CN115073686B - Preparation method of vanillin-containing bio-based flame-retardant smoke suppressant and flame-retardant epoxy resin - Google Patents

Preparation method of vanillin-containing bio-based flame-retardant smoke suppressant and flame-retardant epoxy resin Download PDF

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CN115073686B
CN115073686B CN202210743729.2A CN202210743729A CN115073686B CN 115073686 B CN115073686 B CN 115073686B CN 202210743729 A CN202210743729 A CN 202210743729A CN 115073686 B CN115073686 B CN 115073686B
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epoxy resin
flame
retardant
vanillin
flame retardant
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CN115073686A (en
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屈红强
霍志永
段瑞
马海云
徐建中
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Hebei University
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Hebei University
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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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a preparation method of a vanillin-containing bio-based flame-retardant smoke suppressant and flame-retardant epoxy resin. The flame-retardant smoke suppressant is synthesized by taking vanillin, hexachlorocyclotriphosphazene and melamine as raw materials, has higher thermal stability and flame retardant property, can be singly used at high temperature, can be compounded with PAPP for use, can greatly improve the flame retardant effect of the EP by applying the prepared HCPMM to the epoxy resin (EP), can greatly inhibit the release of smoke and toxic and harmful gases, and has wide industrial application prospect.

Description

Preparation method of vanillin-containing bio-based flame-retardant smoke suppressant and flame-retardant epoxy resin
Technical Field
The invention relates to the technical field of flame retardants, in particular to a preparation method of a biological-based flame-retardant smoke suppressant containing vanillin and flame-retardant epoxy resin.
Background
Vanillin, known under the chemical name 3-methoxy-4-hydroxybenzaldehyde, is an organic compound extracted from the kidney bean, a plant of the family Rutaceae, and is a white to yellowish crystalline or crystalline powder. The product has strong fragrance, and is widely used in industries such as cosmetics, cakes and the like. The vanillin contains benzene ring, active phenolic hydroxyl and aldehyde groups, can react with various functional groups, can be used as a carbon source in an intumescent flame retardant, and can also be used for introducing an acid source and a gas source through the reaction of the functional groups. As a biomass resource, vanillin has the advantages of cleanness, reproducibility and the like, meanwhile, the vanillin has good compatibility with the polymer, and the mechanical property of the polymer is not greatly damaged by the addition of the vanillin.
Therefore, the application of the bio-based material, namely vanillin, as a flame-retardant smoke suppressant in a polymer is receiving more and more attention, but vanillin lacks flame-retardant elements, which indicates that the vanillin alone has poor effect as the flame retardant, so that the flame-retardant elements can be introduced through the reaction between functional groups, and the flame-retardant smoke suppression effect of vanillin is improved.
Disclosure of Invention
The invention aims to provide a novel bio-based flame-retardant smoke suppressant containing vanillin, which is prepared by using bio-based vanillin for flame retardance and a preparation method of the bio-based flame-retardant smoke suppressant.
The second purpose of the invention is to provide the application of the novel vanillin-containing bio-based flame-retardant smoke suppressant in preparing flame-retardant materials.
The invention further provides a flame-retardant epoxy resin, which is used for improving the flame retardance of the epoxy resin and reducing the release of smoke and toxic gas.
The invention is realized in the following way: a preparation method of a biological-based flame-retardant smoke suppressant containing vanillin comprises the following steps: dissolving 0.072mol of hexachlorocyclotriphosphazene in 100mol of tetrahydrofuran, placing the solution in a three-necked flask with condensing reflux, magnetic stirring and nitrogen protection, then dissolving 0.44-0.58 mol of vanillin in 100mL of tetrahydrofuran, dropwise adding the solution into the three-necked flask, reacting for 24-48 hours at 65-75 ℃, filtering, respectively washing with absolute ethyl alcohol and deionized water for three times, and vacuum drying at 60-80 ℃ for 18-24 hours to obtain an intermediate hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene (HCPV);
dissolving 0.001mol of HCPV in 50mL of dimethyl sulfoxide, placing the mixture in a 250mL three-necked flask, regulating the pH to 9-10 by using 1.0mol/L sodium hydroxide solution, weighing 0.002-0.006mol of melamine, adding the melamine into the flask, heating to 80-100 ℃, pre-polymerizing for 2-4 hours, regulating the pH to 2-4 by using hydrochloric acid, then heating to 130-150 ℃ to react for 3-4 hours to generate white floccules, cooling to room temperature, filtering, washing the precipitate twice by deionized water, and obtaining the final product of melamine crosslinked hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene (HCPMM) through freeze drying.
