rises
Warm program (120 DEG C of solidifications 5h, 140 DEG C of solidifications 2h, 180 DEG C of solidification 2h) is solidified, and Temperature fall after a period of time, can be obtained
To fire-retarded epoxy resin.
The oxygen index (OI) of fire-retarded epoxy resin according to made from GB/T 2406-2009 measure the present embodiment is 28%.
The bending modulus that the fire-retarded epoxy resin of the present embodiment is measured according to three-point bending is shown in Table 1.
Embodiment 3
(1) synthesis of intermediate product
1.84g (0.01mol) Cyanuric Chloride and 50mL tetrahydrofurans are added in 250mL three neck round bottom flask,
Again by 4.372g (0.005mol) POSS-NH2It is dissolved in 50mL tetrahydrofuran, stirring is dissolved at -5~0 DEG C of difference, is obtained
To the first solution and the second solution, the second solution is added drop-wise in the first solution, low temperature, room temperature is slowly increased to, together
When add the NaHCO of the first acid binding agent 10%3Solution, pH value is kept to react 6h for neutrality.It is dense that reaction terminates rear rotary evaporation
Contracting solvent, the first acid binding agent salt is removed using distillation water washing, intermediate product, yield are further obtained using acetonitrile precipitation
About 83%.
(2) preparation of POSS-DOPO- triazine derivative flame retardants
The dimethyl sulfoxide of 100mL dioxane and 100mL is mixed into obtain the second organic solvent, takes 2.55g
The intermediate product of (0.0025mol) and 100mL the second organic solvent are added in 500mL three neck round bottom flask and dissolved
To the 3rd solution, then 2.82g (0.005mol) BisDOPO-OH is dissolved in molten to the 4th in 10mL the second organic solvent
Liquid, the 4th solution is slowly dropped in 1h in the 3rd solution, temperature rises to 80 DEG C, addition the second acid binding agent triethylamine dimension
The pH value for holding material is neutrality, reacts 24h.Reaction removes the second acid binding agent salt of generation using distilled water after terminating, then uses
Acetonitrile precipitation obtains the POSS-DOPO- triazine derivative flame retardants, and yield is about 70% (using proton nmr spectra, carbon
The method of spectrum and phosphorus spectrum characterizes final product).
(3) 20g bisphenol A type epoxy resin is weighed in single-necked flask, and heating-up temperature is raised to 85 DEG C, adds 0.1.316g
POSS-DOPO- triazine derivative flame retardants, be stirred for being dissolved to uniform state, weigh 5g curing agent 4,4- diaminourea
Diphenyl-methane adds, and is stirred until homogeneous dissolved state, then is quickly poured into the special die heated, is put into baking oven,
Set heating schedule (120 DEG C of solidifications 5h, 140 DEG C of solidifications 2h, 180 DEG C of solidification 2h) to be solidified, dropped naturally after a period of time
Temperature, it can obtain fire-retarded epoxy resin.
The oxygen index (OI) of fire-retarded epoxy resin according to made from GB/T 2406-2009 measure the present embodiment is 30.4%.
The bending modulus that the fire-retarded epoxy resin of the present embodiment is measured according to three-point bending is shown in Table 1.
