CN105670231A - Preparing method of expandable carbon nitride flame-retardant epoxy resin - Google Patents
Preparing method of expandable carbon nitride flame-retardant epoxy resin Download PDFInfo
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- CN105670231A CN105670231A CN201610238941.8A CN201610238941A CN105670231A CN 105670231 A CN105670231 A CN 105670231A CN 201610238941 A CN201610238941 A CN 201610238941A CN 105670231 A CN105670231 A CN 105670231A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention relates to the technical field of flame retardance of a flame-retardant epoxy resin system, in particular to a preparing method of expandable carbon nitride flame-retardant epoxy resin. Expandable carbon nitride is used as fire retardant, epoxy resin is used as a base body, a curing agent is used for curing, and the flame-retardant epoxy resin composite material is prepared through a physical synergistic effect. A limit oxygen index and a scanning electron microscope photo analysis method is adopted for testing and representation, compared with expandable graphite, expandable carbon nitride is high in compatibility, and a more compact carbon layer is formed after the carbon nitride is heated and expands, has good heat insulation and oxygen insulation effects, and delays or restrains combustion of the system. The high-performance flame-retardant material which is free of halogen, efficient, free of toxicity and low in smoke generation is prepared successfully.
Description
Technical field
The present invention relates to the field of fire-proof technology of fire retarding epoxide resin system, particularly to the technology of preparing of inflatable carbonitride fire retarding epoxide resin.
Background technology
In recent years, rubber, plastics, synthetic fibers, coating, the big synthetic material of adhesive five, polymeric material and goods thereof obtain flourish, they replace just rapidly traditional iron and steel, metal, cement and the natural polymer such as timber, cotton, being applied to each department of the national economy such as industry, agricultural, military affairs, but most of high polymer belongs to combustible material, the fire and the damage to property that thereby result in are increasing. It is reported, the fire incident of nearly 2 years is frequent, national breaking out of fire in 2014 39.5 ten thousand, injured 1493 people of dead 1817 people, direct property loss 43.9 hundred million yuan; 2015, be informed of a case fire 33.8 ten thousand altogether in the whole nation, causes that 1742 people are dead, 1112 people are injured, direct property loss 39.5 hundred million yuan. In consideration of it, brainstrust appeal to adopt as far as possible do not fire, the building and ornament materials of difficult combustion. Therefore, the flame retardant type how improving synthetic high polymer and natural high polymer has become a urgent problem. Epoxy resin belongs to the one of thermosets, progress along with the development of industrial technology and materials industry, epoxy resin make consumption and application increasing, but epoxy resin itself is a kind of inflammable material, for the security of the lives and property of people, it is carried out fire-retardant being very important.
Fire retardant is the flame resistance improving material, in order to make material be reached certain flame-retardancy requirements by ignition resistant substrate, generally need to add considerable amount of fire retardant, but this often worsens the physical and mechanical properties of material, electric property and thermal stability greatly, also can cause some problems of material processing technique aspect simultaneously. Additionally, while improving Flame Retardancy, toxic gas volume and the smoke of generation during thermal decomposition or the burning of material should be reduced as far as possible. According to statistics, the death by accident in fire, having about 80% is cause with poisonous gas and suffocating of cigarette.
Expansible graphite is a kind of novel halogen-free flame-retardant agent expansible graphite (EG) aboundresources occurred in recent years, manufactures simple, cheap, and cigarette nontoxic, low, oneself becomes the focus of current expansion type flame retardant research.
