CN116102955B - Flame-retardant epoxy floor coating and preparation method thereof - Google Patents
Flame-retardant epoxy floor coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L2201/00—Properties
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The application relates to the field of floor coatings, and particularly discloses a flame-retardant epoxy floor coating and a preparation method thereof. The flame-retardant epoxy floor coating comprises the following components in parts by weight, 90-110 parts of epoxy resin; 15-35 parts of phosphorus auxiliary agent; 5-12 parts of a charring agent; 5-15 parts of filler; the phosphorus auxiliary agent is prepared by the following method: continuous nitration reaction: mixing concentrated sulfuric acid with concentrated nitric acid under stirring to obtain mixed acid, mixing phosphaphenanthrene with the mixed acid for reaction, separating an organic phase after the reaction is finished, evaporating a solvent, reacting the obtained product with the mixed acid, neutralizing the organic phase after the reaction is finished, and recrystallizing to obtain nitrophosphaphenanthrene; ammonification reaction: and mixing and reacting the nitrophosphaphenanthrene, hydrochloric acid and a catalyst to obtain the phosphorus auxiliary agent. The flame-retardant epoxy floor coating disclosed by the application can reduce the influence of a phosphorus flame retardant on the thermal stability of epoxy resin, so that the flame retardant property of the coating is further improved.
Description
Technical Field
The application relates to the field of floor coatings, in particular to a flame-retardant epoxy floor coating and a preparation method thereof.
Background
The epoxy resin has excellent corrosion resistance, wear resistance, slip resistance and other characteristics, so that the epoxy resin is applied to floor coatings and has wide application. However, the Limiting Oxygen Index (LOI) of the common epoxy resin is low (about 19.8%), the epoxy resin is easy to ignite, and after ignition, a material matrix is decomposed to generate inflammable gas, so that a chain reaction is formed, and self-extinguishment is difficult. In order to reduce potential safety hazards such as fire hazards, flame retardants are often added to epoxy resin coatings in practical applications.
At present, the flame retardant with the largest yield and usage amount is a halogen flame retardant, but when the flame retardant is burnt, the epoxy resin containing the halogen flame retardant can release a great amount of smoke, and the smoke contains halogenated diphenyl dioxin and diphenyl furan, which can cause harm to the immune and regeneration systems of human bodies and pollute the environment. In order to reduce the harm to human bodies and the pollution to the environment, phosphorus flame retardants are used in the prior art to replace halogen flame retardants, such as a flame retardant epoxy resin coating, which comprises epoxy resin, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 4,4' -diaminodiphenyl sulfone, so that the production of smoke and toxic gas is effectively reduced while the flame retardance is ensured to a certain extent.
However, the introduction of phosphaphenanthrene can reduce the thermal stability of the epoxy resin, so that the ignition time is advanced, and after the content of phosphaphenanthrene in the material reaches a certain degree, the flame retardant property of the material is maintained unchanged, and the improvement of the flame retardant property of the material is limited. Therefore, it is necessary to develop a coating having better flame retardant properties and good thermal stability.
Disclosure of Invention
In order to reduce the influence of phosphaphenanthrene on epoxy resin and further improve the flame retardant property of the material, the application provides a flame retardant epoxy floor coating and a preparation method thereof.
In a first aspect, the application provides a flame-retardant epoxy floor coating, which adopts the following technical scheme:
a flame-retardant epoxy floor coating comprises the following components in parts by weight,
the phosphorus auxiliary agent is prepared by the following method:
continuous nitration reaction: mixing concentrated sulfuric acid with concentrated nitric acid under stirring to obtain mixed acid, mixing phosphaphenanthrene with the mixed acid for reaction, separating an organic phase after the reaction is finished, evaporating a solvent, reacting the obtained product with the mixed acid, neutralizing the organic phase after the reaction is finished, and recrystallizing to obtain nitrophosphaphenanthrene;
ammonification reaction: and mixing and reacting the nitrophosphaphenanthrene, hydrochloric acid and a catalyst to obtain the phosphorus auxiliary agent.