Table 1
| Bending modulus (MPa) | Growth rate (%) | |
| Control group | 2317 | 0 |
| Embodiment 1 | 2446 | 5.56 |
| Embodiment 2 | 2541 | 9.67 |
| Embodiment 3 | 2695 | 16.3 |
Those of ordinary skill in the art understand, when technical scheme changes in following ranges, remain able to
To same as the previously described embodiments or similar technique effect, protection scope of the present invention is still fallen within：
The preparation method of POSS-DOPO- triazine derivative flame retardants with self assembly humidification, including following step
Suddenly：
(1) Cyanuric Chloride and aminopropyl oligomeric silsesquioxane (POSS-NH are weighed2), it is organic molten that first is dissolved in respectively
In agent, stirring is dissolved at -5~0 DEG C, the first solution and the second solution is obtained, the second solution is added drop-wise in the first solution, together
The acid binding agents of Shi Tianjia first maintain the pH value of material, when the ratio of Cyanuric Chloride and aminopropyl oligomeric silsesquioxane is 1: 1
When~1.2, temperature maintains -5~10 DEG C；When the ratio of Cyanuric Chloride and aminopropyl oligomeric silsesquioxane is 1: 2~2.5
When, reaction temperature is slowly increased to room temperature, reacts 2~8h, then removes first organic solvent and obtains middle production after purifying
Thing；First organic solvent includes dichloromethane, chloroform, ether and tetrahydrofuran, and it is water-soluble that first acid binding agent includes sodium carbonate
Liquid, sodium bicarbonate aqueous solution and calcium carbonate aqueous solution；
(2) above-mentioned intermediate product and BisDOPO-OH are dissolved separately in the second organic solvent (see CN104262398A)
In, respectively obtain the 3rd solution and the 4th solution, intermediate product and BisDOPO-OH mol ratio are 1: 2~2.5 or 1: 1
~1.2, the 4th solution is slowly dropped in 1h in the 3rd solution, stirred at 60~80 DEG C, while adds second and ties up acid
Agent, 12~24h of reaction time, is then purified using distilled water and acetonitrile, obtains the POSS-DOPO- pyrrolotriazine derivatives
Fire retardant；Second organic solvent is two kinds of mixing with 1: 1 volume ratio in dichloromethane, dioxane and dimethyl sulfoxide,
Second acid binding agent includes triethylamine, ethylenediamine and isopropylamine；
Above-mentioned purification includes precipitation, centrifugation and freezed.
A kind of preparation method of fire-retarded epoxy resin, above-mentioned POSS-DOPO- triazine derivative flame retardants are in stirring and admittedly
Nano-particle is self-assembled into during change in the epoxy, is specifically comprised the following steps：
(1) glycidyl ether type epoxy resin is weighed in reaction vessel, being heated to 65~130 DEG C, according to 1~30wt%
Ratio add the POSS-DOPO- triazine derivative flame retardants, stirring and dissolving to uniform state, add curing agent, stir
To mix to uniform dissolution state, then be quickly poured into warmed-up mould, be put into baking oven, setting heating schedule is solidified,
Then Temperature fall, the fire-retarded epoxy resin is obtained；The heating schedule is：115~125 DEG C solidification 4~6h, 135~
145 DEG C of solidifications 1.8~2.2h, 175~185 DEG C of 1.8~2.2h of solidification；The curing agent includes aliphatic amine curing agent, virtue
Race's amine curing agent, amide groups amine curing agent, latent solidification amine curing agent and urea substitute curing agent.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still it belong in the range of the present invention covers.
Claims (9)
1. the POSS-DOPO- triazine derivative flame retardants with self assembly humidification, it is characterised in that：Its molecular structural formula
It is as follows：
Wherein R is
R1For
2. the preparation side of the POSS-DOPO- triazine derivative flame retardants with self assembly humidification described in claim 1
Method, it is characterised in that：Comprise the following steps：
(1) Cyanuric Chloride and aminopropyl oligomeric silsesquioxane (POSS-NH are weighed2), it is dissolved in respectively in the first organic solvent ,-
Stirring is dissolved at 5~0 DEG C, the first solution and the second solution is obtained, the second solution is added drop-wise in the first solution, while adds the
One acid binding agent maintains the pH value of material, when the ratio of Cyanuric Chloride and aminopropyl oligomeric silsesquioxane is 1: 1~1.2,
Temperature maintains -5~10 DEG C；When the ratio of Cyanuric Chloride and aminopropyl oligomeric silsesquioxane is 1: 2~2.5, reaction
Temperature is slowly increased to room temperature, reacts 2~8h, then removes first organic solvent and obtains intermediate product after purifying；
(2) above-mentioned intermediate product and BisDOPO-OH are dissolved separately in the second organic solvent, respectively obtain the 3rd solution and
4th solution, intermediate product and BisDOPO-OH mol ratio are 1: 2~2.5 or 1: 1~1.2, by the 4th solution in 1h
It is slowly dropped in the 3rd solution, is stirred at 60~80 DEG C, at the same the second acid binding agent of addition, 12~24h of reaction time, then
Purified using distilled water and acetonitrile, it is fire-retardant to obtain the POSS-DOPO- pyrrolotriazine derivatives with self assembly humidification
Agent.