Expansible graphite expands the heat insulation layer that expands formed and delays or suppress the burning of polymer mainly by own vol, and do not occurred between flame-retardant polymer or chemical action is seldom occurred, and the expanded graphite of formation adhesive force to each other is more weak after EG expansion, after polymeric matrix burns, expanded graphite cannot form firm foamed char, under the effect of flame pressure or heat convection current, the expanded graphite layer on surface is likely to be destroyed, formed " flying dust ", cause the forfeiture of adiabatic expansion layer, and then cause unburned polymer to be ignited, flame continues to propagate, flame retarding efficiency is limited.In recent years, it is used many flame retardant materials mixed with expansible graphite, makes compound flame retardant, make fire retardant mechanism become meteorological and carry out with condensed phase is fire-retardant simultaneously, greatly increase the fire resistance of matrix material. But, although compositional flame-retardant composite fire resistance is improved, but fire retardant addition is still very big, and the compatibility of fire retardant and base material still has much room for improvement, the mechanical property causing polymer matrix composite is subject to serious impact, find a kind of few additive, efficiently and be provided simultaneously with that gas phase is fire-retardant and the research of the fire retardant of the fire-retardant advantage of condensed phase still needs to deeply carry out.
In recent years, due to class graphite phase carbon nitride (g-C3N4) there is suitable photocatalysis band gap, excellent semiconducting behavior, at high temperature excellent stability, make it of great interest. At room temperature, g-C3N4It is by with 3-s-triazine ring (-C6N7) the flat sheet structure that is connected with hydrogen bond between the long-chain molecule honey primary amine that forms, each interannular is connected by the atom N of end, forms the pi-conjugated plane of wireless expansion. Owing to the hydrogen bond between honey primary amine exists, making substantial amounts of honey primary amine define orderly lamella, these pi-conjugated planes are piled up by the mode of class graphite, define the lamellar structure with certain defect. This structure imparts g-C3N4Excellent wearability, chemical heat stability and heat stability etc., have significantly high application prospect at catalyst carrier, energy storage material and fire proofing.
Class graphite phase carbon nitride (g-C3N4) have stable, high temperature resistant, there is the advantages such as suitable band structure, but due to the block structure of its multiple-level stack, thus g-C3N4Surface area only small, seriously constrain the application of its photocatalysis aspect. If the C of layer structure can be had3N4Prepare into g-C3N4Interbed compound, after high temperature puffing processes, its specific surface area will be substantially improved. The mechanism of intumescence of analogy expansible graphite, due to 3-s-triazine ring (-C6N7) on nitrogen-atoms on there are a pair lone pair electrons, reproducibility is slightly larger compared with the carbon atom C in plumbago single slice layer, and every 3 3-s-triazine ring (-C6N7) between there is nano aperture between a bigger atom, this hole can be that the attack of oxidant provides effective attack site, thus g-C3N4Interbed compound and the puffing process of oxidant reaction can produce more difficult combustion gas body; Meanwhile, g-C3N4Expanded by heating be subsequently formed can the fine and close carbon-coating of the effective burning of starvation and substrate, therefore in theory, g-C3N4Interbed compound will be provided simultaneously with the fire-retardant advantage with condensed phase of gas phase as fire retardant. But, although g-C3N4There is the layer structure of class graphite, but its each layer is all formed with hydrogen bonded by the long-chain macromolecule of honey primary amine, g-C3N4Each lamella in all have defect in various degree, cause use sulphuric acid, potassium permanganate and sodium nitrate oxidation intercalation method can destroy its layer structure. Therefore, it is necessary to study a kind of inflatable g-C3N4, to obtaining the high-performance flame-retardant material of Halogen, cigarette efficient, nontoxic, low a new generation.
Summary of the invention
For the defect of prior art, present invention aim at the preparation method that a kind of inflatable carbonitride fire retarding epoxide resin is provided, to improve the anti-flammability of fire retarding epoxide resin.
The present invention comprises the following steps:
1) when magnetic agitation, by the carbonitride (g-C of graphite-structure3N4) be dissolved in concentrated sulphuric acid, prepare carbonitride-concentrated sulfuric acid solution;Carbonitride-concentrated sulfuric acid solution is cooled to 8～10 DEG C, prepares inflatable Carbon Nitride Crystal; Adopt absolute ethanol washing to remove the sulfuric acid solution on inflatable Carbon Nitride Crystal surface inflatable Carbon Nitride Crystal, then by inflatable Carbon Nitride Crystal vacuum drying in vacuum drying case, prepare inflatable carbonitride;
2) after inflatable carbonitride first being mixed with the epoxy resin of de-soak again with the firming agent Homogeneous phase mixing of de-soak, be subsequently placed in curing mold solidify, prepare inflatable carbonitride fire retarding epoxide resin.