By adopting the technical scheme, a plurality of amino groups are generated on the phosphaphenanthrene molecule through continuous nitration reaction and ammonification reaction. The amino group and the epoxy group undergo a ring-opening reaction to cure the epoxy resin. In the process, the phosphorus auxiliary agent is connected to the epoxy resin body, and the phosphaphenanthrene subjected to the nitration reaction and the ammonification reaction has a plurality of amino groups, so that a plurality of reaction sites can be provided, the connection strength of the phosphaphenanthrene and the epoxy resin is effectively improved, the crosslinking degree of the epoxy resin is improved, the influence of the phosphaphenanthrene on the thermal stability of the epoxy resin is effectively reduced, and further the further improvement of the flame retardant property of the phosphaphenanthrene on the epoxy resin is ensured.
Preferably, the weight ratio of the phosphaphenanthrene to the nitric acid is 1 (1.2-1.75).
Preferably, the weight ratio of the nitrophosphaphenanthrene to the hydrochloric acid to the catalyst is 1 (0.8-1): 0.6-0.8.
Through adopting above-mentioned technical scheme, can guarantee abundant nitrosation, provide as far as possible nitro to guarantee the formation of a plurality of amino, thereby provide a plurality of reaction sites for crosslinking solidification, improve epoxy's crosslink strength, thereby reduce the influence of phosphaphenanthrene to epoxy thermal stability, be convenient for further promote the fire behaviour of material.
Preferably, the nitrosed phosphaphenanthrene is pre-reacted with hydroxylamine hydrochloride prior to the ammoniation reaction.
Through adopting above-mentioned technical scheme, after the nitration, through the reaction of benzene ring and hydroxylamine hydrochloride in the phosphaphenanthrene, further increase the quantity of amino on the benzene ring to increase the reaction site volume of phosphaphenanthrene, effectively improved epoxy's crosslink strength, thereby improve the thermal stability of material, guarantee the further promotion to material flame retardant property.
Preferably, the epoxy resin comprises a low epoxy equivalent epoxy resin having an epoxy equivalent of between 190 and 450g/eq and a high epoxy equivalent epoxy resin having an epoxy equivalent of between 700 and 1400g/eq, the weight ratio of the high epoxy equivalent epoxy resin to the low epoxy equivalent epoxy resin being 1 (2-9).
More preferably, the weight ratio of the high epoxy equivalent epoxy resin to the low epoxy equivalent epoxy resin is 1 (5-8).
Through adopting above-mentioned technical scheme, through the epoxy mix use of high epoxy equivalent and low epoxy equivalent, low epoxy can guarantee the crosslink strength of material, reduces the influence of phosphaphenanthrene to the material, improves the stability of material to guarantee the fire behaviour of material. Meanwhile, the epoxy resin with high epoxy equivalent can reduce the influence on the mechanical properties of the material, thereby improving the comprehensive properties of the material.
Preferably, the char-forming agent is one or more of starch, triazine char-forming agent and piperazine char-forming agent.
Through adopting above-mentioned technical scheme, when epoxy takes place to burn, phosphaphenanthrene decomposition reaction produces substances such as metaphosphoric acid and phosphoric acid, promotes the carbonizing agent and forms charcoal, and in the carbonizing process, the gas that phosphaphenanthrene and carbonizing agent pyrolysis produced plays the effect of foaming agent, makes epoxy coating surface produce the charcoal layer, and the charcoal layer has effectively reduced the heat that passes to epoxy coating, cooperates with phosphaphenanthrene, carries out fire-retardant from gaseous phase and condensed phase two aspects to fire-retardant efficiency has effectively been improved.
Preferably, the filler is one or more of aluminum hydroxide, titanium dioxide, magnesium hydroxide and brucite.