In the method, the concentration of the hexachlorocyclotriphosphazene is 0.72mol/L, and the mol ratio of the hexachlorocyclotriphosphazene to the vanillin is 1:6-1:8; HCPV has a concentration of 20mmol/L; the molar ratio of HCPV to melamine is 12-1:6.
The bio-based flame-retardant smoke suppressant containing vanillin prepared by the method can be used for preparing flame-retardant materials, and particularly can be used for preparing flame-retardant epoxy resin.
The flame-retardant epoxy resin specifically comprises epoxy resin and the bio-based flame-retardant smoke suppressant containing vanillin, which is prepared according to the method; the mass ratio of the vanillin-containing bio-based flame-retardant smoke suppressant to the epoxy resin is 1-6:100.
The vanillin-containing bio-based flame-retardant smoke suppressant can be independently or compounded with PAPP to prepare flame-retardant epoxy resin. When compounded with PAPP, the mass ratio of HCPMM to PAPP is 1:0-3, preferably, the mass ratio of HCPMM to PAPP is 1:3.
The preparation method of the flame-retardant epoxy resin provided by the invention comprises the following steps: weighing 100g of epoxy resin in a suction filtration bottle, heating and stirring for 20min at 60 ℃ and 180rpm, then adding the prepared HCPM, stirring for 20min to drive bubbles, adding 11.0g of m-phenylenediamine, and stirring for 20min to ensure that the m-phenylenediamine is uniformly dispersed; pouring a mold, placing in an oven with the vacuum degree of 0.05MPa for 20min at 60 ℃, then transferring into an oven with the vacuum degree of 80 ℃ for heating for 120min, adjusting the temperature to 150 ℃, heating and solidifying for 220min, cooling to room temperature, and taking out a spline to obtain the flame-retardant epoxy resin.
The novel flame retardant HCPHVM is prepared from the vanillin, the melamine and the hexachlorocyclotriphosphazene as raw materials, and the flame retardant smoke suppressant prepared by the method has higher thermal stability and flame retardant property when being used singly or in a compounding way, has better smoke suppressant property, has better application prospect in flame retardance, and provides a new thought for preparing the efficient flame retardant.
The vanillin-containing flame retardant prepared by the invention can be singly or compositely used as a flame retardant to be added into materials needing to improve the flame retardant property to prepare corresponding flame retardant materials, when the vanillin-containing flame retardant is added into epoxy resin, the flame retardant effect of the obtained flame retardant epoxy resin is greatly improved, the generation of smoke can be reduced, and toxic and harmful gases (such as CO and CO) are greatly reduced 2 ) Has wide industrial application prospect.
Drawings
Fig. 1 is a TG chart of the hcvm in example 1 of the present invention.
FIG. 2 is a graph of the Heat Release Rate (HRR) of the composite in cone calorimeter after addition of the epoxy resin and flame retardant.
FIG. 3 is a graph of smoke release rate (SPR) in a cone calorimeter of a composite material after addition of an epoxy resin and a flame retardant.
FIG. 4 is a graph of total smoke generation (TSP) in a cone calorimeter for a composite after epoxy resin and flame retardant addition.
FIG. 5 is a graph of carbon monoxide formation (COP) in cone calorimeter for a composite material after addition of an epoxy resin and flame retardant.
FIG. 6 is a graph showing carbon dioxide formation (CO) in a composite material in cone calorimeter after addition of a flame retardant 2 P) graph.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
The procedures and methods not described in detail in the examples below are conventional methods well known in the art, and the reagents used in the examples are all analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the object of the invention. Hexachlorocyclotriphosphazene and melamine used in the following examples were analytically pure and purchased from Shanghai Meilin Biochemical technologies Co., ltd; vanillin is analytically pure and purchased from the company Miou chemical reagent, inc. of Tianjin, inc., piperazine pyrophosphate is purchased from Huihang chemical industry.
Example 1
7.2mmol of hexachlorocyclotriphosphazene was dissolved in 100mL of tetrahydrofuran and placed in a three-necked flask with condensing reflux, magnetic stirring and nitrogen protection, 52mmol of vanillin was then dissolved in 100mL of tetrahydrofuran and added dropwise to the three-necked flask dropwise, reacted at 70℃for 36 hours, filtered, washed three times with absolute ethanol and deionized water, respectively, and dried under vacuum at 60℃for 24 hours to give the intermediate hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene (HCPV).