In order to prevent bubble from account for the volume of fire retarding epoxide resin, the fire resistance of fire retarding epoxide resin can be affected. The present invention needs to remove the bubble in epoxy resin and curative systems, still epoxy resin and still firming agent is mixed with inflatable carbonitride.
The present invention is first by the carbonitride (g-C of graphite-structure3N4) make inflatable carbonitride, then with inflatable carbonitride (ECN) for fire retardant, epoxy resin is matrix, firming agent, for solidifying, prepares fire-retarding epoxy resin composite material by physics synergistic. Multiple analysis means is adopted to carry out testing and characterizing, to obtaining the high-performance flame-retardant material of Halogen, cigarette efficient, nontoxic, low a new generation.
Further, in step 1) of the present invention, the mixing ratio of concentrated sulphuric acid and graphite phase carbon nitride is 10mL: 3g. This amount ratio guarantees that graphite phase carbon nitride can be dissolved completely in concentrated sulphuric acid, concentrated sulphuric acid can be made fully to be sufficiently mixed with graphite phase carbon nitride, form saturated solution, when temperature reduces time, has white crystal and precipitates out. If the words that the content of carbonitride is a lot, may result in part graphite phase carbon nitride can not be dissolved in concentrated sulphuric acid, if graphite phase carbon nitride content is little, then graphite phase carbon nitride can not form saturated solution after being dissolved in concentrated sulphuric acid, does not have white crystal and precipitate out when reducing temperature.
Dissolving described in described step 1) is the carbonitride (g-C at graphite-structure3N4) and carry out when the mixing temperature of concentrated sulphuric acid is 60～80 DEG C. At this temperature, graphite phase carbon nitride is dissolved in concentrated sulphuric acid gradually, until all dissolving, solution becomes clear light yellow.
Described step 2) in cooldown rate be 2～4 DEG C/h. Along with the slow reduction of temperature, solution starts to precipitate out white inflatable Carbon Nitride Crystal. The purpose of this rate of cooling is to grow out with enabling graphite phase carbon nitride crystal stable and uniform, if rate of cooling is more than this value, it is impossible to precipitate out white crystal. If rate of cooling is too slow, the crystal that smaller particle is very big can be produced.
Vacuum drying temperature conditions described in described step 3) is 40～60 DEG C, vacuum is 66.6～68.6kPa, the time is 2～4h. The purpose arranging this temperature and vacuum degree condition is to remove the dehydrated alcohol of plane of crystal and a small amount of moisture, allows crystal keep dry. If temperature is too low, crystal is not easily dried, if the too high meeting of temperature makes the crystal structure nitrogenizing what is said or talked about change. Vacuum drying 2-4 hour, can be completely dried sample in this time period, takes out stand-by.
Described step 2) described in the epoxy resin of de-soak, the firming agent of de-soak and the mixing quality ratio of inflatable carbonitride be 4: 1: 1, this mass ratio prepares into high performance inflatable carbonitride fire retardant.
Described step 2) described in the temperature respectively 70～75 DEG C of heating of epoxy resin and firming agent de-soak, can bubble in effectively removing system. When during such as bubble removing, temperature is higher than 75 DEG C, it is possible to the molecule structure change of system can be changed.If temperature is lower than 70 DEG C, the bubble of system can not be eliminated.
Shape in a template in order to ensure inflatable carbonitride epoxy resin, step 2 of the present invention) described in solidify temperature be room temperature, the time of solidification is 30～48 hours.