More preferably, the filler is a mixture of magnesium hydroxide and aluminum hydroxide, and the weight ratio of the magnesium hydroxide to the aluminum hydroxide is 1 (2-4).
By adopting the technical scheme, after the carbon layer is generated by combustion, the magnesium hydroxide and the aluminum hydroxide can generate a reinforcing effect on the coating and the carbon layer, so that the strength of the coating and the carbon layer is ensured. Meanwhile, the magnesium hydroxide and the aluminum hydroxide can be heated to generate decomposition reaction and absorb heat, the aluminum hydroxide has larger heat absorption capacity than the magnesium hydroxide, but lower decomposition temperature than the magnesium hydroxide, and the dehydration and heat absorption reaction can be carried out within the range of 23-455 ℃ when the magnesium hydroxide and the aluminum hydroxide are used, so that the combustion of the high polymer material can be inhibited within a wider range. In addition, the concentration of the combustible gas can be reduced by the water vapor generated by the reaction, and residues are deposited on the surface of the polymer to play a role in isolating oxygen, so that the flame retardant effect of the material is further improved.
In a second aspect, the application provides a preparation method of a flame-retardant epoxy floor coating, which adopts the following technical scheme: the preparation method of the flame-retardant epoxy floor coating comprises the following preparation steps: and heating the epoxy resin, then adding the phosphorus auxiliary agent, the char forming agent and the filler, and stirring and mixing to obtain the epoxy floor coating.
By adopting the technical scheme, after the epoxy resin is heated, the fluidity of the resin can be improved, so that the mixing effect of various auxiliary agents, fillers and the epoxy resin is facilitated, the uniform distribution of various components in the coating is ensured, and the performance of each component is ensured.
In summary, the application has the following beneficial effects:
1. because the phosphaphenanthrene is adopted as a flame retardant component, and the phosphaphenanthrene has active P-H groups which are easy to break, the phosphaphenanthrene can react with other unsaturated compounds, so that the phosphaphenanthrene groups are introduced into other molecules to form novel molecules, the flame retardant property of the material is improved, a plurality of amino groups are formed on the phosphaphenanthrene molecules through nitration and ammoniation, in the curing process of the epoxy resin, the amino groups and the epoxy groups are subjected to ring-opening reaction, so that a plurality of positions of the phosphaphenanthrene are connected with the epoxy material, the crosslinking strength of the coating is improved, the influence of the introduction of the phosphaphenanthrene on the thermal stability of the material is reduced, and the improvement effect of the phosphaphenanthrene molecules on the flame retardant property of the material is further improved.
2. According to the application, before the ammoniation reaction, the pre-ammoniation treatment is carried out, so that the number of amino groups on the phosphaphenanthrene structure is further increased, the connection strength of the phosphaphenanthrene and the epoxy resin is further increased, the crosslinking degree of the epoxy resin is further increased, the thermal stability of the epoxy resin is ensured, the ignition point is increased, and the flame retardant property of the material is further improved.