1mmol of HCPV is dissolved in 50mL of dimethyl sulfoxide at 25 ℃, the pH is regulated to about 10 by 1mol/L of sodium hydroxide solution, then the temperature is raised to 90 ℃, 2mmol of melamine is added, the pre-polymerization is carried out for 3 hours at 90 ℃, the pH is regulated to 3 by hydrochloric acid, then the temperature is raised to 140 ℃ for reaction for 3 hours, white floccules appear, the temperature is cooled to room temperature, the filtration is carried out, the precipitate is washed twice by deionized water, and the final product HCPMM is obtained by freeze drying.
Example 2
7.2mmol of hexachlorocyclotriphosphazene was dissolved in 100mL of tetrahydrofuran and placed in a three-necked flask with condensing reflux, magnetic stirring and nitrogen protection, 52mmol of vanillin was then dissolved in 100mL of tetrahydrofuran and added dropwise to the three-necked flask dropwise, reacted at 70℃for 36 hours, filtered, washed three times with absolute ethanol and deionized water, respectively, and dried under vacuum at 60℃for 24 hours to give the intermediate hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene (HCPV).
1mmol of HCPV is dissolved in 50mL of dimethyl sulfoxide at 25 ℃, the pH is regulated to about 10 by 1mol/L of sodium hydroxide solution, then the temperature is raised to 90 ℃, 4mmol of melamine is added, the pre-polymerization is carried out for 3 hours at 90 ℃, the pH is regulated to 3 by hydrochloric acid, then the temperature is raised to 140 ℃ for reaction for 3 hours, white floccules appear, the temperature is cooled to room temperature, the filtration is carried out, the precipitate is washed twice by deionized water, and the final product HCPMM is obtained by freeze drying.
Example 3
7.2mmol of hexachlorocyclotriphosphazene was dissolved in 100mL of tetrahydrofuran and placed in a three-necked flask with condensing reflux, magnetic stirring and nitrogen protection, 52mmol of vanillin was then dissolved in 100mL of tetrahydrofuran and added dropwise to the three-necked flask dropwise, reacted at 70℃for 36 hours, filtered, washed three times with absolute ethanol and deionized water, respectively, and dried under vacuum at 60℃for 24 hours to give the intermediate hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene (HCPV).
1mmol of HCPV is dissolved in 50mL of dimethyl sulfoxide at 25 ℃, the pH is regulated to about 10 by 1mol/L of sodium hydroxide solution, then the temperature is raised to 90 ℃, 6mmol of melamine is added, the pre-polymerization is carried out for 3 hours at 90 ℃, the pH is regulated to 3 by hydrochloric acid, then the temperature is raised to 140 ℃ for reaction for 3 hours, white floccules appear, the temperature is cooled to room temperature, the filtration is carried out, the precipitate is washed twice by deionized water, and the final product HCPMM is obtained by freeze drying.
Comparative example 1
Weighing 100g of epoxy resin in a clean suction filter flask, heating at 60 ℃ and 180rpm, stirring for 20min to drive bubbles, adding 11.0g of m-phenylenediamine, and stirring for 20min to ensure that the m-phenylenediamine is uniformly dispersed; pouring a die, placing in an oven with the vacuum degree of 0.05MPa for 20min at 60 ℃, then transferring into an oven with the vacuum degree of 80 ℃ for heating for 120min, adjusting the temperature to 150 ℃, and heating and curing for 220min; after cooling to room temperature, the bars were removed.
Comparative example 2
Weighing 100g of epoxy resin, putting into a clean suction filter flask, heating and stirring for 20min at 60 ℃ and 180rpm, then adding 4g of piperazine pyrophosphate (PAPP), stirring for 20min to drive bubbles, adding 11.0g of m-phenylenediamine, and stirring for 20min to ensure that the m-phenylenediamine is uniformly dispersed; pouring a die, placing in an oven with the vacuum degree of 0.05MPa for 20min at 60 ℃, then transferring into an oven with the vacuum degree of 80 ℃ for heating for 120min, adjusting the temperature to 150 ℃, heating and solidifying for 220min, cooling to room temperature, and taking out a spline to obtain the EP material.
Example 4
Weighing 100g of epoxy resin, putting into a clean suction filter flask, heating and stirring for 20min at 60 ℃ and 180rpm, then adding 2g of HCPMM prepared in example 1, stirring for 20min to drive off bubbles, adding 11.0g of m-phenylenediamine, and stirring for 20min to ensure that the m-phenylenediamine is uniformly dispersed; pouring a die, placing in an oven with the vacuum degree of 0.05MPa for 20min at 60 ℃, then transferring into an oven with the vacuum degree of 80 ℃ for heating for 120min, adjusting the temperature to 150 ℃, heating and solidifying for 220min, cooling to room temperature, and taking out a spline to obtain the EP material.