The method have the advantages that
First, 3-s-triazine ring (-C6N7) on nitrogen-atoms on there are a pair lone pair electrons, reproducibility is slightly larger compared with the carbon atom C in plumbago single slice layer, and every 3 3-s-triazine ring (-C6N7) between there is nano aperture between a bigger atom, this hole can be that the attack of oxidant provides effective attack site, thus g-C3N4The difficult combustion gas that can produce in the puffing process of interbed compound and oxidant reaction.
Second, inflatable carbonitride decomposes becomes fine and close foamed char, play heat insulation, oxygen barrier effect, the oxygen index (OI) numerical value of epoxy-resin systems can be effectively improved, extend the weightless scope of epoxy resin, delay the decomposition of epoxy-resin systems simultaneously, serve the heat stabilization improving epoxy-resin systems at hot stage.
3rd, inflatable carbonitride and epoxy resin have the good compatibility, and after high-temp combustion, foamed char can adhere well to the surface at epoxy resin, thus having stopped the chance that epoxy resin contacts with oxygen, heat, improve the fire resistance of epoxy-resin systems.
Accompanying drawing explanation
Fig. 1 is the limited oxygen index analysis chart that the present invention prepares different content expansible graphite epoxy resin composite material, carbonitride epoxy resin composite material and inflatable carbonitride epoxy resin composite material.
Fig. 2 is the expanded rear scanning electron microscope (SEM) photograph forming layer of charcoal of inflatable carbonitride epoxy resin composite material that the present invention prepares.
Detailed description of the invention
One, preparation expands carbonitride:
1, in flask, add 30～50mL concentrated sulphuric acid (preferred 10mL), and add the preferred 3g of 10～12g() carbonitride (g-C of graphite-structure3N4). It is placed on, in the thermostat water bath of magnetic stirring apparatus, opening magnetic stirring apparatus, bath temperature is risen to 60～80 DEG C, stir and dissolve to carbonitride, obtain carbonitride-concentrated sulfuric acid solution.
2, carbonitride-concentrated sulfuric acid solution being put into low temperature cold bath, be cooled to 8～10 DEG C with the speed of 2～4 DEG C/h, along with the slow reduction of temperature, solution starts to precipitate out white inflatable Carbon Nitride Crystal, the white inflatable Carbon Nitride Crystal of final acquirement.
3, white inflatable Carbon Nitride Crystal is transferred on sand core funnel, decompression sucking filtration, take solid phase and re-use absolute ethanol washing precipitation 6～8 times, it is placed in again in vacuum drying oven, arrange drying condition be 40～60 DEG C, vacuum be 66.6～68.6kPa, vacuum drying 2～4h, the white granular solid obtained is inflatable carbonitride.
Its structural formula is as follows:
Wherein, n is 1,2 or 3.
By analysis, the inflatable carbonitride every time obtained is all that in above formula, n is the mixture of 1,2 or 3.
Two, fire-retarding epoxy resin composite material is prepared:
1, respectively with expansible graphite, carbonitride and inflatable carbonitride for fire retardant, fire retardant is mixed and made into epoxy resin and firming agent respectively the weighing formula of fire proofing.
(1) preparation fire proofing containing expansible graphite, each example weighs (unit: g) with following table:
(2) preparation fire proofing containing carbonitride, each example weighs (unit: g) with following table:
(3) preparation fire proofing containing inflatable carbonitride, each example weighs (unit: g) with following table:
In the formula of each fire-retarding epoxy resin composite material, the quality of fire retardant (expansible graphite, carbonitride and inflatable carbonitride) accounts for the 0% of fire-retarding epoxy resin composite material gross mass, 5%, 8%, 10%, 12% and 15% respectively above.
Cured above dose is in industry conventional solidified dose.
2, each fire-retarding epoxy resin composite material is prepared:
Epoxy resin, firming agent are respectively placed in beaker, are placed in 70～75 DEG C of water-baths and heat, remove produced bubble when epoxy resin, firming agent weighing respectively.