3. In the application, magnesium hydroxide and aluminum hydroxide are preferably used as fillers, as the magnesium hydroxide and the aluminum hydroxide are heated to generate decomposition reaction and absorb heat, and the decomposition temperatures of the magnesium hydroxide and the aluminum hydroxide are different, when the magnesium hydroxide and the aluminum hydroxide are compounded and used, a wider flame-retardant range can be formed, the flame-retardant effect of the material is improved, meanwhile, the generated vapor is dispersed in a gas phase, the concentration of combustible gas is reduced, the generated residues are deposited on the surface of a polymer and participate in the formation of a carbon layer, the strength of the carbon layer is improved, and the isolation effect of oxygen is ensured, so that the flame-retardant effect of the material is further ensured.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
Examples of preparation of starting materials and/or intermediates
Preparation example 1
The phosphorus auxiliary agent is prepared by the following operations:
continuous nitration reaction: 43.9mL of 65wt% concentrated nitric acid is added into a round bottom flask, a stirrer is added, 44mL of 98wt% concentrated sulfuric acid is added dropwise while stirring, and the prepared mixed acid is divided into two identical parts; under the ice bath condition, dropwise adding a tetrahydrofuran solution of phosphaphenanthrene (prepared by dissolving 40g of phosphaphenanthrene in 100g of tetrahydrofuran) into one part of mixed acid, controlling the dropwise adding time to be 1.5h, heating to 80 ℃ after the dropwise adding is completed, reacting for 2h, cooling to room temperature (25 ℃), layering, taking an organic phase, distilling off a solvent at 120 ℃, mixing the obtained product with another part of mixed acid solution, heating the system temperature to 100 ℃, stirring and reacting for 1.5h, cooling to 70 ℃, mixing the reaction solution with 80mL of deionized water, stirring, cooling and filtering, then adding 50mL of deionized water, stirring at 70 ℃, fully dissolving the product, adding sodium carbonate powder to PH=8, cooling to room temperature, carrying out suction filtration, and recrystallizing by using 30mL of 95wt% ethanol to obtain 53.7g of nitrophosphaphenanthrene.
Ammonification reaction: 45g of nitrophosphaphenanthrene and 34g of catalyst are added into a round-bottom flask, stirred and mixed, 125mL of 30wt% hydrochloric acid solution is dropwise added into the round-bottom flask at the temperature of 23 ℃, the dropwise adding time is controlled to be 0.5h, after the dropwise adding is completed, the system is heated to 100 ℃, the temperature is kept for 1h for reaction, 100mL of 0.6g/mL of sodium hydroxide aqueous solution is added, distillation and distillate collection are carried out, sodium chloride salting out is carried out, liquid-separated extraction is carried out, and potassium hydroxide is dried, thus obtaining the phosphorus-based auxiliary agent.
Wherein the phosphaphenanthrene is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the catalyst is tin powder.
PREPARATION EXAMPLES 2 to 5
A phosphorus-based additive is different from that of preparation example 1 in the addition amounts of phosphaphenanthrene and concentrated nitric acid, and is described in Table 1 below.
TABLE 1
Preparation examples 6 to 9
A phosphorus-based additive is different from that of preparation example 3 in that the amounts of nitrophosphaphenanthrene, hydrochloric acid solution and catalyst added are different from those of preparation example 3, and is described in Table 2 below.
TABLE 2
Preparation example 10
A phosphorus-based auxiliary agent is different from preparation example 3 in that 25mL of deionized water and 3.6g (0.036 mol) of potassium bicarbonate and 2.2g (0.031 mol) of hydroxylamine hydrochloride are stirred for 0.5h, 3.5g (0.016 mol) of phosphaphenanthrene is added, reaction is carried out at 25℃for 2.5h, then 25mL of a 4mol/L aqueous potassium hydroxide solution is added at 5℃for 3h, filtration and water washing are carried out, and the obtained substance is mixed with 50mL of a 1mol/L aqueous hydrochloric acid solution alone, stirred for 1h, filtered and washed with water, dried to obtain pretreated phosphaphenanthrene nitrate, and ammonification reaction is carried out using the obtained product.
Examples
Example 1
The epoxy floor coating comprises the following components in parts by weight as shown in table 3 and is prepared by the following steps:
and heating the epoxy resin to 70 ℃, adding the phosphorus auxiliary agent, the char forming agent and the filler, stirring for 2 hours, and cooling to obtain the epoxy floor coating.
Wherein the epoxy resin is bisphenol A diglycidyl ether, purchased from Hubei cloud magnesium technology Co., ltd., model number 621, the phosphorus auxiliary agent is prepared by preparation example 1, the filler is silicon dioxide, and the char former is pentaerythritol.
Examples 2 to 3
An epoxy floor coating was different from example 1 in that the components and their respective weights are shown in table 3.