3. preparation method as claimed in claim 1, it is characterised in that：The first organic solvent includes dichloro in the step (1)
Methane, chloroform, ether and tetrahydrofuran, first acid binding agent include aqueous sodium carbonate, sodium bicarbonate aqueous solution and carbonic acid
The calcium aqueous solution.
4. preparation method as claimed in claim 1, it is characterised in that：The second organic solvent in the step (2) is dichloro
Two kinds of mixing with 1: 1 volume ratio in methane, dioxane and dimethyl sulfoxide, second acid binding agent include triethylamine,
Ethylenediamine and isopropylamine.
5. preparation method as claimed in claim 1, it is characterised in that：Purification in the step (1) and (2) include precipitation,
Centrifuge and lyophilized.
A kind of 6. preparation method of fire-retarded epoxy resin, it is characterised in that：In claim 1 to 5 described in any claim
The POSS-DOPO- triazine derivative flame retardants with self assembly humidification in stirring and solidification process in epoxy resin
In be self-assembled into nano-particle, specifically comprise the following steps：Glycidyl ether type epoxy resin is weighed in reaction vessel, is heated
To 65~130 DEG C, there are the POSS-DOPO- triazine derivatives of self assembly humidification according to adding 1~30wt% ratio
Thing fire retardant, stirring and dissolving to uniform state, adds curing agent, is stirred until homogeneous dissolved state, then be quickly poured into
In the mould of preheating, baking oven is put into, setting heating schedule is solidified, and then Temperature fall, obtains the flame retardant epoxy tree
Fat；The heating schedule is：115~125 DEG C of 4~6h of solidification, 135~145 DEG C of 1.8~2.2h of solidification, 175~185 DEG C solidify
1.8~2.2h.
7. preparation method as claimed in claim 6, it is characterised in that：The epoxy resin is bisphenol A type epoxy resin.
8. preparation method as claimed in claim 6, it is characterised in that：The curing agent includes aliphatic amine curing agent, virtue
Race's amine curing agent, amide groups amine curing agent, latent solidification amine curing agent and urea substitute curing agent.
9. preparation method as claimed in claim 6, it is characterised in that：The heating schedule is：120 DEG C of solidification 5h, 140 DEG C solid
Change 2h, 180 DEG C of solidification 2h.
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| CN114605717A (en) * | 2022-04-18 | 2022-06-10 | 中广核研究院有限公司 | Halogen-free environment-friendly flame-retardant rubber and preparation method thereof |
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| CN110317479A (en) * | 2019-07-30 | 2019-10-11 | 南通盟鼎新材料有限公司 | A kind of preparation process of mineral composite energy-saving material |
| CN112961314A (en) * | 2021-03-15 | 2021-06-15 | 四川大学 | Preparation method of flame-retardant water-based polyurethane for impregnation of microfiber base cloth |
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| CN114605717B (en) * | 2022-04-18 | 2024-03-22 | 中广核研究院有限公司 | Halogen-free environment-friendly flame retardant rubber and preparation method thereof |
| CN115612252A (en) * | 2022-10-14 | 2023-01-17 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Formula of reactive flame-retardant epoxy resin and preparation method and application thereof |
| CN115612252B (en) * | 2022-10-14 | 2024-05-14 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Reactive flame-retardant epoxy resin formula and preparation method and application thereof |
| CN116653373A (en) * | 2023-07-28 | 2023-08-29 | 浙江葆润应用材料有限公司 | Heat insulation material with fireproof function, preparation method and application thereof |
| CN116653373B (en) * | 2023-07-28 | 2023-10-03 | 浙江葆润应用材料有限公司 | Heat insulation material with fireproof function, preparation method and application thereof |
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