Corresponding fire retardant is poured in the epoxy resin removing bubble, stir, then add the firming agent removing bubble, stir, obtain compound.
Compound is poured in preprepared curing mold, cold curing 30～48 hours, the demoulding, obtain each fire-retarding epoxy resin composite material.
Three, the performance of the fire retardant of any of the above different content is analyzed:
1, use limited oxygen index (LOI) that heat stability and the combustibility of above each fire-retarding epoxy resin composite material are studied.
Layer of charcoal after using scanning electron microscope (SEM) that fire retarding epoxide resin system is heated is analyzed: adopt HC-2 type oxygen index measurer, by the GB4609-84 method specified, respectively the flame-retardant epoxide resin material of different flame-retardant epoxide resin materials and the fire retardant adding different content is carried out limiting oxygen index determination, obtain the limited oxygen index analysis chart of Fig. 1.
In Fig. 1, curve expansible graphite represents the limited oxygen index of fire-retarding epoxy resin composite material and the graph of a relation of expansible graphite content.
In Fig. 1, curve carbonitride represents the limited oxygen index of fire-retarding epoxy resin composite material and the graph of a relation of carbonitride content.
In Fig. 1, the inflatable carbonitride of curve represents the limited oxygen index of fire-retarding epoxy resin composite material and the graph of a relation of inflatable carbonitride content.
From figure 1 it appears that the limited oxygen index of expansible graphite, carbonitride and inflatable carbonitride these three flame-retardant system increases along with the increase of respective flame retardant agent content. After amount of flame-retardant agent is more than 15%, system limited oxygen index growth trend is slow.
Simultaneously it is also seen that inflatable carbonitride flame retardant effect is than the good flame retardation effect of expansible graphite. When inflatable carbonitride consumption is 10%, being equivalent to expansible graphite consumption is 12%. When inflatable carbonitride consumption is 10% time, system oxygen index (OI) just reaches 30.2%. This is because inflatable carbonitride is compared, expansible graphite has the better compatibility, forms finer and close layer of charcoal after expanded by heating, can better play the effect of heat insulation oxygen barrier, so that the fire resistance of system is better.
2, adopt JSM-5900LV type scanning electron microscope, the inflatable carbonitride epoxy resin body of sample used by scanning electron microscope burn under limited oxygen index after charcoal. Sample is scanned after surface gold-plating, obtains the result of Fig. 2.
From figure, 2 it can be seen that inflatable carbonitride expands after being heated, and forms the foamed char with small hole, and the layer of charcoal formed is fine and close, stable and charcoal bedding void is less. The layer of charcoal formed after inflatable carbonitride expanded by heating, can better play the effect of heat insulation oxygen barrier, delay or inhibit the burning of system.
Claims (9)
1. the preparation method of inflatable carbonitride fire retarding epoxide resin, it is characterised in that comprise the following steps:
1) when magnetic agitation, by the carbonitride (g-C of graphite-structure3N4) be dissolved in concentrated sulphuric acid, prepare carbonitride-concentrated sulfuric acid solution; Carbonitride-concentrated sulfuric acid solution is cooled to 8～10 DEG C, prepares inflatable Carbon Nitride Crystal; Adopt absolute ethanol washing to remove the sulfuric acid solution on inflatable Carbon Nitride Crystal surface inflatable Carbon Nitride Crystal, then by inflatable Carbon Nitride Crystal vacuum drying in vacuum drying case, prepare inflatable carbonitride;
2) after inflatable carbonitride first being mixed with the epoxy resin of de-soak again with the firming agent Homogeneous phase mixing of de-soak, be subsequently placed in curing mold solidify, prepare inflatable carbonitride fire retarding epoxide resin.
2. the preparation method of inflatable carbonitride fire retarding epoxide resin according to claim 1, it is characterised in that: in described step 1), concentrated sulphuric acid is 10mL: 3g with the mixing ratio of graphite phase carbon nitride.