TABLE 3 Table 3
Examples 4 to 12
An epoxy floor coating was different from example 2 in the use of phosphorus-based adjuvants as detailed in Table 4 below.
| Examples | Preparation example |
| Example 2 | Preparation example 1 |
| Example 4 | Preparation example 2 |
| Example 5 | Preparation example 3 |
| Example 6 | Preparation example 4 |
| Example 7 | Preparation example 5 |
| Example 8 | Preparation example 6 |
| Example 9 | Preparation example 7 |
| Example 10 | Preparation example 8 |
| Example 11 | Preparation example 9 |
| Example 12 | Preparation example 10 |
TABLE 4 Table 4
Examples 13 to 15
An epoxy floor coating was different from example 12 in that the epoxy resin was a mixture of high epoxy equivalent epoxy resin and low epoxy equivalent epoxy resin, the weight ratio of high epoxy equivalent epoxy resin to low epoxy equivalent epoxy resin was 1:1, and the high epoxy equivalent epoxy resin and the low epoxy equivalent epoxy resin were pre-mixed prior to preparing the epoxy floor coating as detailed in table 5 below.
TABLE 5
Wherein the high epoxy equivalent epoxy resin and the low epoxy equivalent epoxy resin are purchased from south asia of taiwan; the high epoxy equivalent epoxy resin in example 13 was identified as NPES-903 and the low epoxy equivalent epoxy resin was identified as NPES-301; the high epoxy equivalent epoxy resin in example 14 was identified as NPES-903H and the low epoxy equivalent epoxy resin was identified as NPEL-128S; the high epoxy equivalent epoxy resin in example 15 was identified as NPES-907L and the low epoxy equivalent epoxy resin was identified as NPEL-128.
Example 16
An epoxy floor coating was different from example 14 in that the weight ratio of high epoxy equivalent epoxy resin to low epoxy equivalent epoxy resin was 1:2.
Example 17
An epoxy floor coating was different from example 14 in that the weight ratio of high epoxy equivalent epoxy resin to low epoxy equivalent epoxy resin was 1:5.
Example 18
An epoxy floor coating was different from example 14 in that the weight ratio of high epoxy equivalent epoxy resin to low epoxy equivalent epoxy resin was 1:6.
Example 19
An epoxy floor coating was different from example 14 in that the weight ratio of high epoxy equivalent epoxy resin to low epoxy equivalent epoxy resin was 1:8.
Example 20
An epoxy floor coating was different from example 14 in that the weight ratio of high epoxy equivalent epoxy resin to low epoxy equivalent epoxy resin was 1:9.
Example 21
An epoxy floor coating was different from example 14 in that the weight ratio of high epoxy equivalent epoxy resin to low epoxy equivalent epoxy resin was 1:11.
Example 22
An epoxy floor coating differs from example 18 in that the char-forming agent is starch.
Example 23
An epoxy floor coating is different from example 18 in that the char-forming agent is a mixture of triazine char-forming agent and piperazine char-forming agent, and the weight ratio of the triazine char-forming agent to the piperazine char-forming agent is 1:1; wherein, the triazine charring agent is purchased from Jinan backfire new material Co., ltd, the brand is FR501, the piperazine charring agent is piperazine pyrophosphate, and the triazine charring agent is purchased from Jinan blue Acantha commercial Co., ltd.
Example 24
An epoxy floor coating was different from example 23 in that the filler was brucite.
Example 25
An epoxy floor coating was different from example 23 in that the filler was a mixture of magnesium hydroxide and aluminum hydroxide, and the weight ratio of magnesium hydroxide to aluminum hydroxide was 1:1.
Example 26
An epoxy floor coating was different from example 23 in that the filler was a mixture of magnesium hydroxide and aluminum hydroxide, and the weight ratio of magnesium hydroxide to aluminum hydroxide was 1:2.
Example 27
An epoxy floor coating was different from example 23 in that the filler was a mixture of magnesium hydroxide and aluminum hydroxide, and the weight ratio of magnesium hydroxide to aluminum hydroxide was 1:3.