Example 5
According to the process conditions of example 4, 4g of the HCPMM flame retardant prepared in example 1 was added to the epoxy resin, respectively, to prepare the corresponding EP material.
Example 6
The corresponding EP material was prepared by adding 3.5g of the HCPM flame retardant prepared in example 1 and 0.5g of PAPP, respectively, to the epoxy resin according to the process conditions of example 4.
Example 7
The corresponding EP material was prepared by adding 3g of the HCPMM flame retardant prepared in example 1 and 1g of PAPP to the epoxy resin, respectively, according to the process conditions of example 4.
Example 8
The corresponding EP material was prepared by adding 2.5g of the HCPM flame retardant prepared in example 1 and 1.5g of PAPP to the epoxy resin, respectively, according to the process conditions of example 4.
The experimental method comprises the following steps:
CONE calorimetric analysis (CONE): cone calorimetric test using icone plus assay (FTT company, uk) with sample size 100mm x 3mm, irradiation power 50kW/m 2 。
The detection results are as follows:
TABLE 1 influence of the inventive products on the flame retardant properties of flame retardant EP
Table 1 is the cone calorimetric specification data for comparative examples 1, 2 and examples 4, 5, 6, 7 and 8, as seen from comparative example 1 and examples 4 and 5, when HCPMM flame retardant was added alone, PHRR, TSP, SPR, COP and CO compared to comparative example 1 2 P decreases somewhat. By contrast, comparative example 1, comparative example 2 and example 7, PHRR, TSP, COP and CO of the composite when compounded with 3 parts piperazine pyrophosphate (PAPP) using 1 part HCPMM 2 P decreases further.
FIG. 1 is a TG pattern of a HCPM synthesized according to example 1 of the invention, T 95％ The maximum weight loss rate was reached at 221.1℃and 247.4℃at a maximum weight loss rate of 12.47%/min and a final residual mass of 39.76%.
FIGS. 2 to 6 show the Heat Release Rate (HRR), smoke release rate (SPR), total smoke release (TSP), carbon monoxide formation (COP) and carbon dioxide formation (CO) of the epoxy resin composites prepared in comparative example 1 (pure epoxy resin), comparative example 2, examples 4, 5 and 7 in a cone calorimetric test 2 P) graph. As can be seen from FIG. 2, the Peak Heat Release Rate (PHRR) of the pure epoxy resin reaches 1223kW/m 2 The heat release rate is very high, a large amount of heat can be released during combustion, and the heat release device has great harm; after the addition of the flame retardant, it can be seen from the graph that there is a significant decrease in PHRR, especially in example 5, to 886kW/m 2 Which is reduced by 27.6% compared to pure EP. FIG. 3 shows SPR plots with a PSPR of 0.342m for pure EP 2 As for other examples, the PSPR of example 5 was reduced to 0.220m 2 And/s, reduced by 35.7% compared with pure EP. FIG. 4 shows the TSP of pure EP 32.44m 2 Example 5 and example 4 were reduced to 24.88m respectively 2 And 26.87m 2 Reduced by 23.3% and 17.2%, respectively, compared to pure EP, and by comparison with comparative example 2 and example 7, it was found that TSP was reduced by 8.71% and HRR was essentially unchanged when 1 part hcvm was used in combination with 3 parts PAPP. By comparison with example 7, the HRR was found to decrease by 63.4% and TSP was found to increase by 4.4%. FIGS. 5 and 6 are COP and CO, respectively 2 P-graph, COP and CO of pure EP 2 P was 0.037g/s and 0.99g/s, respectively, and example 5 was reduced to 0.023g/s and 0.67g/s, respectively, which were 37.8% and 32.3% lower than pure EP, respectively. As can be seen from comparative examples 1, 2 and 7, there is a synergistic effect between HCPMM and PAPP, in which COP, CO 2 P and HRR were both lower than comparative examples 1 and 2, TSP was 4.4% higher than comparative example 1 and 8.71% lower than comparative example 2. The vanillin-containing flame retardant prepared by the invention has good flame retardant and smoke suppression effects, achieves the purpose of the invention and is consistent with the expected effects.