3. the preparation method of inflatable carbonitride fire retarding epoxide resin according to claim 1, it is characterised in that: dissolving described in described step 1) is the carbonitride (g-C at graphite-structure3N4) and carry out when the mixing temperature of concentrated sulphuric acid is 60～80 DEG C.
4. the preparation method of inflatable carbonitride fire retarding epoxide resin according to claim 1, it is characterised in that: in described step 1), cooldown rate is 2～4 DEG C/h.
5. the preparation method of inflatable carbonitride fire retarding epoxide resin according to claim 1, it is characterised in that: vacuum drying temperature conditions described in described step 1) is 40～60 DEG C, vacuum is 66.6～68.6kPa, the time is 2～4h.
6. the preparation method of inflatable carbonitride fire retarding epoxide resin according to claim 1, it is characterised in that: described step 2) described in the epoxy resin of de-soak, the firming agent of de-soak and the mixing quality ratio of inflatable carbonitride be 4: 1: 1.
7. the preparation method of inflatable carbonitride fire retarding epoxide resin according to claim 1, it is characterized in that: described step 2) in epoxy resin is added in heat abstraction epoxy resin when ambient temperature is 70～75 DEG C bubble, obtain still epoxy resin.
8. the preparation method of inflatable carbonitride fire retarding epoxide resin according to claim 1, it is characterised in that: described step 2) in firming agent added when ambient temperature is 70～75 DEG C the bubble in heat abstraction firming agent, obtain still firming agent.
9. the preparation method of inflatable carbonitride fire retarding epoxide resin according to claim 1, it is characterised in that: described step 2) described in the temperature that solidifies be room temperature, the time of solidification is 30～48 hours.
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| CN109824942A (en) * | 2019-02-26 | 2019-05-31 | 西北师范大学 | The preparation and its application of hybrid inorganic-organic materials composite flame-retardant agent |
| CN110093013A (en) * | 2019-05-07 | 2019-08-06 | 安徽美佳新材料股份有限公司 | A kind of fire-retardant epoxy resin |
| CN110183773A (en) * | 2019-07-03 | 2019-08-30 | 西北师范大学 | The preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material |
| CN110183831A (en) * | 2019-05-21 | 2019-08-30 | 南京工业大学 | Preparation method and application of metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame-retardant material |
| CN112129796A (en) * | 2020-09-18 | 2020-12-25 | 宁波工程学院 | Preparation method of combustion carbon layer for analyzing flame-retardant mechanism |
| CN113621308A (en) * | 2021-09-02 | 2021-11-09 | 青岛信拓海昌工程技术有限公司 | Waterproof flame-retardant heat-insulation coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109824942A (en) * | 2019-02-26 | 2019-05-31 | 西北师范大学 | The preparation and its application of hybrid inorganic-organic materials composite flame-retardant agent |
| CN109824942B (en) * | 2019-02-26 | 2021-04-20 | 西北师范大学 | Preparation and application of organic-inorganic hybrid material composite flame retardant |
| CN110093013A (en) * | 2019-05-07 | 2019-08-06 | 安徽美佳新材料股份有限公司 | A kind of fire-retardant epoxy resin |
| CN110183831A (en) * | 2019-05-21 | 2019-08-30 | 南京工业大学 | Preparation method and application of metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame-retardant material |
| CN110183773A (en) * | 2019-07-03 | 2019-08-30 | 西北师范大学 | The preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material |
| CN110183773B (en) * | 2019-07-03 | 2021-06-25 | 西北师范大学 | Preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material |
| CN112129796A (en) * | 2020-09-18 | 2020-12-25 | 宁波工程学院 | Preparation method of combustion carbon layer for analyzing flame-retardant mechanism |
| CN113621308A (en) * | 2021-09-02 | 2021-11-09 | 青岛信拓海昌工程技术有限公司 | Waterproof flame-retardant heat-insulation coating and preparation method thereof |
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