Example 28
An epoxy floor coating was different from example 23 in that the filler was a mixture of magnesium hydroxide and aluminum hydroxide, and the weight ratio of magnesium hydroxide to aluminum hydroxide was 1:4.
Example 29
An epoxy floor coating was different from example 23 in that the filler was a mixture of magnesium hydroxide and aluminum hydroxide, and the weight ratio of magnesium hydroxide to aluminum hydroxide was 1:5.
Comparative example
Comparative example 1
An epoxy floor coating, different from example 1, in that the phosphorus auxiliary agent is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 4,4' -diaminodiphenyl sulfone is used as a curing agent, and the epoxy floor coating is prepared by the following steps:
and heating the epoxy resin to 70 ℃, adding the phosphorus auxiliary agent, the curing agent, the char forming agent and the filler, stirring for 2 hours, and cooling to room temperature to obtain the epoxy floor coating.
Comparative example 2
An epoxy floor coating, different from example 1, in that the phosphorus-based auxiliary agent was prepared by the following operations:
nitration reaction: 43.9mL of 65wt% concentrated nitric acid is added into a round bottom flask, a stirrer is added, 44mL of 98wt% concentrated sulfuric acid is dropwise added while stirring, under the ice bath condition, a tetrahydrofuran solution of phosphaphenanthrene (prepared by dissolving 40g of phosphaphenanthrene in 100g of tetrahydrofuran) is dropwise added into mixed acid, the dropwise adding time is controlled to be 1.5h, after the dropwise adding is finished, the temperature is raised to 80 ℃, the reaction is carried out for 3h, the room temperature (25 ℃) is cooled, the layers are separated, an organic phase is taken, a solvent is distilled out at 120 ℃, the reaction solution is mixed with 80mL of deionized water, stirred, cooled and filtered, 50mL of deionized water is then added, stirring is carried out at 70 ℃, the product is fully dissolved, sodium carbonate powder is added to pH=8, cooling to the room temperature is carried out, and suction filtration is carried out, 30mL of 95wt% ethanol is used for recrystallization, so that 46.2g of nitrophosphaphenanthrene is obtained.
Ammonification reaction: 45g of nitrophosphaphenanthrene and 34g of tin powder are added into a round-bottom flask, stirred and mixed, 15mL of 30wt% hydrochloric acid solution is dropwise added into the round-bottom flask at the temperature of 23 ℃, the dropwise adding time is controlled to be 0.5h, after the dropwise adding is completed, the system is heated to 100 ℃, the temperature is kept for 1h for reaction, 100mL of 0.6g/mL of sodium hydroxide aqueous solution is added, distillation is carried out, fractions are collected, sodium chloride salting out is used, liquid-separated extraction is carried out, and potassium hydroxide is dried, thus obtaining the phosphorus-based auxiliary agent.
Wherein the phosphaphenanthrene is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Performance test
UL94 flame retardant rating detection: adopting a Jiangsu Zhuo Heng measurement and control technology Co-Ltd CZF-5 type vertical combustion tester to test according to GB/T2408-2008 standard, wherein the spline size is 125mm 13.0mm 3.0mm;
limiting oxygen index detection: adopting a Nanjing Bright Lei Yiqi limited company JF-5 oxygen index determinator to test according to GB/T2406.1-2008 standard, wherein spline sizes are 80mm by 6.5mm by 3.0mm;
and (3) thermal weight loss detection: performing thermal weight loss analysis on 10mg sample by using Q50-TGA thermogravimetric analyzer, heating from 25deg.C to 800deg.C at heating rate of 10deg.C/min under nitrogen atmosphere, and recording corresponding temperature value (T) of sample at mass loss of 5% 5％ ) The higher the temperature value, the better the thermal stability of the sample, namely the better the flame retardant property;
the results of the detection are shown in Table 6 below.