Claims (8)

1. The preparation method of the vanillin-containing bio-based flame-retardant smoke suppressant is characterized by comprising the following steps of: dissolving hexachlorocyclotriphosphazene in tetrahydrofuran, placing the mixture in a three-necked flask with condensing reflux, magnetic stirring and nitrogen protection, dissolving vanillin in the tetrahydrofuran, dropwise adding the mixture into the three-necked flask, reacting for 24-48 hours at 65-75 ℃, filtering, respectively washing with absolute ethyl alcohol and deionized water for three times, and vacuum drying at 60-80 ℃ for 18-24 hours to obtain an intermediate hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene;
dissolving hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene in dimethyl sulfoxide, placing the dimethyl sulfoxide into a three-necked flask, adjusting the pH to 9-10 by using a sodium hydroxide solution, weighing melamine with the concentration of 0.002-0.006mol, adding the melamine, heating to 80-100 ℃, pre-polymerizing for 2-4 hours, adjusting the pH to 2-4 by using hydrochloric acid, then heating to 130-150 ℃ for reacting for 3-4 hours to generate white floccules, cooling to room temperature, filtering, washing the precipitate twice by using deionized water, and obtaining the final product melamine crosslinked hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene through freeze drying; the mol ratio of the hexa- (4-aldehyde-2-methoxy-phenoxy) -cyclotriphosphazene to the melamine is 12-1:6.
2. The method for preparing the vanillin-containing bio-based flame retardant smoke suppressant according to claim 1, wherein the molar ratio of hexachlorocyclotriphosphazene to vanillin is 1:6-1:8.
3. Use of a vanillin-containing bio-based flame retardant smoke suppressant prepared by the method of claim 1 or 2 for preparing a flame retardant material.
4. The use according to claim 3, wherein the flame retardant material is a flame retardant epoxy resin.
5. A flame retardant epoxy resin comprising an epoxy resin and a biobased flame retardant smoke suppressant prepared according to the method of claim 1 or 2; the mass ratio of the bio-based flame-retardant smoke suppressant to the epoxy resin is 1-6:100.
6. The flame retardant epoxy resin of claim 5, further comprising piperazine pyrophosphate, wherein the mass ratio of the bio-based flame retardant smoke suppressant to the piperazine pyrophosphate is 1:0.5-3.
7. The flame retardant epoxy resin of claim 6, wherein the mass ratio of the bio-based flame retardant smoke suppressant to the piperazine pyrophosphate is 1:3.
8. The flame-retardant epoxy resin according to claim 5, wherein the method for preparing the flame-retardant epoxy resin comprises the following steps: weighing epoxy resin, heating and stirring in a suction filtration bottle at 60 ℃ and 180rpm for 20min, then adding a bio-based flame-retardant smoke suppressant, stirring for 20min to drive bubbles, adding m-phenylenediamine, and stirring for 20min to ensure uniform dispersion of the m-phenylenediamine; pouring a mold, placing in an oven with the vacuum degree of 0.05MPa for 20min at 60 ℃, then transferring into an oven with the vacuum degree of 80 ℃ for heating for 120min, adjusting the temperature to 150 ℃, heating and solidifying for 220min, cooling to room temperature, and taking out a spline to obtain the flame-retardant epoxy resin.
CN202210743729.2A 2022-06-28 2022-06-28 Preparation method of vanillin-containing bio-based flame-retardant smoke suppressant and flame-retardant epoxy resin Active CN115073686B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108752637A (en) * 2018-08-01 2018-11-06 河北大学 A kind of ZIF-8 encapsulation hexachlorocyclotriph,sphazene fire retardant, preparation method and application and fire retarding epoxide resin
CN109400651A (en) * 2017-08-15 2019-03-01 中蓝晨光化工研究设计院有限公司 A kind of fire retardant and preparation method thereof of the structure of-DOPO containing phosphonitrile
CN110746646A (en) * 2019-09-16 2020-02-04 皖西学院 Biomass-based flame retardant and preparation method thereof
CN111116663A (en) * 2019-12-11 2020-05-08 华南理工大学 Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof
CN112411184A (en) * 2020-11-02 2021-02-26 苏州大学 Finishing process of formaldehyde-free flame-retardant wool product

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109400651A (en) * 2017-08-15 2019-03-01 中蓝晨光化工研究设计院有限公司 A kind of fire retardant and preparation method thereof of the structure of-DOPO containing phosphonitrile
CN108752637A (en) * 2018-08-01 2018-11-06 河北大学 A kind of ZIF-8 encapsulation hexachlorocyclotriph,sphazene fire retardant, preparation method and application and fire retarding epoxide resin
CN110746646A (en) * 2019-09-16 2020-02-04 皖西学院 Biomass-based flame retardant and preparation method thereof
CN111116663A (en) * 2019-12-11 2020-05-08 华南理工大学 Flame-retardant curing agent containing phosphazene/aromatic imine composite structure and preparation method thereof
CN112411184A (en) * 2020-11-02 2021-02-26 苏州大学 Finishing process of formaldehyde-free flame-retardant wool product

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