TABLE 6
In contrast to comparative example 1, the phosphorus-based auxiliary agent used in examples 1 to 29 was 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide subjected to nitration and nitridation, so that the phosphaphenanthrene structure contained an amino group, and the phosphaphenanthrene and the epoxy resin were subjected to a crosslinking reaction by the reaction of the amino group and the epoxy group in the epoxy resin, so that the phosphaphenanthrene was disposed on the epoxy resin molecule, and it can be seen from the above table 6 that examples 1 to 29 effectively improved the volatilization of the phosphaphenanthrene, and ensured that the phosphaphenanthrene fully exerted a flame retardant effect. Meanwhile, the arrangement of a plurality of amino groups on the phosphaphenanthrene provides a plurality of reaction points of the phosphaphenanthrene and the epoxy resin, so that the crosslinking strength of the epoxy resin is effectively improved, the influence of the phosphaphenanthrene on the thermal stability of the epoxy resin is reduced, and the flame retardant property of the material is further improved.
In comparison with comparative example 2, when the phosphorus-based auxiliary agent was prepared in examples 1 to 29, the mixed acid was divided into two parts and the continuous nitration reaction was carried out in two steps, and it was found that the flame retardant properties of examples 1 to 29 were better in combination with Table 6 above. Of these, the components used in examples 1 to 3 were different in content, and it is found that the flame retardant performance of example 2 was best in combination with Table 6 above.
In comparison with example 2, examples 4-7 produced nitrophosphaphenanthrene with a different weight ratio of phosphaphenanthrene to nitric acid, and as shown in Table 6 above, examples 4-7 exhibited improved thermal stability and flame retardant properties, but examples 6 and 7 exhibited a smaller degree of improvement than examples 4 and 5. In comparison with example 5, examples 8-11 were ammonified with different weight ratios of phosphaphenanthrene, hydrochloric acid and catalyst, and it was found that the heat stability and flame retardant properties of example 5 were optimal in combination with Table 6 above.
In comparison with example 5, the pretreatment of nitrophosphaphenanthrene prior to the ammonification reaction in example 12, combined with Table 6 above, shows an increase in both the limiting oxygen content and the decomposition temperature, indicating an increase in the number of amino groups on the phosphaphenanthrene molecule.
In contrast to example 12, the epoxy resins used in examples 13-15 were mixtures of high epoxy equivalent epoxy resins and low epoxy equivalent epoxy resins, and the epoxy equivalent of the epoxy resins was different, and it is seen with reference to Table 6 above that the flame retardant properties of example 14 were optimal. In comparison with example 14, examples 17-19 are superior to examples 13-15 and examples 16, 21 in flame retardant properties, and wherein example 18 is the most advantageous, as can be seen from the above Table 6, in that the weight ratio of high epoxy equivalent epoxy resin to low epoxy equivalent epoxy resin in examples 16-21 is different.
As is clear from the above Table 6, the flame retardant properties of the coatings prepared in example 23 are better when a mixture of triazine char-forming agent and piperazine char-forming agent is used, as compared with example 18, which is different from the char-forming agent used in examples 22 and 23. In example 27, the magnesium hydroxide and aluminum hydroxide produced a synergistic effect, as seen from the above Table 6, in comparison with example 23, in which the fillers used in examples 24 to 29 were different, effectively improving the flame retardant properties of the coating.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. A flame-retardant epoxy floor coating is characterized by comprising the following components in parts by weight,
90-110 parts of epoxy resin;
15-35 parts of phosphorus auxiliary agent;
5-12 parts of a charring agent;
5-15 parts of filler;
the phosphorus auxiliary agent is prepared by the following method:
continuous nitration reaction: mixing 65wt% of concentrated sulfuric acid and 98wt% of concentrated nitric acid under stirring to obtain mixed acid, mixing phosphaphenanthrene and mixed acid for reaction, separating an organic phase after the reaction is finished, evaporating a solvent, reacting the obtained product with the mixed acid, neutralizing the organic phase after the reaction is finished, and recrystallizing to obtain nitrophosphaphenanthrene;
ammonification reaction: mixing and reacting the nitrophosphaphenanthrene, hydrochloric acid and a catalyst to obtain a phosphorus auxiliary agent;
the phosphaphenanthrene is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the catalyst is tin powder.
2. The flame retardant epoxy floor coating of claim 1, wherein: the weight ratio of the phosphaphenanthrene to the nitric acid is 1 (1.2-1.75).
3. The flame retardant epoxy floor coating of claim 1, wherein: the weight ratio of the nitrophosphaphenanthrene to the hydrochloric acid to the catalyst is 1 (0.8-1) (0.6-0.8).
4. The flame retardant epoxy floor coating of claim 1, wherein: prior to the ammonification reaction, the nitrosylated phosphaphenanthrene is pre-reacted with hydroxylamine hydrochloride.
5. The flame retardant epoxy floor coating of claim 1, wherein: the epoxy resin comprises low epoxy equivalent epoxy resin with the epoxy equivalent of 190-450g/eq and high epoxy equivalent epoxy resin with the epoxy equivalent of 700-1400g/eq, and the weight ratio of the high epoxy equivalent epoxy resin to the low epoxy equivalent epoxy resin is 1 (2-9).
6. The flame retardant epoxy floor coating of claim 5, wherein: the weight ratio of the high epoxy equivalent epoxy resin to the low epoxy equivalent epoxy resin is 1 (5-8).
7. The flame retardant epoxy floor coating of claim 1, wherein: the charring agent is one or more of starch, triazine charring agent and piperazine charring agent.
8. The flame retardant epoxy floor coating of claim 1, wherein: the filler is one or more of aluminum hydroxide, magnesium hydroxide and brucite.
9. The flame retardant epoxy floor coating of claim 8, wherein: the filler is a mixture of magnesium hydroxide and aluminum hydroxide, and the weight ratio of the magnesium hydroxide to the aluminum hydroxide is 1 (2-4).
10. The preparation method of the flame-retardant epoxy floor coating as claimed in any one of claims 1 to 9, which is characterized by comprising the following preparation steps: and heating the epoxy resin, then adding the phosphorus auxiliary agent, the char forming agent and the filler, and stirring and mixing to obtain the epoxy floor coating.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015689A (en) * | 2003-06-27 | 2005-01-20 | Dainippon Ink & Chem Inc | Epoxy resin composition, semiconductor encapsulation material and semiconductor device |
| CN107501859A (en) * | 2017-08-04 | 2017-12-22 | 武汉工程大学 | It is a kind of for the DOPO types curing agent of epoxy-resin systems and its application |
| CN107556458A (en) * | 2017-09-08 | 2018-01-09 | 江苏扬农锦湖化工有限公司 | A kind of phosphor-containing halogen-free type epoxy resin and preparation method thereof and composite flame-proof material |
| CN112048157A (en) * | 2020-09-14 | 2020-12-08 | 陈佳 | Preparation method of flame-retardant epoxy resin composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI397533B (en) * | 2008-04-11 | 2013-06-01 | Chang Chun Plastics Co Ltd | Novel phosphorus-containing compounds and their preparing process and use |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015689A (en) * | 2003-06-27 | 2005-01-20 | Dainippon Ink & Chem Inc | Epoxy resin composition, semiconductor encapsulation material and semiconductor device |
| CN107501859A (en) * | 2017-08-04 | 2017-12-22 | 武汉工程大学 | It is a kind of for the DOPO types curing agent of epoxy-resin systems and its application |
| CN107556458A (en) * | 2017-09-08 | 2018-01-09 | 江苏扬农锦湖化工有限公司 | A kind of phosphor-containing halogen-free type epoxy resin and preparation method thereof and composite flame-proof material |
| CN112048157A (en) * | 2020-09-14 | 2020-12-08 | 陈佳 | Preparation method of flame-retardant epoxy resin composite material |
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